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.
|Number of pages||9|
|Journal||Journal of the American Chemical Society|
|Publication status||Published - 2023 Feb 1|
Bibliographical noteFunding 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).
© 2023 American Chemical Society.
All Science Journal Classification (ASJC) codes
- Colloid and Surface Chemistry