Rational Fluorination of Pyrazolate MOFs: Unlocking High‐Efficiency Acetate Electrosynthesis via CO Reduction

ABSTRACT Electrochemical carbon monoxide reduction (eCORR) to acetate, an indispensable molecular scaffold, represents a paradigm‐shifting strategy for the synthesis of acetate under ambient conditions. The pursuit of advanced electrocatalytic systems enabling efficient multi‐electron transfer pathways remains critical to achieve selective eCORR toward sustainable acetate synthesis. In this study, one fluorine‐substituted pyrazole‐based metal–organic framework (CuPz‐F) was obtained. It showed an outstanding eCORR performance, achieving a remarkable C 2+ Faradaic efficiency of 83.5% and an acetate FE of 45.8%, corresponding to a high acetate partial current density of 249.7 mA cm −2 and a turnover frequency of 1131 h −1 . Comprehensive mechanistic studies demonstrate that pyrazole ligands shorten Cu─Cu distances, lowering the energy barrier for C─C coupling. Concurrently, fluorine substitution electronically stabilizes Cu 2+ centers, thereby strengthening CO adsorption—an essential prerequisite for C─C bond formation. Moreover, F substituents promote water dissociation and enable hydrogen spillover to adjacent Cu sites. Together, electronic modulation, optimized Cu─Cu proximity, and hydrogen spillover synergistically underpin the enhanced eCORR activity toward acetate production. This work provides new insights into the influence of the F substituent in the MOFs' electrocatalysts on eCORR performance, and is highly instructive for the rational design of next‐generation, high‐efficiency electrocatalysts for CO.