title: Mechanistic Insights into the Unique Role of Copper in CO2Electroreduction Reactions.
abstract: Cu demonstrates a unique capability towards CO2electroreduction that can close the anthropogenic carbon cycle; however, its reaction mechanism remains elusive, owing to the obscurity of the solid-liquid interface on Cu surfaces where electrochemical reactions occur. Using a genetic algorithm method in addition to density functional theory, we explicitly identify the configuration of a water bilayer on Cu(2 1 1) and build electrochemical models. These enable us to reveal a mechanistic picture for CO2electroreduction, finding the key intermediates CCO* for the C2H4pathway and CH* for the CH4pathway, which rationalize a series of experimental observations. Furthermore, we find that the interplay between the Cu surfaces, carbon monomers, and water network (but not the binding of CO*) essentially determine the unique capability of Cu towards CO2electroreduction, proposing a new and effective descriptor for exploiting optimal catalysts.
authors.affiliation: Key Laboratory of Automobile Materials, Ministry of Education, Department of Materials Science and Engineering, Jilin University, 130022, Changchun, P.R. China.
authors.forename: Shan Ping
authors.initials: SP
authors.lastname: Liu
authors.affiliation: Key Laboratory of Automobile Materials, Ministry of Education, Department of Materials Science and Engineering, Jilin University, 130022, Changchun, P.R. China.
authors.forename: Ming
authors.initials: M
authors.lastname: Zhao
authors.affiliation: Key Laboratory of Automobile Materials, Ministry of Education, Department of Materials Science and Engineering, Jilin University, 130022, Changchun, P.R. China.
authors.forename: Wang
authors.identifier: 0000-0003-0331-2299
authors.initials: W
authors.lastname: Gao
authors.affiliation: Key Laboratory of Automobile Materials, Ministry of Education, Department of Materials Science and Engineering, Jilin University, 130022, Changchun, P.R. China.
authors.forename: Qing
authors.initials: Q
authors.lastname: Jiang
mesh_terms: D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D019281:Dimerization; D004563:Electrochemistry; D005030:Ethylenes / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry; D008697:Methane / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D010084:Oxidation-Reduction
chemical_list: D005030:Ethylenes; D002245:Carbon Dioxide; D003300:Copper; D006859:Hydrogen; C036216:ethylene; D008697:Methane
keywords: carbon dioxide; density functional theory; electroreduction; intermediates; solid-liquid interface