Computational Studies of Catalyzed Chemical Transformations of Biomass and Derived Intermediates
EMSL Project ID
49734
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. In addition, the major carbon product of combustion is CO2 which is also a highly oxygenated carbon. 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 the environment. 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 the following areas: (1) Development of structure/function relationships in transition metal oxide catalysts for biomass conversion with Earth abundant metals. (2) Development of new homogeneous catalysts for CO2 hydrogenation; (3) Steam reforming of methanol on single site Au1-Ox-(OH)y-Naz clusters; (4) Prediction of the influence of solvent over Earth-abundant metal alloy catalysts for the selective ring opening of cyclic ethers and hydrogenolysis of polyols; (5) Exploring the effects of the aqueous phase on the alkylation of bio-derived model oxygenates (phenol and 2,5-dimethylfuran) with ethanol over H-ZSM-5 zeolite; (6) Predicting how metal nanoparticles supported on redox active oxides can be used for CO2 reduction to energy carriers; and (7) Determining the roles of gas-phase molecular shuttles in heterogeneous catalysis. A team of researchers from four universities and PNNL with direct and close 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. The effort falls within the EMSL Molecular Transformations Theme of 'Transformations critical to molecular-scale biological and chemical processes associated with alternative energy production,' and the BER basic science subgoal: 'Provide the basic science to enable a sustainable and commercially viable lignocellulosic biomass-derived advanced biofuels and bioproducts industry.'
Project Details
Project type
Large-Scale EMSL Research
Start Date
2017-10-01
End Date
2018-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
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(2):432–443. doi:10.1021/acs.jpcb.7b01115
Jin Q., B. Chen, Z. Ren, X. Liang, N. Liu, and D. Mei. 2018. "A Theoretical Study on Reaction Mechanisms and Kinetics of Thiophene Hydrodesulfurization over MoS2 Catalysts." Catalysis Today 312. PNNL-SA-130462. doi:10.1016/j.cattod.2018.02.013
Jin Q., N. Liu, B. Chen, and D. Mei. 2018. "Mechanisms of Semiconducting 2H to Metallic 1T Phase Transition in Two-dimensional MoS2 Nanosheets." Journal of Physical Chemistry C 122, no. 49:28215-28224. PNNL-SA-137922. doi:10.1021/acs.jpcc.8b10256
Lo B.W., L. Ye, G.Z. Change, K. Purchase, S. Day, C. Tang, and D. Mei, et al. 2018. "Dynamic Modification of Pore Opening of SAPO-34 by Adsorbed Surface Methoxy Species during Induction of Catalytic Methanol-to-Olefins Reactions." Applied Catalysis. B, Environmental 237. PNNL-SA-135309. doi:10.1016/j.apcatb.2018.05.090
Mei D., Z. Ren, N. Liu, B. Chen, and J. Li. 2018. "Nucleation of Cun (n = 1-5) Clusters and Equilibrium Morphology of Cu Particles Supported on CeO2 Surface: A Density Functional Theory Study." Journal of Physical Chemistry C 122, no. 48:27402–27411. PNNL-SA-137468. doi:10.1021/acs.jpcc.8b07993
Rangarajan S, CT Maravelias, and E Mavrikakis. 2017. "Sequential-Optimization-Based Framework for Robust Modeling and Design of Heterogeneous Catalytic Systems." Journal of Physical Chemistry C 121(46):25847–25863. doi:10.1021/acs.jpcc.7b08089
Ren Z., F. Peng, B. Chen, D. Mei, and J. Li. 2017. "A combined experimental and computational study of water-gas shift reaction over rod-shaped Ce0.75M0.25O2 (M = Ti, Zr, and Mn) supported Cu catalysts." International Journal of Hydrogen Energy 42, no. 51:30086-30097. PNNL-SA-129864. doi:10.1016/j.ijhydene.2017.10.047
Ren Z, N Liu, B Chen, J Li, and D Mei. 2018. "Theoretical Investigation of the Structural Stabilities of Ceria Surfaces and Supported Metal Nanocluster in Vapor and Aqueous Phases." Journal of Physical Chemistry C 122(9):4828-4840. doi:10.1021/acs.jpcc.7b10208
Roling LT, and E Mavrikakis. 2017. "Toward Rational Nanoparticle Synthesis: Predicting Surface Intermixing in Bimetallic Alloy Nanocatalysts." Nanoscale 9:15005-15017. doi:10.1039/c7nr04779g
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 14:797--805. doi:10.1039/c7sm01981e
Wang X., N. Liu, Q. Zhang, X. Liang, B. Chen, and D. Mei. 2020. "Thermodynamic and Kinetic Roles of H-2 on Structure Evolution of Urchin-like Co: A density functional theory study." Particuology 48, no. SI:2-12. PNNL-SA-135307. doi:10.1016/j.partic.2018.08.007
Xu L, D Kirvassilis, Y Bai, and E Mavrikakis. 2018. "Atomic and Molecular Adsorption on Fe(110)." Surface Science 667:54-65. doi:10.1016/j.susc.2017.09.002
Zhao M, AO Elnabawy, M Vara, L Xu, Z Hood, X Yang, KD Gilroy, L Figueroa-Cosme, M Chi, E Mavrikakis, and Y Xia. 2017. "Facile Synthesis of Ru-Based Octahedral Nanocages with Ultrathin Walls in a Face-Centered Cubic Structure." Chemistry of Materials 29(21):9227–9237. doi:10.1021/acs.chemmater.7b03092
Zhao P., L. Ye, Z. Sun, B.W. Lo, H. Woodcock, C. Huang, and C. Tang, et al. 2018. "Entrapped Single Tungstate Site in Zeolite for Cooperative Catalysis of Olefin Metathesis with Brønsted Acid Site." Journal of the American Chemical Society 140, no. 21. PNNL-SA-134054. doi:10.1021/jacs.8b03012
Zhao Y., H. Wang, J. Han, X. Zhu, D. Mei, and Q. Ge. 2019. "Simultaneous Activation of CH4 and CO2 for Concerted C-C Coupling at the Oxide-Oxide Interfaces." ACS Catalysis 9, no. 4:3187-3197. PNNL-SA-138001. doi:10.1021/acscatal.9b00291