| Autor: |
Rebstock JA; Department of Chemistry and Biochemistry, The Ohio State University Columbus Ohio 43210 USA baker.2364@osu.edu., Zhu Q; Department of Chemistry and Biochemistry, The Ohio State University Columbus Ohio 43210 USA baker.2364@osu.edu., Baker LR; Department of Chemistry and Biochemistry, The Ohio State University Columbus Ohio 43210 USA baker.2364@osu.edu. |
| Jazyk: |
angličtina |
| Zdroj: |
Chemical science [Chem Sci] 2022 Jun 15; Vol. 13 (25), pp. 7634-7643. Date of Electronic Publication: 2022 Jun 15 (Print Publication: 2022). |
| DOI: |
10.1039/d2sc01878k |
| Abstrakt: |
Hydrated cations present in the electrochemical double layer (EDL) are known to play a crucial role in electrocatalytic CO 2 reduction (CO 2 R), and numerous studies have attempted to explain how the cation effect contributes to the complex CO 2 R mechanism. CO 2 R is a structure sensitive reaction, indicating that a small fraction of total surface sites may account for the majority of catalytic turnover. Despite intense interest in specific cation effects, probing site-specific, cation-dependent solvation structures remains a significant challenge. In this work, CO adsorbed on Au is used as a vibrational Stark reporter to indirectly probe solvation structure using vibrational sum frequency generation (VSFG) spectroscopy. Two modes corresponding to atop adsorption of CO are observed with unique frequency shifts and potential-dependent intensity profiles, corresponding to direct adsorption of CO to inactive surface sites, and in situ generated CO produced at catalytic active sites. Analysis of the cation-dependent Stark tuning slopes for each of these species provides estimates of the hydrated cation radius upon adsorption to active and inactive sites on the Au electrode. While cations are found to retain their bulk hydration shell upon adsorption at inactive sites, catalytic active sites are characterized by a single layer of water between the Au surface and the electrolyte cation. We propose that the drastic increase in catalytic performance at active sites stems from this unique solvation structure at the Au/electrolyte interface. Building on this evidence of a site-specific EDL structure will be critical to understand the connection between cation-dependent interfacial solvation and CO 2 R performance.
Competing Interests: The authors declare no competing financial interest.
(This journal is © The Royal Society of Chemistry.) |
| Databáze: |
MEDLINE |
| Externí odkaz: |
|
