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Solvent-mediated outer-sphere CO 2 electro-reduction mechanism over the Ag111 surface.
- Source :
-
Chemical science [Chem Sci] 2022 Feb 24; Vol. 13 (13), pp. 3803-3808. Date of Electronic Publication: 2022 Feb 24 (Print Publication: 2022). - Publication Year :
- 2022
-
Abstract
- The electrocatalytic CO <subscript>2</subscript> reduction reaction (CO <subscript>2</subscript> RR) is one of the key technologies of the clean energy economy. Molecular-level understanding of the CO <subscript>2</subscript> RR process is instrumental for the better design of electrodes operable at low overpotentials with high current density. The catalytic mechanism underlying the turnover and selectivity of the CO <subscript>2</subscript> RR is modulated by the nature of the electrocatalyst, as well as the electrolyte liquid, and its ionic components that form the electrical double layer (EDL). Herein we demonstrate the critical non-innocent role of the EDL for the activation and conversion of CO <subscript>2</subscript> at a high cathodic bias for electrocatalytic conversion over a silver surface as a representative low-cost model cathode. By using a multiscale modeling approach we demonstrate that under such conditions a dense EDL is formed, which hinders the diffusion of CO <subscript>2</subscript> towards the Ag111 electrocatalyst surface. By combining DFT calculations and ab initio molecular dynamics simulations we identify favorable pathways for CO <subscript>2</subscript> reduction directly over the EDL without the need for adsorption to the catalyst surface. The dense EDL promotes homogeneous phase reduction of CO <subscript>2</subscript> via electron transfer from the surface to the electrolyte. Such an outer-sphere mechanism favors the formation of formate as the CO <subscript>2</subscript> RR product. The formate can undergo dehydration to CO via a transition state stabilized by solvated alkali cations in the EDL.<br />Competing Interests: There are no conflicts to declare.<br /> (This journal is © The Royal Society of Chemistry.)
Details
- Language :
- English
- ISSN :
- 2041-6520
- Volume :
- 13
- Issue :
- 13
- Database :
- MEDLINE
- Journal :
- Chemical science
- Publication Type :
- Academic Journal
- Accession number :
- 35432905
- Full Text :
- https://doi.org/10.1039/d1sc07119j