Source: UNIVERSITY OF TENNESSEE submitted to NRP
VALUE ADDDED CHEMICALS AND MATERIALS FROM BIOMASS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
HATCH
Reporting Frequency
Annual
Accession No.
0228646
Grant No.
(N/A)
Cumulative Award Amt.
(N/A)
Proposal No.
(N/A)
Multistate No.
(N/A)
Project Start Date
May 1, 2012
Project End Date
Apr 30, 2017
Grant Year
(N/A)
Program Code
[(N/A)]- (N/A)
Recipient Organization
UNIVERSITY OF TENNESSEE
2621 MORGAN CIR
KNOXVILLE,TN 37996-4540
Performing Department
Center for Renewable Carbon
Non Technical Summary
Among the portfolio of alternative energy sources, biomass stands out as the only source of liquid fuels and chemicals. Recognizing this unique attribute, the integrated biorefinery concept has been developed to produce a suite of chemicals from renewable carbon sources that can substitute for the fossil carbon molecules that we rely on today. This integrated program will develop new front-end biomass fractionation processes to yield pure product streams for downstream conversion to fuels, value-added chemicals, and materials. The program will emphasize the development of lignin as a precursor for carbon products, including fiber for high-value products. Also, new chemicals for polymer synthesis will be developed as potential matrices for carbon fiber composites. The results of this work will improve the economic viability of the integrated biorefinery and the value of bioenergy sources will be enhanced.
Animal Health Component
100%
Research Effort Categories
Basic
(N/A)
Applied
100%
Developmental
(N/A)
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
5110699200030%
5110699202020%
5111629200020%
5111629202030%
Knowledge Area
511 - New and Improved Non-Food Products and Processes;

Subject Of Investigation
1629 - Perennial grasses, other; 0699 - Trees, forests, and forest products, general;

Field Of Science
2020 - Engineering; 2000 - Chemistry;
Goals / Objectives
This research program is comprised of five discrete, but closely related projects designed to introduce new chemicals and materials from renewable carbon resources into the marketplace. Importantly, progress in any individual project does not rely on any other; however, effective coordination of the individual projects affords real synergy that will lead to broad impacts. The following objectives define our program: 1) Explore the complex relationships between biomass chemical composition and structure, and the ability to provide pure process streams using innovative separations technologies, including organosolv fractionation and ionic liquids; 2) Advance chemical and biochemical catalysis as a platform technology to develop new transformation pathways for the production of high-value organic chemicals from carbohydrate and lignin streams isolated from biorefining systems (e.g., developed in objective 1); 3) Develop the capacity to design biomass/refining technologies that provide precursors (i.e., lignin and cellulose nanocrystals) optimized for further processing in advanced material systems (e.g., objective 1 and 2); and, 4) Create new testing and design protocols to accelerate development of biobased composite materials with functionally innovative performance characteristics enabled by novel renewable carbon building blocks, and innovative manufacturing processes (e.g., from objective 2 and 3).
Project Methods
Biobased products will provide the economic incentive required to support a robust biorefining industry. Integrating production of these high value chemicals and materials with high volume, low value biofuels will result in an overall profitable operation that also reduces the nation's dependence on foreign supplies of strategic raw materials, diminishes the environmental footprint of chemical and materials manufacture, and dramatically increases the contribution of the domestic rural economy to the nation's industrial sector. This program will provide further information and insight into the potential for fractionation of agricultural and forest biomass into pure process streams for further conversion to fuels, chemicals, and materials. The individual projects are closely aligned to address key aspects of the broader system, providing improved economic viability. Research will advance high-throughput technologies and multivariate statistical methods to routinely provide fundamental information on chemical and physical characteristics of the feedstock. Near infrared, infrared, and pyrolysis-GC/MS spectroscopies have considerable potential for on-line or at-line assessment of biomass, and are the focus of this element of the project. With information on chemical and physical properties of the biomass available, organosolv technology will be further developed for biomass fractionation, as will innovative, ionic liquid media. A structured experimental approach will be used to better define the impact of reaction conditions and solvent characteristics on separations efficiency. Also, NMR and vibrational spectroscopy will be used to evaluate the level of control over lignin structure and properties that is available through these fractionation methods. Fundamental chemical transformation pathways for both lignin and carbohydrates will be studied using model compounds representative of potential biorefinery product streams. A key target of this work is ketoglutaric acid, and work will focus on its development as a monomer for polyester formulations. Value-added utilization of lignin is important to economic viability of the biorefinery, and is a major goal of the program. Lignin preparations from either the organosolv or ionic liquid technologies will be fully characterized in terms of structure and thermal properties. Research will evaluate the potential of the different lignins as a precursor for a portfolio of carbon products, including fibers and foams. In related work, the potential to isolate cellulose nanocrystals from biorefinery operations will be developed, as well. Processes to more effectively utilize this valuable material as reinforcement in polymer composites will be developed. Finally, new approaches to evaluate novel materials and accelerate their adoption into the market place will be advanced. Our hypothesis is that an iterative "smart" testing regime can be integrated into a processing platform to develop advanced composite structures using renewable bio-based components. This highly integrated program will yield new, value-added chemicals and materials that will improve the economics of fuel production.

Progress 05/01/12 to 04/30/17

Outputs
Target Audience:Agricultural producers, the scientific community at large, academia, national laboratories, federal and state agencies, private industry, public interest groups, the government sector, land-grant institutions, biofuel industry leaders, and additional stakeholders. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Faculty Training Dr. Joseph J. Bozell was chosen as a Fulbright Fellow in 2015 and a Fulbright Specialist in 2016. Research related to this award was carried out in 2015 - 2016 at Ghent University in Belgium. Graduate Students Training Ernesto Zuleta - Ph. D. expected 2018 Valerie Garcia-Negron - M.S. Materials Science and Engineering 2017. Processing-property-structure relationships of carbonaceous materials derived from renewable lignin products Nathan Meek - M.S. Civil Engineering 2016. Development of lignin carbon fiber and reinforced composites Mark Banholzer - M. S. 2016, lignin maximization: analyzing the impact of different feedstocks and feedstock ratios using organosolv fractionation James Daleiden - M. S. 2016, Biotransformation of Lignin Model compounds--Concept for hydrocarbon dropin fuel from lignocellulosic Biomass Andreas Attwenger - M. S. 2013, Value-added lignin-based carbon fiber from organosolv fractionation of poplar and switchgrass Hagen Maraun - M. S. 2013, Maximizing lignin yield using experimental design: analyzing the impact of solvent composition and feedstock particle size on the organosolv process in the presence of feedstock contamination Astner, Lignin Yield Maximization of Lignocellulosic Biomass by Taguchi Robust Product Design using Organosolv Fractionation Q. Liu - M.S. Pretreatment and posttreatment approaches for reducing biomass inorganic impurities during gasification The cellulose nanofiber developing work has included the training of five Ph.D. students (Qijun Zhang, Dong Xing, Libo Ma, Jingjing Fu, Jingda Huang). Preenaa Moyer - M. S. Biosystems Engineering 2017; Biomass processing using ionic liquids" effects of 3-methylimidazolium cations and carboxylates anions. Holly Haber - M.S. Biosystems Engineering; expected to graduate in May 2018 Jing Wang - PhD Biosystems Engineering 2016; The impacts of biopolymer-ionic liquid interactions on the utilization of lignocellulosic biomass. Postdoc training Nibedita Sanyal, Zhe Jiang, C. J. O'Lenick, Diana Cedeno, Sabornie Chatterjee, Ashok Ganta, Berenger Biannic, Kun Cheng, Costyl Njiojob, Rebecca Key, William Hartwig, Shahirina Alam, Yagya Regmi, Parthapratim Das, Kalavathy Rajan, Rangana Wijayapala, Omid Hosseinaei, Rohit Uppal, Pyoungchung Kim; Jingming Tao; Warren Edmunds; Priyanka Bhattacharya Undergrad interns Anton Astner, Rene Buchinger, Hagen Maraun, Stacy Warwick, Portia Nottingham, Lukas Delbeck, John Anderson, Felix Weishaupt, Christian Pfeffer, Thomas Kastenhuber, Jeffrey Mann, Gimgun Loi, Kristen Edds, Nathan Meek, Edy Cicilio, Emmanuel Deleon, Sarra Acado, Andrew Whisler, Breckinridge Sharbel, Chet Greer. Technicians Anton Astner, Jimmy Mynes, Alexandra Peeden, Eldon English, Valerie Garcia-Negron, Derek Cressy, Choo Hamilton, Keonhee Kim, Lindsey Kline, Mark Alexander. Hosted International Researchers Xuemei Li, Kyungkeun Noh How have the results been disseminated to communities of interest?Results have been disseminated through multiple publications in high impact journals, presentations at professional meetings, presentations to lay audiences, and interaction with industrial and government stakeholders. This has included visits by USDA and DOE scientists and program managers along with visits from industry such as: Volkswagen, Mitsubishi, Domtar, Valmet, Perkin Elmer, Georgia Pacific, M&G Gruppo, Huntsman, Louisiana Pacific, Proton Power, Novozymes, Huber, AssuredBio, Shaw Corporation, Graftech, YanFeng, and Sweetwater Energy. The Center for Renewable Carbon participates in the annual Ag Day research showcase at the Unviersity of Tennessee. This carnival-style event is open to members of the community and takes place for a four-hour block before a high-profile SEC football game in the fall of each year. In 2016, the CRC's booth on "Hot-melt extrusion of renewable fibers" won the award for Best Booth. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? I.High-throughput biomass analysis methods. We have constructed near and mid infrared predictive models for the determination of the chemical composition of a variety of lignocellulosic biomass. Properties of interests include cellulose, hemicellulose, lignin, extractives, ash, carbon, and moisture content. These models have been tested and validated under varying environmental conditions (laboratory, bioprocessing facilties, field). The well characterized biomass samples used to construct these models have been tagged and were added to CRC biomass library, which contains over a thousand different samples. We have inititiated a new collaboration with Perten Instruments, a leading supplier of advanced analytical instruments for the food and agricultural industries. Through this partnsership, we have had access to new and advanced spectrometers that we have tested for the bioenergy industry. II.Biomass Fractionation. Organosolv Refining. Work in this period has carried out investigation of solvent fractionation to provide selective and efficient production of cellulose, hemicellulose and lignin from feedstocks common to the southeastern US (switchgrass, poplar, and more recently, southern yellow pine), suitable for transformation to biofuels or high value chemicals. Statistical experimental design has been key to optimizing process yields and effectiveness, and generating maximum amounts of data with a minimum number of experiments. This effort continues to be critical to the success of multiple programs and proposals developed within our center, providing individual lignocellulosic components for PIs within the center and collaborators outside of UT. We have an ongoing partnership with TennEra to supply lignin for the production of carbon fiber and composites. This collaboration led to process design for scaleup of fractionation operation of the process at largest scale to date (multi-kg). Lignin has been of particular interest in these studies, and our program has examined production of both cellulose and lignin as part of a co-product manufacturing concept. Ionic Liquid Refining. We have taken advantage of the unique property of ionic liquid at dissolving whole lignocellulosic biomass to investigate the manufacture of fibers and fibers. We demonstrated the dissolution of biomass in the most commonly used ionic liquid, i.e. 1-ethyl-3methylimidazolium acetate (EmimAc), was enhanced after the partial removal of hemicellulose, the least soluble biomass component in EmimAc. The?resulting biomass−IL solution was successfully then cast into free-standing films using?different coagulating solvents, yet preserving the polymeric nature of the?biomass constituents. Methanol coagulated films exhibited a cocontinuous 3D-?network structure with dispersed domains of less than 100 nm. The?consolidated films with controllable morphology and structural order demonstrated tensile properties better than those of quasi-isotropic wood. The developed methods for producing these biomass derivatives have potential for fabricating novel green materials with superior performance from woody and grassy biomass. Value-Added Chemicals. Condensed-phase biomass conversion. We target utility of lignin and carbohydrates using innovative catalysts to convert them to high value chemicals. During this program, we synthesized and tested a wide range of Co-Schiff base catalysts for conversion of lignin and lignin models to high value aromatics. Our efforts identified structural components necessary for efficient catalysis, and have identified factors that deactivate the catalyst. In parallel, we developed new catalysts for the benzylic oxidation of lignin and lignin models, leading to a unique three metal catalyst able to generate high value aromatics from lignin and lignin models. This work led to a patent that was licensed by TennEra LLC. We have also used computational evaluation extensively in this work to understand and control the process. Current work is examining these catalysts for development of improved wood pulping processes, in partnership with the Forest Service and ORNL. Additional work converted carbohydrate based bolaforms and dissolved cellulose into nanostructural materials. We used these observations to construct catalyst delivery systems for the conversion of whole biomass to value-added chemicals. Our efforts targeted improved synthesis of the catalyst delivery system through several different approaches, resulting in novel catalysts able to convert lignin models into high value aromatics. ?Vapor-phase biomass conversion. We have investigated a pair of catalyst families for vapor-phase upgrading (VPU) of pyrolysis oil vapors. The first family includes mixed-metal oxides that contain magnesium, zinc, and aluminum. These materials have shown utility for cellulose and whole biomass deoxygenation to potentially produce liquid products that are enriched in furanic compounds.In addition to the mixed-metal oxides, we have investigated new phosphide-carbide heterostructures for VPU of biomass. We have demonstrated that the product composition of catalytic fast pyrolysis depends on the ratio of phosphide to carbide in these catalysts. We believe that new active sites are generated at the junction between the phosphide and carbide species due to a very low lattice mismatch between these structures. Future investigations will include probing these new active sites using advanced spectroscopic techniques as well as scaling these reactions to determine the composition of bio-oil produced during CFP. III.Advanced Materials. Carbon Fiber Production - A focus of our research program has been to upgrade lignin either from pulp residues or as part of a biorefinery process to high value materials. Over the past five years, we have produced multiple products from lignin. First, we successfully produced 100% switchgrass lignin, 100% hardwood lignin carbon fiber composites. These materials demonstrated promise as a fiber reinforcement as they possessed superior adhesion properties with a polymer matrix without the aid of an adhesion promoter compared to commercial PAN fibers that had been sized. Second, we have demonstrated that we can improve processing and fiber properties by using blends of lignins from different feedstocks. Third, we produced lignin based battery anode materials materials from both kraft lignin and biorefinery lignin. These materials, because of their nano-graphitic structure, demonstrated superior cycling and in certain cases improved capacity over flake graphite. Fourth, the nanographitic carbon material produced from lignin demonstrated high efficacy per surface area at capturing methyl mercury in water. This was accomplished with low sulphate release which can exasperbate the production of MeHg. Our discovery is important for environmental remediation of mercury contaminated streams at a low cost with a renewable product. Cellulose Nanofiber (NFC) - We have developed an environmentally friendly and robust semitransparent superhydrophobic coating through CVD modification for reducing surface free energy after a simple two-spraying process, which included initially spraying a commercial spray paint as adhesive onto substrate surfaces to support high-adhesion-stress and then spraying NFC ethanol suspension to build suitable roughness. The resulting NFC superhydrophobic coating showed good self-cleaning properties. In addition, the coating also exhibited outstanding abrasion resistance and durability and could retain superhydrophobic properties after sandpaper abrasion, finger-wipe, knife-scratch, long-time impregnation in water, UV radiation, and long-time staying at low temperature. We manufactured carbon nanofibers (CNF) from carbonized cellulose nanofibers (CCNF) by carbonizing freeze-dried cellulose nanofibers first, then preparing acrylonitrile-butadiene-styrene (ABS)/CCNF nanocomposites by extruder.

Publications

  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Bozell, J. J. Approaches to selective catalytic conversion of lignin: a grand challenge for biorefinery development. Top. Curr. Chem. 2014, 353, 229-256.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Bozell, J. J.; Astner, A.; Baker, D.; Biannic, B.; Cedeno, D.; Elder, T.; Hosseinaei, O.; Delbeck, L.; Kim, J. W.; O'Lenick, C. J.; Young, T. Integrating separation and conversion-conversion of biorefinery process streams to biobased chemicals and fuels. Bioenergy Res. 2014, 7, 856-866.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Eberhardt, T. L.; Labb�, N.; So, C. L.; Kim, K.; Reed, K. G.; Leduc, D. J.; Warren, J. M. Effects of long-term elevated CO2 treatment on the inner and outer bark chemistry of sweetgum (Liquidambar styraciflua L.) trees. Trees, 2015, 29(6), 1735-1747, DOI: 10.1007/s00468-015-1254-8
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Jarrell, T. M.; Marcum, C. L.; Sheng, H. M.; Owen, B. C.; O'Lenick, C. J.; Maraun, H.; Bozell, J. J.; Kenttamaa, H. I. Characterization of organosolv switchgrass lignin by using high performance liquid chromatography/ high resolution tandem mass spectrometry using hydroxide-doped negative-ion mode electrospray ionization. Green Chem. 2014, 16, 2713-2727.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Sammond, D. W.; Yarbrough, J. M.; Mansfield, E.; Bomble, Y. J.; Hobdey, S. E.; Decker, S. R.; Taylor, L. E.; Resch, M. G.; Bozell, J. J.; Himmel, M. E.; Vinzant, T. B.; Crowley, M. F. Predicting enzyme adsorption to lignin films by calculating enzyme surface hydrophobicity. J. Biol. Chem. 2014, 289, 20960-20969.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Wu, Q.; Meng, Y.; Wang, S.; Li, Y.; Fu, S.; Ma, L.; Harper, D. P. Rheological behavior of cellulose nanocrystal suspension: Influence of concentration and aspect ratio. Journal of Applied Polymer Science. 2014. 131(15) 40525. DOI: 10.1002/app.40525
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Liu, C., Y. Zhang, S. Wang, Y. Meng, and O. Hosseinaei. Micromechanical properties of the interphase in cellulose nanofiber-reinforced PF bondlines. BioResources, 2014. 9(3): 5529-5541.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Kim, P.; Hensley, D.; Labb�, N. Nutrient release from switchgrass derived biochar pellets embedded with fertilizers. Geoderma, 2014, 232-234, 341-351, DOI: 10.1016/j.geoderma.2014.05.017
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Kim, P.; Weaver, S.; Noh, K.; Labb�, N. Characteristics of bio-oils produced by an intermediate semipilot scale pyrolysis auger reactor equipped with multistage condensers. Energy and Fuels, 2014, 28(11), 6966-6973, DOI: 10.1016/j.geoderma.2014.05.017
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Martin, M. Z.; Labb�; N.; Wagner, R. J. 2014. Applications of high resolution laser: induced breakdown spectroscopy for environmental and biological samples. Laser induced breakdown spectroscopy, Springer Series in Optical Sciences, eds. S. Musazzi and U. Perini, vol. 182, pp 439-456.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Baxter, L. H.; Mazarei, M.; Labb�, N.; Kline, L. M. et al. Two-year field analysis of reduced recalcitrance transgenic switchgrass. Plant Biotechnology Journal, 2014, 12(7), 914-924, DOI: 10.1111/pbi.12195
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Biannic, B.; Bozell, J. J. Efficient cobalt-catalyzed oxidative conversion of lignin models to benzoquinones. Org. Lett. 2013, 15, 2730-2733.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Dyer, C.; Jiang, Z.; Bozell, J.; Rials, T.; Heller, W. T.; Dadmun, M. D. Effect of chain atructure on the miscibility of cellulose acetate blends: A small-angle neutron scattering study. Soft Matter 2013, 9, 3402-3411.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Elder, T.; Bozell, J. J.; Cedeno, D. The effect of axial ligand on the oxidation of syringyl alcohol by Co(salen) adducts. Phys. Chem. Chem. Phys. 2013, 15, 7328-7337.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Petersen, G.; Bozell, J.; White, J. In Process Development for Renewable Materials; Imhof, P., van der Wall, J. K., Eds.; Wiley: New York, 2013.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Sammons, R. J.; Harper, D. P.; Labbe�, N.; Bozell, J. J.; Elder, T.; Rials, T. G. Characterization of organosolv lignins using thermal and FT-IR spectroscopic analysis. Bioresources. 2013. 8(2): 2752-2767.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Schreiber, S. B.; Bozell, J. J.; Hayes, D. G.; Zivanovic, S. Introduction of primary antioxidant activity to chitosan for application as a multifunctional food packaging material. Food Hydrocolloids 2013, 33, 207-214.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Shi, Z. Q.; Cai, Z. Y.; Wang, S. Q.; Zhong, Q. X.; Bozell, J. J. Short-time ultrasonication treatment in enzymatic hydrolysis of biomass. Holzforschung 2013, 67, 891-897.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Wu, Y., S. Wang, D. Zhou, Y. Zhang, X. Wang and R. Yang. Biodegradable poly(vinyl alcohol) nanocomposites made from rice straw fibrils: Mechanical and thermal properties. Journal of Composite Materials. 2013. 47(12): 1449-1459.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Q Wu, Y Meng, K Concha, S Wang, Y Li, L Ma, S Fu. Influence of temperature and humidity on nano-mechanical properties of cellulose nanocrystal films made from switchgrass and cotton. Industrial Crops and Products. 2013. 48: 28-35.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Kline, L. M.; Johnson, A. M.; Kim, P. C.; Jackson, S.; Labb�, N. Monitoring switchgrass composition to optimize harvesting periods for bioenergy and value-added products. Biomass & Bioenergy, 2013, 56, 29-37, DOI: 10.1016/j.biombioe.2013.04.023
  • Type: Journal Articles Status: Published Year Published: 2012 Citation: Kim, J. W.; Harper, D. P.; Taylor, A. M. Effect of epoxy embedment on micromechanical properties of brown-rot-decayed wood. Wood and Fiber Science. 2012. 44(1): 103-107.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Kim, P.; Johnson, A. M.; Essington, M. E.; Radosevich, M. A.; Kwon, W. T.; Lee, S. H.; Rials, T. G.; Labb�, N. Effect of pH on surface characteristics of switchgrass-derived biochars produced by fast pyrolysis. Chemosphere, 2013, 90(10), 2623-2630, DOI: 10.1016/j.chemosphere.2012.11.021
  • Type: Journal Articles Status: Published Year Published: 2012 Citation: Cedeno, D.; Bozell, J. J. Catalytic oxidation of para-substituted phenols with cobalt-Schiff base complexes/O2-selective conversion of syringyl and guaiacyl lignin models to benzoquinones. Tetrahedron Lett. 2012, 53, 2380-2383.
  • Type: Journal Articles Status: Published Year Published: 2012 Citation: Liu, L.; Ye, X. P.; Bozell, J. J. A comparative review of petroleum-based and bio-based acrolein production. ChemSusChem 2012, 5, 1162-1180.
  • Type: Journal Articles Status: Published Year Published: 2012 Citation: Labb�, N.; Kline, L. M.; Moens, L.; Kim, K.; Kim, P.; Hayes, D. G. Activation of lignocellulosic biomass by ionic liquid for biorefinery fractionation. Bioresource Technology, 2012, 104, 701-707.
  • Type: Journal Articles Status: Published Year Published: 2012 Citation: Jean-Philippe, S. R.; Labb�, N.; Franklin, J. A.; Johnson, A. M. Detection of mercury and other metals in mercury contaminated soils using mid-infrared spectroscopy. Proceedings of the International Academy of Ecology and Environmental Sciences, 2012, 2, 139-149.
  • Type: Journal Articles Status: Published Year Published: 2012 Citation: Jean-Philippe, S. R.; Labb�, N., Damay, J., Franklin, J. A., Hughes, K. Effect on mercuric compounds on pine and sycamore germination and early survival. American Journal of Plant Science, 2012, 3,150-158.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2017 Citation: Biobased Platform Targets - What Chemical Should We Make? Joseph J. Bozell, Presented at the Bioprivileged Molecules through Integrated Biology and Chemistry workshop, January 5-6, 2017, Hyatt Regency Crystal City, Arlington, VA
  • Type: Conference Papers and Presentations Status: Other Year Published: 2017 Citation: Bozell, J. J., Can the biorefinery survive cheap oil? approaches to high value chemical products from carbohydrates and lignin; Presented at the 12th Exploring Lignocellulosic Biomass Conference, Reims, France, June 24th, 2016
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Astner, A., Bozell, J. J., Optimizing Solvent Fractionation for Loblolly Pine using Response Surface Methodology: Impact on Component Properties, Presented at the 2016 IBSS annual meeting, Oak Ridge, TN, July 27-28, 2016
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Astner, A., Bozell, J. J., Young, T. Y., Rials, T., Kim, K., Hossaeinei, O., Labb� N., Thermal and Chemical Properties of Organosolv Lignins isolated from Loblolly Pine using Response Surface Design, Presented at the 2016 IBSS annual meeting, Oak Ridge, TN, July 27-28, 2016
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Bozell, J. J., Designing catalysts for converting biorefinery lignin and carbohydrates to high value chemicals, Presented at University of Copenhagen, Copenhagen, Denmark, January 15th, 2016
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Tao, J., Hosseinaei, O., Kim, P., Harper, D., Bozell, J., Rials, T., Labb�, N., Chemical and thermal characterization of organosolv yellow poplar lignins fractionated by different time periods, presented at the 251st national meeting of the American Chemical Society, San Diego, CA, March 13-17 2016; CELL-11
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Key, R., Bozell, J. J., Design of novel tri- and tetradentate Co-Schiff base complexes for selective catalytic cleavage of lignin, presented at the 251st national meeting of the American Chemical Society, San Diego, CA, March 13-17 2016; CELL-48
  • Type: Journal Articles Status: Published Year Published: 2012 Citation: Kim, J. W.; Park, S.; Harper, D. P.; Rials, T. G. Structure and thermo-mechanical properties of stretched cellulose films. Journal of Applied Polymer Science. 2012. DOI: 10.1002/app.38149
  • Type: Journal Articles Status: Published Year Published: 2012 Citation: Henry, N.; Harper, D. P.; Dadmun, M. Optimizing noncovalent interactions between lignin and synthetic polymers to develop effective compatibilizers. Macromolecular Chemistry and Physics. 2012. doi: 10.1002/macp.201100633.
  • Type: Journal Articles Status: Published Year Published: 2012 Citation: Kaboorani, A., Riedl, B., Blanchet, P., Fellin, M., Hosseinaei, O., Wang, S. Nanocrystalline Cellulose (NCC): A renewable nano-material for polyvinyl acetate (PVA) adhesive. European Polymer Journal. 2012. 48(11): 1829-1837.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2017 Citation: The great experiment: separation and conversion of lignocellulosic biomass for the production of high value chemicals, Joseph J. Bozell, Presented at the Great Experiment Symposium, Knoxville, TN, March 13th, 2017
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Hartwig, W., Bozell, J. J., Synthesis of glycal-based bolaamphiphile cobalt-Schiff base complexes for catalytic breakdown of lignin in whole biomass, presented at the 252nd national meeting of the American Chemical Society, Philadelphia, PA, August 21-25, 2016; ORGN-660
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Bozell, J. J., Biorefinery survival in an era of cheap oil: approaches to high value chemical products from carbohydrates and lignin, presented at the 12th International Conference on Renewable Resources and Biorefineries, Ghent, Belgium, May 30th, 2016
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Bozell, J. J., Designing catalysts for converting biorefinery lignin and carbohydrates to high value chemicals, Presented at University of Geneva, Geneva, Switzerland, January 18th, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Bozell, J. J., Designing catalysts for converting biorefinery lignin and carbohydrates to high value chemicals, Presented at Utrecht University Utrecht, Netherlands, January 13th, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Bozell, J. J., Designing catalysts for converting biorefinery lignin and carbohydrates to high value chemicals, Presented at Ghent University Ghent, Belgium, November 19th, 2015.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Ernesto C. Zuleta S., Joseph J. Bozell, Catalytic oxidation of para-substituted phenols with cobalt organometallic catalysts and nitroxyl radicals. Presented at: Center for Direct Catalytic Conversion of Biomass to Biofuels C3Bio, Annual Meeting, West Lafayette, IN, October 2015 (Poster).
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Synthesis of glycal-based bolaamphiphiles tethered to cobalt-Schiff base complexes for catalyst delivery to lignocellulosic biomass; Joseph J. Bozell, Costyl N. Njiojob, Brian Long, Presented at the 249th annual meeting of the American Chemical Society, Wednesday, March 25th, 2015
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Studies towards cobalt-catalyzed conversion of biorefinery lignin to value-added chemicals and fuels, Bozell, Joseph J.; Biannic, Berenger; Ngnouomeuchi, Costyl N.; Key, Rebecca E.; Zuleta, Ernesto C.; Hartwig, William T. presented at Energy Frontier Research Centers Primary Investigator Meeting, Washingon, D.C. October 26-27, 2015.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Bozell, J. J., Elder, T., Biannic, B., Cedeno, D., Chatterjee, S., Cheng, K., Njiojob, C., Catalysis for conversion of biorefinery lignin to high value chemicals - structural and computational analysis for improved catalyst design, Presented at the 18th ISWFPC, BOKU, Vienna, Austria, September 9 - 11, 2015.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Can the biorefinery survive cheap oil? Approaches to high value chemical products from carbohydrates and lignin; Joseph J. Bozell, presented at the 2015 Sun Grant regional meeting, Auburn University, February 3rd, 2015
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Biorefining in an era of cheap oil. Approaches to high value chemical products from carbohydrates and lignin; Joseph J. Bozell, presented at the UT Plant Research Center Colloquium, April 30th, 2015
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Organic synthesis and catalysis for conversion of carbohydrates and lignin; Joseph J. Bozell, presented at the regional University research symposium, VPI, Blacksburg, VA, May 21, 2015
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Synthesis of glycal bolaform-linked cobalt catalysts for use in targeted delivery to biomass; William T. Hartwig (speaker), Costyl Njiojob Ngnouomeuchi, Joseph J. Bozell, presented at the C3Bio Annual Meeting, October 2015
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Design of novel tridentate Co-Schiff base complexes for the catalysis of para-substituted phenolic lignin models to para-benzoquinone; Rebecca E. Key (speaker) and Joseph J. Bozell, presented at the C3Bio Annual Meeting, Purdue University, October 2015
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Design of novel, supported metallo-Schiff base catalysts for the conversion of both whole biomass and biorefinery lignin into high value, low-molecular-weight aromatics; Rebecca E. Key, William T. Hartwig, Costyl N. Njiojob, Ernesto C. Zuleta, Joseph J. Bozell, presented at the DOE EFRC MidTerm review, Washington, DC, December 2015
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Cobalt-catalyzed oxidation of p-substituted phenols: developments toward an efficient conversion of lignin to high value chemicals (first prize winner SEC conference), Berenger Biannic (presenter), Joseph J. Bozell SEC Symposium Atlanta, GA 2/10-2/12/13
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Enhancing the value of lignin through bacterial conversion, Ashley M. Frank (presenter), James J. Daleiden, Joseph J. Bozell, Alison Buchan, ASM National meeting Denver, May 2013
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Second generation catalytic processes for the conversion of biorefinery lignin to chemicals and fuels, Joseph J. Bozell, Berenger Biannic, Diana Cedeno, Alison Buchan, Ashley M. Frank, James J. Daleiden Tiffany M. Jarrell, Hilkka I. Kenttamaa, Presented at the EFRC Annual summit, Washington, DC July 18th, 2013
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Integrating separation and conversion - catalytic oxidation of lignin models and organosolv lignin to high value aromatics, Joseph J. Bozell, presented at the USP Conference on Synthetic Biology for Biomass and Biofuels Production, University of S�o Paulo, S�o Paulo, Brazil, August 21st, 2013
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Adding value to lignin by enabling its catalytic conversion, Mahdi Abu-Omar, Joseph J. Bozell, Alison Buchan, Clint Chapple, Hilkka Kentt�maa, Presented at the C3Bio annual meeting and review, Purdue University 8/30/13
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Development of building blocks and intermediates for fine chemistry, Joseph J. Bozell, presented at the II Brazilian Symposium on Biorefineries, Brasilia, Brazil, September 26th, 2013
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Solvent Fractionation as a Pretreatment for Energy Crops, Joseph J. Bozell, Hagen Maraun, Anton Astner and Timothy G. Rials (presenter), presented at AAIC meeting Washington, DC 10/8/13
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Development of building blocks and intermediates for fine chemistry, Joseph J. Bozell, Presented to UTIA sponsored visit by LSU delegation, December 3rd, 2013
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Catalytic oxidation of organosolv lignin - structural and computational analysis for improved catalyst design, Joseph J. Bozell, Thomas Elder, Berenger Biannic, Diana Cedeno, Sabornie Chatterjee, Kun Cheng, Anselm Payen Symposium, ACS National meeting Dallas, TX, March 2014
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Mann, J. K.; Chmely, S. C. Synthesis, characterization, and catalytic screening reactions of N-hetercyclic carbene-containing iron carbonyl complexes. Presented at the 251st American Chemical Society National Meeting & Exposition, San Diego, CA, March 13-17, 2016; CHED-1054
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Regmi, Y. N.; Chmely, S. C. Nickel phosphide and molybdenum carbide composite materials for biomass upgrading. Presented at the 252nd American Chemical Society National Meeting & Exposition, Philadelphia, PA, August 21-25, 2016; CATL-146
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Chmely, S. C.; Regmi, Y. N.; Ciesielski, P. N. Depolymerization and valorization of technical lignin using Ni and Fe boride catalysts. Presented at the 252nd American Chemical Society National Meeting & Exposition, Philadelphia, PA, August 21-25, 2016; CATL-263
  • Type: Conference Papers and Presentations Status: Other Year Published: 2017 Citation: Harper, D. P.; O. Hosseinaei. 2017. Melt Extrusion of Lignin Carbon-fiber Precursors: The Path Forward for Low-cost Fibers or Unrealizable Dream? 253rd American Chemical Society National Meeting and &Exposition. April 2 - 6, 2017, San Francisco, CA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Harper, D. P.; Baker, D. A.; Meek, N.; Penumadu, D. 2013. Biocomposites from lignin-based carbon fibers. 245th ACS National Meeting, New Orleans, LA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2017 Citation: Keffer, D. J.; V. Garc�a-Negr�n, D. P. Harper, O. Rios. 2017. One Man's Trash is Another Man's Treasure: Repurposing a Pulp & Paper Industry Waste Stream for Transportation Applications. 1st International Workshop on Sustainability Innovation in Transportation Infrastructure, Knoxville, TN, March 2017.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Harper, D. P. 2016. Use of lignin based carbons for energy storage applications. Frontiers in Biorefining, November 8 - 11, 2016, St. Simons Island, GA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2012 Citation: Harper, D. P.; Baker, D. A.; Bozell, J. J.; Labb�, N. 2012. Lignin as a Feedstock for Renewable Carbon Materials. American Chemical Society Spring Annual Meeting, March 25-29, San Diego, CA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Hosseinaei, O.; Harper, D. P.; Bozell, J. J.; Rials, T. G. 2016. Organosolv and Kraft Lignin: Fractionation and Conversion to Melt Spun and Electrospun Carbon Fibers. 2016 AIChE Annual Meeting. November 13-18, 2016. San Francisco, CA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Garcia-Negron, V.; Harper, D. P.; Keffer, D. J.; Rios, O. 2016. Sustainable Energy Systems: High Performance Li-ion Battery Components from Renewable Resources. Society of Hispanic Professional Engineers 2016. November 2 - 6, 2016, Seattle, WA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Hosseinaei, O.; Harper, D. P.; Bozell, J. J.; Rials, T. G. 2016. Lignin-based carbon fibers: improved spinning and conversion process to carbon fiber. 4th International Conference Process Technology for the Forest & Biobased Industries 2016. October 25 - 26, 2016, St. Simons Island, GA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Young, S.; Meek, N.; Penumadu, D.; Harper, D. P.; Hosseinaei, O.; Rials, T. G. Meltspun Lignin Carbon Fibers for Reinforced Polymeric Composite Applications. TMS 2016. Febuary 14 - 18, 2016; Nashville, TN.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Young, S.; Uppal, R.; Penumadu, D.; Harper, D. P. 2013. Fluorescence from Polymers in Uniaxially Stretched Melt Spun Scintillation Fiber Mats. 2013 TMS Annual Meeting & Exhibition.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Harper, D. P.; Uppal, R. 2015. Foams from lignin. Southeastern Sun Grant Center's Southern Crossroads: Progress in the Science & Technology of Biomass, February 2 - 4. Auburn, AL.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2012 Citation: Baker, D. A.; Harper, D. P.; Rials, T. G. 2012. Carbon fiber from extracted commercial softwood lignin. The Fiber Society 2012 Fall Conference, Boston, MA, Nov. 7-9, 2012.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Regmi, Y.N.; Chmely, S.C.; Labb�, N. Exploring transition metal carbides and phosphides for Ex-Situ catalytic fast pyrolysis. AIChE Annual Meeting; San Francisco, CA, November 13-18, 2016
  • Type: Conference Papers and Presentations Status: Other Year Published: 2017 Citation: Hamilton, C., K. Kim, M. T. Alexander, S. W. Jackson, J. H. Park, and N. Labb�. Evaluating the quality and performance of switchgrass grown in East Tennessee. The Great Experiment Conference, March 13-14, 2017, Knoxville, TN.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Meek, N.; Penumadu, D.; Harper, D. P.; Hosseinaei, O.; Rials, T. G. 2015. Evaluation of Mechanical and Interfacial Properties of Individual Lignin Carbon Fiber and Layered Composites. Society for Composites 30th Technical Conference, September 28-30, 2015 Michigan State University, East Lansing, Michigan.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Hosseinaei, O.; Harper, D. P.; Bozell, J. J.; Rials, T. G. 2015. Methyl isobutyl ketone/ethanol organosolv lignin: characterization and conversion to carbon fiber. 249th ACS National Meeting & Exposition, April 2015, Denver, CO.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Wang, J.; Chmely, S.; Rials, T.; Labb�, N. Biomass fractionation through an ionic liquid process, Symposium on Biotechnology for Fuels and Chemicals, Baltimore, MD, April 25-28, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2017 Citation: Kim, K., C. Hamilton, J. H. Park, S. W. Jackson, and N. Labb�. Non-structural components of three switchgrass varieties over three growing seasons. The Great Experiment Conference, March 13-14, 2017, Knoxville, TN.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2017 Citation: Labb�, N., J. Wang, R. Boy, J. K. Keum, D. Cullen, J. Chen, D. P. Harper, L. Tetard, T. G. Rials, and A. K. Naskar. The role of lignin in the performance of regenerating lignocellulosic materials. America Chemical Society National Meeting, April 2-6, 2017, San Francisco, CA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2017 Citation: Tao, J., A. Bruce, B. H. Ownley, K. D. Gwinn, D. H. D'Souza, N. Moustaid-Moussa, and N. Labb�. Developing potentials of switchgrass extractives in an integrated biorefinery. The Great Experiment Conference, March 13-14, 2017, Knoxville, TN.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Chmely, S. C.; Das, P. Light-activated iron bifunctional catalysts for transfer hydrogenations of polar double bonds. 249th National Meeting of the American Chemical Society, Denver, CO, March 22-26, 2015.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Labb�, N.; Chmely, S. C.; Hamilton, C.; Kim, K. Inorganics in lignocellulosic biomass. 37th 37th Sympsosium on Biotechnology for Fuels and Chemicals, San Diego, CA, April 27-30, 2015.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Kim, K.; Hamilton, C.; Chmely, S. C.; Labb�, N. Reducing inorganics in lignocellulosic biomass utilizing microwave assisted acid extraction. Switchgrass III, Prairie & Native Grass International Conference, Knoville, TN, September 30-October 2, 2015.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Garcia-Negron, V.; N. Phillip, D. Wood, C. Daniel, J. Li, D. J. Keffer, O. Rios, D. P. Harper.PosterProcessing-structure-property relationships for lignin-based carbonaceous materials used in energy storage applications, November 2016. Oak Ridge Chapter American Society of Materials, Knoxville, TN. Won travel award.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Garc�a-Negr�n, V.; N. Phillip, D. Wood, C. Daniel, J. Li, D. J. Keffer, O. Rios, D. P. Harper; "Sustainable Energy Systems: High Performance Lithium-Ion Battery Components from Renewable Resources"; UTIA "Science Day"; April 26, 2016; The University of Tennessee, Knoxville, TN. 1st Place.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Gwinn, K., D. Yates, B. Ownley, N. Labb�. Seasonal variation in the antibacterial activity of latex-like resin from Sciadopitys verticillata. Annual meeting of the American Phytopathological Society., July 30- August 3, 2016, Tampa, FL.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Kim P., N. Abdoulmoumine, J. Lloyd, N. Labb�. Recycling of used railroad ties via a thermochemical process using a semi-pilot scale auger reactor system. AIChE annual meeting, November 13-18, 2016, San Francisco, CA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Eberhardt T.L., N. Labb�, L. J. Samuelson, J. Dahlen. Potential impacts of a changing global environment on the utilization of forest resources. Society of American Foresters meeting, November 2016, Madison, WI.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Kim P., J. Lloyd, J. Kim, N. Labb�. Recycling of used railroad ties via two-staged pyrolysis for production of wood preservatives and bio-oil: pyrolytic investigation by TGA and Py-GC/MS. 2015 The International Research group on Wood Protection annual meeting (IRG 46), May 10-14, 2015, Vi�a del Mar, Chile.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: J. Tao, O. Hosseinaei, P. Kim, D. P. Harper, J. J. Bozell, T. G. Rials, and N. Labbe. 2015. Influences of Organosolv Fractionation Time on Thermal and Chemical Properties of Lignins. Carbon Fibers and Their Composites. Symposium/Workshop American Carbon Society, April 16 - 17. Oak Ridge, TN.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: V. Garc�a-Negr�n (presenter), N. Phillip, D. Wood, C. Daniel, J. Li, D. J. Keffer, O. Rios, D. P. Harper; "Sustainable Energy Systems: High Performance Lithium-Ion Battery Components from Renewable Resources"; The World Conference on Carbon 2016; July10-15, 2016; State College, PA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Meek, N.; Penumadu, D.; Hosseinaei, O.; Harper, D. P. 2015. Mechanical and interfacial characterization of single lignin carbon fiber for composite manufacture. Carbon Fibers and Their Composites. Symposium/Workshop American Carbon Society, April 16 - 17. Oak Ridge, TN.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Hosseinaei, O.; Harper, D. P.; Bozell, J. J.; Rials, G. 2015. Melt Spun and Electrospun Carbon Fibers from Different Lignin Precursors. Carbon Fibers and Their Composites. Symposium/Workshop American Carbon Society, April 16 - 17. Oak Ridge, TN.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Uppal, R.; Harper, D. P. 2015. Lignin Based Novel Carbon Foams Carbon Fibers and Their Composites. Symposium/Workshop American Carbon Society., April 16 - 17. Oak Ridge, TN.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: V. Garcia-Negron, N. Phillip, D. Wood, C. Daniel, J. Li, D. J. Keffer, O. Rios, and D. P. Harper. Sustainable energy systems: High performance lithium-ion battery components from renewable resources, April 2016. UTK Women in STEM, Knoxville, TN
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Bruce, A., B. Ownely, J. Tao, N. Labb�, K. Gwinn, D. D'Souza, N. Moustaid-Moussa. Switchgrass extractives inhibit plant pathogenic fungi. Annual meeting of the American Phytopathological Society., July 30- August 3, 2016, Tampa, FL.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Labb� N., S. Chmely, C. Hamilton, K. Kim. Inorganics in lignocellulosic biomass. 37th Symposium on Biotechnology for Fuels and Chemicals. Feedstocks: Structure, Composition, Properties, April 27-30, 2015, San Diego, CA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Garrison R., S. Scoggin, N. Siriwardhana, N. Labb�, B. H. Ownley, K. D. Gwinn, D. H. D'Souza, N. Moustaid-Moussa. Anti-inflammatory effects of extracts from a bioenergy crop, switchgrass, in cultured adipocytes. Experimental Biology meeting, March 28-April 1, 2015, Boston MA
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Labb� N., J. Tao, L. M. Kline, A. Bruce, B. H. Ownley, K. D. Gwinn, D. H. D'Souza, N. Moustaid-Moussa. Developing an integrated biorefinery: potentials of switchgrass extractives. Sun Grant Regional Conference on Southern Crossroads: Progress in the Science & Technology of Biomass Production, Processing and Use, February 2-4, 2015, Auburn, AL.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Elder T., N. Labb�, C. Greer, N. Stewart, H. Baxter, M. Mazarei. Impacts of inorganics on the thermal behavior of switchgrass. Sun Grant Regional Conference on Southern Crossroads: Progress in the Science & Technology of Biomass Production, Processing and Use, February 2-4, 2015, Auburn, AL.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Larson J. A., T. E. Yu, C. N. Boyer, B. C. English, N. Labb�, L. M. Kline, D.D. Tyler. Effect of particle size and bale wrap on storage losses and quality of switchgrass. Sun Grant Regional Conference on Southern Crossroads: Progress in the Science & Technology of Biomass Production, Processing and Use, February 2-4, 2015, Auburn, AL.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Hayes D. G., L. M. Kline, N. Labb�, A. Womac. Ionic liquids for the dissolution, pretreatment, and analysis of lignocellulosic biomass. Sun Grant Regional Conference on Southern Crossroads: Progress in the Science & Technology of Biomass Production, Processing and Use, Auburn, AL, February 2-4, 2015, Auburn, AL.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Garrison R., S. Scoggin, N. Siriwardhana, N. Labb�, B. H. Ownley, K. D. Gwinn, D. H. D'Souza, L. Ramalingam, N. Moustaid-Moussa. Anti-inflammatory effects of extracts from a bioenergy crop, switchgrass, in adipocytes. Sun Grant Regional Conference on Southern Crossroads: Progress in the Science & Technology of Biomass Production, Processing and Use, February 2-4, 2015, Auburn, AL.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Tao, J.; Hosseinaei, O.; Kim, P.; Harper, D. P.; Bozell, J. J.; Rials, T. G.; Labb�, N. 2014. Effects of fractionation time on thermal and chemical properties of organosolv lignins. Frontiers in Biorefining 2014. St. Simons Island, GA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Wang, J.; Tao, J.; Harper, D. P.; Rials, T. G.; Labb�, N. 2014. Impacts of autohydrolysis on solubility of biomass in ionic liquid. Frontiers in Biorefining 2014. St. Simons Island, GA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Willis J. D., L. M. Kline, S. M. Allen, P. Bhattacharya, A. G. Collins, J. N. Grant, G. Montgomery, N. Labb�, C. N. Stewart, Jr. Development of switchgrass (Panicum virgatum L.) transformable cell suspension culture and a screening system for rapid assessment of cell wall genes for improved biomass for biofuels. World Forum on Biology, In Vitro Cellular & Developmental Biology- Animal May 31-June 4, 2014, Savannah, GA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Bruce, A., B. Ownely, N. Labb�, K. Gwinn, D. D'Souza, N. Moustaid-Moussa. Switchgrass extractives have potential as a value-added biopesticide against plant pathogens and foodborne pathogens. APS-CPS Joint Meeting, August 9-13, 2014, Minneapolis, MN.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Hatcher C. N., L. Alexander, M. Mazarei, E. Haynes, H. Baxter, C. Hamilton, N. Labb�, R. Dixon, Z. Wang, C. N. Stewart Jr. Development of hybrid switchgrass for improved biomass traits and field assessment. Integrated Biomass Supply System annual meeting, University of Tennessee, October 8-10, 2014, Knoxville, TN.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Yu T.E., C. Boyer, K. Castillo, B.C. English, J.A. Larson, N. Labb�, L.M. Kline. Analyzing the quality of perennial grass from a densification technology in lignocellulosic biomass feedstock supply system. 4th Pan-American Congress on Plants and Bioenergy, June 4-7, 2014, Guelph, Canada.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Labb� N., J. Wang. Isolating lignin through an ionic liquid process. 247th American Chemical Society National Meeting, March 17-21, 2014, Dallas, TX.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Kim P., N. Labb�, K. Noh. Fractionation of bio-oil vapors by multi stage condensers. 247th American Chemical Society national meeting, March 17-21, 2014, Dallas, TX.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Labb� N., J. Wang, D. P. Harper, T. G. Rials. Impacts of auto-hydrolysis on biomass solubility in ionic liquid. Gordon Research Conference on Ionic Liquids. August 17-22, 2014, Newry, MA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Greer, C.E., S. Acado, P. Kim, N. Labb�, S. C. Chmely. Ex-situ vapor-phase upgrading of pyrolysis vapors using layered double hydroxide catalysts. 248th American Chemical Society Meeting, August 10-14, 2014, San Francisco, CA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Lenaghan S., N. Labb�, C. N. Stewart, Jr. Development of an automated platform for rapid screening of genetically modified switchgrass. Frontiers in Biorefining, October 21-24, 2014, St Simons Island, GA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Ren S., X. Ye, A. Borole, P. Kim, N. Labb�. Characterization of aqueous phase bio-oil derived from switchgrass pyrolysis. Proceedings of AIChE Annual Meeting, AIChE annual meeting, November 16-21, 2014, Atlanta, GA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Labb� N. Natural variability of switchgrass and its impact on feedstock quality for bioenergy production. 35th Symposium on Biotechnology for Fuels and Chemicals, April 29-May 2, 2013, Portland, OR.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Alexander M., N. Labb�, S. W. Jackson. On-farm performance, yield, and chemical composition of 3 switchgrass varieties. Switchgrass II Conference, September 10-12, 2013, Madison, WI.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Elder T., N. Labb�, P. Kim. Low field, time-domain NMR of biochar. 246th American Chemical Society national meeting, September 8-12, 2013, Indianapolis, MN.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2012 Citation: Labb� N., L. M. Kline. Isolation and characterization of lignins through an ionic liquid fractionation approach. Sun Grant national conference meeting, October 2-5, 2012, New Orleans, LA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Ownely, B., N. Labb�, K. Gwinn, M. Dee, P. Filson, A. L. Vu, D. D'Souza, N. Moustaid-Moussa. Development of switchgarss extractives as a value added biopesticide against bacterial spot (Xanthomonas perforans) of tomato. APS-MSA Joint Meeting, August 10-14, 2013, Austin, TX.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Rials T. G., J. J. Bozell, N. Labb�. Biomass pretreatment and cell wall fractionation. Southeastern Conference Symposium, February 10-12, 2013, Atlanta, GA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2012 Citation: Baxter H. L., M. Mazarei, N. Labb�, L. M. Kline, M. T. Windham, D. G. J. Mann, C. Fu, J. N. Grant, C. R. Poovaiah, H. Shen, W. A. Wuddineh, A. Ziebell, M. F. Davis, F. Chen, T. J. Tschaplinski, J. R. Mielenz, Z. Y. Wang, R. A. Dixon, C. N. Stewart Jr. Field-based experiments on low-lignin switchgrass as a feedstock for lignocellulosic biofuel production. Sun Grant national conference, Science for Biomass Feedstock Production and Utilization, October 2-5, 2012, New Orleans, LA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2012 Citation: Larson J. A., B. C. English, T. E. Yu, N. Labb�, D. D. Tyler. Effects of outdoor storage on the composition of switchgrass. Sun Grant national conference meeting, October 2-5, 2012, New Orleans, LA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2012 Citation: Harper, D. P.; Baker, D. A.; Bozell, J. J. 2012. Lignin as a Feedstock for a New Generation of Bio-based Materials. Proceedings of the 2nd Conference on Processing Technologies for the Forest and Biobased Products, St. Simons Island, GA. Nov. 6-7.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Meng, Y. 2014. Carbonization of Microfibril Cellulose Aerogel: Surface, Structure and Absorption Properties. The TAPPI International Conference on Nanotechnology for the Forest Products Industry held on June 23-26, 2014 in Vancouver, Canada (First Place Award of Poster Competition).
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Meng, Y., Q. Wu, T. Young, T. Rials, S. Wang. 2015. Development of Value-Added Nanomaterials from Switchgrass (Panicum virgatum L.). Praitie & Native Grass International Conference, Sept. 30-Oct. 2, Knoxville, TN (Poster).
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Edmunds, C. W.; Hamilton, C.; Kim, K.; Andr�, N.; Labb�, N. Rapid detection of ash and inorganic in bioenergy feedstocks using Fourier transform infrared spectroscopy coupled with partial least-squares regression. Energy & Fuels, 2017, 31 (6), 6080-6088, DOI: 10.1021/acs.energyfuels.7b00249
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Fu, J., L. Fan, C. He, Z. Lu, S. Wang. 2015. Cellulose nanocrystals reinforced silica aerogels: microstructure and mechanical properties. 2015 TAPPI International Conference for Renewable Materials. June 22-25, 2015. Atlanta, GA. (Poster).
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Wang S. 2015. Wood Science and Nanotechnology: Overview and Our Efforts. Oct. 14, 2015, Kangwon National University, South Korea.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Chmely, S. C. Thermochemical conversion of biomass to fuels and other products. Presented at National Bioenergy Day 2015 Webinar, October 21, 2015. (invited)
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Alonso, D. M.; Hakim, S.; Zhou, S.; Won, W.; Hosseinaei, O.; Tao, J.; Garcia-Negron, V.; Motagamwala, A. H.; Mellmer, M. A.; Huang, K.; Houtman, C. J.; Labb�, N.; Harper, D.; Maravelias, C.; Runge, T.; Dumesic, J. A. Increasing the revenue from lignocellulosic biomass: Maximizing feedstock utilization., Science Advances, 2017. DOI: e1603301 DOI: 10.1126/sciadv.1603301.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Edmunds, C. W.; Hamilton, C.; Kim, K.; Chmely, S. C.; Labb�, N. Using a chelating agent to generate low ash bioenergy feedstock. Biomass Bioenerg., 2017, 96, 12-18.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Hashmi, M.; Sun, Q.; Tao, J.; Wells Jr., T.; Ali Shah, A.; Labb�, N.; Ragauskas, A. J. Comparison of autohydrolysis and ionic liquid 1-butyl-3-methylimidazolium acetate pretreatment to enhance enzymatic hydrolysis of sugarcane bagasse. Bioresource Technology, 2017, 224, 714-720, DOI: 10.1016/j.biortech.2016.10.089
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Garcia-Negron, V. G. M. S. Thesis. Processing-property-structure relationships of carbonaceous materials derived from renewable lignin products. The University of Tennessee. 2017.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Kandhola, G.; Rajan, K.; Labb�, N.; Chmely, S. C.; Heringer, N.; Kim, J.-W.; Hood, E. E.; Carrier, D. J. "Beneficial effects of Trametes versicolor pretreatment on saccharification and lignin enrichment of organosolv-pretreated pinewood. RSC Adv., 2017, 7, 45652-45661.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Willis, J. D., Grant, J. N.; Mazarei, M.; Kline, L. M.; Rempe, C. S.; Collins, A. G.; Turner, G. B.; Decker, S. R.; Sykes, R.W.; Davis, M. F.; Labb�, N.; Jurat-Fuentes, J. L.; Stewart, C. N. The TcEG-1 beetle (Tribolium castaneum) cellulase produced in transgenic switchgrass is active at alkaline pH and auto-hydrolyzes biomass for increased cellobiose release. Biotechnology for Biofuels, 2017, 10:230, DOI: 10.1186/s13068-017-0918-6.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Kim, P.; Taylor, A.; Lloyd, J.; Kim, J.-W; Abdoulmoumine, N.; Labb�, N. A two-step thermochemical process for adding value to used railroad wood ties and reducing environmental impacts. ACS Sustainable Chemistry & Engineering, 2017, 5 (10), 9485-9493, DOI: 10.1021/acssuschemeng.7b02666
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Liu, Q.; Chmely, S. C.; Abdoulmoumine, N. Biomass treatment strategies for thermochemical conversion. Energ. Fuels, 2017, 31, 3525-3536.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Feng, X., Z. Yang, S. Chmely, Q. Wang, S. Wang, Y, Xie. Lignin-Coated Cellulose Nanocrystal Filled Methacrylate Composites Prepared via 3D Stereolithography Printing: Mechanical Reinforcement and Thermal Stabilization. Carbohydrate Polymers. 2017. 169: 272-281 (DOI: 10.1016/j.carbpol.2017.04.001).
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Regmi, Y. N.; Roy, A.; Goenaga, G. A.; McBride, J. R.; Rogers, B. R.; Zawodzinski, T. A.; Labb�, N.; Chmely, S. C. Electrocatalytic activity and stability enhancement through preferential deposition of phosphide on carbide. ChemCatChem, 2017, 9, 1-9.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Yue, Z.; Vakili, A.; Houseinaei, O.; Harper, D. P. Lignin-based Carbon Fibers: Accelerated Stabilization of Lignin Fibers in Presence of Hydrogen Chloride. Journal of Applied Polymer Science. 2017. DOI: 10.1002/app.45507.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: L. Ma, Y. Zhang, S. Wang. Fabrication and characterization of Acrylonitrile-Butadiene-Styrene (ABS) nanocomposites reinforced with cellulose nanocrystal via solution casting method. Polymer Composites. 2017. 8(S1): E167-173.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Feng, X., Z. Yang, S.S. Rostom, M. Dadmun, Y. Xie, S. Wang. Structural, mechanical, and thermal properties of 3D printed L-CNC/acrylonitrile butadiene styrene nanocomposites. Journal of Applied Polymer Science. 2017. 134(31): 45082 (DOI: 10.1002/app.45082).
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Haber, H.; Kim, P.; Chmely, S. C.; Lloyd, J.; Regmi, Y. N.; Abdoulmoumine, N.; Labb�, N. Environmentally friendly process for recovery of wood preservative from used copper naphthenate-treated railraod ties. ACS Sustainable Chemistry and Engineering, 2017, 5(11), 10806-10814, DOI: 10.1021/acssuschemeng.7b02760
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Hosseinaei, O.; D. P. Harper, D. P.; Bozell, J. J.; Rials, T. G. Improving Processing and Performance of Pure Lignin Carbon Fibers through Hardwood and Herbaceous Lignin Blends. International Journal of Molecular Sciences. 2017. DOI: 10.3390/ijms18071410.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Oyedeji, O., Daw, C. S.; Labb�, N., Ayres, P.; Abdoulmoumine, N. Kinetics of the release of elemental precursors of syngas and syngas contaminants during switchgrass devolatilization. Bioresource Technology, 2017, 244, 525-533. DOI: 10.1016/j.biortech.2017.07.167
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Das, P.; Elder, T.; Brennessel, W. W.; Chmely, S. C. Iron piano-stool complexes containing NHC ligands outfitted with pendent arms: synthesis, characterization, and screening for catalytic transfer hydrogenation. RSC Adv., 2016, 6, 88050-88056.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Huang, J., S. Lyu, F. Fu, Y. Wu, S. Wang. Green preparation of cellulose nanocrystals/polyvinyl alcohol composite superhydrophobic coating. RSC Advances. 2017. 7: 20152-20159.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Wang, J.; Boy, R.; Nguyen, N.; Keum, J.; Cullen, D.; Chen, J.; Soliman, M.; Littrell, K.; Harper, D.; Tetard, L.; Rials, T.; Naskar, A.; Labb�, N. Controlled assembly of lignocellulosic biomass components and properties of reformed materials. ACS Sustainable Chemistry & Engineering, 2017, 5 (9), 8044-8052, DOI: 10.1021/acssuschemeng.7b01639
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Wu, Q., X. Li, S. Fu, Q. Li, S. Wang. Estimation of aspect ratio of cellulose nanocrystals by viscosity measurement: Influence of surface charge density and NaCl concentration. Cellulose. 2017. 24(8): 3255-3264.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Garcia-Negron, V.; Phillip, N.; Wood, D.; Daniel, C.; Li, J.; Keffer, D. J.: Rios, O.; Harper, D. P. Processing-Structure-Property Relationships for Lignin-based Carbonaceous Materials used in Energy Storage Applications. Energy Technology. 2016. DOI: 10.1002/ente.201600646.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Guo, P.; Anderson, J. D.; Bozell, J. J.; Zivanovic, S. The effect of solvent composition on grafting gallic acid onto chitosan via carbodiimide. Carbohydr. Polym. 2016, 140, 171-180.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Hosseinaei, O.; Harper, D. P.; Bozell, J. J.; Rials, T. Role of physicochemical structure of organosolv hardwood and herbaceous lignins on carbon fiber performance. ACS Sustainable Chemistry & Engineering. 2016. DOI: 10.1021/acssuschemeng.6b01828.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Key, R. E.; Bozell, J. J. Recent progress toward lignin valorization via selective catalytic technologies and the tailoring of its biosynthetic pathways. ACS Sus. Chem. Eng. 2016, 4, 5123-5135.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Kim, P.; Rials, T. G.; Labb�, N.; Chmely, S. C. Screening of mixed-metal oxide species for catalytic ex situ vapor-phase deoxygenation of cellulose by py-GC/MS coupled with multivariate analysis. Energ. Fuels, 2016, 30, 3167-3174.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Meek, N. M. S. Thesis. Development of Lignin Carbon Fiber and Reinforced Composites. The University of Tennessee. 2016.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Meek, N.; Penumadu, D; Hosseinaei, O.; Harper, D. P.; Young, S.; Rials, T. G. Mechanical, interfacial, and structural lignin carbon fiber characterization and composite panel manufacture. Composite Science and Technology. 2016. DOI: 10.1016/j.compscitech.2016.10.016.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Njiojob, C.; Bozell, J. J.; Long, B. L.; Elder, T.; Key, R. E.; Hartwig, W. T. Enantioselective syntheses of lignin models - an efficient synthesis of ?-O-4 dimers and trimers using the Evans chiral auxiliary. Chem. Eur. J. 2016, 22, 12506-12517.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Sun, Q.; Khunsupat, R.; Akato, S. K.; Tao, J.; Labb�, N.; Gallego, N. C.; Bozell, J.; Rials, T. G.; Tuskan, G. A.; Tschaplinski, T.; Naskar, A. M.; Ragauskas, A. J. Physicochemical characteristics of poplar lignin carbon precursors before and after melt rheology. Green Chem. 2016, 18, 5015-5024.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Kim, P.; Lloyd, J; Kim, J.; Abdoulmoumine, N.; Labb�, N. Recovery of creosote from used railroad ties by thermal desorption. Energy, 2016, 111, 226-236, doi: 10.1016/j.energy.2016.05.117
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Kim, P.; Lloyd, J.; Kim, J.; Labb�, N. Thermal desorption of creosote remaining in used railroad ties: Investigation by TGA (thermogravimetric analysis) and Py-GC/MS (pyrolysis-gas chromatography/mass spectrometry). Energy, 2016, 96, 294-302, DOI: 10.1016/j.energy.2015.12.061
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Xu, D., Y. Zhang, H. Zhou, Y. Meng, S. Wang. Characterization of adhesive penetration in wood bondlines by means of scanning thermal microscopy (SThM). Holzforschung, 2016. 70(4): 323-330. DOI: 10.1515/hf-2014-0360.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Rena, S.; Ye, X. P.; Borole, A. P.; Kim, P.; Labb�. N. Analysis of switchgrass-derived bio-oil and associated aqueous phase generated in a semi-pilot scale auger pyrolyzer. Journal of Analytical and Applied Pyrolysis. 2016, 119, 97-103 DOI: 10.1016/j.jaap.2016.03.013
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Tao, J.; Hosseinaei, O.; Delbeck, L.; Kim, P.; Harper, D. P.; Bozell, J. J.; Rials, T. G.; Labb�, N. Effects of organosolv fractionation time on thermal and chemical properties of lignins. RSC Adv. 2016, 6, 79228-79235.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Xing, D., J. Li, X. Wang, S. Wang. In situ measurement of heat-treated wood cell wall at elevated temperature by nanoindentation. Industrial Crops and Products 2016. 87: 142-149. DOI: 10.1016/j.indcrop.2016.04.017.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: L. Ma, Y. Zhang, S. Wang. Modified treatment for carbonized cellulose nanofiber application in composites. Composites A, 2016. 90: 786-793.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Wight, J. P.; Allen, F. L.; Ashworth, A. J.; Tyler, D. D.; Labb�, N.; Rials, T. G. Comparison of near infrared reflectance spectroscopy with combustion and chemical methods for soil carbon measurements in agricultural soils. Communications in Soil Science and Plant Analysis, 2016, 47(6), 731-742 DOI: 10.1080/00103624.2016.1146750
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: J. Huang, S. Lv, F. Fu, H. Chang, S. Wang. Preparation of Superhydrophobic Coating with Excellent Abrasion Resistance and Durability Using Renewable Nanofibrillated Cellulose. RSC Advances, 2016. 6, 106194 - 106200. DOI: 10.1039/C6RA23447J.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: 19. Boyer, C.; Yu, T. E.; English, B. C.; Larson, J. A.; Labb�, N.; Kline, L. M. Impact of an innovated storage technology on the quality of preprocessed switchgrass bales. AIMS Bioengineering, 2016, 3(2), 125-138, DOI: 10.3934/bioeng.2016.2.125
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Aboytes-Ojeda, M.; Castillo-Villar, K. K.; Yu, T. E.; Boyer, C. N.; English, B. C.; Larson, J. A.; Kline, L. M.; Labb�, N. A principal component analysis in switchgrass chemical composition. Energy, 2016, 9, 913-924.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Kim, P.; Weaver, S.; Labb�, N. Effect of sweeping gas flow rates on temperature-controlled multistage condensation of pyrolysis vapors in an auger intermediate pyrolysis system. Journal of Analytical and Applied Pyrolysis, 2016, 118, 325-334, DOI: 10.1016/j.jaap.2016.02.017
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Kline, L.; Labb�, N., Boyer, C.; Yu, T. E.; English, B. C.; Larson, J. A. Investigating the impact of biomass quality on near-infrared models for switchgrass feedstocks. AIMS Bioengineering, 2016, 3(1), 1-22, DOI: 10.3934/bioeng.2016.1.1
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Astner, A. F.; Young, T. M.; Bozell, J. J. Lignin yield maximization of mixed biorefinery feedstocks by organosolv fractionation using Taguchi Robust Product Design. Biomass Bioenergy 2015, 73, 209-216.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: �etin, N.; Ozmen-�etin, N.; Harper, D. P. Vinyl acetate-modified microcrystalline cellulose-reinforced HDPE composites prepared by twin-screw extrusion. Turkish Journal of Agriculture and Forestry. 2015, 39: 39-47.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Golding, C.; Gwinn, K. D.; Peeden, A.; Bozell, J.; Trout-Fryxell, R. T. Acarcidal activity of eastern red cedar. Med. Vet. Entomol. 2015, in press.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Njiojob, C.; Rhinehart, J. L.; Bozell, J.; Long, B. L. Synthesis of enantiomerically pure lignin dimer models for catalytic selectivity studies. J. Org. Chem. 2015, 80, 1771-1780.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Starr, T.; Harper, D. P.; Rials, T. G. The effects of electron beam irradiation dose on the mechanical performance or red maple. Bioresources. 2015, 10(1) 956-969.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Meng, Y., S. Wang, T. M. Young, P. Liu, C. Contescu, and B. Huang. Ultralight carbon aerogel from nanocellulose as highly selective oil absorption materials. Cellulose. 2015. 22:435-447 (DOI :10.1007/s10570-014-0519-5).
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Meng, Y., X. Wang, Z. Wu, S. Wang, T.Y. Young. Optimization of cellulose nanofibrils carbon aerogel fabrication using response surface methodology. European Polymer Journal. 2015. 73: 137-148.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Ma, L., Y. Zhang, Y. Meng, P. Anusonti-Inthra, S. Wang. Preparing cellulose nanocrystal/acrylonitrile-butadiene-styrene nanocomposites using the master-batch method. Carbohydrate Polymers, 2015. 125:352-359.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Zhang, Y.; R. Yang, Y. Wu, S. Wang, C. Liu, X. Zhong, J. Wu. Effect of growth period on cell-wall mechanical property of elephant grass. BioResources, 2015.10(3): 4252-4262.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Xing, D., S. Wang, J. Li. Effect of artificial weathering on the properties of industrial-scale heat treated wood. BioResources. 2015. 10(4): 8238-8252.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Lewis, A. J.; Ren, S.; Ye, X.; Kim, P.; Labb�, N.; Borole, A. P. Hydrogen production from switchgrass via an integrated pyrolysis-microbial electrolysis process. Bioresource Technology, 2015, 195, 231-241, DOI: 10.1016/j.biortech.2015.06.085
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Kim, K.; Labb�, N., Warren, J.M.; Elder, T.; Rials, T. G. Chemical and anatomical changes in Liquidambar styraciflua L. xylem after long term exposure to elevated CO2. Environmental Pollution, 2015, 198, 179-185 DOI: 10.1016/j.envpol.2015.01.006
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Ryu, S.; Labb�, N., Trinh, C. T. Simultaneous saccharification and fermentation of cellulose in ionic liquid for efficient production of alpha-ketoglutaric acid by Yarrowia lipolytica. Applied Microbiology and Biotechnology, 2015, 99(10), 4237-4244, DOI: 10.1007/s00253-015-6521-5
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Ratnaweera, D. R.; Saha, D.; Pingali, S. V.; Labb�, N.; Naskar, A. K.; Dadmun, M. The impact of lignin source on its self-assembly in solution. RSC Advances, 2015, 5(82), 67258-67266, DOI: 10.1039/C5RA13485D
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Biannic, B.; Bozell, J.; Elder, T. Steric effects in the design of Co-Schiff base complexes for the catalytic oxidation of lignin models to para-benzoquinones. Green Chem. 2014, 16, 3635-3642.


Progress 10/01/15 to 09/30/16

Outputs
Target Audience:Agricultural producers, the scientific community at large, academia, national laboratories, federal and state agencies, private industry, public interest groups, the government sector, land-grant institutions, biofuel industry leaders, and additional stakeholders. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Professional training in this period has included bringing two postdocs (Rebecca Key and William Hartwig), and a graduate student (Ernesto Zuleta) into the group to carry out research related to the production of biobased chemicals. Our work in biomass fractionation has trained three research technicians (Jimmy Mynes, Alex Peeden and Anton Astner), and has formed the basis of a recent MS graduate, Marc Banholzer.Professional training in this period also included two postdocs (Yagya Regmi and Kalavathy Rajan) and an undergraduate student (Jeff Mann). The high-throughput biomass analysis work has included the training of two postdocs (Warren Edmunds and Jingming Tao), two research associates (Choo Hamilton and Keonhee Kim), and a Master student (Holly Boxter). The ionic liquid fractionation effort has included the training of a PhD student (Jing Wang who graduated in June 2016), a Master student (Preenaa Venagupol), and a research scientist (Pyounhgchung Kim). Professional training for advanced materials included one postdoc (Omid Hosseinaei) and two master students (Nathan Meek, Valerie Garcia-Negron) relating to the production of carbon based materials and composites from lignin. Each student and post-doc presented their research at professional meetings a minimum of twice and published their results and generated intellectual property. The cellulose nanofiber developing work has included the training of five Ph.D. students (Qijun Zhang, Dong Xing, Libo Ma, Jingjing Fu, Jingda Huang). How have the results been disseminated to communities of interest?Results have been disseminated via the publications and presentations described above. What do you plan to do during the next reporting period to accomplish the goals?We will continue our effort in developing robust infrared models to predict biomass properties that are relevant to thermochemical processes. We will transition to near infrared spectroscopy with the main goal of developing lab models that we will be able to transfer and test at a pilot scale. In term of our ionic liquid fractionation effort, we have identified two new ILs that have potential to perform better than our currently tested IL. We plan to investigate these ILs and to identify enzymes that would perform in this type of media, which would make the fractionation approach a one-pot process. We will use the ORNL wet spinning facility to produce biomass fibers that we will characterize and convert to composite materials. For condensed-phase reductive catalytic treatments of lignin, we intend to investigate the production of nanomaterials with regular and repeatable morphologies and their ability to afford reduced products from lignin. These investigations will inform the design of new catalyst materials for this process. We also intend to investigate reductive catalytic fraction of biomass to directly remove high-value products from whole biomass via in-situ lignin conversion. These investigations have tremendous industrial potential, given the absence of an economical means to fractionate and convert biomass into fuels and chemicals. For vapor-phase upgrading of biomass, we intend to continue our collaborative efforts with national labs using our mixed oxide, carbide, and phosphide catalysts. The oxide catalysts will be subjected to scale-up testing to produce liquid products from biomass. The phosphide and carbide catalysts require additional bench-scale testing, but will follow the research template we have employed with the oxide catalysts (i.e. bench-scale testing at UTIA using py-GC/MS, bench-scale testing at NREL using py-MBMS, then semi-pilot-scale testing TBD). With our preliminary inorganics removal results in hand, we intend to investigate other chelating agents for their ability to lower the inorganic content of biomass. Although EDTA has superior reactivity to water or mineral acids, it is difficult to remidate on an industrial scale as it is not biodegradable. We will investigate other biodegradable chelating agents to determine their removal reactivity and compare those results to our EDTA benchmark. We will investigate the use of these new biodegradable chelating agents to remove cupper from used railroad ties after their thermal treatment to desorb and recover remaining the preservatives. Our preliminary results on chemical modifications of lignin for incorporation into novel materials suggests that methacrylate pendents will allow for additional advanced composite materials. For instance, we intend to incorporate other acrylate polymers with H-modified lignin and test their mechanical properties. We also intend to investigate H-lignin crosslinking using UV photons or electrons. Carbon material research research will continue by scaling up the production of lignin based precursors for mercury sorption and battery anode materials. The influence of carbonization kinetics, activation, and feedstock are currently being investigate. Short fiber carbon fiber composites are being produced based upon previous results in continuous fiber composites. We will continue to explore more energy efficient method to manufacture cellulose nanofibers and develop high value products, such as supercapacitor.

Impacts
What was accomplished under these goals? I.High-throughput biomass analysis methods: Ash and inorganics such as alkali and alkali metals are detrimental to thermochemical conversion of lignocellulosic biomass. Identifying and quantifying these elements is now recognized by the bioenergy industry as a critical step. We have demonstrated that Fourier transform infrared spectroscopy, a rapid and non destructive technique, coupled with multivariate statistical tools, can be used to monitor the inorganic features of biomass that ultimately impact downstream processes. In addition to ash content and composition, models for estimating carbon and energy content are being constructed. Ultimately, online monitoring of these biomass properties would be necessary to assess the quality of feedstock being delivered to biorefineries and to reduce operational risks associated to supply chain disruptions. II.Biomass Fractionation - Organosolv fractionation: Our research addressed key issues in feedstock conversion and fractionation. Our work has carried out a multifaceted investigation of solvent fractionation as a means to provide selective and efficient production of individual cellulose, hemicellulose and lignin process streams from feedstocks common to the Southeast, suitable for subsequent transformation to advanced biofuels or high value products. Our approach provides a viable biorefinery "front end" producing building blocks much more readily converted into biobased chemicals and advanced biofuels than whole biomass itself. Our effort has demonstrated that our fractionation system using a 16/34/50 mixture of methyl isobutyl ketone (MIBK), ethanol and water in the presence of a sulfuric acid catalyst is effective for fractionating feedstocks expected to be central to biorefinery operations in the Southeast. Evaluation of the individual process components after fractionation allows a more complete understanding of reactivity differences between these components in downstream treatments, and will ultimately lead to more efficient thermochemical processes for fuel and chemical production. With the advent of hybrid poplar supplies, we are now in a position to supply individual fractions to partners for thermochemical processes targeting advanced biofuels. Ionic liquid fractionation: The biorefining industry must develop technologies for converting renewable carbon into a diverse portfolio of high value products to support the biofuel production in an economically viable and sustainable manner. Lignocellulosic biomass has a complex structure that has evolved to resist to physical, chemical, and biological attacks. To overcome this recalcitrance, most of pretreatment and fractionation processes require high severity conditions to deconstruct biomass, which often result in the degradation or underutilization of, at least, one of the biomass constitutents. We have demonstrated that the activation of biomass with an ionic liquid (IL) at low temperature (≤60 ?C) prevents the loss of valuable biomass carbon while significantly reducing the recalcitrance of the feedstock. We have also demonstrated that an integrated process where an autohydrolysis is performed prior to the IL activation, significantly improves the solubilty of biomass in the IL. We found that 93% of cellulose in the IL-regenerated biomass were enzymatically converted to glucose within 6 hours. Finally, from this fractionation process, we isolated 70 % of the lignin present in the starting material with a purity of 90%. Our NMR data showed that this isolated lignin possessed a chemical structure similar to the lignin in the wood. Moreover, the higher solubility of autohydrolyzed biomass in IL, allowed us to generate biomass-IL gels that had adequate properties for solvent spinning. We hypotheize that by controlling the biomass carbohydrates/lignin ratio we will be able to produce biomass fibers with unique properties that will have various potential applications. III.Value-Added Chemicals - Condensed-phase biomass conversion: One broad research focus of the CRC is to increase the utility of lignin by developing innovative catalysts able to efficiently convert lignin to high value aromatics in high yield and selectivity. We have broadly divided these efforts into (1) oxidative catalysis using Co-Schiff base catalysts, (2) direct catalyst delivery via pendent bolaforms, and (3) reductive catalysis using alloyed nanomaterials. Through our ongoing investigations, we intend to demonstrate the durability, recyclability, and overall industrial relevance of our novel catalyst species. We believe that these results will position us to develop new fractionation processes with industrial relevance to the southeast region. Vapor-phase biomass conversion: In addition, we have been investigating thermochemical routes to biomass valorization. These investigations have primarily focused on (1) catalytic fast pyrolysis, but they also include necessary pre-processing steps, including (2) inorganics removal from whole biomass. The results of these investigations will ultimately allow for the production of a liquid product from solid biomass that is ostensibly identical to liquid petroleum, and could be stored, processed, converted, and/or valorized in an analogous manner. IV.Advanced Materials - Carbon Fiber Production: A focus of our research program has been to upgrade lignin either from pulp residues or as part of a biorefinery process to high value materials. Over the course of the past year, we have produced multiple products from lignin. First, we successfully produced 100% switchgrass lignin and 100% hybrid poplar lignin carbon fiber composites from lignin. These materials demonstrated promise as a fiber reinforcement as they possessed superior adhesion properties with a polymer matrix without the aid of an adhesion promoter compared to commercial PAN fibers that had been sized. Second, we produced lignin based battery anode materials materials from both kraft lignin and biorefinery lignin. These materials, because of their nano-graphitic structure, demonstrated superior cycling and in certain cases improved capacity over flake graphite. Third, the nanographitic carbon material produced from lignin demonstrated high efficacy per surface area at capturing methyl mercury in water. This was accomplished with low sulphate release which can exasperbate the production of MeHg. Our discovery is important for environmental remediation of mercury contaminated streams at a low cost with a renewable product. Cellulose Nanofiber (NFC): In this reporting period, we were focus on developing unique application using cellulose nanofibers: (1) We have developed an environmentally friendly and robust semitransparent superhydrophobic coating through CVD modification for reducing surface free energy after a simple two-spraying process. The resulting NFC superhydrophobic coating showed good self-cleaning properties. In addition, the coating also exhibited outstanding abrasion resistance and durability and could retain superhydrophobic properties after sandpaper abrasion, finger-wipe, knife-scratch, long-time impregnation in water, UV radiation, and long-time staying at low temperature. (2) We manufactured carbon nanofibers (CNF) from carbonized cellulose nanofibers (CCNF) by carbonizing freeze-dried cellulose nanofibers first, then preparing acrylonitrile-butadiene-styrene (ABS)/CCNF nanocomposites by extruder. To increase the dispersibility and operability of the CCNF, the ultrasound-assisted master batch method was adopted to make an ABS/CCNF master batch. Dicumyl peroxide and maleic anhydride were added to increase the interface compatibility between the CCNF and the ABS by reactive extrusion. The tensile strength of ABS/CCNF was improved 36% compared to that of ABS. The improved properties demonstrated that the approach used in this study has the potential to solve the bottleneck issues of mass producing and applying CNF in a green way.

Publications

  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Tao, J., Hosseinaei, O., Kim, P., Harper, D., Bozell, J., Rials, T., Labb�, N., Chemical and thermal characterization of organosolv yellow poplar lignins fractionated by different time periods, presented at the 251st national meeting of the American Chemical Society, San Diego, CA, March 13-17, 2016; CELL-11
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Key, R., Bozell, J. J., Design of novel tri- and tetradentate Co-Schiff base complexes for selective catalytic cleavage of lignin, presented at the 251st national meeting of the American Chemical Society, San Diego, CA, March 13-17, 2016; CELL-48
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Hartwig, W., Bozell, J. J., Synthesis of glycal-based bolaamphiphile cobalt-Schiff base complexes for catalytic breakdown of lignin in whole biomass, presented at the 252nd national meeting of the American Chemical Society, Philadelphia, PA, August 21-25, 2016; ORGN-660
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Bozell, J. J., Elder, T., Biannic, B., Cedeno, D., Chatterjee, S., Cheng, K., Njiojob, C., Catalysis for conversion of biorefinery lignin to high value chemicals  structural and computational analysis for improved catalyst design, Presented at the 18th ISWFPC, BOKU, Vienna, Austria, September 9 -11, 2015.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Mann, J. K.; Chmely, S. C. Synthesis, characterization, and catalytic screening reactions of N-hetercyclic carbene-containing iron carbonyl complexes. Presented at the 251st American Chemical Society National Meeting & Exposition, San Diego, CA, March 13-17, 2016; CHED-1054
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Regmi, Y. N.; Chmely, S. C. Nickel phosphide and molybdenum carbide composite materials for biomass upgrading. Presented at the 252nd American Chemical Society National Meeting & Exposition, Philadelphia, PA, August 21-25, 2016; CATL-146
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Chmely, S. C.; Regmi, Y. N.; Ciesielski, P. N. Depolymerization and valorization of technical lignin using Ni and Fe boride catalysts. Presented at the 252nd American Chemical Society National Meeting & Exposition, Philadelphia, PA, August 21-25, 2016; CATL-263
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Kim, P.; Aboulmoumine, N.; Lloyd, J.; Labb�, N. Recycling of Used Railroad Ties Via a Thermochemical Process Using a Semi-Pilot Scale Auger Reactor System. AIChE Annual Meeting; San Francisco, CA, November 13-18, 2016
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Regmi, Y.N.; Chmely, S.C.; Labb�, N. Exploring transition metal carbides and phosphides for Ex-Situ catalytic fast pyrolysis. AIChE Annual Meeting; San Francisco, CA, November 13-18, 2016
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Bruce, A. ; Ownley, B. H.; Tao, J.; Labb�, N.; Gwinn, K. D., DSouza, D. H., Moustaid-Moussa, N. Switchgrass extractives inhibit plant pathogenic fungi. APS Annual meeting; Tampa, FL, July 30-August 3, 2016
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Yates, D.I.; Ownley, B.H.; Labb�, N.; Gwinn, K.D. Seasonal Variation in the Antibacterial Activity of Latex-like Resin from Sciadopitys verticillata. APS Annual meeting; Tampa, FL, July 30-August 3, 2016
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Tao, J.; Tarafder, A.; Labb�, N. Characterization of switchgrass extractives by supercritical chromatography. Frontier in Biorefining International Conference; St Simons Island, GA, November 8-11, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Venugopal, P.; Wang, J.; Labb�, N. Fractionation of lignocellulosic biomass using ionic liquid 1-ethyl-3methylimidazolium acetate. Frontier in Biorefining International Conference; St Simons Island, GA, November 8-11, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: V. Garc�a-Negr�n (presenter), N. Phillip, D. Wood, C. Daniel, J. Li, D. J. Keffer, O. Rios, D. P. Harper; Sustainable Energy Systems: High Performance Lithium-Ion Battery Components from Renewable Resources; The World Conference on Carbon 2016; July10-15, 2016; State College, PA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Wang, J.; Chmely, S.; Rials, T.; Labb�, N. Biomass fractionation through an ionic liquid process, Symposium on Biotechnology for Fuels and Chemicals, Baltimore, MD, April 25-28, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Eberhardt, T. L.; Labb�, N; Samuelson, L. J.; Dahlen, Joseph; So C. Potential impacts of a changing global environment on the utilization of forest resources. SAF National Convention, Madison, WI, November 2-6, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: D. P. Harper. 2016. Use of lignin based carbons for energy storage applications. Frontiers in Biorefining, November 8  11, 2016, St. Simons Island, GA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: O. Hosseinaei, D. P. Harper, Joseph J. Bozell, T. Rials. 2016. Organosolv and Kraft Lignin: Fractionation and Conversion to Melt Spun and Electrospun Carbon Fibers. 2016 AIChE Annual Meeting. November 13-18, 2016. San Francisco, CA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: O. Hosseinaei, D. P. Harper, Joseph J. Bozell, T. Rials. 2016. Lignin-based carbon fibers: improved spinning and conversion process to carbon fiber. 4th International Conference Process Technology for the Forest & Biobased Industries 2016. October 25  26, 2016, St. Simons Island, GA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: S. Young, N. Meek, D. Penumadu, D. Harper, O. Hosseinaei, T. Rials. Meltspun Lignin Carbon Fibers for Reinforced Polymeric Composite Applications. TMS 2016. Febuary 14  18, 2016; Nashville, TN.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Wang S. 2015. Wood Science and Nanotechnology: Overview and Our Efforts. Oct. 14, 2015, Kangwon National University, South Korea (invited).
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Bozell, J. J., Can the biorefinery survive cheap oil? approaches to high value chemical products from carbohydrates and lignin, presented at the 12th Exploring Lignocellulosic Biomass Conference, Reims, France, June 24th, 2016
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Bozell, J. J., Biorefinery survival in an era of cheap oil: approaches to high value chemical products from carbohydrates and lignin, presented at the 12th International Conference on Renewable Resources and Biorefineries, Ghent, Belgium, May 30th, 2016
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Bozell, J. J. Designing catalysts for converting biorefinery lignin and carbohydrates to high value chemicals, Presented at University of Geneva, Geneva, Switzerland, January 18th, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Bozell, J. J. Designing catalysts for converting biorefinery lignin and carbohydrates to high value chemicals, Presented at University of Copenhagen, Copenhagen, Denmark, January 15th, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Bozell, J. J. Designing catalysts for converting biorefinery lignin and carbohydrates to high value chemicals, Presented at Utrecht University Utrecht, Netherlands, January 13th, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Bozell, J. J. Designing catalysts for converting biorefinery lignin and carbohydrates to high value chemicals, Presented at Ghent University Ghent, Belgium, November 19th, 2015.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Bozell, J. J. Renewable feedstocks in the biorefinery: catalyst design for biomass conversion, presented at Ghent University, Ghent, Belgium, December 22nd, 2015.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Chmely, S. C. Thermochemical conversion of biomass to fuels and other products. Presented at National Bioenergy Day 2015 Webinar, October 21, 2015. (invited)
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Chmely, S. C. The integrated biorefinery: chemicals & products from renewable carbon, presented at the Farragut High School Seminar Series, November 10, 2015. (invited)
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Astner. A., Bozell, J. J., Optimizing solvent fractionation for loblolly pine using response surface methodology: impact on component properties; presented at the IBSS 2016 annual meeting, Oak Ridge, TN July 27-28, 2016
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Bozell, J. J.; Biannic, B.; Ngnouomeuchi, C. N.; Key, R. E.; Zuleta, E. C.; Hartwig, W. T. Studies towards cobalt-catalyzed conversion of biorefinery lignin to value-added chemicals and fuels, presented at Energy Frontier Research Centers Primary Investigator Meeting, Washingon, D.C. October 26-27, 2015.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Labb�, N.; Hamilton, C.; Kim, K.; Edmunds, W. Biomass to feedstock, presented at the IBSS annual meeting, Oak Ridge, TN July 27-28, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Chmely, S. C.; Labb�, N. Developing an integrated biorefinery at the Center for Renewable Carbon. Presented at the Joint ORNL/NTRC-UTIA meeting for thermochemical conversion, Knoxville, TN, October 9, 2015.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Chmely, S. C. An integrated thermochemical process to valorize lignocellulosic biomass. Presented at the Berry College Cheminar Colloquim Series (invited), Rome, GA February 25, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Chmely, S. C. Interdisciplinary education and outreach activities at the University of Tennessee: The evolution of an outreach program, presented at the IBSS 2016 annual meeting, Oak Ridge, TN July 27-28, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Chmely, S. C. Vapor-phase upgrading of pyrolysis vapors using mixed oxide, carbide, and phosphide catalysts, presented at the IBSS 2016 annual meeting, Oak Ridge, TN July 27-28, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Abdoulmoumine, N.; Chmely, S. C.; Harper, D. P.; Labb�, N. An integrated thermochemical process to valorize lignocellulosic biomass. Presented to Daniel Cassidy, program manager for Biomass Research and Development Initiative, USDA, Washington, D. C. February 9, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Abdoulmoumine, N.; Chmely, S. C.; Labb�, N. Thermochemical conversion activities at the Center for Renewable Carbon. Presented at the Joint ORNL/FEERC-CRC meeting for thermochemical conversion, Oak Ridge, TN, April 19, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Chmely, S. C. Catalyst innovations for value-added chemicals. Presented at the Joint UTIA-ORNL Technical Exchange meeting, Oak Ridge, TN, August 16, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Labb�, N. Biomass characterization and processing, presented at Oak Ridge National Laboratory, Oak Ridge, TN, August 8, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Labb�, N. Biomass fractionation using ionic liquid, presented at the Biomim Meeting, Oslo, Norway, June 13-15, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Labb�, N. Biomass characterization and processing. Presented at the Joint UTIA-ORNL Technical Exchange meeting, Oak Ridge, TN, August 16, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Harper, D. P.; Chmely, S. C. Photo-curable lignin-based polymers for fibers, adhesives, and additive manufacturing. Presented to Andrew Lovinger, program manager for Division of Materials Research, Polymers program, NSF, Washington, D. C., February 10, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Abdoulmoumine, N.; Chmely, S. C.; Harper, D. P.; Labb�, N. An integrated thermochemical process to valorize lignocellulosic biomass. Presented to Kevin Craig, program manager for Bioenergy Technologies Office (BETO), Office of Energy Efficiency & Renewable Energy (EERE), DOE, Washington, D. C., February 10, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Liu, Q.; Chmely, S. C.; Labb�, N.; Abdoulmoumine, N. Effect of hot water extraction on inorganics removal in switchgrass. Presented at the Knoxville section meeting of the American Institute of Chemical Engineers, Knoxville, TN March 17, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Astner, A. F., Bozell, J. J., Young, T. M., Rials, T., Kim, K., Hosseinaei, O., Labb�, N. Thermal and chemical properties of organosolv lignins isolated from loblolly line using response surface design, presented at the IBSS 2016 annual meeting, Oak Ridge, TN, July 27-28, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Kim, K; Hamilton, C.; McCord, J.; Rials, T.; Labb�, N. Investigating the quality of hybrid poplar as a biochemical feedstock for bioenergy production, presented at the IBSS annual meeting, Oak Ridge, TN, July 27-28, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Hamilton, C; Edmunds, C.W.; Kim, K.; Chmely, S.; Labb�, N. Ash removal for bioenergy feedstock improvement using chelating agents, presented at the IBSS annual meeting, Knoxville, TN, July 27-28, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: McCann, F.; Labb�, N. Two dimensional hetero-correlation spectroscopy to investigate inorganics in bioenergy feedstocks, presented at the IBSS annual meeting, Oak Ridge, TN, July 27-28, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Edmunds, C. W.; Kim, K.; Rials, T.; Labb�, N. Blending of biomass to produce a high-quality feedstock for thermochemical conversion, presented at the IBSS annual meeting, Oak Ridge, TN, July 27-28, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Regmi, Y. N.; Chmely, S. C.; Labb�, N. Exploring transition metal carbides and phosphides for Ex-Situ catalytic fast pyrolysis, presented at the Knoxville section meeting of the American Institute of Chemical Engineers, Knoxville, TN, March 17, 2016.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Zuleta, E. C.; Bozell, J. J. Catalytic oxidation of para-substituted phenols with cobalt organometallic catalysts and nitroxyl radicals, presented at Center for Direct Catalytic Conversion of Biomass to Biofuels C3Bio, Annual Meeting, West Lafayette, IN, October 2015.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: V. Garc�a-Negr�n, N. Phillip, D. Wood, C. Daniel, J. Li, D. J. Keffer,O. Rios, D. P. Harper; Sustainable Energy Systems: High Performance Lithium-Ion Battery Components from Renewable Resources; UTIA Science Day; April 26, 2016; The University of Tennessee, Knoxville, TN.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Tao, J.; Hosseinaei, O.; Delbeck, L.; Kim, P.; Harper, D. P.; Bozell, J. J.; Rials, T. G.; Labb�, N. Effects of organosolv fractionation time on thermal and chemical properties of lignins. RSC Adv. 2016, 6, 79228-79235.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Njiojob, C.; Rhinehart, J. L.; Bozell, J.; Long, B. L. Synthesis of enantiomerically pure lignin dimer models for catalytic selectivity studies. J. Org. Chem. 2015, 80, 1771-1780.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Sun, Q.; Khunsupat, R.; Akato, S. K.; Tao, J.; Labb�, N.; Gallego, N. C.; Bozell, J.; Rials, T. G.; Tuskan, G. A.; Tschaplinski, T.; Naskar, A. M.; Ragauskas, A. J. Physicochemical characteristics of poplar lignin carbon precursors before and after melt rheology. Green Chemistry 2016, 18, 5015-5024.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Njiojob, C.; Bozell, J. J.; Long, B. L.; Elder, T.; Key, R. E.; Hartwig, W. T. Enantioselective syntheses of lignin models - an efficient synthesis of ?-O-4 dimers and trimers using the Evans chiral auxiliary. Chem. Eur. J. 2016, 22, 12506-12517.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Key, R. E.; Bozell, J. J. Recent progress toward lignin valorization via selective catalytic technologies and the tailoring of its biosynthetic pathways. ACS Sus. Chem. Eng. 2016, 4, 5123-5135.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Guo, P.; Anderson, J. D.; Bozell, J. J.; Zivanovic, S. The effect of solvent composition on grafting gallic acid onto chitosan via carbodiimide. Carbohydr. Polym. 2016, 140, 171-180.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Astner, A. F.; Young, T. M.; Bozell, J. J. Lignin yield maximization of mixed biorefinery feedstocks by organosolv fractionation using Taguchi Robust Product Design. Biomass Bioenergy 2015, 73, 209-216.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Kim, P.; Rials, T. G.; Labb�, N.; Chmely, S. C. Screening of mixed-metal oxide species for catalytic ex situ vapor-phase deoxygenation of cellulose by py-GC/MS coupled with multivariate analysis. Energy Fuel 2016, 30, 3167-3174.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Das, P.; Elder, T.; Brennessel, W. W.; Chmely, S. C. Iron piano-stool complexes containing NHC ligands outfitted with pendent arms: synthesis, characterization, and screening for catalytic transfer hydrogenation. RSC Adv. 2016, 6, 88050-88056.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Aboytes-Ojeda M., K. K. Castillo-Villar, T. E. Yu, C. N. Boyer, B. C. English, J. A. Larson, L. M. Kline, and N. Labb�. A principal component analysis in switchgrass chemical composition. Energy 2016, 9, 913; doi:10.3390/en9110913.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Kim, P.; Lloyd, J.; Kim, J.; Abdoulmoumine, N.; Labb�, N. Recovery of creosote from used railroad ties by thermal desorption. Energy 2016, 111, 226-236.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Kim, P.; Lloyd, J.; Kim, J.; Labb�, N. Thermal desorption of creosote remaining in used railroad ties: Investigation by TGA (thermogravimetric analysis) and Py-GC/MS (pyrolysis-gas chromatography/mass spectrometry). Energy 2016, 96, 294-302.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Rena, S.; Ye, X. P; Borole, A. P.; Kim, P.; Labb�, N. Analysis of switchgrass-derived bio-oil and associated aqueous phase generated in a semi-pilot scale auger pyrolyzer. Journal of Analytical and Applied Pyrolysis 2016, 119, 97-103.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Wight, J.P.; Allen, F.L.; Ashworth, A. J.; Tyler, D. D.; Labb�, N.; Rials, T.G.. Comparison of near infrared reflectance spectroscopy with combustion and chemical methods for soil carbon measurements in agricultural soils. Communications in Soil Science and Plant Analysis 2016, 47, 731-742.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Kim, P.; Weaver, S.; Labb�, N. Effect of sweeping gas flow rates on temperature-controlled multistage condensation of pyrolysis vapors in an auger intermediate pyrolysis system. Journal of Analytical and Applied Pyrolysis 2016, 118, 325-334.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Kline, L.K.; Labb�, N.; Boyer, C.; Yu, T. E.; English, B.C.; Larson, J.A. Investigating the impact of biomass quality on near-infrared models for switchgrass feedstocks. AIMS Bioengineering 2016, 3, 1-22.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: V. Garcia-Negron, N. Phillip, D. Wood, C. Daniel, J. Li, D. J. Keffer, O. Rios, D. P. Harper. Processing-Structure-Property Relationships for Lignin-based Carbonaceous Materials used in Energy Storage Applications. Energy Technology. 2016. DOI: 10.1002/ente.201600646.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: O. Hosseinaei, D. P. Harper, J. J. Bozell, T. G. Rials. 2016. Role of physicochemical structure of organosolv hardwood and herbaceous lignins on carbon fiber performance. ACS Sustainable Chemistry & Engineering. DOI: 10.1021/acssuschemeng.6b01828.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: N. Meek, D. Penumadu, O. Hosseinaei, D. P. Harper, S. Young, T. G. Rials. Mechanical, interfacial, and structural lignin carbon fiber characterization and composite panel manufacture. Composite Science and Technology. 2016. DOI: 10.1016/j.compscitech.2016.10.016.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Xu, D., Y. Zhang, H. Zhou, Y. Meng, S. Wang. 2016. Characterization of adhesive penetration in wood bondlines by means of scanning thermal microscopy (SThM). Holzforschung 70(4): 323-330. DOI: 10.1515/hf-2014-0360.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Xing, D., J. Li, X. Wang, S. Wang. 2016. In situ measurement of heat-treated wood cell wall at elevated temperature by nanoindentation. Industrial Crops and Products 87: 142-149. DOI: 10.1016/j.indcrop.2016.04.017.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: L. Ma, Y. Zhang, S. Wang. 2016. Modified treatment for carbonized cellulose nanofiber application in composites. Composites A 90: 786-793.
  • Type: Journal Articles Status: Published Year Published: 2016 Citation: J. Huang, S. Lv, F. Fu, H. Chang, S. Wang. 2016. Preparation of Superhydrophobic Coating with Excellent Abrasion Resistance and Durability Using Renewable Nanofibrillated Cellulose. RSC Advances, 6, 106194 - 106200. DOI: 10.1039/C6RA23447J.


Progress 10/01/14 to 09/30/15

Outputs
Target Audience:Agricultural producers, the scientific community at large, academia, national laboratories, federal and state agencies, private industry, public interest groups, the government sector, land-grant institutions, biofuel industry leaders, and additional stakeholders. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Four undergraduates (Elizabeth Edds, John Proffitt, Angela Sipaseuth and Jeff Mann); two M.S. students (Valerie Garcia-Negron, Nathan Meek); two Ph.D. students (Libo Ma, Yujie Meng); and five Post-doctoral fellows (Omid Housseinaei, Rohit Uppal, Stephen Young, Partha Das, and Rangana Wijayapala) got the training through this project. Finally, a Knox-county schoolteacher (Eldon English) participated in research in PI Chmely's lab over the summer. Additionally, several undergraduate (Forrest McCann) and graduate students (Jing Wang, Chet Greer), research associates (Choo Hamilton, Anna Kim, Lindsey Kline) and post-doctoral research associates (Jingming Tao, Pyoungchung Kim), involved in the mentioned above projects were trained in using high throughput technologies for biomass characterization and new approaches for biomass conversion. How have the results been disseminated to communities of interest?The PIs, students, and post-docs presented their findings at regional, national and international meetings. We are working with four companies to develop technology around lignin based carbon products. What do you plan to do during the next reporting period to accomplish the goals?We intend to continue investigating other solid catalysts for the vapor-phase upgrading of pyrolysis oil vapors. PIs Chmely and Labbé have hired an additional postdoctoral scholar, Yagya Regmi, to continue these efforts. In addition, we will focus on additional nano-alloy catalysts capable of catalyzing transfer hydrogenolysis of lignin. These reactions will allow for the production of aromatic platform chemicals using sustainable catalytic materials based on iron and nickel. Finally, we will continue to monitor the effects of chemical transformations of lignin on its thermal properties. We intend to employ alcohol protecting groups in an effort to lower the glass transition temperature of lignin and demonstrate what effects this has on the extrusion of lignin fibers. Concerning the ionic liquid fractionation work, we intend to investigate the process with various types of biomass to demonstrate the flexibility of the system. We will also assess the impact of the cellulose/lignin ratio on the properties of the corresponding films.

Impacts
What was accomplished under these goals? I.High-throughput biomass analysis methods - Spectroscopic models were constructed to predict the chemical composition (i.e. cellulose, hemicellulose, lignin and extractives content) of various biomass types. In addition, we demonstrated that it is possible to predict the inorganic composition of lignocellulosic biomass by mid infrared spectroscopy. We have been using these predictive models to screen switchgrass and hybrid poplar material for improved traits for both, thermochemical and biochemical conversion processes. II. Biomass Fractionation. Organosolv Refining - Lignin, a potential low-cost, high volume output process stream derived from lignocellulosic biomass is currently being researched to better support the economics of the future biorefinery. Organosolv processes, the treatment of renewable raw materials with solvents to effect a separation, offers a means to produce a highly pure lignin stream for eventual conversion to high value biobased chemicals and materials. Our process treats the biomass source with a ternary mixture of methyl isobutyl ketone (MIBK), ethanol and water in the presence of an acid promoter. Standard conditions use a 16/34/50 ratio of MIBK/EtOH/H2O at times between 60-180 minutes, temperatures of 120-160oC, and H2SO4 concentrations of 0.025 - 0.2M. The ratio of solvent components is chosen so that the mixture remains as a single liquid phase at all times during the separation. The solvent mixture selectively dissolves the lignin and hemicellulose components, leaving the cellulose as an undissolved material that can be washed, fiberized, and further purified. The soluble fraction containing the lignin and hemicellulose is treated with water, causing a phase separation to give an organic phase containing the lignin. Our current effort is applying this methodology in three applications. First, lignin is being generated as part of a partnership between the CRC and TennEra, a local company interested in conversion of the lignin into lightweight, biobased carbon fiber, a material with a huge potential upside in the production of lightweight components for the automotive and aerospace industries. Our effort has carried out several campaigns on both switchgrass and poplar feedstocks, leading to multi-kg supplies of lignin for further testing. We are currently planning the next stage of process scaleup to generate sufficient lignin for industrial evaluation. Second, our research is investigating the separation of mixed feedstock streams (switchgrass/poplar) at a variety of different proportions. This activity is important in demonstrating that differences in feedstock availability over the course of a growing season is not a factor in supplying cellulose or lignin to a biorefinery operation. Our results show that mixed feedstocks undergo separation as effectively as pure feedstock streams. Finally, we have carried out evaluation of softwoods as a feedstock, as such materials are a major source of biomass in the southeast. Interestingly, softwoods are much less effective as feedstocks in organosolv processes. Our recent work shows that modifying the standard solvent ratio in the organosolv process affords methodology for fractionation southern yellow pine. By using statistical experimental design, we have been able to optimize the yield of lignin from these processes. Further work has investigated the thermal properties of the isolated lignins and correlated them with the conditions used during the fractionation. Our current results show that temperature and the size of particles used during the fractionation are the most significant factors controlling lignin yield, while acid level has the greatest impact on the lignin's glass transition temperature. Ionic Liquid - We demonstrated that a partial removal of hemicellulose by hot water generates cellulose-enriched biomass that is highly soluble in the ionic liquid 1-ethyl-3-methyl imidazolium acetate. The biomass-IL solution was found to possess adequate characteristics for wet spinning. We therefore produced biomass films that have very promising properties for various applications. III. Value-Added Chemicals. Production of Biobased Chemicals - We are continuing to develop chemical catalysts capable of transforming biomass fractions into bio-based chemicals and products. We have concluded research on mixed-metal oxide solid base catalysts for catalytic upgrading of pyrolysis oil vapors, and have demonstrated that these catalysts increase the yield of furans while simultaneously decrease the oxygen content of pyrolysis vapors, and have submitted a publication pertaining to this work. We demonstrated through py-GC/MS that the product slate of cellulose pyrolysis is affected by the ratio of Mg:Al in our novel catalyst species. Precise control over this product slate is crucial to maximize the yield of useful chemical synthons via thermochemical conversion of biomass.We investigated homogeneous iron catalysts capable of catalyzing transfer hydrogenation of polar double bonds. These catalysts could be useful to control the hydrogen bonding schemes in lignin (see below). In addition, these species are capable of sustainable transformations of aldehyde and ketone moieties that are also generally useful in the production of other fine and platform chemicals. We demonstrated that catalyst function is dependent upon UV radiation of the reaction pot, since catalyst activation by light irradiation is necessary for reaction turnover.We investigated production of methyl furan from furfural using novel nickel-iron nano-alloy catalysts via transfer hydrogenolysis. Our proposed catalyst is cheaply produced from earth-abundant metals and is magnetic, which makes it easily separable and recyclable. We have shown that methyl furan, a potential drop-in hydrocarbon fuel or fuel additive, is produced at moderate temperatures using reducing equivalents provided by 2-propanol. In addition, this recyclable heterogeneous species could be useful in the catalytic reduction of other biomass fractions, which is currently under investigatio IV. Advanced Materials. Carbohydrate Nanomaterials -We have prepared a high CNC-content master batch through the master-batch method to improve the dispersibility, the thermal stability, and the compatibility between the Cellulose nanocrystal (CNC) and the matrix. The CNC master-batch was then used to produce the ABS/CNC nanocomposites via melt extrusion. The goal of this work was to put forward one way to use CNC on an industrial scale with good operability and cost effectiveness. Compared with freeze-dried CNC and CNC gel, the advantages of master-batch CNC are these: (i) the volume of CNC master batch can be reduced to a suitable size for making composites or transportation; (ii) the stability and adaptability of CNC is increased. The CNCs are coated with ABS, which is hydrophobic. The coating will reduce the CNC's absorption of water from outside, and the content of CNC in the master batch can be adjusted according to the requirements of the final product?(iii) compared with solvent-exchange method, the master-batch method needs less solvent, and the solvent can be collected and reused. Carbon Fiber Production - We investigated how to control the thermal properties of lignin by altering the ability of the polymer to undergo inter- and intramolecular hydrogen bonding. We demonstrated that reduction of the lignin polymer leads to an increase in its glass transition temperature, which has implications for extrusion of lignin into fibers for carbon fiber production. Use of stoichiometric amounts of sodium borohydride imparts a measureable difference in hydroxyl group content, which we were able to monitor using 31P NMR spectroscopy.

Publications

  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Astner, A. F., Young, T. M., Bozell, J. J. 2015. Lignin yield maximization of mixed biorefinery feedstocks by organosolv fractionation using Taguchi Robust Product Design, Biomass Bioenergy. 73, 209-216.
  • Type: Journal Articles Status: Awaiting Publication Year Published: 2016 Citation: Zivanovic, S., Guo, P., Anderson, J., Bozell, J. J. 2016. The Effect of Solvent Composition on Grafting Gallic Acid onto Chitosan via Carbodiimide, Carb. Polym.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Kim P, J. Lloyd, J. Kim, N. Labb�. Recycling of used railroad ties via two-staged pyrolysis for fractionation of wood preservatives and bio-oil: pyrolytic characterization by TGA and Py-GC/MS. The International Research Group on Wood Protection, May 10-14, 2015.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: S. Wang, X. Wang, Y. Meng, L. Ma, D. Xing, Y. Wang, J. Fu, D. Xu. 2015. Nanomechanical Measurements and Cellulose Nano Material Development at University of Tennessee. International Symposium for the 40th Anniversary of the Institute of Forest Science. Oct. 13, 2015. Gangwon-do, South Korea.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Meng, Y., Q. Wu, T. Young, T. Rials, S. Wang. 2015. Development of Value-Added Nanomaterials from Switchgrass (Panicum virgatum L.). Praitie & Native Grass International Conference, Sept. 30-Oct. 2, Knoxville, TN (Poster).
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Fu, J., L. Fan, C. He, Z. Lu, S. Wang. 2015. Cellulose nanocrystals reinforced silica aerogels: microstructure and mechanical properties. 2015 TAPPI International Conference for Renewable Materials. June 22-25, 2015. Atlanta, GA. (Poster).
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Meek, N., Penumadu, D., Housseinaei, O., Harper, D. Mechanical and interfacial characterization of single lignin carbon fiber for composite manufacture. CARBON FIBERS AND THEIR COMPOSITES. Symposium/Workshop American Carbon Society. April 16  17. Oak Ridge, TN. (Poster)
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Uppal, R., Harper, D., Lignin Based Novel Carbon Foams. CARBON FIBERS AND THEIR COMPOSITES. Symposium/Workshop American Carbon Society. April 16  17. Oak Ridge, TN. (Poster)
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Omid Hosseinaei, David Harper, Joseph Bozell, Timothy Rials. Melt Spun and Electrospun Carbon Fibers from Different Lignin Precursors. Symposium/Workshop American Carbon Society. April 16  17. Oak Ridge, TN. (Poster)
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Jingming Tao, Omid Hosseinaei, Pyoungchung Kim, David Harper, Joseph Bozell, Timothy Rials, Nicole Labb�. Influences of Organosolv Fractionation Time on Thermal and Chemical Properties of Lignins. CARBON FIBERS AND THEIR COMPOSITES. Symposium/Workshop American Carbon Society. April 16  17. Oak Ridge, TN. (Poster)
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Omid Hosseinaei, David Harper, Joseph J. Bozell and Tim Rials. Methyl isobutyl ketone/ethanol organosolv lignin: characterization and conversion to carbon fiber. 249th ACS National Meeting & Exposition, 2015, Denver, CO. (Presentation)
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Nathan Meek, Dayakar Penumadu, David Harper, Omid Hosseinaei, Timothy Rials. Evaluation of Mechanical and Interfacial Properties of Individual Lignin Carbon Fiber and Layered Composites, American Society for Composites 30th Technical Conference September 28-30, 2015 Michigan State University, East Lansing, Michigan. (Presentation and Paper)
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: David Harper, Rohit Uppal. Foams from lignin. Southeastern Sun Grant Center's Southern Crossroads: Progress In the Science & Technology of Biomass Production, Processing and Use Regional Meeting. February 2  4. Auburn, AL.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: S. C. Chmely, P. Das, Light-activated iron bifunctional catalysts for transfer hydrogenations of polar double bonds, 249th National Meeting of the American Chemical Society, Denver, CO, March 22-26, 2015 (oral).
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: N. Labb�, S. C. Chmely, C. Hamilton, K. Kim, Inorganics in lignocellulosic biomass, 37th 37th Sympsosium on Biotechnology for Fuels and Chemicals, San Diego, CA, April 27-30, 2015 (oral)
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: K. Kim, C. Hamilton, S. C. Chmely, N. Labb�, Reducing inorganics in lignocellulosic biomass utilizing microwave assisted acid extraction, Switchgrass III, Prairie & Native Grass International Conference, Knoville, TN, September 30-October 2, 2015 (poster)
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Labb� N., J. Tao, L. Kline, A. Bruce, B.H. Ownley, K.D. Gwinn, N. Moustaid-Moussa, H. Jameel, C.E. Aizpurua Gonzalez. 2015. Developing an integrated biorefinery: potentials of switchgrass extractives. Sun Grant Regional Meeting, Auburn, AL.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Kim K., C. Hamilton, J. McCord, T.G. Rials, N. Labb�. 2015. Investigating hybrid poplar as an advancing energy crop for bioenergy production. Integrated Biomass Supply System Annual Meeting, Auburn, AL
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Garrison R., S. Scoggin, N. Siriwardhana, N. Labb�, B.H. Ownley, K.D. Gwinn, D.H. DSouza, L. Ramalingam, N. Moustaid-Moussa. 2015. Anti-inflammatory effects of extracts from a bioenergy crop, switchgrass, in adipocytes. Sun Grant Regional Conference on Southern Crossroads: Progress in the Science & Technology of Biomass Production, Processing and Use, Auburn, AL.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Hayes D.G., L.M. Kline, N. Labb�, A. Womac. 2015. Ionic liquids for the dissolution, pretreatment, and analysis of lignocellulosic biomass. Sun Grant Regional Conference on Southern Crossroads: Progress in the Science & Technology of Biomass Production, Processing and Use, Auburn, AL.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Larson J.A., T.E. Yu, C.N. Boyer, B.C. English, N. Labb�, L.M. Kline, D.D. Tyler. 2015. Effect of particle size and bale wrap on storage losses and quality of switchgrass. Sun Grant Regional Conference on Southern Crossroads: Progress in the Science & Technology of Biomass Production, Processing and Use, Auburn, AL.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Elder T., N. Labb�, C. Greer, N. Stewart, H. Baxter, M. Mazarei. 2015. Impacts of inorganics on the thermal behavior of switchgrass. Sun Grant Regional Conference on Southern Crossroads: Progress in the Science & Technology of Biomass Production, Processing and Use, Auburn, AL.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Labb� N., J. Wang, D. P. Harper, and T. G. Rials. 2014. Impacts of auto-hydrolysis on biomass solubility in ionic liquid. Gordon Research Conference on Ionic liquids, Newry, ME.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Labb� N., and J. Wang. 2014. Isolating lignin through an ionic liquid process. 247th American Chemical Society National Meeting, Dallas, TX.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Hatcher C.N., L. Alexander, M. Mazarei, E. Haynes, H. Baxter, C. Hamilton, N. Labb�, R. Dixon, Z. Wang, C.N. Stewart Jr. 2014. Development of hybrid switchgrass for improved biomass traits and field assessment. Integrated Biomass Supply System Annual Meeting, University of Tennessee, Knoxville, TN.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Deleon E., W. Gray, P. Kim, A.C. Sherfy, N. Labb�. 2014. Biosolid-derived biochar for phosphate remediation. ASA-SSSA-CSSA International Meetings, Long Beach, CA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Ren S., X. Ye, A. Borole, P. Kim, N. Labb�. 2014. Characterization of aqueous phase bio-oil derived from switchgrass pyrolysis. Proceedings of AIChE Annual Meeting, AIChE Annual Meeting, Atlanta, GA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Ernesto C. Zuleta S, Joseph J. Bozell, Enhancing catalytic oxidation of lignin with N-oxo compounds. Poster presentation. Presented at: Postdoc Research Symposium, ORNL, Oak Ridge, TN. July 2015.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Key, R. E., Bozell, J. J. 2015. Design of novel tridentate Co-Schiff base complexes for the catalysis of para-substituted phenolic lignin models to para-benzoquinones. C3Bio Annual Meeting, West Lafayette, IN USA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Key, R. E., Hartwig, W. T., Njiojob, C. N., Zuleta, E. C., Chapple, C., Bozell, J. J.. Design of novel, supported metallo-Schiff base catalysts for the conversion of both whole biomass and biorefinery lignin into high value, low-molecular-weight aromatics. C3Bio Mid-Term Review, Bethesda, MD USA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Lenaghan S., N. Labb�, C.N. Stewart, Jr. 2014. Development of an automated platform for rapid screening of genetically modified switchgrass. Frontiers in Biorefining, St Simons Island, GA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Wang J., J. Tao, D.P. Harper, T.G. Rials, N. Labb�. 2014. Impacts of autohydrolysis on solubility of biomass in ionic liquid. Frontiers in Biorefining, St Simons Island, GA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Tao J., O. Hosseinaei, P. Kim, D.P. Harper, J.J. Bozell, T.G. Rials, N. Labb�. 2014. Effects of fractionation time on thermal and chemical properties of organosolv lignins. Frontiers in Biorefining, St Simons Island, GA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Joseph J. Bozell, Thomas Elder, Berenger Biannic, Diana Cedeno, Sabornie Chatterjee, Kun Cheng, Costyl Njiojob, Catalysis for conversion of biorefinery lignin to high value chemicals  structural and computational analysis for improved catalyst design, Presented at the 18th ISWFPC, BOKU, Vienna, Austria, September 9 - 11, 2015.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Bozell, J. J., Biorefining in an era of cheap oil. Approaches to high value chemical products from carbohydrates and lignin, Presented at the Plant Research Center Colloquium, University of Tennessee, April 30th, 2015.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Synthesis of glycal-based bolaamphiphiles tethered to cobalt-Schiff base complexes for catalyst delivery to lignocellulosic biomass, Joseph J. Bozell, Costyl N. Njiojob, Brian Long, Presented at the 249th annual meeting of the American Chemical Society, Denver, CO, March 25th, 2015.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Bozell, J. J., Can the biorefinery survive cheap oil? Approaches to high value chemical products from carbohydrates and lignin, Presented at the 2015 Sun Grant regional meeting, Auburn University, February 3rd, 2015.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Chmely, S. C. 2015. Research, Education, and Outreach Activities at the Center for Renewable Carbon. July 2015. Academies of Nashville Teacher Externship hosted by LP Building Products, Nashville, TN (invited).
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Chmely, S. C. 2015. Thermochemical conversion of biomass to fuels and other products. National Bioenergy Day Webinar Series, online (invited).
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Chmely, S. C. 2015. Catalysis for biomass conversion. Mid-Atlantic Regional Biomaterial Science Meeting, May 20-21, 2015. Blacksburg, VA (invited).
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Wang S. 2015. Recent progress on nanomechanical measurements and cellulose nano material development at The University of Tennessee. Sept. 28, University of Sao Paulo, Piracicaba, Brazil (invited).
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Wang S. 2015. Nanomechanical measurements and cellulose nano material development: Recent progress at University of Tennessee. July 28, Mississippi State University, Starkville (invited).
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Wang S. 2015. Recent progress on nanomechanical measurements and cellulose nano material development. Central South University of Forestry and Technology, Changsha, Sept. 3, 2015, China (invited).
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Wang S. 2015. Nanomechanical measurements and cellulose nano material development at University of Tennessee. Sept. 4th, Xiangtan University, Xiangtan, China (invited).
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Meng, Y., T. Young, S. Wang. 2015. Investigation of nanoporous carbon synthesized from cellulose nanocrystals and lignin. 2015 TAPPI International Conference for Renewable Materials. June 22-25, 2015. Atlanta, GA. (Poster).
  • Type: Conference Papers and Presentations Status: Other Year Published: 2015 Citation: Harper, D., Carbon Products Based on Lignin. Washington State University. August 6, 2015. (Invited)
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Y. Zhang, R. Yang, Y. Wu, S. Wang, C. Liu, X. Zhong, J. Wu. 2015. Effect of growth period on cellwall mechanical property of elephant grass. BioResournces, 10(3): 4252-4262.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Meng, Y., X. Wang, Z. Wu, S. Wang, T.Y. Young. 2015. Optimization of cellulose nanofibrils carbon aerogel fabrication using response surface methodology. European Polymer Journal 73: 137-148.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Ma, L., Y. Zhang, Y. Meng, P. Anusonti-Inthra, S. Wang. 2015. Preparing cellulose nanocrystal/acrylonitrile-butadiene-styrene nanocomposites using the master-batch method. Carbohydrate Polymers, 125:352-359.
  • Type: Journal Articles Status: Awaiting Publication Year Published: 2015 Citation: L. Ma, Y. Zhang, S. Wang. 2015. Fabrication and characterization of Acrylonitrile-Butadiene-Styrene (ABS) nanocomposites reinforced with cellulose nanocrystal via solution casting method. Polymer Composites.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Xing, D., S. Wang, J. Li. 2015. Effect of artificial weathering on the properties of industrial-scale heat treated wood. BioResources 10(4): 8238-8252.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Meng, Y., T. Young, P. Liu, C. Contescu, B. Huang, S. Wang. 2015. Ultralight carbon aerogel from nanocellulose as a highly selective oil absorption materials. Cellulose 22:435-447.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Cetin, N., N. Ozmen Cetin, and D. P. Harper. 2015. Vinyl acetate-modified microcrystalline cellulose-reinforced HDPE composites prepared by twin-screw extrusion. Turkish Journal of Agriculture and Forestry.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Eberhardt T.L., N. Labb�, C.L. So, K. Kim, K.G. Reed, D.J. Leduc, J.M. Warren. 2015. Effects of long-term elevated CO2 treatment on the inner and outer bark chemistry of sweetgum (Liquidambar styraciflua L.) trees. Trees. 29, 1735-1747.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Kim K., N. Labb�, J.M. Warren, T. Elder, T.G. Rials. 2015. Chemical and anatomical changes in Liquidambar styraciflua L. xylem after long term exposure to elevated CO2. Environmental Pollution. 198, 179-185.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Lewis A.J., S. Ren, X. Ye, P. Kim, N. Labb�, A.P. Borole. 2015. Hydrogen production from switchgrass via an integrated pyrolysis-microbial electrolysis process. Bioresource Technology. 195, 231-241.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Ryu S., N. Labb�, C.T. Trinh. 2015. Simultaneous saccharification and fermentation of cellulose in ionic liquid for efficient production of alpha-ketoglutaric acid by Yarrowia lipolytica. Applied Microbiology and Biotechnology. 99, 4237-4244.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Ratnaweera D.R., D. Saha, S.V. Pingali, N. Labb�, A.K. Naskar, M. Dadmun. 2015. The impact of lignin source on its self-assembly in solution. RSC Advances. 5, 67258-67266.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Kim P., D. Hensley, and N. Labb�. 2014. Nutrient release from switchgrass derived biochar pellets embedded with fertilizers. Geoderma. 232-234, 341-351.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Kim P., S. Weaver, K. Noh, and N. Labb�. 2014. Characteristics of bio-oils produced by an intermediate semipilot scale pyrolysis auger reactor equipped with multistage condensers. Energy and Fuels. 28, 6966-6973.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Baxter L.H., M. Mazarei, N. Labb�, L.M. Kline et al. 2014. Two-year field analysis of reduced recalcitrance transgenic switchgrass. Plant Biotechnology Journal. 12, 914-924.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Martin, M. Z., N. Labb�, and R. J. Wagner. 2014. Applications of high resolution laser: induced breakdown spectroscopy for environmental and biological samples. Laser Induced Breakdown Spectroscopy, Springer Series in Optical Sciences, vol. 182, pp 439-456.
  • Type: Journal Articles Status: Submitted Year Published: 2015 Citation: P. Kim, T. G. Rials, N. Labb�, S. C. Chmely, Screening of mixed-metal oxide species for catalytic ex-situ vapor-phase deoxygenation of cellulose by py-GC/MS coupled with multivariate analysis, submitted to Energy Fuels, 2015.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Njiojob, C. N.; Rhinehart, J. L.; Bozell, J. J.; Long, B. K. J. Org. Chem. 2015, 80, 17711780.
  • Type: Journal Articles Status: Awaiting Publication Year Published: 2015 Citation: Golding, C., Gwinn, K. D., Peeden, A., Bozell, J., Trout-Fryxell, R. T. 2015. Acarcidal activity of eastern red cedar. Med. Vet. Entomol.
  • Type: Journal Articles Status: Submitted Year Published: 2015 Citation: Sun, Q., Khunsupat, R., Akato, S. K., Tao, J., Labb�, N., Gallego, N. C., Bozell, J., Rials, T. G., Tuskan, G. A., Tschaplinski, T., Naskar, A. M., Ragauskas, A. J. 2015. Physicochemical characteristics of poplar lignin carbon precursors before and after melt rheology. Energ. Environ. Sci.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Abu-Omar, M., Agrawal, R., Bozell, J., Carpita, N. 2015. Tailoring Biomass for Biochemical, Chemical or Thermochemical Catalytic Conversion, FASEB J. 29.


Progress 10/01/13 to 09/30/14

Outputs
Target Audience: Agricultural producers, the scientific community at large, academia, national laboratories, federal and state agencies, private industry, public interest groups, the government sector, land-grant institutions, biofuel industry leaders, and additional stakeholders. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? In 2014, PI Chmely supported 2 undergraduate researchers and one postdoctoral scholar. In addition, he hosted a Knox County schoolteacher over the summer to aid in the development of an educational module based on biomass conversion to be used in middle and high school classrooms. Two Ph.D. students (Cong Liu, Yujie Meng) were trained under PI Wang on the production of carbon aerogel from nanocellulose. Three research associates, one Master student, one PhD student, and two postdoctoral scholars were supported by PI Labbé to develop spectroscopic models and fractionation methods. PI Bozell trained two PhD students and one postdoctoral scholar in organic chemistry to produce value-added chemicals from biomass. How have the results been disseminated to communities of interest? We have presented our experimental results at a number of professional conferences, including the national meeting of the American Chemical Society, Frontiers in Biorefining Conference, Gordon Conference, Symposium on Biotechnology for Fuels and Chemicals, and the Minorities in Agriculture, Natural Resources, and Related Sciences. Moreover, we have presented our findings at the Department of Energy's Biomass 2014 conference, which included a number of government agency and private industry representatives. What do you plan to do during the next reporting period to accomplish the goals? We will continue to improve our spectroscopic models and develop new models for other bioenergy feedstocks such as pine. We will optimize our fractionation process to obtain high stability and reactivity of cellulases and hemicellulases in ionic liquid-biomass mixtures. We intend to continue the mechanistic investigations of our novel catalyst systems in an effort to gain insight into the design and implementation of these and other systems. This will require the use of model compounds and reactions. In addition, we intend to apply our VPU catalysts to a pilot-scale pyrolysis system. This will allow us to isolate bio-oil and characterize it in an effort to elucidate the effects of our system on the production of bio-oil. Taken together, these experiments will aid in the production of novel biomass conversion technologies, which will ultimately enable the future bio-economy in the US.

Impacts
What was accomplished under these goals? I. High-throughput biomass analysis methods. We have developed spectroscopic models to predict the chemical composition (i.e. cellulose, hemicellulose, lignin, extractives, and ash) of various bioenergy crops. Specifically, near and mid infrared models were constructed for single feedstocks such as switchgrass and hybrid poplar. Effort has also focused on developing mixed feedstock models that will allow us to assess lower quality biomass with unknown origin. More recently, because of the growing challenges that ash and inorganics represent during biomass conversion, we have been developing mid infrared and laser induced breakdown methods to predict inorganic composition of biomass. These models are constantly being tested and improved by incorporation of additional samples. Biomass quality based on harvest time, storage conditions, and pre-processing methods are being evaluated and the robustness and stability of the spectroscopic models tested prior to deployment. II. Biomass Fractionation. a. Ionic Liquid Refining -The naturel recalcitrance of lignocellulosic biomass to mechanical, chemical, and biological degradation is a major barrier that any biorefinery must overcome to develop an integrated, viable, and economical process. More than ten years ago, the Department of Energy initiated a major program on reducing the recalcitrance of biomass through genetic modification/improvement of selected bioenergy crops. Another appealing approach to address this challenge is to develop fractionation processes that are "feedstock agnostic". Ionic liquids (IL) have emerged as a novel class of green nonaqueous solvent that possess unique properties and compelling advantageous over traditional aqueous solvents. Their capability to dissolve cellulose and whole biomass under low severity with minimal degradation of biomass is attractive to maximize the utilization of the three major components of biomass. Through our research, we have developed an ionic liquid fractionation process and showed that it can be used for processing of softwood, hardwood, and herbaceous, demonstrating the ability of the IL system to fractionate any type of lignocellulosic biomass. We are currently investigating the stability and reactivity of enzymes in IL-biomass mixtures with the goal to selectivity generate clean streams with desired properties. III. Value-Added Chemicals. a. Production of Biobased Chemicals -We have been developing chemical catalysts capable of transforming biomass fractions into bio-based chemicals and products. One such catalyst system is a mixed metal oxide catalyst derived from layered double hydroxide starting materials. We have shown this system as able to reduce the oxygen content of pyrolysis oil vapors by ex-situ vapor-phase upgrading (VPU) reactions. One suite of products from these gas-phase reactions of cellulose is furans, which have been identified as platform precursors to other chemicals and products, as well as precursors to drop-in diesel fuels. Our catalyst system increases the yield of various furans during the catalytic fast pyrolysis of cellulose. We have also detected a decrease in the number of oxygenated compounds in the pyrolysis vapors, which could indicate a decrease in oxygen content of the condensed bio oil. High oxygen content has been implicated in the instability and corrosiveness of bio-oil, and a reduction in oxygen could lead to a better liquid product amenable to additional upgrading reactions. In another project, we have developed homogenous iron-based catalysts for the reduction of polar double bonds. These model systems are potentially applicable to the chemical reduction of lignin to platform chemicals such as BTX. Our system is capable of clean reductions in the absence of auxiliary chemicals (such as added base or even hydrogen gas) and is derived from sustainable and inexpensive iron metal. In both of the aforementioned cases, we are currently investigating the mechanism of these reactions in an effort to tune catalyst reactivity and selectivity. IV. Advanced Materials. a. Carbohydrate Nanomaterials - Nanocellulose has attracted high scientific and practical interest relatively recently because it is a biobased, green, sustainable, nontoxic and renewable inherent of cellulose from abundant resources and because of its unique intrinsic properties as a nanomaterial. We synthesized a sponge-like carbon aerogel from nanocellulose, the basic plant molecular structure that forms a green plant's cell wall and which is the most abundant organic polymer on Earth. This carbon aerogel has super-absorbing ability for many oils and organic solvents, up to 64 times its own weight. Those characteristics, along with good recyclability, give the carbon aerogel great potential to be used to separate oil from water and to clean up large-scale oil spills. We have investigated, by means of nanoindentation, the effect of cellulose nanomaterials (CNF-L, CNF-C, and CNC) on the mechanical properties of the interphase in reinforced bondlines. Results showed that cellulose nano-materials can improve the mechanical properties of both adhesives and the cell wall structure. CNF-C had the most obvious reinforcing effect on the elastic modulus (Er) and hardness within the glue line. With modification, the Er and hardness reached 13.0 and 0.436 GPa, respectively, in the S2 layer far from the glue line. In comparison, the control sample had an Er and hardness of 7.31 and 0.256 GPa, respectively. b. Carbon Fiber Production - Carbon fibers are continuing to be produced from lignin in our laboratory. We have successfully produced carbon fibers from hardwood, softwood, and switchgrass feedstocks. In addition, we have made a 100% lignin carbon fiber and epoxy resin composite. We continue to explore new processing methods to form carbon fiber and carbon products, such as foams, from lignin. We have produced highly porous fibers by dry-spinning, nanofibers from electro-spinning, and low density foams. These fiber products have very high surface areas that makes them ideal for electrodes, membranes, and filtration.

Publications

  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Martin, M. Z., N. Labb�, and R. J. Wagner. Applications of high resolution laser: induced breakdown spectroscopy for environmental and biological samples. Laser Induced Breakdown Spectroscopy, Springer Series in Optical Sciences, 2014, vol. 182, 439-456.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: N. C. Boyde, S. C. Chmely, T. P. Hanusa, A. L. Rheingold, W. W. Brennessel, Structural Distortions in M[E(SiMe3)2]3 complexes (M = Group 15, f-element; E  N, CH): is three a crowd? Inorg. Chem., 2014, 53, 9703-9714.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: M. R. Sturgeon, S. Kim, K. Lawrence, R. S. Paton, S. C. Chmely, M. Nimlos, T. D. Foust, G. T. Beckham, A Mechanistic Investigation of Acid-Catalyzed Cleavage of Aryl-Ether Linkages: Implications for Lignin Depolymerization in Acidic Environments, ACS Sustainable Chem. Eng., 2014, 3, 472-485.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: M. R. Sturgeon, M. H. OBrien, P. N. Ciesielski, R. Katahira, J. S. Kruger, S. C. Chmely, J. Hamlin, K. Lawrence, G. B. Hunsinger, T. D. Foust, R. M. Baldwin, M. J. Biddy, G. T. Beckham, Lignin Depolymerisation by Nickel Supported Layered-Double Hydroxide Catalysts, Green Chem., 2014, 16, 824-835.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Andr� N., Young T.M. (2014) Real-Time Process Modeling of Oriented Strand Board Panels. (Peer-Reviewed) Proceedings of the 3rd International Conference on Processing Technologies for the Forest and Bio-based Products Industries (PTF BPI 2014). Kuchl/Salzburg, Austria, September 24-26, 2014.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Riegler M., Andr� N., Gronalt M., Young T.M. (2014) Dynamic real-time simulation of continuous bulk material flow. (Peer-Reviewed) Proceedings of the 3rd International Conference on Processing Technologies for the Forest and Bio-based Products Industries (PTF BPI 2014). Kuchl/Salzburg, Austria, September 24-26, 2014.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Young T., Otjen J., Andr� N. (2014) Quantifying the natural variation of formaldehyde emissions for wood composite panels. (Peer-Reviewed) Proceedings of the 3rd International Conference on Processing Technologies for the Forest and Bio-based Products Industries (PTF BPI 2014). Kuchl/Salzburg, Austria, September 24-26, 2014.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Bozell JJ, Astner A, Baker D, Biannic B, Cedeno D, Elder T, Hosseinaei O et al. (2014) Integrating Separation and Conversion  Conversion of Biorefinery Process Streams to Biobased Chemicals and Fuels. BioEnergy Res 7(3). doi:10.1007/s12155-014-9424-x.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Jarrell TM, Marcum CL, Sheng H, Owen BC, OLenick CJ, Maraun H, Bozell JJ, Kentt�maa HI. Characterization of Organosolv Switchgrass Lignin by using High Performance Liquid Chromatography/High Resolution Tandem Mass Spectrometry using Hydroxide-Doped Negative-Ion Mode Electrospray Ionization. Green Chem., 2014, 16, 2713. doi:10.1039/c3gc42355g.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Shi Z, Cai Z, Wang S, Zhong Q, Bozell JJ. Short-Time Ultrasonication Treatment in Enzymatic Hydrolysis of Biomass. Holzforschung 2013; 67(8): 891897. DOI 10.1515/hf-2013-0024.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Meng, Y. 2014. Carbonization of Microfibril Cellulose Aerogel: Surface, Structure and Absorption Properties. The TAPPI International Conference on Nanotechnology for the Forest Products Industry held on June 23-26, 2014 in Vancouver, Canada (First Place Award of Poster Competition).
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: C. E. Greer, S. Acado, P. Kim, N. Labb�, S.C. Chmely. 248th National ACS Meeting, San Francisco, CA, Aug 10-14, 2014 - Poster presented: Ex-situ vapor-phase upgrading of pyrolysis vapors using layered double hydroxide catalysts.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: P. Das, S.C. Chmely. 248th National ACS Meeting, San Francisco, CA, Aug 10-14, 2014 - Poster presented: Iron-mediated conversion of levulinic acid and formic acid to gamma-valerolactone
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: P. Das, S.C. Chmely. 248th National ACS Meeting, San Francisco, CA, Aug 10-14, 2014 - Paper presented: Iron-based molecular catalysts for the transfer hydrogenation of carbonyls
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Sarah Acado, S. C. Chmely, N. Labb�, P. Kim, and P. Bhattacharya. 29th National Conference of the Minorities in Agriculture, Natural Resources and Related Sciences, Birmingham, AL, March 26-30, 2014 - Poster presented: Catalytic vapor-phase upgrading of pyrolysis oil vapors.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Tao, J., O. Hosseinaei, P. Kim, D. P. Harper, J. J. Bozell, T. G. Rials, and N. Labbe. 2014. Effects of fractionation time on thermal and chemical properties of organosolv lignins. Third International Conference Frontiers in Biorefining, St Simons Island, GA, Oct. 21-24, 2014.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: P. Das, S.C. Chmely. 248th National ACS Meeting, San Francisco, CA, Aug 10-14, 2014 - Poster presented: Precious metal-free catalysts for clean energy conversion and development of fuels from renewable resources
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: N. Labb�, P. Kim, C. E. Greer, S. Acado, and P. Bhattacharya, S.C Chmley. 7th US Department of Energy Biomass Conference, Washington, D.C., July 29-30, 2014 - Poster presented: Catalytic fast pyrolysis of cellulose using novel basic catalysts.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Wang, J., J. Tao, D. P. Harper, T. G. Rials, and N. Labb�. 2014. Impacts of autohydrolysis on solubility of biomass in ionic liquid. Third International Conference Frontiers in Biorefining, St Simons Island, GA, Oct. 21-24, 2014.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Kline, L. M., N. Labb�, S. Lenaghan, and C. N. Stewart, Jr. Examination of pyrolysis-gas chromatography/mass spectrometry for rapid lignin quantification in callus and suspension cells. ARPA-E Petro Program Industry Meeting, 2014
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Labb�, N., and J. Wang. Isolating lignin through an ionic liquid process. 247Th American Chemical Society National Meeting. March 16-20, 2014, Dallas, TX
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Lenaghan, S., N. Labb�, and C. N. Stewart, Jr. 2014. Development of an automated platform for rapid screening of genetically modified switchgrass. Frontiers in Biorefining. St Simons Island, GA, Oct. 21-24, 2014.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Ren, S., X. Ye, A. Borole, P. Kim, and N. Labb�. 2014. Characterization of Aqueous Phase Bio-Oil Derived from Switchgrass Pyrolysis. Proceedings of AIChE Annual Meeting, AIChE Annual Meeting, Atlanta, GA, Nov. 19, 2014.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Lenaghan, S., N. Labb�, K. Burris, W. Liu, J. D. Willis, L. M. Kline, G. Pigna, A. G. Collins, J. Grant, M. R. Rudis, S. Allen, and C. N. Stewart, Jr. 2014. High throughput transformable switchgrass culture system. ARPA-E Petro Program Industry Meeting.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Labb�, N., J. Wang, D. P. Harper, and T. G. Rials. Impacts of auto-hydrolysis on biomass solubility in ionic liquid. Gordon Research Conference on Ionic liquids. Aug. 17-22, 2014, Newry, MA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Bruce, A., B. H. Ownley, N. Labb�, K. D. Gwinn, D. H. D'Souza, and N. Moustaid-Moussa. 2014. Switchgrass extractives have potential as a value-added biopesticide against plant pathogens and foodborne pathogens. APS-CPS Meeting, Minneapolis, Aug 9-13.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Deleon, E., W. Gray, P. Kim, A. C. Sherfy, and N. Labb�. Biosolid-derived biochar for phosphate (P) remediation. ASA-SSSA-CSSA International Meetings, Nov. 2-5, 2014, Long Beach, CA.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Willis, J. D., L. M. Kline, S. M. Allen, P. Bhattacharya, A. G. Collins, J. N. Grant, G. Montgomery, N. Labb�, and C. N. Stewart, Jr. 2014. Development of Switchgrass (Panicum virgatum L.) Transformable Cell Suspension Culture and a Screening System for Rapid Assessment of Cell Wall Genes for Improved Biomass for Biofuels. SIVB Annual meeting.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Willis, J. D., L. M. Kline, S. M. Allen, P. Bhattacharya, A. G. Collins, J. N. Grant, N. Labb�, and C. N. Stewart, Jr. 2014. Development of switchgrass (Panicum virgatum L.) transformable cell suspension culture and a screening system for rapid assessment of cell wall genes for improved biomass for biofuels. ARPA-E Energy Innovation Summit, Washington, D.C.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Yu, T. E., C. Boyer, K. Castillo, B. C. English, J. A. Larson, N. Labb�, and L. M. Kline. 2014. Analyzing the Quality of Perennial grass from a Densification Technology in Lignocellulosic Biomass Feedstock Supply System. 4th Pan-American Congress on Plants and Bioenergy, June 4-7, Guelph, Canada.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Wu, Q., Y. Meng, S. Wang, Y. Li, S. Fu, L. Ma, and D. P. Harper. 2014. Rheological behavior of cellulose nanocrystal suspension: Influence of concentration and aspect ratio. Journal of Applied Polymer Science, 40525, 8.
  • Type: Journal Articles Status: Awaiting Publication Year Published: 2014 Citation: Meng, Y., S. Wang, T. M. Young, P. Liu, C. Contescu, and B. Huang. 2014. Ultralight carbon aerogel from nanocellulose as highly selective oil absorption materials. Cellulose, (in print, DOI :10.1007/s10570-014-0519-5).
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Liu, C., Y. Zhang, S. Wang, Y. Meng, and O. Hosseinaei. 2014. Micromechanical properties of the interphase in cellulose nanofiber-reinforced PF bondlines. BioResources, 9(3): 5529-5541.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Baxter, H., M. Mazarei, N. Labb�, L. M. Kline, Q. Cheng, M. T. Windham, D. G. J. Mann, C. Fu, A. Ziebell, R. Sykes, M. Rodriguez, M. Davis, J. Mielenz, R. A. Dixon, Z. Y. Wang, and C. N. Stewart, Jr. 2014. Two-year field analysis of decreased recalcitrance transgenic switchgrass. Plant Biotechnology Journal. 12, 914-924.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Kim, P., D. Hensley, and N. Labb�. 2014. Nutrient release from switchgrass derived biochar pellets embedded with fertilizers. Geoderma. 232-234, 341-351.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Kim, P., S. Weaver, K. Noh, and N. Labb�. 2014. Characteristics of bio-oils produced by an intermediate semipilot scale pyrolysis auger reactor equipped with multistage condensers. Energy and Fuels. 28, 6966-6973.


Progress 01/01/13 to 09/30/13

Outputs
Target Audience: Agricultural producers, the scientific community at large, academia, national laboratories, federal and state agencies, private industry, public interest groups, the government sector, land-grant institutions, biofuel industry leaders, and additional stakeholders. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Ph.D. students are being trained by this project. This project has provided the opportunity to interact with colleagues at professional conferences such as the American Chemical Society. Further,PIs have interacted with colleagues at the USDA, Washington State University, and other departments at the University of Tennessee. How have the results been disseminated to communities of interest? Within the Hatch program, our group is investigating catalysis, both chemical and biochemical, and tailored for the inherent structural features of biomass. We are carrying out fundamental investigation into the nature, mechanism, and control of catalyst interaction with biorefinery carbohydrates and lignin for the purposes of developing new, selective, high-yield processes for biobased products (high value organics; HVOs) and fuel production. We strive for molecular-level understanding of the processes necessary for effective conversion of renewable carbon, and frame that understanding within knowledge of potential HVO target structures. Our investigation of fundamental questions on the catalytic transformation of biorefinery building blocks with candidate targets is developing knowledge that affords processes for controlled structural modification of biorefinery components, deconstruction of lignin to low molecular weight aromatics, oxidation of lignin to HVOs, separation of biomass to provide key building blocks and approaches to new self assembling materials. In parallel, we carry out a program looking at advanced methodology for biomass separation, providing the cellulose, hemicellulose and lignin raw materials needed as process streams for biorefinery operation. Targets for this technology will be proven by include carbon fiber, LMW HVOs, new advanced organic materials, biobased polymers and biohydrocarbons. (1) Biomass fractionation/organosolv or ionic liquid refining. Most recently, our work has focused on lignin isolation and conversion. Lignin is 25% of terrestrial biomass and a key source of renewable carbon, but its structural complexity prevents easy incorporation as a starting material for chemicals or fuels. Our work is developing selective chemical and biocatalytic systems able to this heterogeneity. (2) Value added chemicals (HVOs)/chemical catalysis platform. In contrast the structure of carbohydrates is regular and understood. However, they possess many sites of very similar reactivity, making it difficult to develop selective conversion processes. Our work exploits catalytic systems able to achieve high selectivity in the presence of functional groups of similar reactivity. (3) The petrochemical industry achieves significant control over their conversion processes because they understand these systems at the molecular level. Our research pursues analogous control for renewable carbon sources, which provides the ability to tailor processes for eventual end users. (4) By demonstrating the scientific background and foundation for these new processes, we will be able to demonstrate the transfer of this knowledge to practical biorefinery operation through industrial stakeholders and endusers. Due to the advantages of cellulose nanocrystals (CNCs) high modulus, low density, high aspect ratio, and negligible thermal expansion, they have attracted much attention from materials scientists. As a functional material, the mechanical properties of CNC films are very important. The CNC films studied in the previous researches were all prepared by sulfuric acid hydrolysis and were not modified, but the moduli of these CNC films had a considerable range, from 2 to 8.3 GPa. Our recent research has solved this mystery. The results show that the environmental conditions had a great influence on the mechanical properties of pure CNC films and attracted a great attention. The paper, published in Industrial Crops and Products 6 months ago, has been downloaded or viewed 382 times since publication (measured through 31 October). We have produced carbon fibers from the lignin that exceed properties of those that have been reported in the literature. These properties are approaching that of the Department of Energy’s requirements for automotive applications. What do you plan to do during the next reporting period to accomplish the goals? Attend conferences and present our findings. Attend seminars (Monthly Plant Research Center Seminars and other seminars at UT and ORNL). PIs plan on seeking more funding through the USDA, Department of Defense, DOE, and NSF this coming year.

Impacts
What was accomplished under these goals? The following outputs were completed during 2013: I. High-throughput biomass analysis methods. Over the past year, more robust near infrared models were developed that can now be used to rapidly determine the chemical composition of switchgrass in a matter of a few seconds. The new models were constructed with more than 280 switchgrass samples and can predict cellulose, hemicellulose, total carbohydrates, lignin, extractives, and ash content in any switchgrass sample. The models were tested on switchgrass samples collected at various locations in Alabama. As part of a large switchgrass trial, over 1300 switchgrass samples were collected from 600 acres in Tennessee and analyzed for their quality (chemical composition) and performance (sugars release). To our knowledge, this is the first commercial trial for switchgrass in the southeastern of the U.S. In addition, a NIR model for hybrid poplar is also under construction and in the coming year, additional samples collected from various locations in Tennessee, South Carolina, and Florida will be added to the model. II. Biomass Fractionation. Organosolv Refining - Lignin, a potential low-cost, high volume output process stream derived from lignocellulosic biomass is currently being researched to better support the economics of the future biorefinery. In this work, experimental design was used to determine the optimal level for each process factor in an organosolv fractionation process that targets maximum attainable lignin yield, even in the presence of feedstock contaminants. The process factors studied were two different fractionation times (56, 90 min), two different fractionation temperatures (140°C, 160°C), three mixed feedstock loadings containing mixtures of switchgrass (Panicum virgatum) and tulip poplar (Liriodendron tulipifera) in three different weight ratios ([10/90], [50/50], [90/10]), three different poplar chip sizes (coarse, medium, fine), three different solvent compositions containing different ratios of the fractionation solvents methyl isobutylketone (MIBK), ethanol (EtOH) and water (H2O) ([07/30/63], [16/34/50], [62/27/11]), and three different acid concentrations (0.025, 0.05, 0.1 M). Based on the results found it is predicted that an estimated mean lignin yield of ~ 90 wt % is attainable if the levels of the organosolv process are set to a fractionation time of 90 minutes at a fractionation temperature of 160°C, use of a feedstock mixture containing 10% switchgrass and 90% medium poplar particles, and the use of the 16/34/50 solvent mixture with an added acid concentration of 0.1 M. Ionic Liquid Refining – Through an ionic liquid activation followed by a regeneration and enzymatic saccharification step, a lignin-rich fraction was isolated from switchgrass. While the activation increased the accessibility of the cellulosic fraction (over 92% of cellulose was converted to glucose), the hemicellulosic fraction was not completely hydrolyzed during the saccharification step. This finding leads us to evaluate the removal of the hemicellulose prior to the ionic liquid activation step. Through this step we discovered that a higher and faster solubility of biomass in IL is achieved when hemicellulose-free biomass is used. This finding will allow us to work with higher loading biomass during the ionic liquid activation phase which will have some very significant impact on the overall process. In addition, the hemicellulose fraction, which was obtained through a simple autohydrolysis step, was assessed and found to contain between 20 to 50 g/L of sugars. This clean sugars fraction has potential to be utilized for the productions of chemicals, fuels and/or materials. III. Value-Added Chemicals. Production of Biobased Chemicals - Our focus is to increase the utility of lignin by developing innovative catalysts able to efficiently convert lignin to high value aromatics (e.g., benzoquinones, aromatic aldehydes, etc.) in high yield and selectivity. Our focus has been on Co-Schiff base catalysts and understanding informed design of the catalyst’s steric and electronic environment can be exploited to increase reactivity. Simple, 1st generation catalysts oxidize S models well, but show poor reactivity with G models. However, addition of a hindered base affords an improvement in reactivity with G models. Using this information, we have embarked on a synthesis of second generation catalysts that incorporate these best features in a single complex, and find that the combination of Co, a hindered base and a substituted Schiff base ligand gives catalysts with the highest reactivity observed to date. In the last annual report, we described our initial successful development of a viable route for the preparation of a few unsymmetrical cobalt-salen complexes. We have now developed a general approach for synthesizing new, unsymmetrical and more highly reactive Co Schiff base complexes in good yield. The new catalysts display good reactivity with monomeric S and G models, and also with multiple dimeric systems. The success of these complexes has prompted additional investigation of how the steric environment around the Co affects its reactivity. Accordingly, we have synthesized a new family of catalysts that move the appended hindered base in closer proximity to the Co center. We find that these new systems retain the ability to oxidize both S and G models, but at a lower rate. However, we now find that the structural modifications in comparison to first generation catalysts improve the reactivity for G oxidation to a point equal to or greater than that observed for S models. Oxidation yields for benzoquinones of 60-75% are observed, along with the production of 10-20 substituted benzaldehydes. We have continued computational and mechanistic evaluation of the oxidation in order to understand the impact of catalyst structure on reactivity in collaboration with Dr. Thomas Elder of the US Forest Service. IV. Advanced Materials. 1) Carbohydrate Nanomaterials - The steady and dynamic rheological behaviors of two CNC (cellulose nanocrystal) suspensions were investigated over a wide range of concentrations. The viscosity, storage and loss modules increased with increasing CNC concentration, and both CNC suspensions showed three regions in a viscosity-concentration graph. The two critical concentrations depended on the aspect ratio and corresponded to the overlap and gelation concentration. Due to the higher aspect ratio, switchgrass CNC suspension transitioned to a biphasic state and formed a hydrogel at lower concentrations than cotton CNC suspensions. Furthermore, the complex viscosities of both CNC suspensions were higher than their apparent viscosities; therefore, neither CNC suspension followed the Cox–Merz rule, which may be attributed to the existence of a liquid crystal domain in each suspension. 2) Carbon Fiber Production - Carbon fibers are have been produced from lignin in our laboratory. The lignin feedstocks came from kraft lignin (solvent extracted) and organosolv lignins from poplar and switchgrass. The lignin was extruded on both single and multifilament spinning equipment. The fiber properties for both softwood kraft and organosolv poplar produced fibers that exceeded 80 GPa modulus and 1.2 GPa in strength. Investigation of composites from these fibers are continuing to be investigated.

Publications

  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Biannic, B., and J. J. Bozell. 2013. Efficient Cobalt-Catalyzed Oxidative Conversion of Lignin Models to Benzoquinones. Organic Letters, 15:2730-2733.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Dyer, C., M. Dadmun, J. J. Bozell, Z. Jiang, and W. Heller. 2013. Effect of chain structure on the miscibility of cellulose acetate blends: a small-angle neutron scattering study. Soft Matter, 9:3402-3411.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Elder, T., J. J. Bozell, and D. Cedeno. 2013. The effect of axial ligand on the oxidation of syringyl alcohol by cobalt-salen adducts. Chemical Physics and Physical Chemistry, 15: 7328-7337.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Sammons R.J., D. P. Harper, N. Labbe, J. J. Bozell, T. Elder, and T. G. Rials. 2013. Characterization of organosolv lignins using thermal and FT-IR spectroscopic analysis. Bioresources, 8, 2752-2767.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Schreiber, S., J. J. Bozell, D. G. Hayes, and S. Zivanovic. 2013. Introduction of primary antioxidant activity to chitosan for application as a multifunctional food packaging material. Food Hydrocolloids, 33:207-214.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Shimleck, L., J. L. Monteiro de Matos, G. I. B. Muniz, C. Espey, A. M. Taylor, and D. P. Harper. 2013. Examination of wood properties of plantation grown Pernambuco (caesalpinia Echinata). International Association of Wood Anatomists Journal, 34(1):34-48.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Shi, Z., Z. Cai, S. Wang, Q. Zhong, and J. J. Bozell. 2013. Pretreatment in Enzymatic Hydrolysis of Biomass: Material Status and Their Responsibility to Ultrasonic. Holzforschung, 67(8): 891-897.
  • Type: Journal Articles Status: Awaiting Publication Year Published: 2014 Citation: Wu, Q., Y Meng, S Wang, Y Li, S Fu, L Ma, D Harper. 2014. Rheological behavior of cellulose nanocrystal suspension: Influence of concentration and aspect ratio. Journal of Applied Polymer Science (in print, DOI: 10.1002/app.40525).
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Wu, Y., S. Wang, D. Zhou, Y. Zhang, X. Wang and R. Yang. 2013. Biodegradable poly(vinyl alcohol) nanocomposites made from rice straw fibrils: Mechanical and thermal properties. Journal of Composite Materials 47(12): 1449-1459.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Q Wu, Y Meng, K Concha, S Wang, Y Li, L Ma, S Fu. 2013. Influence of temperature and humidity on nano-mechanical properties of cellulose nanocrystal films made from switchgrass and cotton. Industrial Crops and Products 48: 28-35.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Kim, P., A. M. Johnson, M. E. Essington, M. A. Radosevich, W. T. Kwon, S. H. Lee, T. G. Rials, and N. Labb�*. 2013. Effect of pH on surface characteristics of switchgrass-derived biochars produced by fast pyrolysis. Chemosphere, 90, 2623-2630.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Kline, L. M., A. M. Johnson, P. Kim, S. W. Jackson, and N. Labbe*. 2013. Monitoring switchgrass composition to optimize harvesting periods for bioenergy and value-added products. Biomass and Bioenergy, 56, 29-37.
  • Type: Books Status: Published Year Published: 2013 Citation: G. Petersen, J. J. Bozell, and J. White. 2013. Selecting Targets in Catalytic Process Development for Renewable Materials: Catalytic Process Development for Renewable Materials.
  • Type: Other Status: Other Year Published: 2013 Citation: Baker, D. A., J. J. Bozell, and O. Hosseinaei. 2013. Process for the separation of lignin from lignocellulosic biomass and conversion of lignin to carbon fiber, Invention disclosure.
  • Type: Other Status: Other Year Published: 2013 Citation: Bozell, J. J., A. Astner, and M. Bahnholzer. 2013. Separation of organosolv black liquor using centrifugation, Invention disclosure.
  • Type: Other Status: Other Year Published: 2013 Citation: Bozell, J. J., and B. Biannic. 2013. Efficient cobalt-catalyzed oxidative degradation of lignin, Invention disclosure.
  • Type: Other Status: Other Year Published: 2013 Citation: Bozell, J. J., and H. Maraun. 2013. High biomass dissolution using organosolv fractionation, Invention disclosure.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Cobalt-Catalyzed Oxidation of p-Substituted Phenols: Developments Toward an Efficient Conversion of Lignin to High Value Chemicals (first prize winner SEC conference), Berenger Biannic (presenter), Joseph J. Bozell SEC Symposium Atlanta, GA 2/10-2/12/13
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Enhancing the Value of Lignin Through Bacterial Conversion, Ashley M. Frank (presenter), James J. Daleiden, Joseph J. Bozell, Alison Buchan, ASM National meeting Denver, May 2013
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Second generation catalytic processes for the conversion of biorefinery lignin to chemicals and fuels, Joseph J. Bozell (presenter), Berenger Biannic, Diana Cedeno, Alison Buchan, Ashley M. Frank, James J. Daleiden Tiffany M. Jarrell, Hilkka I. Kenttamaa, Presented at the EFRC Annual summit, Washington, DC July 18th, 2013
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Solvent Fractionation as a Pretreatment for Energy Crops, Joseph J. Bozell, Hagen Maraun, Anton Astner and Timothy G. Rials (presenter), presented at AAIC meeting Washington, DC 10/8/13
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: (Invited) Integrating separation and conversion  catalytic oxidation of lignin models and organosolv lignin to high value aromatics, Joseph J. Bozell, presented at the USP Conference on Synthetic Biology for Biomass and Biofuels Production, University of S�o Paulo, S�o Paulo, Brazil, August 21st, 2013
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Adding value to lignin by enabling its catalytic conversion, Mahdi Abu-Omar, Joseph J. Bozell (presenter), Alison Buchan, Clint Chapple, Hilkka Kentt�maa, Presented at the C3Bio annual meeting and review, Purdue University 8/30/13
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: (Invited) Development of building blocks and intermediates for fine chemistry, Joseph J. Bozell, presented at the II Brazilian Symposium on Biorefineries, Brasilia, Brazil, September 26th, 2013
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Development of building blocks and intermediates for fine chemistry, Joseph J. Bozell, Presented to UTIA sponsored visit by LSU delegation, December 3rd, 2013
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: (Invited) Catalytic oxidation of organosolv lignin  structural and computational analysis for improved catalyst design, Joseph J. Bozell (presenter), Thomas Elder, Berenger Biannic, Diana Cedeno, Sabornie Chatterjee, Kun Cheng, Anselm Payen Symposium, ACS National meeting Dallas, TX, March 2014 (abstract submitted 2013)
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Harper, D.; Meek, N.; Baker, D.; Penumadu, D.; Biocomposites from lignin-based carbon fibers. 245th American Chemical Society National Meeting & Exposition. New Orleans, LA. April 7-11, 2013.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Natural variability of switchgrass and its impacts on feedstock quality for bioenergy production. Labbe N., 35th Symposium on Biotechnology for Fuels and Chemicals Portland, OR, April 29-May 2, 2013.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Demonstration of on-farm production of a dedicated energy crop incorporating multiple varieties of switchgrass seed. Alexander, M.T., S.W. Jackson, and N. Labbe. 2013 USDA-ARS Switchgrass II Conference, Madison, WI, September 10-12, 2013.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Low-filed time-domain NMR of biochar. T. Elder, N. Labbe, P. Kim. 246th ACS national meeting & exposition, Indianaplois, IN, September 8-12, 2013.


Progress 01/01/12 to 12/31/12

Outputs
OUTPUTS: This research program is comprised of five discrete, but closely related projects designed to introduce new chemicals and materials from renewable carbon resources into the marketplace. Importantly, progress in an individual project does not rely on any other; however, effective coordination of the individual projects affords real synergy that will lead to board impacts. The following outputs were completed during 2012: Several industrial lignins have been purified by various means to decrease both ash and carbohydrate contents. These purified lignins were then sequentially solvent extracted to obtain derivatives with differing chemical, thermal, and polymer properties. Some of these lignin derivatives have been selected to manufacture products and to be catalytically converted to chemicals. Work has been performed towards obtaining lignins suitable for products and chemicals via organosolv fractionation. The particular organosolv process has been altered to improve lignin yields, purity, and molecular weight properties. Lignins from yellow poplar, hybrid poplar, and switchgrasses have been melt-spun and converted into carbon fibers. In each case, lignins have been fully characterized for their properties. Carbon fibers have been produced from several sources of lignin. The fibers were successfully spun, stabilized, and carbonized. Stabilization rates were slower than desired at 0.012C/min. These fibers are being analyzed and prepared to manufacture composite specimens. Single fiber carbon fiber composites from organosolv lignin precursors were manufactured from two candidate epoxy resin systems. The critical fiber length for each composite was evaluated. The lignin composite exhibited 75 percent of the interfacial shear strength of that of the synthetic fibers. Cellulose nanocrystals (CNC) were derived from Switchgrass and cotton by sulfuric acid hydrolysis method. Influence of humidity and temperature on mechanical properties of CNC filmswere investigated by comparing nanoindentation measurements on the same film under different humidity and temperature conditions. Compared to the CNC film derived from cotton, both the reduced modulus (Er) and hardness (H) of Switchgrass-CNC films were greater. Additionally, the mechanical properties of the CNC films declined with increases in relative humidity. Taguchi Robust Product Design was used to optimize the production of lignin from organosolv fractionation of mixed poplar/switchgrass feedstocks. An experimental matrix was employed that defined three controllable (inner array) design factors as temperature (120-160 degrees C), sulfuric acid concentration (0.025-0.1 mol/L) and feedstock ratio of switchgrass and poplar. By applying the array design at three levels of each parameter, a significant relationship between process-temperature level and feedstock ratios was found. The maximum lignin yield was 18.4 wt percent using a solvent-based black liquor separation method. Representative lignin samples gave an average lignin value of 91% with selected lignin samples exhibiting residual sugar levels of < 0.5 percent. PARTICIPANTS: Tim Rials: University of Tennessee, Center for Renewable Carbon (PI); Darren Baker: University of Tennessee, Center for Renewable Carbon (PI); David Harper: University of Tennessee, Center for Renewable Carbon (PI); Joe Bozell: University of Tennessee, Center for Renewable Carbon (PI); Nicole Labbe: University of Tennessee, Center for Renewable Carbon (PI); Siqun Wang: University of Tennessee, Center for Renewable Carbon (PI); Kendrick Styles: University of Tennessee (Student Worker); Andreas Attwenger: University of Tennessee (MS, Austria); Omid Hosseinaei: University of Tennessee (Postdoc); Yujie Meng: University of Tennessee (MS Student); Nathan Meek: University of Tennessee (Undergraduate C.E.) TARGET AUDIENCES: Agricultural producers, the scientific community at large, academia, national laboratories, federal and state agencies, private industry, public interest groups, the government sector, land-grant institutions, biofuel industry leaders, and additional stakeholders. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
The impact of the rapid manufacture of carbon nanofibers from refined lignins has been to provide lignins possessing superior solution and thermal properties suitable for industrial scale electrospinning and rapid conversion into carbon nanofibers. Carbon nanofibers are most frequently manufactured by the electrospinning of polyacrylonitrile and the use of lignin as an alternative is quicker, less energy intensive, and more environmentally efficient. The technology is patent pending and under review for commercialization. The impact of melt-spinning of kraft softwood lignin and conversion to carbon fiber is the first demonstration of the pilot-scale manufacture of fibers from softwood kraft lignin that is available as a commercial product (Indulin AT) and in very large quantities. If the purification and refining are scaled up and optimized it may be possible to use this as a source of lignin for carbon fiber manufacture. The petrochemical industry achieves significant control over their conversion processes because they understand these systems at the molecular level. Our research pursues analogous control for renewable carbon sources, which provides the ability to tailor processes for eventual end users. By demonstrating the scientific background and foundation for these new processes, we will be able to demonstrate the transfer of this knowledge to practical biorefinery operation through industrial stakeholders and end users. Over this past year, near infrared spectroscopic models were developed to rapidly determine the chemical composition of switchgrass. The models were constructed with over 90 samples to predict cellulose, hemicellulose, lignin, extractives, and total carbohydrates content in switchgrass. The models are being employed in several projects allowing us to rapidly determine the chemical composition of switchgrass samples in a matter of minutes instead of days or weeks. For example, we are using these models to investigate the impacts that growth location and switchgrass varieties have on biomass chemical composition. In addition to near infrared, we have set up a pyrolysis gas chromatography system to investigate biomass chemical composition. We have developed methodologies to collect reproductive data and obtain information on chemical structure of lignin. Researchers have investigated the impact of ionic liquid (especially 1-ethyl-3-methyl imidazolium acetate, EmimAce) on biomass structure and recalcitrance. It was found that under mild conditions, EmimAce reduces cellulose crystallinity and the recalcitrance of the biomass, making the cellulose more accessible for enzymatic saccharification. Researchers have also demonstrated that commercial enzymes "celluclast" remained active in 30 percent of EmimAce and effectively hydrolyzed cellulose in various biomass types. Researchers are now screening enzymes to identify hemicellulases to entirely hydrolyze cellulose and hemicellulose into monosugars and release lignin in its most native form.

Publications

  • Elder, T., Bozell, J., Cedeno, D., The Effect of Axial Ligand on the Oxidation of Syringyl Alcohol by Co(salen) Adducts, Phys. Chem. Chem. Phys. 2013, in press.
  • Kaboorani, A., Riedl, B., Blanchet, P., Fellin, M., Hosseinaei, O., Wang, S. 2012. Nanocrystalline Cellulose (NCC): A renewable nano-material for polyvinyl acetate (PVA) adhesive. European Polymer Journal 48(11): 1829-1837.
  • L. Liu, X. P. Ye, J. Bozell, A comparative review of petroleum based and bio-based acrolein production, ChemSusChem 2012, 5, 1162-1180.
  • Labbe N., L. M. Kline, L. Moens, K. Kim, P.C. Kim, D.G. Hayes. 2012. Activation of lignocellulosic biomass by ionic liquid for biorefinery fractionation. Bioresource Technology, 104, 701-707.
  • Owen, B., Haupert, L., Jarrell, T., Marcum, C. Parsell, T., Abu-Omar, M., Bozell, J., Black, S., Kenttamaa, H., High Performance Liquid Chromatography/High-Resolution Multiple Stage Tandem Mass Spectrometry Using Negative-Ion Mode Hydroxide-Doped Electrospray Ionization for the Characterization of Lignin Degradation Products, Anal. Chem. 2012, 84, 6000-6007.
  • Q Wu, Y Meng, K Concha, S Wang, Y Li, L Ma, S Fu. 2013. Influence of temperature and humidity on nano-mechanical properties of cellulose nanocrystal films made from switchgrass and cotton. Industrial Crops and Products (in print).
  • Wang Y, M. A. Radosevich, D. G. Hayes, and N. Labbe. 2011. Compatible ionic liquid-cellulases system for hydrolysis of lignocellulosic biomass. Biotechnology and Bioengineering. 108, 1042-1048.
  • Evidence for Complex Molecular Architectures for Solvent-Extracted Lignins., Harton, S.E., Pingali, S.V., Nunnery, G.A., Baker, D.A. et al., ACS MacroLetters, 568-573, 1 (2012).
  • On the characterization and spinning of an organic- purified lignin towards the manufacture of low-cost carbon fiber. D.A. Baker, N.C. Gallego & F.S Baker, J. Appl. Polym. Sci., 227-234, 124 (2012).
  • Biannic, B., Bozell, J., Efficient Cobalt-Catalyzed Oxidative Conversion of Lignin Models to Benzoquinones, J. Amer. Chem. Soc. 2013, submitted
  • Bozell, J., Catalytic oxidation of lignin for the production of low molecular weight aromatics, Plants Bionerg. 2013, submitted
  • D. Cedeno, J. J. Bozell, Catalytic oxidation of para-substituted phenols with cobalt Schiff base complexes/O2 - selective conversion of syringyl and guaiacyl lignin models to benzoquinones, Tetrahedron Lett. 2012, 53, 2380-2383.
  • Dyer, C., Jiang, Z., Bozell, J., Rials, T., Heller, W. T., Dadmun, M., Effect of chain structure on the miscibility of cellulose acetate blends: a small-angle neutron scattering study, Soft Matter 2013, 9, 3402-3411.