108 research outputs found
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CATALYSIS SCIENCE INITIATIVE: From First Principles Design to Realization of Bimetallic Catalysts for Enhanced Selectivity
In this project, we have integrated state-of-the-art Density Functional Theory (DFT) models of heterogeneous catalytic processes with high-throughput screening of bimetallic catalytic candidates for important industrial problems. We have studied a new class of alloys characterized by a surface composition different from the bulk composition, and investigated their stability and activity for the water-gas shift reaction and the oxygen reduction reaction. The former reaction is an essential part of hydrogen production; the latter is the rate-limiting step in low temperature H2 fuel cells. We have identified alloys that have remarkable stability and activity, while having a much lower material cost for both of these reactions. Using this knowledge of bimetallic interactions, we have also made progress in the industrially relevant areas of carbohydrate reforming and conversion of biomass to liquid alkanes. One aspect of this work is the conversion of glycerol (a byproduct of biodiesel production) to synthesis gas. We have developed a bifunctional supported Pt catalyst that can cleave the carbon-carbon bond while also performing the water-gas shift reaction, which allows us to better control the H2:CO ratio. Knowledge gained from the theoretical metal-metal interactions was used to develop bimetallic catalysts that perform this reaction at low temperature, allowing for an efficient coupling of this endothermic reaction with other reactions, such as Fischer-Tropsch or methanol synthesis. In our work on liquid alkane production from biomass, we have studied deactivation and selectivity in these areas as a function of metal-support interactions and reaction conditions, with an emphasis on the bifunctionality of the catalysts studied. We have identified a stable, active catalyst for this process, where the selectivity and yield can be controlled by the reaction conditions. While complete rational design of catalysts is still elusive, this work demonstrates the power of combining the insights gained from theoretical models and the work of experiments to develop new catalysts for current and future industrial challenges
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Atomic-Scale Design of Iron Fischer-Tropsch Catalysts: A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach
Work continued on the development of a microkinetic model of Fischer-Tropsch synthesis (FTS) on supported and unsupported Fe catalysts. The following aspects of the FT mechanism on unsupported iron catalysts were investigated on during this third year: (1) the collection of rate data in a Berty CSTR reactor based on sequential design of experiments; (2) CO adsorption and CO-TPD for obtaining the heat of adsorption of CO on polycrystalline iron; and (3) isothermal hydrogenation (IH) after Fischer Tropsch reaction to identify and quantify surface carbonaceous species. Rates of C{sub 2+} formation on unsupported iron catalysts at 220 C and 20 atm correlated well to a Langmuir-Hinshelwood type expression, derived assuming carbon hydrogenation to CH and OH recombination to water to be rate-determining steps. From desorption of molecularly adsorbed CO at different temperatures the heat of adsorption of CO on polycrystalline iron was determined to be 100 kJ/mol. Amounts and types of carbonaceous species formed after FT reaction for 5-10 minutes at 150, 175, 200 and 285 C vary significantly with temperature. Mr. Brian Critchfield completed his M.S. thesis work on a statistically designed study of the kinetics of FTS on 20% Fe/alumina. Preparation of a paper describing this work is in progress. Results of these studies were reported at the Annual Meeting of the Western States Catalysis and at the San Francisco AIChE meeting. In the coming period, studies will focus on quantitative determination of the rates of kinetically-relevant elementary steps on unsupported Fe catalysts with/without K and Pt promoters by SSITKA method. This study will help us to (1) understand effects of promoter and support on elementary kinetic parameters and (2) build a microkinetics model for FTS on iron. Calculations using periodic, self-consistent Density Functional Theory (DFT) methods were performed on models of defected Fe surfaces, most significantly the stepped Fe(211) surface. Binding Energies (BE's), preferred adsorption sites and geometries of all the FTS relevant stable species and intermediates were evaluated. Each elementary step of our reaction model was fully characterized with respect to its thermochemistry and comparisons between the stepped Fe(211) facet and the most-stable Fe(110) facet were established. In most cases the BE's on Fe(211) reflected the trends observed earlier on Fe(110), yet there were significant variations imposed on the underlying trends. Vibrational frequencies were evaluated for the preferred adsorption configurations of each species with the aim of evaluating the entropy-changes and preexponential factors for each elementary step. Kinetic studies were performed for the early steps of FTS (up to CH{sub 4} formation) and CO dissociation. This involved evaluation of the Minimum Energy Pathway (MEP) and activation energy barrier for the steps involved. We concluded that Fe(211) would allow for far more facile CO dissociation in comparison to other Fe catalysts studied so far, but the other FTS steps studied remained mostly unchanged
The SolventâSolid Interface of Acid Catalysts Studied by High Resolution MAS NMR
High-resolution magic angle spinning (HRMAS) NMR spectroscopy was used to study the eïŹect of mixed solvent systems on the acidity at the solidâliquid interface of solid acid catalysts. A method was developed that can exploit beneïŹts of both solution and solid-state NMR (SSNMR) by wetting porous solids with small volumes of liquids (ÎŒL/mg) to create an interfacial liquid that exhibits unique motional dynamics intermediate to an isotropic liquid and a rigid solid. Results from these experiments provide information about the inïŹuence of the solvent mixtures on the acidic properties at a solidâliquid interface. Importantly, use of MAS led to spectra with full resolution between water in an acidic environment and that of bulk water. Using mixed solvent systems, the chemical shift of water was used to compare the relative acidity as a function of the hydration level of the DMSO-d6 solvent. Nonlinear increasing acidity was observed as the DMSO-d6 became more anhydrous. 1H HR-MAS NMR experiments on a variety of supported sulfonic acid functionalized materials, suggest that the acid strength and number of acid sites correlates to the degree of broadening of the peaks in the 1H NMR spectra. When the amount of liquid added to the solid is increased (corresponding to a thicker liquid layer), fully resolved water phases were observed. This suggests that the acidic proton was localized predominantly within a 2 nm distance from the solid. EXSY 1Hâ1H 2D experiments of the thin layers were used to determine the rate of proton exchange for diïŹerent catalytic materials. These results demonstrated the utility of using (SSNMR) on solidâliquid mixtures to selectively probe catalyst surfaces under realistic reaction conditions for condensed phase systems
A lignocellulosic ethanol strategy via nonenzymatic sugar production: Process synthesis and analysis
The work develops a strategy for the production of ethanol from lignocellulosic biomass. In this strategy, the cellulose and hemicellulose fractions are simultaneously converted to sugars using a Îł-valerolactone (GVL) solvent containing a dilute acid catalyst. To effectively recover GVL for reuse as solvent and biomass-derived lignin for heat and power generation, separation subsystems, including a novel CO2-based extraction for the separation of sugars from GVL, lignin and humins have been designed. The sugars are co-fermented by yeast to produce ethanol. Furthermore, heat integration to reduce utility requirements is performed. It is shown that this strategy leads to high ethanol yields and the total energy requirements could be satisfied by burning the lignin. The integrated strategy using corn stover feedstock leads to a minimum selling price of $5 per gallon of gasoline equivalent, which suggests that it is a promising alternative to current biofuels production approaches
Production of Hexane-1,2,5,6-tetrol from Biorenewable Levoglucosanol over Pt-WOx/TiO2
We have investigated the synthesis of hexane-1,2,5,6-tetrol (hereafter "tetrol") from aqueous solutions of biomass-derived levoglucosanol (hereafter "Lgol") using a (10 wt %)Pt-(10 wt %)WOx/TiO2 catalyst in both batch and continuous flow reactors. The tetrol selectivity was over 90% with Lgol feed concentrations of 10-30 wt %. Most of the Lgol feed stereochemistry was preserved (notably 91%), with threo-Lgol (hereafter "t-Lgol") and erythro-Lgol (hereafter "e-Lgol") converting to (S,S)-tetrol and (S,R)-tetrol, respectively. The rate of Lgol conversion was found to be first-order in the Lgol concentration, suggesting that the catalyst surface is not saturated with Lgol. The measured reaction order for H2 was zero, which is consistent with either a mechanism involving acid-catalyzed irreversible C-O bond cleavage of Lgol followed by metal-catalyzed hydrogenation of reactive intermediates or one where all of the metal sites are saturated with H2. When the reaction was run in a continuous flow reactor, the catalyst exhibited deactivation with increasing time-on-stream but was found partially regenerable with a consecutive calcination and reduction treatment. Deactivation was concluded to be caused mainly by carbon deposition, with some W-leaching from the catalyst in the initial stages of reaction. The here demonstrated understanding of reaction kinetics and catalyst stability could facilitate the development of improved processes to produce hexane-1,2,5,6-tetrol from biomass
Solvent-Enabled Nonenyzmatic Sugar Production from Biomass for Chemical and Biological Upgrading
We recently reported a nonenzymatic biomass deconstruction process for producing carbohydrates using homogeneous mixtures of Îł-valerolactone (GVL) and water as a solvent. A key step in this process is the separation of the GVL from the aqueous phase, enabling GVL recycling and the production of a concentrated aqueous carbohydrate solution. In this study, we demonstrate that phenolic solventsâsec-butylphenol, nonylphenol, and lignin-derived propyl guaiacolâare effective at separating GVL from the aqueous phase using only small amounts of solvent (0.5â
g per g of the original water, GVL, and sugar hydrolysate). Furthermore, using nonylphenol, we produced a hydrolysate that supported robust growth and high yields of ethanol (0.49â
g EtOH per g glucose) at an industrially relevant concentration (50.8â
gâLâ1 EtOH). These results suggest that using phenolic solvents could be an interesting solution for separating and/or detoxifying aqueous carbohydrate solutions produced using GVL-based biomass deconstruction processes
Product Binding Enforces the Genomic Specificity of a Yeast Polycomb Repressive Complex
We characterize the Polycomb system that assembles repressive subtelomeric domains of H3K27 methylation (H3K27me) in the yeast Cryptococcus neoformans. Purification of this PRC2-like protein complex reveals orthologs of animal PRC2 components as well as a chromodomain-containing subunit, Ccc1, which recognizes H3K27me. Whereas removal of either the EZH or EED ortholog eliminates H3K27me, disruption of mark recognition by Ccc1 causes H3K27me to redistribute. Strikingly, the resulting pattern of H3K27me coincides with domains of heterochromatin marked by H3K9me. Indeed, additional removal of the C. neoformans H3K9 methyltransferase Clr4 results in loss of both H3K9me and the redistributed H3K27me marks. These findings indicate that the anchoring of a chromatin-modifying complex to its product suppresses its attraction to a different chromatin type, explaining how enzymes that act on histones, which often harbor product recognition modules, may deposit distinct chromatin domains despite sharing a highly abundant and largely identical substrateâthe nucleosome
Product Binding Enforces the Genomic Specificity of a Yeast Polycomb Repressive Complex
We characterize the Polycomb system that assembles repressive subtelomeric domains of H3K27 methylation (H3K27me) in the yeast Cryptococcus neoformans. Purification of this PRC2-like protein complex reveals orthologs of animal PRC2 components as well as a chromodomain-containing subunit, Ccc1, which recognizes H3K27me. Whereas removal of either the EZH or EED ortholog eliminates H3K27me, disruption of mark recognition by Ccc1 causes H3K27me to redistribute. Strikingly, the resulting pattern of H3K27me coincides with domains of heterochromatin marked by H3K9me. Indeed, additional removal of the C. neoformans H3K9 methyltransferase Clr4 results in loss of both H3K9me and the redistributed H3K27me marks. These findings indicate that the anchoring of a chromatin-modifying complex to its product suppresses its attraction to a different chromatin type, explaining how enzymes that act on histones, which often harbor product recognition modules, may deposit distinct chromatin domains despite sharing a highly abundant and largely identical substrateâthe nucleosome
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