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In situ spectroelectrochemical probing of CO redox landscape on copper single-crystal surfaces


Shao, Feng; Wong, Jun Kit; Low, Qi Hang; Iannuzzi, Marcella; Li, Jingguo; Lan, Jinggang (2022). In situ spectroelectrochemical probing of CO redox landscape on copper single-crystal surfaces. Proceedings of the National Academy of Sciences of the United States of America, 119(29):e2118166119.

Abstract

Electrochemical reduction of CO$_{(2)}$to value-added chemicals and fuels is a promising strategy to sustain pressing renewable energy demands and to address climate change issues. Direct observation of reaction intermediates during the CO$_{(2)}$reduction reaction will contribute to mechanistic understandings and thus promote the design of catalysts with the desired activity, selectivity, and stability. Herein, we combined in situ electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy and ab initio molecular dynamics calculations to investigate the CORR process on Cu single-crystal surfaces in various electrolytes. Competing redox pathways and coexistent intermediates of CO adsorption (*CO$_{atop}$and *CO$_{bridge}$), dimerization (protonated dimer *HOCCOH and its dehydrated *CCO), oxidation (*CO$_{2}$$^{−}$and *CO$_{3}$$^{2−}$), and hydrogenation (*CHO), as well as Cu-O$_{ad}$/Cu-OH$_{ad}$species at Cu-electrolyte interfaces, were simultaneously identified using in situ spectroscopy and further confirmed with isotope-labeling experiments. With AIMD simulations, we report accurate vibrational frequency assignments of these intermediates based on the calculated vibrational density of states and reveal the corresponding species in the electrochemical CO redox landscape on Cu surfaces. Our findings provide direct insights into key intermediates during the CO$_{(2)}$RR and offer a full-spectroscopic tool (40–4,000 cm$^{−1}$) for future mechanistic studies.

Abstract

Electrochemical reduction of CO$_{(2)}$to value-added chemicals and fuels is a promising strategy to sustain pressing renewable energy demands and to address climate change issues. Direct observation of reaction intermediates during the CO$_{(2)}$reduction reaction will contribute to mechanistic understandings and thus promote the design of catalysts with the desired activity, selectivity, and stability. Herein, we combined in situ electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy and ab initio molecular dynamics calculations to investigate the CORR process on Cu single-crystal surfaces in various electrolytes. Competing redox pathways and coexistent intermediates of CO adsorption (*CO$_{atop}$and *CO$_{bridge}$), dimerization (protonated dimer *HOCCOH and its dehydrated *CCO), oxidation (*CO$_{2}$$^{−}$and *CO$_{3}$$^{2−}$), and hydrogenation (*CHO), as well as Cu-O$_{ad}$/Cu-OH$_{ad}$species at Cu-electrolyte interfaces, were simultaneously identified using in situ spectroscopy and further confirmed with isotope-labeling experiments. With AIMD simulations, we report accurate vibrational frequency assignments of these intermediates based on the calculated vibrational density of states and reveal the corresponding species in the electrochemical CO redox landscape on Cu surfaces. Our findings provide direct insights into key intermediates during the CO$_{(2)}$RR and offer a full-spectroscopic tool (40–4,000 cm$^{−1}$) for future mechanistic studies.

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Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Health Sciences > Multidisciplinary
Uncontrolled Keywords:Multidisciplinary
Language:English
Date:19 July 2022
Deposited On:14 Jul 2023 09:45
Last Modified:29 Jun 2024 01:37
Publisher:National Academy of Sciences
ISSN:0027-8424
OA Status:Hybrid
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1073/pnas.2118166119
PubMed ID:35858341
  • Content: Published Version
  • Language: English
  • Licence: Creative Commons: Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)