Trinuclear Cu(I) Metal–Organic Framework Inspires the Activation of *CO2 Via Electrostatic Tension to Boost the Electrochemical Conversion of CO2‐to‐Methanol

The metal-organic frameworks (MOFs) as favorable candidates, are applied to the reduction reaction of CO₂ due to the unique affinity for CO₂ molecules and abundant monometallic active sites. However, most MOF-based electrocatalysts require a carbonization process to overcome their potentially poor conductivity and inert catalytic activity. Here, a semiconducting trinuclear Cu(I)-MOF undergone low-temperature activation (CuTz-1-300) is directly employed as an electrocatalyst for producing methanol. The CuTz-1-300 achieves a methanol faradaic efficiency of 56.41% at the working potential of -0.97 V versus the reversible hydrogen electrode in 0.5 m KHCO₃ electrolyte. The experiments and DFT calculations imply that the generation of ^*COOH is the rate-determining step for methanol, and ^*CO prefers to be further reduced instead of releasing as a CO product. Specifically, the unique CuN₃ is correspond to nearby BF_4, ^- producing subtle synergistic electronic effects that CO₂ binding with a relatively strong C···F interaction to BF₄ ^- and weak C─H···O interactions from phenyl groups to enhance the localized CO₂ concentration by electrostatic tension. This work demonstrates the use of ionic MOF with positive univalent Cu to improve the efficiency of electrocatalytic CO₂ reduction.