CuO (111) Microcrystalline Evoked Indium–Organic Framework for Efficient Electroreduction of CO2 to Formate

Abstract Electrochemical reduction of carbon dioxide (CO 2 RR) to formate is economically beneficial but suffers from poor selectivity and high overpotential. Herein, enriched microcrystalline copper oxide is introduced on the surface of indium‐based metal–organic frameworks. Benefiting from the CuO (111) microcrystalline shell and formed catalytic active In–Cu interfaces, the obtained MIL‐68(In)/CuO heterostructure display excellent CO 2 RR to formate with a Faradaic efficiency (FE) as high as 89.7% at low potential of only −0.7 V vs. RHE in a flow cell. Significantly, the membrane electrode assembly (MEA) cell based on MIL‐68(In)/CuO exhibit a remarkable current density of 640.3 mA cm −2 at 3.1 V and can be stably operated for 180 h at 2.7 V with a current density of 200 mA cm −2 . The ex/in situ electrochemical investigations reveal that the introduction of CuO increases the formation rate of the carbon dioxide reduction intermediate * HCOO − and inhibits the competitive hydrogen evolution reaction. This work not only provides an in‐depth study of the mechanism of the CO 2 RR pathways on In/Cu composite catalyst but also offers an effective strategy for the interface design of electrocatalytic carbon dioxide reduction reaction.