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Title: Revisiting Competing Paths in Electrochemical CO2 Reduction on Copper via Embedded Correlated Wavefunction Theory

Abstract

We re-evaluate two key steps in the mechanism of CO2 reduction on copper at a higher level of theory capable of correcting inherent errors in density functional theory (DFT) approximations, namely, embedded correlated wavefunction (ECW) theory. Here, we consider the CO reduction step on Cu(111), which is critical to understanding reaction selectivity. Here, we optimize embedding potentials at the periodic plane-wave DFT level using density functional embedding theory (DFET). All possible adsorption sites (adsites) for each adsorbate then are screened with ECW theory at the catalytically active site to refine the local electronic structure. Unsurprisingly, DFT and ECW theory predict different adsite preferences, largely because of DFT’s inability to properly situate the CO 2π* level. Differing preferred adsites suggest that different reaction pathways could emerge from DFT versus ECW theory. Starting from these preferred ECW theory adsites, we then obtain reaction pathways at the plane-wave DFT level using the climbing-image nudged elastic band method to determine minimum energy paths. Thereafter, we perform ECW calculations at the catalytically active site to correct the energetics at each interpolated structure (image) along the reaction pathways. Via this approach, we confirm that the first step in CO reduction via hydrogen transfer on Cu(111) ismore » to form hydroxymethylidyne (*COH) instead of formyl (*CHO). Although the prediction to preferentially form *COH is consistent with that of DFT, the two theories predict quite different structural and mechanistic behaviors, suggesting that verification is needed for other parts of the mechanism of CO2 reduction, which is the subject of ongoing work.« less

Authors:
 [1]; ORCiD logo [2]
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  1. Princeton Univ., NJ (United States)
  2. 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:
1704062
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 16; Journal Issue: 10; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
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; Embedding; Adsorption; Metal clusters; Energy

Citation Formats

Zhao, Qing, and Carter, Emily A. Revisiting Competing Paths in Electrochemical CO2 Reduction on Copper via Embedded Correlated Wavefunction Theory. United States: N. p., 2020. Web. doi:10.1021/acs.jctc.0c00583.
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Zhao, Qing, & Carter, Emily A. Revisiting Competing Paths in Electrochemical CO2 Reduction on Copper via Embedded Correlated Wavefunction Theory. United States. https://doi.org/10.1021/acs.jctc.0c00583
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Zhao, Qing, and Carter, Emily A. Thu . "Revisiting Competing Paths in Electrochemical CO2 Reduction on Copper via Embedded Correlated Wavefunction Theory". United States. https://doi.org/10.1021/acs.jctc.0c00583. https://www.osti.gov/servlets/purl/1704062.
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@article{osti_1704062,
title = {Revisiting Competing Paths in Electrochemical CO2 Reduction on Copper via Embedded Correlated Wavefunction Theory},
author = {Zhao, Qing and Carter, Emily A.},
abstractNote = {We re-evaluate two key steps in the mechanism of CO2 reduction on copper at a higher level of theory capable of correcting inherent errors in density functional theory (DFT) approximations, namely, embedded correlated wavefunction (ECW) theory. Here, we consider the CO reduction step on Cu(111), which is critical to understanding reaction selectivity. Here, we optimize embedding potentials at the periodic plane-wave DFT level using density functional embedding theory (DFET). All possible adsorption sites (adsites) for each adsorbate then are screened with ECW theory at the catalytically active site to refine the local electronic structure. Unsurprisingly, DFT and ECW theory predict different adsite preferences, largely because of DFT’s inability to properly situate the CO 2π* level. Differing preferred adsites suggest that different reaction pathways could emerge from DFT versus ECW theory. Starting from these preferred ECW theory adsites, we then obtain reaction pathways at the plane-wave DFT level using the climbing-image nudged elastic band method to determine minimum energy paths. Thereafter, we perform ECW calculations at the catalytically active site to correct the energetics at each interpolated structure (image) along the reaction pathways. Via this approach, we confirm that the first step in CO reduction via hydrogen transfer on Cu(111) is to form hydroxymethylidyne (*COH) instead of formyl (*CHO). Although the prediction to preferentially form *COH is consistent with that of DFT, the two theories predict quite different structural and mechanistic behaviors, suggesting that verification is needed for other parts of the mechanism of CO2 reduction, which is the subject of ongoing work.},
doi = {10.1021/acs.jctc.0c00583},
journal = {Journal of Chemical Theory and Computation},
number = 10,
volume = 16,
place = {United States},
year = {Thu Aug 20 00:00:00 EDT 2020},
month = {Thu Aug 20 00:00:00 EDT 2020}
}
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