Computational Studies of Catalyzed Chemical Transformations of Biomass
EMSL Project ID
47800
Abstract
There is a critical need to develop new, renewable sources of energy as well as feedstocks for the chemical industry. Biomass is a carbon neutral source of energy and can also address issues related to the sustainability of petroleum-based resources. An issue with biomass is that it is heavily oxygenated (glucose = (C(H2O))6) and catalytic processes are needed to convert the oxygenated biomass into deoxygenated fuels and intermediates. We propose electronic structure theoretical studies of a variety of catalytic processes for the conversion of biomass intermediates to useful fuels and feedstocks. These processes are explicitly controlled by the intrinsic bonds that form between the reactants or intermediates and the active catalytic site as well as by the local nanoscale environment/interface about the site. Catalytic behavior is governed by the size and shape, interaction with the support, composition and atomic configuration for metal alloys and mixed metal oxides, and the influence of solvent. The potential role of an aqueous solvent is important for biomass conversions because of the source of the raw material. We propose to use advanced computational chemistry approaches implemented on EMSL's massively parallel computers to develop a quantitative description of catalytic processes for biomass conversion to develop new design criteria and new understanding of the physical phenomena that occur at different spatial and temporal scales that underlie the catalytic behavior. We will apply computational chemistry at the density functional theory (molecular and plane-wave) and correlated molecular orbital theory levels to study a range of catalytic processes including: acid-base (Bronsted and Lewis) and redox reactions representative of relevant biomass transformations (e.g. deoxygenation, hydrogenolysis, dehydration, and hydroalkylation) on polyoxometalates and (MO3)n (M= Group VIB) clusters of glycerol, levulinic acid, and gamma-valerolactone; polyol and ring-opening hydrogenolysis over bifunctional metal catalysts; formic acid decomposition on Au nanoparticles and bimetallic alloys; selective hydrogenation of lactic acid on Cu-based and Pt-based bimetallic alloys; aldol condensation over metal and metal oxide particles; and hydroalkylation of cyclohexanol in mesoporous zeolites for lignin conversion. A team of researchers from four universities and PNNL with direct ties to experimental efforts will address these problems using appropriate computational methods with the goal of understanding interfacial processes and advancing our ability to understand catalytic processes leading to the design of new catalysts. The proposed computational work is being done in close collaboration with experimental teams, a number of which use EMSL resources or are located in the EMSL.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2013-10-01
End Date
2015-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Co-Investigator(s)
Team Members
Related Publications
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Steam Reforming of Ethylene Glycol over MgAl2O4 Supported Rh, Ni, and Co Catalysts
Mei D, VM Lebarbier, R Xing, KO Albrecht, and RA Dagle. 2015. "Steam Reforming of Ethylene Glycol over MgAl2O4 Supported Rh, Ni, and Co Catalysts." ACS Catalysis 6(1):315-325. doi:10. 1021/acscatal. 5b01666
Heterogeneous Reduction Pathways for Hg(II) Species on Dry Aerosols: A First-Principles Computational Study
Tacey S A,Xu L ,Mavrikakis E ,Schauer J J 2016. "Heterogeneous Reduction Pathways for Hg(II) Species on Dry Aerosols: A First-Principles Computational Study" Journal of Physical Chemistry A 120(13):2106–2113. 10.1021/acs.jpca.5b12769
Active sites and mechanisms for H 2 O 2 decomposition over Pd catalysts
Plauck A D,Stangland E E,Dumesic J A,Mavrikakis E 2016. "Active Sites and Mechanisms for H2O2 Decomposition over Pd Catalysts" Proceedings of the National Academy of Sciences of the United States of America 113(14):E1973–E1982. 10.1073/pnas.1602172113
Effects of Chain Length on the Mechanism and Rates of Metal-Catalyzed Hydrogenolysis of n-Alkanes
Hibbitts D D,Flaherty D W,Iglesia E 2016. "Effects of Chain Length on the Mechanism and Rates of Metal-Catalyzed Hydrogenolysis of n-Alkanes" Journal of Physical Chemistry C 120(15):8125–8138. 10.1021/acs.jpcc.6b00323
Direct Visualization of Catalytically Active Sites at the FeO–Pt(111) Interface
Kudernatsch W, G Peng, H Zeuthen, Y Bai, LR Merte, L Lammich, F Besenbacher, M Mavrikakis, and S Wendt. 2015. "Direct Visualization of Catalytically Active Sites at the FeO-Pt(111) Interface." ACS Nano. doi:10.1021/acsnano.5b02339
Controlling the electronic structure of graphene using surface-adsorbate interactions
Matyba P ,Carr A ,Chen C ,Miller D L,Peng G ,Stefan M ,Mavrikakis E ,Dessau D S,Keller M W,Kapteyn H C,Murnane M M 2015. "Controlling the Electronic Structure of Graphene Using Surface-Adsorbate Interactions" Physical Review B 92():041407. 10.1103/PhysRevB.92.041407
The nature of the Fe–graphene interface at the nanometer level
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doi: 10.1039/c4nr04956j
First-Principles Mechanistic Analysis of Dimethyl Ether Electro-Oxidation on Monometallic Single-Crystal Surfaces
Herron JA, PA Ferrin, and E Mavrikakis. 2014. "First-Principles Mechanistic Analysis of Dimethyl Ether Electro-Oxidation on Monometallic Single-Crystal Surfaces." Journal of Physical Chemistry C 118(42):24199–24211. doi:10.1021/jp505919x
Catalytically active Au-O(OH) x - species stabilized by alkali ions on zeolites and mesoporous oxides
M. Yang, S. Li, Y. Wang, J. A. Herron, Y. Xu, L. F. Allard, S. Lee, J. Huang, M. Mavrikakis, and M. Flytzani-Stephanopoulos. 2015. "Catalytically active Au-O(OH)x- species stabilized by alkali ions on zeolites and mesoporous oxides." Science 346 (6216): 1498-1501.
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doi: 10.1126/science.1260526
Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction
X. Wang, S. Choi, L. T. Roling, M. Luo, C. Ma, L. Zhang, M. Chi, J. Liu, Z. Xie, J. A. Herron, M. Mavrikakis, and Y. Xia. 2015. "Palladium?platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction." Nature Communications 6(7594)
doi:10.1038/ncomms8594
doi:10.1038/ncomms8594
Platinum-based nanocages with subnanometer-thick walls and well-defined, controllable facets
Zhang L ,Roling L T,Wang X ,Vara M ,Chi M ,Liu J ,Choi SI ,Park J ,Herron J A,Xie Z ,Mavrikakis E ,Xia Y 2015. "Platinum-based Nanocages with Subnanometer-thick Walls and Well-defined, Controllable Facets" Science 349(6246):412-416. 10.1126/science.aab0801
Stability of surface and subsurface hydrogen on and in Au/Ni near-surface alloys
Celik FE, and M Mavrikakis. 2015. "Stability of Surface and Subsurface Hydrogen on and in Au/Ni Near-Surface Alloys." Surface Science. doi:10.1016/j.susc.2015.01.001
A Comprehensive Study of Formic Acid Oxidation on Palladium Nanocrystals with Different Types of Facets and Twin Defects
Sang-Il C, JA Herron, J Scaranto, H Huang, Y Wang, X Xia, T Lv, J Park, HC Peng, M Mavrikakis, and Y Xia. 2015. "A Comprehensive Study of Formic Acid Oxidation on Palladium Nanocrystals with Different Types of Facets and Twin Defects." ChemCatChem. doi:10.1002/cctc.201500094
Electrocatalytic Oxidation of Ammonia on Transition-Metal Surfaces: A First-Principles Study
Herron JA, P Ferrin, and M Mavrikakis. 2015. "Electrocatalytic Oxidation of Ammonia on Transition-Metal Surfaces: A First-Principles Study." The Journal of Physical Chemistry C. doi:10.1021/jp512981f
Density Functional Theory Calculations and Analysis of Reaction Pathways for Reduction of Nitric Oxide by Hydrogen on Pt(111)
Farberow CA, JA Dumesic, and M Mavrikakis. 2014. "Density Functional Theory Calculations and Analysis of Reaction Pathways for Reduction of Nitric Oxide by Hydrogen on Pt(111)." ACS Catalysis 4(10):3307–3319. doi:10.1021/cs500668k
Kinetic, Spectroscopic, and Theoretical Assessment of Associative and Dissociative Methanol Dehydration Routes in Zeolites
Jones AJ, and E Iglesia. 2014. "Kinetic, Spectroscopic, and Theoretical Assessment of Associative and Dissociative Methanol Dehydration Routes in Zeolites." Angewandte Chemie International Edition 126(45):12373-12377. doi:10.1002/ange.201406823
Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory study
Herron JA, J Scaranto, PA Ferrin, S Li, and M Mavrikakis. 2014. "Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory Study." ACS Catalysis 4(12):4434–4445. doi:10.1021/cs500737p
First-Principles Study of Phenol Hydrogenation on Pt and Ni Catalysts in Aqueous Phase
Yoon Y, RJ Rousseau, RS Weber, D Mei, and JA Lercher. 2014. "First-principles Study of Phenol Hydrogenation on Pt and Ni Catalysts in Aqueous Phase." Journal of the American Chemical Society 136(29):10287-10298. doi:10.1021/ja501592y
Water clustering on nanostructured iron oxide films
Merte LR, R Bechstein, G Peng, F Rieboldt, CA Farberow, H Zeuthen, J Knudsen, E Laegsgaard, S Wendt, M Mavrikakis, and F Besenbacher. 2014. "Water Clustering on Nanostructured Iron Oxide Films." Nature Communications 5:4193. doi:10.1038/ncomms5193
Atomic and molecular adsorption on Au(111)
Santiago-Rodrguez Y, JA Herron, MC Curet-Arana, and M Mavrikakis. 2014. "Atomic and Molecular Adsorption on Au(111)." Surface Science 627:57-69. doi:10.1016/j.susc.2014.04.012
Atomic Layer-by-Layer Deposition of Pt on Pd Nanocubes for Catalysts with Enhanced Activity and Durability toward Oxygen Reduction
Xie S, C Sang-Il, N Lu, LT Roling, JA Herron, L Zhang, J Park, J Wang, MJ Kim, Z Xie, M Mavrikakis, and Y Xia. 2014. "Atomic Layer-by-Layer Deposition of Pt on Pd Nanocubes for Catalysts with Enhanced Activity and Durability toward Oxygen Reduction." Nano Letters 14(6):3570-3576. doi:10.1021/nl501205j
Advanced solution methods for microkinetic models of catalytic reactions: A methanol synthesis case study
Rubert-Nason P, M Mavrikakis, CT Maravelias, LC Grabow, and LT Biegler. 2013. "Advanced Solution Methods for Microkinetic Models of Catalytic Reactions: A Methanol Synthesis Case Study." AIChE Journal 60(4):1336–1346. doi:10.1002/aic.14322
Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces
Chen C, Y Kang, Z Huo, Z Zhu, W Huang, H Xin, J Snyder, D Li, JA Herron, M Mavrikakis, M Chi, KL More, Y Li, NM Markovic, GA Somorjai, P Yang, and VR Stamenkovic. 2014. "Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces." Science 343(6177):1339-1343. doi:10.1126/science.1249061
Site-Specific Imaging of Elemental Steps in Dehydration of Diols on TiO2(110)
Acharya DP, Y Yoon, Z Li, Z Zhang, X Lin, R Mu, L Chen, BD Kay, RJ Rousseau, and Z Dohnalek. 2013. "Site-Specific Imaging of Elemental Steps in Dehydration of Diols on TiO2(110)." ACS Nano 7(11):10414-10423. doi:10.1021/nn404934q
Tree Growth—Hybrid Genetic Algorithm for Predicting the Structure of Small (TiO2)n, n = 2–13, Nanoclusters
Chen M, and DA Dixon. 2013. "Tree Growth?Hybrid Genetic Algorithm for Predicting the Structure of Small (TiO2)n, n = 2?13, Nanoclusters." Journal of Chemical Theory and Computation 9(7):3189–3200. doi:10.1021/ct400105c
Effects of potassium doping on CO hydrogenation over MoS2 catalysts: A first-principles investigation
Andersen A, SM Kathmann, MA Lilga, KO Albrecht, RT Hallen, and D Mei. 2014. "Effects of Potassium Doping on CO Hydrogenation Over MoS2 Catalysts: A First-Principles Investigation." Catalysis Communications 52:92-97. doi:10.1016/j.catcom.2014.02.011
Electronic structure predictions of the properties of non-innocent P-ligands in group 6B transition metal complexes
Garner EB, AJ Arduengo, III, R Streubel, and DA Dixon. 2013. "Electronic Structure Predictions of the Properties of Non-innocent P-ligands in Group 6B Transition Metal Complexes ." Dalton Transactions 43:2069-2078. doi:10.1039/C3DT52056K
Significant Quantum Effects in Hydrogen Activation
Kyriakou G, ER Davidson, G Peng, LT Roling, S Singh, MB Boucher, MD Marcinkowski, M Mavrikakis, A Michaelides, and ECH Sykes. 2014. "Significant Quantum Effects in Hydrogen Activation." ACS Nano 8(5):4827-4835. doi:10.1021/nn500703k
Consequences of Metal–Oxide Interconversion for C–H Bond Activation during CH4 Reactions on Pd Catalysts
Chin YH, C Buda, M Neurock, and E Iglesia. 2013. "Consequences of Metal–Oxide Interconversion for C–H Bond Activation during CH4 Reactions on Pd Catalysts." Journal of the American Chemical Society 135(41):15425-15442. doi:10.1021/ja405004m
On the composition of bimetallic near-surface alloys in the presence of oxygen and carbon monoxide
Herron JA, and M Mavrikakis. 2014. "On the Composition of Bimetallic Near Surface Alloys in the Presence of Oxygen and Carbon Monoxide." Catalysis Communications 52:65-71. doi:10.1016/j.catcom.2013.10.021