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

Metal–organic frameworks (MOFs)‐related Cu materials are promising candidates for promoting electrochemical CO2 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 (C2). 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 CO2RR. 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 FEC2H4 of 56% and FEC2 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. Anionic HKUST‐1 (a‐HKUST‐1) as a pre‐catalyst for CO2 reduction reaction, which can be reconstructed into metallic Cu with low coordinated sites under operation conditions, delivers an ethylene faradaic efficiency of 56% and multi‐carbon products faradaic efficiency of ≈80% at a current density of 150 mA cm−2 in a flow cell.