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Mechanistic Insights into the Unique Role of Copper in CO 2 Electroreduction Reactions
Author(s) -
Liu Shan Ping,
Zhao Ming,
Gao Wang,
Jiang Qing
Publication year - 2017
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201601144
Subject(s) - electrochemistry , density functional theory , copper , carbon fibers , bilayer , reaction mechanism , catalysis , mechanism (biology) , monomer , chemistry , materials science , electrode , computational chemistry , membrane , polymer , organic chemistry , physics , biochemistry , composite number , composite material , quantum mechanics
Cu demonstrates a unique capability towards CO 2 electroreduction 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 CO 2 electroreduction, finding the key intermediates CCO* for the C 2 H 4 pathway and CH* for the CH 4 pathway, 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 CO 2 electroreduction, proposing a new and effective descriptor for exploiting optimal catalysts.