Promoting CO2-to-CO Electroreduction via the Active-Site Engineering of Atomically Precise Silver Nanoclusters

Hoeun Seong; Minji Choi; Sojung Park; Hyun Woo Kim; Jiyoung Kim; Wooyul Kim; Jong Suk Yoo; Dongil Lee

doi:10.1021/acsenergylett.2c02018

Promoting CO₂-to-CO Electroreduction via the Active-Site Engineering of Atomically Precise Silver Nanoclusters

Hoeun Seong, Minji Choi, Sojung Park, Hyun Woo Kim, Jiyoung Kim, Wooyul Kim, Jong Suk Yoo, Dongil Lee

Department of Chemical Engineering

Research output: Contribution to journal › Article › peer-review

27 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	4177-4184
Number of pages	8
Journal	ACS Energy Letters
Volume	7
Issue number	12
DOIs	https://doi.org/10.1021/acsenergylett.2c02018
State	Published - 9 Dec 2022

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@article{5013f2474eb040718d46febd40a911dc,

title = "Promoting CO2-to-CO Electroreduction via the Active-Site Engineering of Atomically Precise Silver Nanoclusters",

abstract = "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.",

author = "Hoeun Seong and Minji Choi and Sojung Park and Kim, {Hyun Woo} and Jiyoung Kim and Wooyul Kim and Yoo, {Jong Suk} and Dongil Lee",

year = "2022",

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doi = "10.1021/acsenergylett.2c02018",

language = "English",

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journal = "ACS Energy Letters",

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T1 - Promoting CO2-to-CO Electroreduction via the Active-Site Engineering of Atomically Precise Silver Nanoclusters

AU - Seong, Hoeun

AU - Choi, Minji

AU - Park, Sojung

AU - Kim, Hyun Woo

AU - Kim, Jiyoung

AU - Kim, Wooyul

AU - Yoo, Jong Suk

AU - Lee, Dongil

PY - 2022/12/9

Y1 - 2022/12/9

N2 - 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.

AB - 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.

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Promoting CO₂-to-CO Electroreduction via the Active-Site Engineering of Atomically Precise Silver Nanoclusters

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