Enhancing chemical stability and catalytic ability of <scp>MOF</scp> ‐303 and Al‐ <scp>TCPP</scp> over electrochemical <scp>CO</scp> ₂ reduction: Insights into Cu and Co metalation

Abstract The electrochemical reduction of CO 2 (eCO 2 RR) presents a promising strategy for mitigating carbon emissions while generating valuable fuels and chemicals. However, the limited chemical stability of metal–organic frameworks (MOFs) in electrochemical environments remains a significant challenge. This study explores the structural robustness and catalytic performance of MOF‐303 and Al‐TCPP frameworks, modified via Cu and Co metalation, for CO 2 reduction applications. A comprehensive investigation of their physicochemical properties, electrochemical stability across diverse electrolyte conditions, and catalytic efficiency was conducted. Structural integrity was analyzed using powder x‐ray diffraction, scanning electron microscopy, Brunauer–Emmett–Teller, x‐ray photoelectron spectroscopic, and x‐ray absorption spectroscopic techniques, revealing improved stability and electronic tuning upon metalation. Electrochemical studies demonstrated that Cu‐functionalized materials favored hydrocarbon production (CH 4 , C 2 H 4 ), whereas Co‐modified catalysts exhibited high selectivity toward CO formation with suppressed hydrogen evolution. Stability assessments across a broad pH range confirmed superior resilience of Cu‐modified MOFs, particularly in neutral and mild alkaline environments. The findings highlight the critical role of post‐synthetic metalation in enhancing MOF stability and catalytic selectivity, paving the way for scalable and durable MOF‐based eCO 2 RR technologies. This work provides valuable insights into rational MOF design strategies for efficient CO 2 electroreduction, contributing to sustainable carbon conversion pathways.