Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio) C3Bio develops transformational knowledge and technologies for the direct conversion of plant lignocellulosic biomass to advanced (drop ‐ in) biofuels and other biobased products, currently derived from oil, by the use of new chemical catalysts and thermal treatments. RESEARCH PLAN AND DIRECTIONS We will maximize the energy and carbon efficiencies of advanced biofuels production by the design of both thermal and chemical conversion processes and the biomass itself. Impacts are to more than double the carbon captured into fuel molecules and expand the product range to alkanes and other energy ‐ rich fuels.
Sample Preparation for Biomass Biomaterials Microscopy Scientific Achievement a c drying b sample a" b thermocouple chamber CO 2 chambers hot(and(cold(water( cylinder Optimized and standardized a set of deionized' controllers water' mul+2 grid' holder' condenser( hybrid biological and materials ‐ science chamber staining' solu+on' vacuum water(heater chamber sample preparation techniques to staining' water(chiller bath''' water(convec, on(pla/ orm( enable consistently high quality multi ‐ scale microscopy analysis of biomass. Significance and Impact • Provides a single “go ‐ to” reference for the field that shares details and tips that are not possible to fully convey in the typical manuscript methods section. • Facilitates direct, quantitative comparison between samples prepared and imaged by these methods. Research Details Donohoe, B. S.; Ciesielski, P. N.; and Vinzant, T. B. ‐ NREL’s Biomass Surface Characterization Laboratory (BSCL) is a leader in P RESERVATION AND PREPARATION OF LIGNOCELLULOSIC BIOMASS SAMPLES FOR MULTI ‐ SCALE MICROSCOPY multi ‐ scale microscopic structural analysis of biomass conversion processes. ANALYSIS , In: Michael E. Himmel (ed.), Biomass ‐ C3Bio enabled a critical transition in the BSCL workflow to include Conversion: Methods and Protocols , Methods in quantitative image analysis as the final goal of all imaging efforts. Molecular Biology, 908 , 31 ‐ 47 (2012). [10.1007/978 ‐ 1 ‐ 61779 ‐ 956 ‐ 3_4] ‐ The impact quantitative image analysis has had on informing sample prep and image acquisition is reflected in this chapter. Work was performed at NREL
Tandem Mass Spectrometric Analysis of Degraded Cellulose Scientific Achievement Chloride anion 377 100 [M+ 35 Cl]¯ attachment Demonstrated that chloride anion 90 [M+ 35 Cl]¯ Cellobiose 215 [M+ 35 Cl]¯ mass spectrum Xylose 80 Fructose attachment/atmospheric pressure 185 70 for a mixture of Relative Abundance ionization generates only one ion for 60 three compounds 50 ( 35 Cl and 37 Cl each carbohydrate in a mixture and 40 379 Fructose Isotopes facilitate that multistage tandem mass 217 30 [C 6 H 9 O 5 ]¯ 187 Identification) 20 161 spectrometry can be used to 10 0 determine the ions’ structures. 140 160 180 200 220 240 260 280 300 320 340 360 380 400 Isolation of m/z Significance and Impact ion of m/z 377 followed by Allows more detailed characterization fragmentation of mixtures of pyrolyzed and other ‐ wise degraded cellulose than before. Research Details ‐ Used linear quadrupole ion trap and a variety of ionization methods to ionize pure carbohydrates ‐ After identification of the best ionization method, Vinueza, N.R., Gallardo, V.A., Klimek, J.F., Carpita, N., and Kenttämaa, H.I. examined known mixtures of carbohydrates ANALYSIS OF CARBOHYDRATES BY ATMOSPHERIC PRESSURE CHLORIDE ANION Measured tandem mass spectra up to MS 4 to ATTACHMENT TANDEM MASS SPECTROMETRY, Fuel, 105 , 235 ‐ 246 (2013). ‐ gather useful structural information from the Work was performed at Purdue University fragmentation patterns of the carbohydrates
Fe III (POP) Catalyst for HMF Oxidation to FDCA Scientific Achievement HMF conversion and product distribution, % 120 A porphyrin ‐ based porous organic polymer (POP) loaded with Fe 3+ catalyst is a thermally stable and 100 recyclable catalyst for oxidation of O CHO hydroxymethylfurfural (HMF) to 2,5 ‐ furandicarboxylic HO 80 acid (FDCA) in water using molecular oxygen. Significance and Impact HOOC O COOH 60 • In C3Bio, we have shown that maleic acid catalysis Before catalysis CHO converts glucose in non ‐ crystalline polymers in 40 HOOC O CHO O biomass to HMF. CHO 20 • Saha et al achieved quantitative conversion of HMF with >85% selectivity in water under mild reaction 0 conditions. After catalysis 0 2 4 6 8 10 12 • The catalyst retained Fe(III) oxidation state after Time, h catalysis and metal does not leach into solution. Saha, B.; Gupta, D.; Abu ‐ Omar, M. M.; • FDCA is a promising replacement for petroleum ‐ Modak, A.; and Bhaumik, A. P ORPHYRIN derived terephthalic acid for polyester production. BASED POROUS ORGANIC POLYMER SUPPORTED IRON (III) CATALYST FOR EFFICIENT AEROBIC OXIDATION OF 5 ‐ HYDROXYMETHYLFURFURAL Research Details INTO 2,5 ‐ FURANDICARBOXYLIC ACID . Journal of Catalysis , 299, 316 ‐ 320 (2013). • Characterization of the catalyst showed uniform nanospheres of dimension 50 ‐ 100 nm [10.1016/j.jcat.2012.12.024] which self ‐ assemble to larger sizes. Work was performed at Purdue • Hydroxymethyl group ( ‐ CH 2 OH) of HMF oxidized first followed by oxidation of –CHO group. University and University of Delhi. • The data support a hypothesis that the reaction progresses via a free radical chain Catalyst was prepared by collaborator at Indian Association for the Cultivation mechanism with the formation of peroxyl radical in the catalytic cycle. of Science.
3D Electron Tomography of Pretreated Biomass Informs Atomic Modeling of Cellulose Microfibrils Scientific Achievement Averagae radius of curvature (nm) • Using 3D electron tomography and novel computational analysis tools, we modeled and quantified the macromolecular architecture of thermochemically treated biomass. Significance and Impact • This study produced the first measurements of cellulose microfibril curvature. We investigated the significance of this parameter by Tomographic subvolumes showing space curves construction and evaluation of atomic fit to cellulose microfibrils (scale bars 10 nm) models that exhibited the geometry obtained from the microscopy data. The radius of curvature of the • Our results and analyses have microfibrils was measured from the fitted curves. Atomistic models were elucidated new relationships between constructed using the extracted the nanostructure and energetics of geometric parameters. Kink defects plant cellulose that may be exploited in were predicted in the atomic models when the fibril was bent about certain Original atomic Energy ‐ minimized catalytic conversion processes. crystallographic directions. coordinates atomic coordinates Ciesielski, P. N.; Matthews, J. F.; Tucker, M. P.; Beckham, G. T.; Crowley, M. F.; Himmel, M. E.; Donohoe, B. S. 3D E LECTRON T OMOGRAPHY OF P RETREATED B IOMASS I NFORMS A TOMIC M ODELING OF C ELLULOSE M ICROFIBRILS . ACS Nano, 7 , 8011 ‐ 8019. 2013 . DOI: 10.1021/nn4031542. Work performed at the National Renewable Energy Laboratory
Catalytic cleavage and hydrodeoxygenation of lignin models Scientific Achievement A combined Zn/Pd/C catalyst effectively cleaved the lignin β‐ O ‐ 4 linkage and subsequently hydrodeoxygenated the aromatic fragments without loss of aromatic functional groups. The catalyst is robust and fully recyclable without the need for additional zinc. Significance and Impact The β‐ O ‐ 4 linkage is the most abundant repeating subunit of the lignin macromolecule. Devising a catalyst that can selectively cleave this type of ether linkage and undergo hydrodeoxygenation provides a means of unzipping the very complex polymeric structure into smaller, manageable molecules that have higher energy value. Parsell TH, Owen BC, Klein I, Jarrell TM, Marcum CL, Haupert LJ, Amundson LM, Research Details Kenttämaa HI Ribeiro F, Miller JT, Abu ‐ Omar MM. Cleavage and − In a typical experiment: substrate, 5 wt% Zn/Pd/C, and methanol (15 mL) were added to a dry glass hydrodeoxygenation (HDO) of C–O sleeve, placed into a stainless steel Parr reactor and sealed. While stirring, the mixture was purged with bonds relevant to lignin conversion UHP grade H 2 for ca. 1–2 min., pressurized with H 2 (30–300 psi, 2–20.4 bar), and heated to 150 ⁰ C. using Pd/Zn synergistic catalysis. Chem. − The monomeric lignin surrogate substrates were 4 ‐ (hydroxymethyl) ‐ 2 ‐ methoxyphenol, 4 ‐ hydroxy ‐ 3 ‐ Sci., 4 , 806 ‐ 813 (2013). methoxybenzaldehyde, and 4 ‐ (methoxymethyl) ‐ 2 ‐ methoxyphenol. The dimeric lignin surrogate was [10.1039/C2SC21657D] guaiacylglycerol ‐β‐ guaiacyl. − Reaction products were characterized using HPLC coupled to an LQIT mass spectrometer equipped with Work was performed at Purdue an ESI source using negative ion mode. University and Argonne National Lab
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