Highly Efficient Electroreduction of CO2 to Ethanol via Asymmetric C-C Coupling by a Metal-Organic Framework with Heterodimetal Dual Sites

The electroreduction of CO2 into value-added liquid fuels holds great promise for addressing global environmental and energy challenges. However, achieving highly selective yielding of multi-carbon oxygenates through the electrochemical CO2 reduction reaction (eCO(2)RR) is a formidable task, primarily due to the sluggish asymmetric C-C coupling reaction. In this study, a novel metal-organic framework (CuSn-HAB) with unprecedented heterometallic Sn<middle dot><middle dot><middle dot>Cu dual sites (namely, a pair of SnN2O2 and CuN4 sites bridged by mu-N atoms) was designed to overcome this limitation. CuSn-HAB demonstrated an impressive Faradic efficiency (FE) of 56(2)% for eCO(2)RR to alcohols, achieving a current density of 68 mA cm(-2) at a low potential of -0.57 V (vs RHE). Notably, no significant degradation was observed over a continuous 35 h operation at the specified current density. Mechanistic investigations revealed that, in comparison to the copper site, the SnN2O2 site exhibits a higher affinity for oxygen atoms. This enhanced affinity plays a pivotal role in facilitating the generation of the key intermediate *OCH2. Consequently, compared to homometallic Cu<middle dot><middle dot><middle dot>Cu dual sites (generally yielding ethylene product), the heterometallic dual sites were proved to be more thermodynamically favorable for the asymmetric C-C coupling between *CO and *OCH2, leading to the formation of the key intermediate *CO-*OCH2, which is favorable for yielding ethanol product.