Anionic Metal–Organic Framework Derived Cu Catalyst for Selective CO2 Electroreduction to Hydrocarbons

Abstract Metal–organic frameworks (MOFs)‐related Cu materials are promising candidates for promoting electrochemical CO 2 reduction to produce valuable chemical feedstocks. However, many MOF materials inevitable undergo reconstruction under reduction conditions; therefore, exploiting the restructuring of MOF materials is of importance for the rational design of high‐performance catalyst targeting multi‐carbon products (C 2 ). Herein, a facile solvent process is choosed to fabricate HKUST‐1 with an anionic framework (a‐HKUST‐1) and utilize it as a pre‐catalyst for alkaline CO 2 RR. The a‐HKUST‐1 catalyst can be electrochemically reduced into Cu with significant structural reconstruction under operating reaction conditions. The anionic HKUST‐1 derived Cu catalyst (aHD–Cu) delivers a FE C2H4 of 56% and FE C2 of ≈80% at −150 mA cm −2 in alkaline electrolyte. The resulting aHD‐Cu catalyst has a high electrochemically active surface area and low coordinated sites. In situ Raman spectroscopy indicates that the aHD–Cu surface displays higher coverage of *CO intermediates, which favors the production of hydrocarbons.