Full atomistic reaction mechanism with kinetics for CO reduction on Cu(100) from ab initio molecular dynamics free-energy calculations at 298 K

Cheng, Tao; Xiao, Hai; Goddard, III, William A.

doi:10.1073/pnas.1612106114

Title: Full atomistic reaction mechanism with kinetics for CO reduction on Cu(100) from ab initio molecular dynamics free-energy calculations at 298 K

Journal Article · 06 February 2017 · Proceedings of the National Academy of Sciences of the United States of America

DOI: https://doi.org/10.1073/pnas.1612106114 · OSTI ID:1342801

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Joint Center for Artificial Photosynthesis, California Institute of Technology, Pasadena, CA 91125,, Materials and Process Simulation Center (MC139-74), California Institute of Technology, Pasadena, CA 91125

Significance Converting CO ₂ to fuels is of great interest nowadays. Copper (Cu) is the only metal that produces hydrocarbon products, making it of interest for learning the reaction mechanisms underlying the selectivity and activity of Cu catalysts. In this report, we examine the reaction mechanism of CO reduction on Cu(100) at pH 7 including explicitly the aqueous solvent with ab initio molecular metadynamics simulations (AIMμD) free-energy calculations, which we find to explain all experimental observations. We expect that this understanding will suggest how to modify the Cu catalyst or replace it with a new material to enhance production of just a single such product while reducing the energy requirements (overpotential).

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Research Organization:: California Inst. of Technology (CalTech), Pasadena, CA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: SC0004993

OSTI ID:: 1342801

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 8 Vol. 114; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Full atomistic reaction mechanism with kinetics for CO reduction on Cu(100) from ab initio molecular dynamics free-energy calculations at 298 K

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