Room‐Temperature Rapid Synthesis of Crystalline Ag─C Coordinated MOFs for Highly Efficient Acidic CO 2 Electroreduction

ABSTRACT The acidic CO 2 electroreduction reaction (eCO 2 RR) shows great promise in addressing carbonation issues encountered under neutral/alkaline conditions. However, it remains challenged by low selectivity arising from high proton availability, as well as catalyst degradation due to the corrosive and reductive nature of acidic media. In this work, we demonstrate a room‐temperature and rapid (< 5 min) synthesis of a novel crystalline Ag–C coordinated metal‐organic framework (TEPT‐AgC‐MOF) employing 4′‐(4‐ethynylphenyl)‐2,2′:6′,2″‐terpyridine as the ligand, enabling gram‐scale production. The incorporation of strongly covalent Ag–C bonds significantly enhances the structural stability of the catalyst under acidic conditions. Moreover, the triazine‐containing ligands in conjunction with a modulated electronic structure collectively enhance CO 2 adsorption, activation, and reduction efficiency. The resulting catalyst delivers outstanding eCO 2 RR performance in acid, achieving a CO Faradaic efficiency of 94.5%, a partial current density of 417.5 mA·cm −2 , and a turnover frequency (TOF) of 7357 h −1 , surpassing those of most reported Ag‐based acidic catalysts. Notably, this study not only establishes a facile route for synthesizing Ag‐MOFs, but also constitutes the first investigation into crystalline Ag–C coordinated MOFs as electrocatalysts for the acidic eCO 2 RR.