Atomically precise metal nanoclusters (NCs) are promising catalysts for the electrochemical CO2reduction reaction (CO2RR) and are effective model catalysts for the identification of active sites. We report the metal-dependent CO2RR activities of Au25(SR)18and Ag25(SR)18(SR = thiolate). While both NCs produced CO as a main CO2RR product, the Au25NC exhibited a significantly higher CO2RR activity than the Ag25NC. Theoretical and operando studies revealed that the CO2RR limiting potential for the Au25NC was significantly smaller than that for the Ag25NC, while both NCs contained the partially dethiolated metal sites as the active sites. Active-site engineering was performed by replacing the Ag12(SR)18shell of the Ag25(SR)18NC with the Au12(SR)18shell to generate a core-shell AuAg12@Au12(SR)18NC, which exhibited dramatically enhanced CO2RR activity compared with the Ag25(SR)18NC. The AuAg12@Au12NCs exhibited stable CO2-to-CO electroreduction at a commercially relevant current density of 200 mA/cm2and a full-cell potential of 2.1 V in a zero-gap CO2electrolyzer.
|Number of pages||8|
|Journal||ACS Energy Letters|
|Publication status||Published - 2022 Dec 9|
Bibliographical noteFunding Information:
This work was supported by the National Research Foundation of Korea (NRF) (Grants No. NRF-2022R1A2C3003610 and NRF-2021R1A5A1084921) and the Carbon-to-X Project (Project No. 2020M3H7A1096388 and 2021M3H7A1026177) through the NRF funded by the Korean government (MSIT). DFT calculations were performed using the computational resources in the Korea Institute of Science and Technology Information (KSC-2021-CRE-0532).
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All Science Journal Classification (ASJC) codes
- Chemistry (miscellaneous)
- Renewable Energy, Sustainability and the Environment
- Fuel Technology
- Energy Engineering and Power Technology
- Materials Chemistry