Mechanistic studies toward the rational design of oxide catalysts for carbon dioxide hydrogenation
01 Jan 2021-Vol. 17, pp 211-270
TL;DR: In this article, a computer-assisted rational design of heterogeneous catalysts has become a central theme of computational studies on industrial catalysis, which may contribute significantly to our impending transition from a fossil fuel-based energy and chemical industry into a renewable energy-based one.
Abstract: Computer-assisted rational design of heterogeneous catalysts has become a central theme of computational studies on industrial catalysis, which may contribute significantly to our impending transition from a fossil fuel-based energy and chemical industry into a renewable energy-based one. To this end, integrated research efforts in mechanistic elucidation of the relevant catalytic reactions remain essential, but emphasis must be further placed on the development of effective approaches in the rational design of industrial catalysts, where traditional methodologies must be combined with the new information-based technologies.
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TL;DR: In this paper , in situ IR and XPS are performed to investigate the O1s binding energies of the adsorbates induced by CO2 and H2O treatments along with density functional theory (DFT) simulations to further correlate the calibrated assignments with surface structures.
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5,052 citations
2,885 citations
TL;DR: In this paper, a method for finding free energy barriers for transitions in high-dimensional classical and quantum systems is presented and used to calculate the dissociative sticking probability of H 2 on a metal surface within the transition state theory.
1,880 citations
TL;DR: In this paper, a method for finding free energy barriers for transitions in high-dimensional classical and quantum systems is presented and used to calculate the dissociative sticking probability of H2 on a metal surface within transition state theory (TST).
Abstract: A practical method for finding free energy barriers for transitions in high-dimensional classical and quantum systems is presented and used to calculate the dissociative sticking probability of H2 on a metal surface within transition state theory (TST). The reversible work involved in shifting the system confined to a hyperplane from the reactant region towards products is evaluated directly. Quantum mechanical degrees of freedom are included by using Feynman Path Integrals with the hyperplane constraint applied to the centroid of the cyclic paths. An optimal dividing surface for the rate estimated by TST is identified naturally in the course of the reversible work evaluation. The free energy barrier is determined relative to the reactant state directly, so an estimate of the transition rate can be obtained without requiring a solvable reference model for the transition state. The method has been applied to calculations of the sticking probability of a thermalized hydrogen gas on a Cu(110) surface. The two hydrogen atoms were included quantum mechanically, and over two hundred atoms in the Cu crystal where included classically. The activation energy for adsorption and desorption was determined and found to be significantly lowered by tunneling at low temperature. The calculated values agree quite well with experimental estimates. Dynamical corrections to the classical TST rate estimate were evaluated and found to be small.
1,572 citations
TL;DR: A direct comparison between the activity of ZnCu and ZnO/Cu model catalysts for methanol synthesis is reported, highlighting a synergy of Cu andZnO at the interface that facilitates methenol synthesis via formate intermediates.
Abstract: The active sites over commercial copper/zinc oxide/aluminum oxide (Cu/ZnO/Al2O3) catalysts for carbon dioxide (CO2) hydrogenation to methanol, the Zn-Cu bimetallic sites or ZnO-Cu interfacial sites, have recently been the subject of intense debate. We report a direct comparison between the activity of ZnCu and ZnO/Cu model catalysts for methanol synthesis. By combining x-ray photoemission spectroscopy, density functional theory, and kinetic Monte Carlo simulations, we can identify and characterize the reactivity of each catalyst. Both experimental and theoretical results agree that ZnCu undergoes surface oxidation under the reaction conditions so that surface Zn transforms into ZnO and allows ZnCu to reach the activity of ZnO/Cu with the same Zn coverage. Our results highlight a synergy of Cu and ZnO at the interface that facilitates methanol synthesis via formate intermediates.
1,037 citations