Electrochemical Hydrogenation of CO on Cu(100): Insights from Accurate Multiconfigurational Wavefunction Methods

Qing Zhao, John Mark P. Martirez, Emily A. Carter

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

Abstract

Copper (Cu) remains the most efficacious electrocatalyst for electrochemical CO2reduction (CO2R). Its activity and selectivity are highly facet-dependent. We recently examined the commonly proposed rate-limiting CO hydrogenation step on Cu(111) via embedded correlated wavefunction (ECW) theory and demonstrated that only this higher-level theory yields predictions consistent with potential-dependent experimental kinetics. Here, to understand the differing activities of Cu(111) and Cu(100) in catalyzing CO2R, we explore CO hydrogenation on Cu(100) using ECW theory. We predict that the preferred pathway involves the reduction of adsorbed CO (*CO) to *COH via proton-coupled electron transfer (PCET) at working potentials, although *CHO also may form with a kinetically accessible but higher barrier. In contrast, our earlier work on Cu(111) concluded that *COH and *CHO formation via PCET are equally feasible. This work illustrates one possible origin of the facet dependence of CO2R mechanisms and products on Cu electrodes and sheds light on how the selectivity of CO2R electrocatalysts can be controlled by the surface morphology.

Original languageEnglish (US)
Pages (from-to)10282-10290
Number of pages9
JournalJournal of Physical Chemistry Letters
Volume13
Issue number44
DOIs
StatePublished - Nov 10 2022

All Science Journal Classification (ASJC) codes

  • General Materials Science
  • Physical and Theoretical Chemistry

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