Revisiting Understanding of Electrochemical CO2 Reduction on Cu(111): Competing Proton-Coupled Electron Transfer Reaction Mechanisms Revealed by Embedded Correlated Wavefunction Theory
Abstract
Copper (Cu) electrodes, as the most efficacious of CO2 reduction reaction (CO2RR) electrocatalysts, serve as prototypes for determining and validating reaction mechanisms associated with electrochemical CO2 reduction to hydrocarbons. As in situ electrochemical mechanism determination by experiments is still out of reach, such mechanistic analysis typically is conducted using density functional theory (DFT). The semilocal exchange-correlation (XC) approximations most often used to model such catalysis unfortunately engender a basic error: predicting the wrong adsorption site for CO (a key CO2RR intermediate) on the most ubiquitous facet of Cu, namely, Cu(111). This longstanding inconsistency casts lingering doubt on previous DFT predictions of the attendant CO2RR kinetics. Here, we apply embedded correlated wavefunction (ECW) theory, which corrects XC functional error, to study the CO2RR on Cu(111) via both surface hydride (*H) transfer and proton-coupled electron transfer (PCET). We predict that adsorbed CO (*CO) reduces almost equally to two intermediates, namely, hydroxymethylidyne (*COH) and formyl (*CHO) at –0.9 V vs the RHE. In contrast, semilocal DFT approximations predict a strong preference for *COH. With increasing applied potential, the dominance of *COH (formed via potential-independent surface *H transfer) diminishes, switching to the competitive formation of both *CHO and *COH (both formed via potential-dependent PCET).more »
- Authors:
-
[2];
[3]
- Princeton Univ., NJ (United States)
- Univ. of California, Los Angeles, CA (United States)
- Princeton Univ., NJ (United States); Univ. of California, Los Angeles, CA (United States)
- Publication Date:
- Research Org.:
- Princeton Univ., NJ (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1808091
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 143; Journal Issue: 16; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 30 DIRECT ENERGY CONVERSION; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 36 MATERIALS SCIENCE; 54 ENVIRONMENTAL SCIENCES; Transfer reactions; free energy; proton coupled electron transfer; chemical structure; chemical reactions; electrochemistry
Citation Formats
Zhao, Qing, Martirez, John P., and Carter, Emily A. Revisiting Understanding of Electrochemical CO2 Reduction on Cu(111): Competing Proton-Coupled Electron Transfer Reaction Mechanisms Revealed by Embedded Correlated Wavefunction Theory. United States: N. p., 2021.
Web. doi:10.1021/jacs.1c00880.
Zhao, Qing, Martirez, John P., & Carter, Emily A. Revisiting Understanding of Electrochemical CO2 Reduction on Cu(111): Competing Proton-Coupled Electron Transfer Reaction Mechanisms Revealed by Embedded Correlated Wavefunction Theory. United States. https://doi.org/10.1021/jacs.1c00880
Zhao, Qing, Martirez, John P., and Carter, Emily A. Wed .
"Revisiting Understanding of Electrochemical CO2 Reduction on Cu(111): Competing Proton-Coupled Electron Transfer Reaction Mechanisms Revealed by Embedded Correlated Wavefunction Theory". United States. https://doi.org/10.1021/jacs.1c00880. https://www.osti.gov/servlets/purl/1808091.
@article{osti_1808091,
title = {Revisiting Understanding of Electrochemical CO2 Reduction on Cu(111): Competing Proton-Coupled Electron Transfer Reaction Mechanisms Revealed by Embedded Correlated Wavefunction Theory},
author = {Zhao, Qing and Martirez, John P. and Carter, Emily A.},
abstractNote = {Copper (Cu) electrodes, as the most efficacious of CO2 reduction reaction (CO2RR) electrocatalysts, serve as prototypes for determining and validating reaction mechanisms associated with electrochemical CO2 reduction to hydrocarbons. As in situ electrochemical mechanism determination by experiments is still out of reach, such mechanistic analysis typically is conducted using density functional theory (DFT). The semilocal exchange-correlation (XC) approximations most often used to model such catalysis unfortunately engender a basic error: predicting the wrong adsorption site for CO (a key CO2RR intermediate) on the most ubiquitous facet of Cu, namely, Cu(111). This longstanding inconsistency casts lingering doubt on previous DFT predictions of the attendant CO2RR kinetics. Here, we apply embedded correlated wavefunction (ECW) theory, which corrects XC functional error, to study the CO2RR on Cu(111) via both surface hydride (*H) transfer and proton-coupled electron transfer (PCET). We predict that adsorbed CO (*CO) reduces almost equally to two intermediates, namely, hydroxymethylidyne (*COH) and formyl (*CHO) at –0.9 V vs the RHE. In contrast, semilocal DFT approximations predict a strong preference for *COH. With increasing applied potential, the dominance of *COH (formed via potential-independent surface *H transfer) diminishes, switching to the competitive formation of both *CHO and *COH (both formed via potential-dependent PCET). Furthermore, our results also demonstrate the importance of including explicitly modeled solvent molecules in predicting electron-transfer barriers and reveal the pitfalls of overreliance on simple surface *H transfer models of reduction reactions.},
doi = {10.1021/jacs.1c00880},
journal = {Journal of the American Chemical Society},
number = 16,
volume = 143,
place = {United States},
year = {Wed Apr 14 00:00:00 EDT 2021},
month = {Wed Apr 14 00:00:00 EDT 2021}
}
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