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<p>Critical influence of local active-site concentration and configuration on CO<sub>2</sub> reduction selectivity remains rarely explored, due to the challenge in constructing well-defined structures. In this study, we employ a molten salt-assisted strategy to synthesize Ce-O<sub>V</sub>-Cu cascade catalyst with tunable configurations and relative concentrations of Cu and Ce-O<sub>V</sub> sites. Two distinct geometries were constructed: one featuring dense Cu sites surrounding Ce-O<sub>V</sub>, and another with isolated Cu centers encapsulated by Ce-O<sub>V</sub>. These configurations effectively direct the key *CHO or *COH intermediates toward either coupling with *CO or hydrogenation with *H, thereby switching product selectivity. The CuCe<sub>10</sub>O<sub><i>x</i></sub> catalyst with isolated copper centers achieves a high CH<sub>4</sub> Faradaic efficiency (FE) of 61.7% at −1.6 V vs. reversible hydrogen electrode (RHE), whereas the local Cu-rich Cu<sub>10</sub>CeO<sub><i>x</i></sub> variant favors C<sub>2</sub> production with a maximum FE of 61.5% at −1.4 V vs. RHE. Mechanistic studies reveal that locally concentrated Cu sites exhibit strong *CO<sub>2</sub> binding affinity, enhancing *CO surface coverage and facilitating *CO–*COH coupling; while Ce-O<sub>V</sub>-rich regions with isolated copper center supply abundant availability *H, promoting deep protonation of *CHO intermediate toward CH<sub>4</sub>. This work offers valuable insights into catalyst design, where manipulating structural chemistry guides catalytic processes toward targeted CO<sub>2</sub>RR products.</p>

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Active site concentration steers the reaction pathway of CO2 electroreduction

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年5月21日

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  • Xiaoyue Zhu,
  • Zijian Li,
  • Yuhang Zhang,
  • Yanru Geng,
  • Min Gyu Kim,
  • Haeseong Jang,
  • Shangguo Liu,
  • Xien Liu,
  • Qing Qin

摘要

Critical influence of local active-site concentration and configuration on CO2 reduction selectivity remains rarely explored, due to the challenge in constructing well-defined structures. In this study, we employ a molten salt-assisted strategy to synthesize Ce-OV-Cu cascade catalyst with tunable configurations and relative concentrations of Cu and Ce-OV sites. Two distinct geometries were constructed: one featuring dense Cu sites surrounding Ce-OV, and another with isolated Cu centers encapsulated by Ce-OV. These configurations effectively direct the key *CHO or *COH intermediates toward either coupling with *CO or hydrogenation with *H, thereby switching product selectivity. The CuCe10Ox catalyst with isolated copper centers achieves a high CH4 Faradaic efficiency (FE) of 61.7% at −1.6 V vs. reversible hydrogen electrode (RHE), whereas the local Cu-rich Cu10CeOx variant favors C2 production with a maximum FE of 61.5% at −1.4 V vs. RHE. Mechanistic studies reveal that locally concentrated Cu sites exhibit strong *CO2 binding affinity, enhancing *CO surface coverage and facilitating *CO–*COH coupling; while Ce-OV-rich regions with isolated copper center supply abundant availability *H, promoting deep protonation of *CHO intermediate toward CH4. This work offers valuable insights into catalyst design, where manipulating structural chemistry guides catalytic processes toward targeted CO2RR products.