Computational Catalyst Design: Controlling Chemical Transformations to Minimize Environmental Impact
EMSL Project ID
47408
Abstract
There is a critical need to develop new, renewable sources of energy as well as chemical feedstocks. 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 fuels and intermediates. Catalysis is governed by a delicate balance between a myriad of competing bond making and breaking processes including adsorption, reaction, desorption, and surface diffusion that occur at active catalytic centers. 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. For example, supported metal particles and metal oxides are complicated by their complex and ill-defined structure. Catalytic behavior is governed by the size and shape, interaction with the support, composition and atomic configuration for metal alloys and mixed metal oxides, the influence of solvent, and the presence of electric fields or applied potentials. The 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 catalysts to develop new design criteria and new understanding of the physical phenomena that occur at different spatial and temporal scales that underlie catalytic behavior. Catalysis is about improving kinetics and catalyst design will require quantitative information about transition states for critical reaction processes. Currently information about transition states, especially geometric and spectral information, is only readily accessible by computational methods. Such information is critical if we are to develop new catalytic materials and processes. Computational chemistry is an enabling tool for addressing challenges in the optimal design of processes for controlling and enabling chemical transformations leading to processes that have high selectivity and minimal environmental impact, and are optimal in their use of energy. Catalysis takes place at interfaces and we propose to study chemical reactions occurring at the solid/gas, solid/liquid, and cluster/liquid interfaces. We will apply computational chemistry at the density functional theory 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 polyoxometalates, (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 Cu(111), Au(111) and Au nanoparticles; selective hydrogenation of lactic acid on Cu(111); catalytic conversion of syngas to hydrocarbons over Co and Ru nanoclusters; and the reactivity of metal/metal-oxide interfaces (FeOx/Pd(111)) for the water gas shift reaction. A team of researchers from four universities with 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.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2012-10-01
End Date
2013-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Co-Investigator(s)
Team Members
Related Publications
Bokatzian SS, ML Stover, CE Plummer, DA Dixon, and CJ Cassady. 2014. "An Experimental and Computational Investigation into the Gas-Phase Acidities of Tyrosine and Phenylalanine: Three Structures for Deprotonated Tyrosine." Journal of Physical Chemistry B 118(44):12630–12643. doi:10.1021/jp510037c
Carrasquillo-Flores R, JMR Gallo, K Hahn, JA Dumesic, and M Mavrikakis. 2013. "Density Functional Theory and Reaction Kinetics Studies of the Water–Gas Shift Reaction on Pt–Re Catalysts." ChemCatChem 5(12):3690-3699. doi:10.1002/cctc.201300365
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
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
He J, C Zhao, D Mei, and JA Lercher. 2014. "Mechanisms of Selective Cleavage of C?O Bonds in Di-aryl Ethers in Aqueous Phase." Journal of Catalysis 309:280-290. doi:10.1016/j.jcat.2013.09.012
He J, L Lu, C Zhao, D Mei, and JA Lercher. 2014. "Mechanisms of Catalytic Cleavage of Benzyl Phenyl Ether in Aqueous and Apolar Phases." Journal of Catalysis 311(2014):41-51. doi:10.1016/j.cat.2013.10.024
Hibbitts DD, and M Neurock. 2013. "Influence of Oxygen and pH on the Selective Oxidation of Ethanol on Pd Catalysts." Journal of Catalysis 299:261-271. doi:10.1016/j.jcat.2012.11.016
Hibbitts DD, Q Tan, and M Neurock. 2014. "Acid Strength and Bifunctional Catalytic Behavior of Alloys Comprised of Noble Metals and Oxophilic Metal Promoters." Journal of Catalysis 315:48–58. doi:10.1016/j.jcat.2014.03.016
Singh S, S Li, R Carrasquillo-Flores, AC Alba-Rubio, JA Dumesic, and M Mavrikakis. 2014. "Formic Acid Decomposition on Au catalysts: DFT, Microkinetic Modeling, and Reaction Kinetics Experiments." AIChE Journal 60(4):1303-1319. doi:10.1002/aic.14401
Yang L, MB Vukmirovic, D Su, K Sasaki, JA Herron, M Mavrikakis, S Liao, and RR Adzic. 2013. "Tuning the Catalytic Activity of Ru@Pt Core?Shell Nanoparticles for the Oxygen Reduction Reaction by Varying the Shell Thickness." Journal of Physical Chemistry C 117(4):1748-1753. doi:10.1021/jp309990e
Ye J, C Liu, D Mei, and Q Ge. 2013. "Active Oxygen Vacancy Site for Methanol Synthesis from CO2 Hydrogenation on In2O3(110): A DFT Study." ACS Catalysis 3(6):1296-1306. doi:10.1021/cs400132a