Ag Atom Induces Microstrain Environment around Cd Sites to Construct Diatomic Sites for Almost 100% CO<sub>2</sub>-to-CO Electroreduction.

Hua, Jiahui; Dai, Zhongqin; Cheng, Kehao; Wang, Zhongliao; Shao, Chunfeng; Jiang, Yong; Dai, Kai; Wang, Lei · Nano Lett · 2024

basic_science · Level V

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Abstract

Deeply understanding how local microstrain environment around diatomic sites influences their electronic state and adsorption is crucial for improving electrochemical CO<sub>2</sub> reduction (eCO<sub>2</sub>R) reaction; however, precise engineering of the atomic microstrain environment is challenging. Herein, we fabricate Ag-CdTMT electrocatalysts with AgN<sub>2</sub>S<sub>2</sub>-CdN<sub>2</sub>S<sub>2</sub> diatomic sites by anchoring Ag to the nodes of CdTMT (TMT = 2,4,6-trimercaptotriazine anion) coordination polymers. The Ag-CdTMT catalysts achieve approximately 100% Faradaic efficiency for CO reduction with an industrial level current density (∼200 mA cm<sup>-2</sup> in H-cell). The embedded Ag atoms induce the formation of Ag-Cd diatomic sites with local microstrain, stretching Cd-N/S bonds, and reinforcing electron localization at Cd sites. The microstrain engineering and adjacent Ag atoms synergistically reduced Cd 4d-C 2p antibonding orbital occupancy for intensifying *COOH adsorption as the rate-determining step. This study provides novel insights into customizing the electronic structure of diatomic sites through strain engineering.