Transplanting Gold Active Sites into Non-Precious-Metal Nanoclusters for Efficient CO2-to-CO Electroreduction

Hoeun Seong; Yongsung Jo; Vladimir Efremov; Yujin Kim; Sojung Park; Sang Myeong Han; Kiyoung Chang; Jiwoo Park; Woojun Choi; Wooyul Kim; Chang Hyuck Choi; Jong Suk Yoo; Dongil Lee

doi:10.1021/jacs.2c09170

Transplanting Gold Active Sites into Non-Precious-Metal Nanoclusters for Efficient CO₂-to-CO Electroreduction

Hoeun Seong, Yongsung Jo, Vladimir Efremov, Yujin Kim, Sojung Park, Sang Myeong Han, Kiyoung Chang, Jiwoo Park, Woojun Choi, Wooyul Kim, Chang Hyuck Choi, Jong Suk Yoo, Dongil Lee

Department of Chemistry

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

Abstract

Electrocatalytic CO₂ reduction reaction (CO₂RR) is greatly facilitated by Au surfaces. However, large fractions of underlying Au atoms are generally unused during the catalytic reaction, which limits mass activity. Herein, we report a strategy for preparing efficient electrocatalysts with high mass activities by the atomic-level transplantation of Au active sites into a Ni₄ nanocluster (NC). While the Ni₄ NC exclusively produces H₂, the Au-transplanted NC selectively produces CO over H₂. The origin of the contrasting selectivity observed for this NC is investigated by combining operando and theoretical studies, which reveal that while the Ni sites are almost completely blocked by the CO intermediate in both NCs, the Au sites act as active sites for CO₂-to-CO electroreduction. The Au-transplanted NC exhibits a remarkable turnover frequency and mass activity for CO production (206 mol_CO/mol_NC/s and 25,228 A/g_Au, respectively, at an overpotential of 0.32 V) and high durability toward the CO₂RR over 25 h.

Original language	English
Pages (from-to)	2152-2160
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	145
Issue number	4
DOIs	https://doi.org/10.1021/jacs.2c09170
Publication status	Published - 2023 Feb 1

Bibliographical note

Funding Information:
This work was supported by the National Research Foundation of Korea (NRF) grants (nos. NRF-2022R1A2C3003610, 2021R1A5A1030054, and NRF-2021R1A5A1084921) and the Carbon-to-X Project (Project No. 2020M3H7A1096388 and 2021M3H7A1026177) through the NRF funded by the Korea government (MSIT). DFT calculations were performed using the computational resources in the Korea Institute of Science and Technology Information (KSC-2021-CRE-0532). The computational part of the work was supported by the 2021 Research Fund of the University of Seoul. This work was also partially supported by MSIT and the Pohang Accelerator Laboratory (PAL), Korea (2022-2nd-2D-002, 2022-3rd-8C-038).

Publisher Copyright:
© 2023 American Chemical Society.

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/jacs.2c09170

Cite this

@article{c58bcb816fcf49b1a7d7a0cc72228a55,

title = "Transplanting Gold Active Sites into Non-Precious-Metal Nanoclusters for Efficient CO2-to-CO Electroreduction",

abstract = "Electrocatalytic CO2 reduction reaction (CO2RR) is greatly facilitated by Au surfaces. However, large fractions of underlying Au atoms are generally unused during the catalytic reaction, which limits mass activity. Herein, we report a strategy for preparing efficient electrocatalysts with high mass activities by the atomic-level transplantation of Au active sites into a Ni4 nanocluster (NC). While the Ni4 NC exclusively produces H2, the Au-transplanted NC selectively produces CO over H2. The origin of the contrasting selectivity observed for this NC is investigated by combining operando and theoretical studies, which reveal that while the Ni sites are almost completely blocked by the CO intermediate in both NCs, the Au sites act as active sites for CO2-to-CO electroreduction. The Au-transplanted NC exhibits a remarkable turnover frequency and mass activity for CO production (206 molCO/molNC/s and 25,228 A/gAu, respectively, at an overpotential of 0.32 V) and high durability toward the CO2RR over 25 h.",

author = "Hoeun Seong and Yongsung Jo and Vladimir Efremov and Yujin Kim and Sojung Park and Han, {Sang Myeong} and Kiyoung Chang and Jiwoo Park and Woojun Choi and Wooyul Kim and Choi, {Chang Hyuck} and Yoo, {Jong Suk} and Dongil Lee",

note = "Funding Information: This work was supported by the National Research Foundation of Korea (NRF) grants (nos. NRF-2022R1A2C3003610, 2021R1A5A1030054, and NRF-2021R1A5A1084921) and the Carbon-to-X Project (Project No. 2020M3H7A1096388 and 2021M3H7A1026177) through the NRF funded by the Korea government (MSIT). DFT calculations were performed using the computational resources in the Korea Institute of Science and Technology Information (KSC-2021-CRE-0532). The computational part of the work was supported by the 2021 Research Fund of the University of Seoul. This work was also partially supported by MSIT and the Pohang Accelerator Laboratory (PAL), Korea (2022-2nd-2D-002, 2022-3rd-8C-038). Publisher Copyright: {\textcopyright} 2023 American Chemical Society.",

year = "2023",

month = feb,

day = "1",

doi = "10.1021/jacs.2c09170",

language = "English",

volume = "145",

pages = "2152--2160",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

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T1 - Transplanting Gold Active Sites into Non-Precious-Metal Nanoclusters for Efficient CO2-to-CO Electroreduction

AU - Seong, Hoeun

AU - Jo, Yongsung

AU - Efremov, Vladimir

AU - Kim, Yujin

AU - Park, Sojung

AU - Han, Sang Myeong

AU - Chang, Kiyoung

AU - Park, Jiwoo

AU - Choi, Woojun

AU - Kim, Wooyul

AU - Choi, Chang Hyuck

AU - Yoo, Jong Suk

AU - Lee, Dongil

N1 - Funding Information: This work was supported by the National Research Foundation of Korea (NRF) grants (nos. NRF-2022R1A2C3003610, 2021R1A5A1030054, and NRF-2021R1A5A1084921) and the Carbon-to-X Project (Project No. 2020M3H7A1096388 and 2021M3H7A1026177) through the NRF funded by the Korea government (MSIT). DFT calculations were performed using the computational resources in the Korea Institute of Science and Technology Information (KSC-2021-CRE-0532). The computational part of the work was supported by the 2021 Research Fund of the University of Seoul. This work was also partially supported by MSIT and the Pohang Accelerator Laboratory (PAL), Korea (2022-2nd-2D-002, 2022-3rd-8C-038). Publisher Copyright: © 2023 American Chemical Society.

PY - 2023/2/1

Y1 - 2023/2/1

N2 - Electrocatalytic CO2 reduction reaction (CO2RR) is greatly facilitated by Au surfaces. However, large fractions of underlying Au atoms are generally unused during the catalytic reaction, which limits mass activity. Herein, we report a strategy for preparing efficient electrocatalysts with high mass activities by the atomic-level transplantation of Au active sites into a Ni4 nanocluster (NC). While the Ni4 NC exclusively produces H2, the Au-transplanted NC selectively produces CO over H2. The origin of the contrasting selectivity observed for this NC is investigated by combining operando and theoretical studies, which reveal that while the Ni sites are almost completely blocked by the CO intermediate in both NCs, the Au sites act as active sites for CO2-to-CO electroreduction. The Au-transplanted NC exhibits a remarkable turnover frequency and mass activity for CO production (206 molCO/molNC/s and 25,228 A/gAu, respectively, at an overpotential of 0.32 V) and high durability toward the CO2RR over 25 h.

AB - Electrocatalytic CO2 reduction reaction (CO2RR) is greatly facilitated by Au surfaces. However, large fractions of underlying Au atoms are generally unused during the catalytic reaction, which limits mass activity. Herein, we report a strategy for preparing efficient electrocatalysts with high mass activities by the atomic-level transplantation of Au active sites into a Ni4 nanocluster (NC). While the Ni4 NC exclusively produces H2, the Au-transplanted NC selectively produces CO over H2. The origin of the contrasting selectivity observed for this NC is investigated by combining operando and theoretical studies, which reveal that while the Ni sites are almost completely blocked by the CO intermediate in both NCs, the Au sites act as active sites for CO2-to-CO electroreduction. The Au-transplanted NC exhibits a remarkable turnover frequency and mass activity for CO production (206 molCO/molNC/s and 25,228 A/gAu, respectively, at an overpotential of 0.32 V) and high durability toward the CO2RR over 25 h.

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