Atomically Dispersed Cu Catalysts on Sulfide-Derived Defective Ag Nanowires for Electrochemical CO₂ Reduction

Date

2023

Authors

Ma, Z.
Wan, T.
Zhang, D.
Yuwono, J.A.
Tsounis, C.
Jiang, J.
Chou, Y.-H.
Lu, X.
Kumar, P.V.
Ng, Y.H.

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Journal article

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ACS Nano, 2023; 17(3):2387-2398

Statement of Responsibility

Zhipeng Ma, Tao Wan, Ding Zhang, Jodie A. Yuwono, Constantine Tsounis, Junjie Jiang, Yu-Hsiang Chou, Xunyu Lu, Priyank V. Kumar, Yun Hau Ng, Dewei Chu, Cui Ying Toe, Zhaojun Han, and Rose Amal

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Abstract

Single-atom catalysts (SACs) have shown potential for achieving an efficient electrochemical CO2 reduction reaction (CO2RR) despite challenges in their synthesis. Here, Ag2S/Ag nanowires provide initial anchoring sites for Cu SACs (Cu/Ag2S/Ag), then Cu/Ag(S) was synthesized by an electrochemical treatment resulting in complete sulfur removal, i.e., Cu SACs on a defective Ag surface. The CO2RR Faradaic efficiency (FECO2RR) of Cu/Ag(S) reaches 93.0% at a CO2RR partial current density (jCO2RR) of 2.9 mA/cm2 under −1.0 V vs RHE, which outperforms sulfur-removed Ag2S/Ag without Cu SACs (Ag(S), 78.5% FECO2RR with 1.8 mA/cm2jCO2RR). At −1.4 V vs RHE, both FECO2RR and jCO2RR over Cu/Ag(S) reached 78.6% and 6.1 mA/cm2, which tripled those over Ag(S), respectively. As revealed by in situ and ex situ characterizations together with theoretical calculations, the interacted Cu SACs and their neighboring defective Ag surface increase microstrain and downshift the d-band center of Cu/Ag(S), thus lowering the energy barrier by ∼0.5 eV for *CO formation, which accounts for the improved CO2RR activity and selectivity toward related products such as CO and C2+ products.

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Published: February 2, 2023

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© 2023 American Chemical Society

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