Abstract
Ag is a promising catalyst for the production of carbon monoxide (CO) via the electrochemical reduction of carbon dioxide (CO2ER). Herein, we study the role of the formate (HCOO−) intermediate *OCHO, aiming to resolve the discrepancy between the theoretical understanding and experimental performance of Ag. We show that the first coupled proton-electron transfer (CPET) step in the CO pathway competes with the Volmer step for formation of *H, whereas this Volmer step is a prerequisite for the formation of *OCHO. We show that *OCHO should form readily on the Ag surface owing to solvation and favorable binding strength. In situ surface-enhanced Raman spectroscopy (SERS) experiments give preliminary evidence of the presence of O-bound bidentate species on polycrystalline Ag during CO2ER which we attribute to *OCHO. Lateral adsorbate interactions in the presence of *OCHO have a significant influence on the surface coverage of *H, resulting in the inhibition of HCOO− and H2 production and a higher selectivity towards CO.
Original language | English |
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Pages (from-to) | 1345-1349 |
Journal | Angewandte Chemie - International Edition |
Volume | 58 |
Issue number | 5 |
DOIs | |
Publication status | Published - 2019 |
Keywords
- adsorbate-adsorbate interactions
- DFT
- electrocatalysis
- in situ studies
- Raman spectroscopy
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Dive into the research topics of 'Lateral adsorbate interactions inhibit HCOO− while promoting CO selectivity for CO2 electrocatalysis on silver'. Together they form a unique fingerprint.Datasets
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Data underlying the research on CO2 electrocatalysis on Ag surfaces
Pidko, E. A. (Creator), Li, G. (Creator), Bohra, D. (Creator) & Smith, W. A. (Creator), TU Delft - 4TU.ResearchData, 14 Aug 2020
DOI: 10.4121/12789893
Dataset/Software: Dataset