Computational Studies of Catalyzed Chemical Transformations of Biomass-Derived Intermediates
EMSL Project ID
48772
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 (Brønsted and Lewis) and redox reactions representative of relevant biomass transformations (e.g. deoxygenation, hydrogenolysis, dehydration, and hydroalkylation) on transition metal oxide clusters including Group 4, 5, 7, and 8 clusters and polyoxometalates with alcohols, polyols, levulinic acid, and gamma-valerolactone; polyol and ring-opening hydrogenolysis over bifunctional metal catalysts; formic acid decomposition on transition metals and and bimetallic alloys; direct synthesis of hydrogen peroxide from H2 and O2 catalyzed by transition metals and alloys; aldol condensation and C-C Coupling over metal and metal oxide particles; CO2 reduction to C1 energy carriers on reducible oxide supported metal clusters, and the Effects of water on the selective C-O bond cleavage of diaryl ethers over transition Metal Catalysts for lignin transformations. 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
2015-10-01
End Date
2017-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Co-Investigator(s)
Team Members
Related Publications
A DFT study of chlorine coverage over late transition metals and its implication on 1,2-dichloroethane hydrodechlorination
Xu L., E.E. Stangland, and M. Mavrikakis. 2018. "A DFT Study of Chlorine Coverage Over Late Transition Metals and its Implication on 1,2-dichloroethane Hydrodechlorination." Catalysis Science & Technology. doi:10.1039/C7CY02647A
Density functional theory study of thermodynamic and kinetic isotope effects of H2/D2 dissociative adsorption on transition metals
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Redox‐Triggered Orientational Responses of Liquid Crystals to Chlorine Gas
Szilvasi T., N. Bao, K. Nayani, H. Yu, P. Rai, R.J. Twieg, and M. Mavrikakis, et al. 2018. "Redox-Triggered Orientational Responses of Liquid Crystals to Chlorine Gas." Angewandte Chemie 57, no. 31:9665-9669. doi:10.1002/anie.201803194
Quantum chemical calculations to determine partitioning coefficients for HgCl2 on iron-oxide aerosols
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The role of iron-oxide aerosols and sunlight in the atmospheric reduction of Hg(II) species: A DFT+U study
Tacey S.A., T. Szilvasi, L. Xu, J.J. Schauer, and M. Mavrikakis. 2018. "The Role of Iron-oxide Aerosols and Sunlight in the Atmospheric Reduction of Hg(II) Species: A DFT+U Study." Applied Catalysis B: Environmental 234. doi:10.1016/j.apcatb.2018.04.049
Ethane dehydrogenation on pristine and AlOx decorated Pt stepped surfaces
Peng G., D. Gerceker, M. Kumbhalkar, J.A. Dumesic, and M. Mavrikakis. 2018. "Ethane Dehydrogenation on Pristine and AlOx Decorated Pt Stepped Surfaces." Catalysis Science & Technology 8. doi:10.1039/c8cy00398j
Ethylene versus ethane: A DFT-based selectivity descriptor for efficient catalyst screening
Xu L., E.E. Stangland, and M. Mavrikakis. 2018. "Ethylene versus Ethane: A DFT-based Selectivity Descriptor for Efficient Catalyst Screening." Journal of Catalysis 362. doi:10.1016/j.jcat.2018.03.019
Atomic and Molecular Adsorption on Cu(111)
Xu L., J. Lin, Y. Bai, and M. Mavrikakis. 2018. "Atomic and Molecular Adsorption on Cu(111)." Topics in Catalysis 9, no. 11:736–750. doi:10.1007/s11244-018-0943-0
Computational Chemistry‐Guided Design of Selective Chemoresponsive Liquid Crystals Using Pyridine and Pyrimidine Functional Groups
Yu H., T. Szilvasi, P. Rai, R.J. Twieg, M. Mavrikakis, and N.L. Abbott. 2018. "Computational Chemistry-Guided Design of Selective Chemoresponsive Liquid Crystals Using Pyridine and Pyrimidine Functional Groups." Advanced Functional Materials 28, no. 13:1703581. doi:10.1002/adfm.201703581
Mechanistic Study of Nitric Oxide Reduction by Hydrogen on Pt(100) (I): A DFT Analysis of the Reaction Network
Bai Y., and E. Mavrikakis. 2018. "Mechanistic Study of Nitric Oxide Reduction by Hydrogen on Pt(100) (I): A DFT Analysis of the Reaction Network." Journal of Physical Chemistry B 122, no. 2:432–443. doi:10.1021/acs.jpcb.7b01115
Sequential-Optimization-Based Framework for Robust Modeling and Design of Heterogeneous Catalytic Systems
Rangarajan S., C.T. Maravelias, and E. Mavrikakis. 2017. "Sequential-Optimization-Based Framework for Robust Modeling and Design of Heterogeneous Catalytic Systems." Journal of Physical Chemistry C 121, no. 46:25847–25863. doi:10.1021/acs.jpcc.7b08089
The role of anions in adsorbate-induced anchoring transitions of liquid crystals on surfaces with discrete cation binding sites
Szilvasi T., and N. Bao. 2017. "The Role of Anions in Adsorbate-induced Anchoring Transitions of Liquid Crystals on Surfaces with Discrete Cation Binding Sites." Soft Matter 14. doi:10.1039/c7sm01981e
Toward rational nanoparticle synthesis: predicting surface intermixing in bimetallic alloy nanocatalysts
Roling L.T., and E. Mavrikakis. 2017. "Toward Rational Nanoparticle Synthesis: Predicting Surface Intermixing in Bimetallic Alloy Nanocatalysts." Nanoscale 9. doi:10.1039/c7nr04779g
Atomic and molecular adsorption on Fe(110)
Xu L., D. Kirvassilis, Y. Bai, and E. Mavrikakis. 2018. "Atomic and Molecular Adsorption on Fe(110)." Surface Science 667. doi:10.1016/j.susc.2017.09.002
Ethylene Dimerization and Oligomerization to 1-Butene and Higher Olefins with Chromium-Promoted Cobalt on Carbon Catalyst
Xu Z., J. Chada, L. Xu, D. Zhao, D.C. Rosenfeld, J.L. Rogers, and I. Hermans, et al. 2018. "Ethylene Dimerization and Oligomerization to 1-Butene and Higher Olefins with Chromium-Promoted Cobalt on Carbon Catalyst." ACS Catalysis 8, no. 3:2488–2497. doi:10.1021/acscatal.7b03205
Reactivity and Selectivity Descriptors for the Activation of C–H Bonds in Hydrocarbons and Oxygenates on Metal Oxides
Deshlahra P, and E Iglesia. 2016. "Reactivity and Selectivity Descriptors for the Activation of C?H Bonds in Hydrocarbons and Oxygenates on Metal Oxides." Journal of Physical Chemistry C 120(30):16741–16760. doi:10.1021/acs.jpcc.6b04604
Toward More Complete Descriptors of Reactivity in Catalysis by Solid Acids
Deshlahra P, and E Iglesia. 2016. "Toward More Complete Descriptors of Reactivity in Catalysis by Solid Acids." ACS Catalysis 6(8):5386–5392. doi:10.1021/acscatal.6b01402
Promotional effect of surface hydroxyls on electrochemical reduction of CO2 over SnO /Sn electrode
Cui C, J Han, X Zhu, X Liu, H Wang, D Mei, and Q Ge. 2016. "Promotional Effect of Surface Hydroxyls on Electrochemical Reduction of CO2 over SnOx/Sn electrode." Journal of Catalysis 343:257-265. doi:10.1016/j.jcat.2015.12.001
Synthesis Gas Conversion over Rh-Based Catalysts Promoted by Fe and Mn
Liu Y, F Goeltl, I Ro, MR Ball, C Sener, I Barbosa Araga, D Zanchet, GW Huber, E Mavrikakis, and JA Dumesic. 2017. "Synthesis Gas Conversion over Rh-Based Catalysts Promoted by Fe and Mn." ACS Catalysis 7(7):4550–4563. doi:10.1021/acscatal.7b01381
Thermal Stability of Metal Nanocrystals: An Investigation of the Surface and Bulk Reconstructions of Pd Concave Icosahedra
Gilroy KD, AO Elnabawy, TH Yang, LT Roling, J Howe, E Mavrikakis, and Y Xia. 2017. "Thermal Stability of Metal Nanocrystals: An Investigation of the Surface and Bulk Reconstructions of Pd Concave Icosahedra." Nano Letters 17:3655?3661. doi:10.1021/acs.nanolett.7b00844
Design of Chemoresponsive Liquid Crystals through Integration of Computational Chemistry and Experimental Studies
Szilvasi T, LT Roling, H Yu, P Rai, S Choi, RJ Twieg, E Mavrikakis, and NL Abbott. 2017. "Design of Chemoresponsive Liquid Crystals through Integration of Computational Chemistry and Experimental Studies." Chemistry of Materials 29(8):3563–3571. doi:10.1021/acs.chemmater.6b05430
Understanding the Thermal Stability of Palladium–Platinum Core–Shell Nanocrystals by In Situ Transmission Electron Microscopy and Density Functional Theory
Vara M, LT Roling, X Wang, AO Elnabawy, Z Hood, M Chi, E Mavrikakis, and Y Xia. 2017. "Understanding the Thermal Stability of Palladium–Platinum Core–Shell Nanocrystals by In Situ Transmission Electron Microscopy and Density Functional Theory." ACS Nano 11(5):4571–4581. doi:10.1021/acsnano.6b08692
DFT Insights into the Competitive Adsorption of Sulfur- and Nitrogen-Containing Compounds and Hydrocarbons on Co-Promoted Molybdenum Sulfide Catalysts
Rangarajan S, and E Mavrikakis. 2016. "DFT Insights into the Competitive Adsorption of Sulfur- and Nitrogen-Containing Compounds and Hydrocarbons on Co-Promoted Molybdenum Sulfide Catalysts." ACS Catalysis 6:2904-2917. doi:10.1021/acscatal.6b00058
On the Structure Sensitivity of Formic Acid Decomposition on Cu Catalysts
Li S, Scaranto J, Zavarin M 2016. "On the Structure Sensitivity of Formic Acid Decomposition on Cu Catalysts" Topics in Catalysis 59(17):1580-1588. 10.1007/s11244-016-0672-1
Ab initio molecular dynamics of solvation effects on reactivity at electrified interfaces
Herron J A,Morikawa Y ,Mavrikakis E 2016. "Ab Initio Molecular Dynamics of Solvation Effects on Reactivity at Electrified Interfaces" Proceedings of the National Academy of Sciences of the United States of America 113(34):E4937-E4945. 10.1073/pnas.1604590113
On the Preferred Active Sites of Promoted MoS2 for Hydrodesulfurization with Minimal Organonitrogen Inhibition
Rangarajan S, Mavrikakis E 2017. "On the Preferred Active Sites of Promoted MoS2 for Hydrodesulfurization with Minimal Organonitrogen Inhibition" ACS Catalysis 7(1):501-509. 10.1021/acscatal.6b02735
Density functional theory studies of HCOOH decomposition on Pd(111)
Scaranto J, Mavrikakis E. 2016. "Density Functional Theory Studies of HCOOH Decomposition on Pd(111)" Surface Science 650():111-120. doi: 10.1016/j.susc.2015.11.020
Towards first-principles molecular design of liquid crystal-based chemoresponsive systems
Roling L T,Scaranto J ,Herron J A,Yu H ,Choi S ,Abbott N L,Mavrikakis E 2016. "Towards First-Principles Molecular Design of Liquid Crystal-Based Chemoresponsive Systems" Nature Communications 7():13338. 10.1038/ncomms13338
Synthesis and Characterization of Ru Cubic Nanocages with a Face-Centered Cubic Structure by Templating with Pd Nanocubes
Zhao M, Figueroa-Cosme L, Elnabawy A O, Vara M, Yang X, Roling L T, Chi M, Mavrikakis E, Xia Y. 2016. "Synthesis and Characterization of Ru Cubic Nanocages with a Face-Centered Cubic Structure by Templating with Pd Nanocubes" Nano Letters 16(8):5310-5317. doi: 10.1021/acs.nanolett.6b02795
Synthesis and Characterization of Pt–Ag Alloy Nanocages with Enhanced Activity and Durability toward Oxygen Reduction
Yang X ,Roling L T,Vara M ,Elnabawy A O,Zhao M ,Hood Z ,Bao S ,Zavarin M ,Xia Y 2016. "Synthesis and Characterization of Pt-Ag Alloy Nanocages with Enhanced Activity and Durability toward Oxygen Reduction" Nano Letters 16(10):6644-6649. 10.1021/acs.nanolett.6b03395
Adsorption of Small Alkanes on ZSM-5 Zeolites: Influence of Brønsted Sites
Yeh YH, RJ Gorte, S Rangarajan, and E Mavrikakis. 2016. "Adsorption of Small Alkanes on ZSM-5 Zeolites: Influence of Brønsted Sites." Journal of Physical Chemistry C 120(22):12132-12138. doi:10.1021/acs.jpcc.6b03855
Kinetic and Theoretical Insights into the Mechanism of Alkanol Dehydration on Solid Brønsted Acid Catalysts
Knaeble W J, Iglesia E 2016. "Kinetic and Theoretical Insights into the Mechanism of Alkanol Dehydration on Solid Bronsted Acid Catalysts" Journal of Physical Chemistry C 120(6):3371-3389. 10.1021/acs.jpcc.5b11127
Anharmonicity and Confinement in Zeolites: Structure, Spectroscopy, and Adsorption Free Energy of Ethanol in H-ZSM-5
Alexopoulos K, MS Lee, Y Liu, Y Zhi, Y Liu, MF Reyniers, GB Marin, VA Glezakou, RJ Rousseau, and JA Lercher. 2016. "Anharmonicity and Confinement in Zeolites: Structure, Spectroscopy and Adsorption Free Energy of Ethanol in H-ZSM-5." Journal of Physical Chemistry C 120(13):7172-7182. doi:10. 1021/acs. jpcc. 6b00923
On the Structure Sensitivity of Dimethyl Ether Electro-oxidation on Eight FCC Metals: A First-Principles Study
Herron J A, Ferrin P A, Mavrikakis E 2014. "On the Structure Sensitivity of Dimethyl Ether Electro-oxidation on Eight FCC Metals: A First-Principles Study" Topics in Catalysis 58():1159-1173. 10.1007/s11244-015-0495-5
Promotional effects of chemisorbed oxygen and hydroxide in the activation of C–H and O–H bonds over transition metal surfaces
Hibbitts D.D., and M. Neurock. 2016. "Promotional Effects of Chemisorbed Oxygen and Hydroxide in the Activation of C–H and O–H Bonds Over Transition Metal Surfaces." Surface Science 650. doi:10.1016/j.susc.2016.01.012
Adsorption of nitrogen- and sulfur-containing compounds on NiMoS for hydrotreating reactions: A DFT and vdW-corrected study
Rangarajan S ,Mavrikakis E 2015. "Adsorption of Nitrogen- and Sulfur-Containing Compounds on NiMoS for Hydrotreating Reactions: A DFT and vdW-Corrected Study" AIChE Journal 61(12):4036-4050. 10.1002/aic.15025
Key Roles of Lewis Acid–Base Pairs on ZnxZryOz in Direct Ethanol/Acetone to Isobutene Conversion
Sun J, RA Baylon, C Liu, D Mei, KJ Martin, P Venkitasubramanian, and Y Wang. 2016. "Key Roles of Lewis Acid-base Pairs on ZnxZryOz in Direct Ethanol/Acetone to Isobutene Conversion." Journal of the American Chemical Society 138(2):507-517. doi:10. 1021/jacs. 5b07401
Preferential activation of CO near hydrocarbon chains during Fischer–Tropsch synthesis on Ru
Hibbitts D D, Dybeck E, Lawlor T, Neurock M, Iglesia E 2016. "Preferential Activation of CO Near Hydrocarbon Chains During Fischer-Tropsch Synthesis on Ru" Journal of Catalysis 337():91-101. 10.1016/j.jcat.2016.01.010
1,2-Ethanediol and 1,3-Propanediol Conversions over (MO3)3 (M = Mo, W) Nanoclusters: A Computational Study
Fang Z, Zetterholm P, Dixon D A 2016. "1,2-Ethanediol and 1,3-Propanediol Conversions over (MO3)3 (M =" Journal of Physical Chemistry A 120(11):1897-1907. 10.1021/acs.jpca.6b00158
Identification of O-rich structures on platinum(111)-supported ultrathin iron oxide films
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HCOOH decomposition on Pt(111): A DFT study
Scaranto J, Mavrikakis E. 2016. "HCOOH Decomposition on Pt(111): A DFT Study" Surface Science 68():201-211. doi: 10.1016/j.susc.2015.09.023
Dimethyl ether electro-oxidation on platinum surfaces
Roling LT, JA Herron, W Budiman, PA Ferrin, and E Mavrikakis. 2016. "Dimethyl Ether Electro-oxidation on Platinum Surfaces." Nano Energy. doi:10.1016/j.nanoen.2016.02.041
An Adsorption Study of CH4 on ZSM-5, MOR, and ZSM-12 Zeolites
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Chloroform Hydrodechlorination over Palladium–Gold Catalysts: A First‐Principles DFT Study
Xu L, X Yao, A Khan, and E Mavrikakis. 2016. "Chloroform Hydrodechlorination over Palladium-Gold Catalysts: A First-Principles DFT Study." ChemCatChem 8(9):1739-1746. doi:10.1002/cctc.201600144