Copper‐Silver Bimetallic Metal‐Covalent Organic Frameworks with Unique Intermediate Interlayer Transfer Effects for Enhanced Electrocatalytic CO 2 to Ethylene Conversion

Abstract The electrochemical reduction of CO 2 to ethylene (C 2 H 4 ) offers a promising approach to mitigating greenhouse gas emissions while generating high‐value chemical products. However, achieving both high C 2 H 4 selectivity and long‐term catalyst stability remains a significant challenge for single‐atom catalysts, primarily due to the absence of adjacent active sites required for the coupling of reaction intermediates. Herein, a bimetallic metal‐covalent organic framework (MCOF) with precisely tunable Cu‐Ag spatial configurations was developed to enhance CO 2 ‐to‐C 2 H 4 conversion through a synergistic catalytic mechanism. By optimizing the Cu/Ag molar ratio to 1:1 (Ag 0.5 Cu 0.5 ‐CTC‐TAPT), the catalyst achieves a Faradaic efficiency for C 2 H 4 (FE(C 2 H 4 )) of 51.5% ± 0.9% at a reduction potential of ‐1.774 V versus (vs.) RHE, along with a current density of 439.0 ± 7.3 mA cm −2 and excellent stability (FE(C 2 H 4 ) > 40% over 10 h), outperforming most single‐metal M/COFs and MOF‐based electrocatalysts that predominantly yield C1 products. In situ spectroscopic analysis and mechanistic studies indicate that Ag sites primarily facilitate CO generation, while neighboring Cu sites promote C─C bond formation. This work introduces a novel design strategy for constructing COF‐based materials with adjacent heterogeneous metal active sites, highlighting their significant potential for the electrochemical conversion of CO 2 into valuable C2+ chemicals.