Metal–Organic Framework Supported Low-Nuclearity Cluster Catalysts for Highly Selective Carbon Dioxide Electroreduction to Ethanol

It is still a great challenge to achieve high selectivity of ethanol in CO₂ electroreduction reactions (CO₂RR) because of the similar reduction potentials and lower energy barrier of possible other C₂₊ products. Here, we report a MOF-based supported low-nuclearity cluster catalysts (LNCCs), synthesized by electrochemical reduction of three-dimensional (3D) microporous Cu-based MOF, that achieves a single-product Faradaic efficiency (FE) of 82.5 % at −1.0 V (versus the reversible hydrogen electrode) corresponding to the effective current density is 8.66 mA cm⁻². By investigating the relationship between the species of reduction products and the types of catalytic sites, it is confirmed that the multi-site synergism of Cu LNCCs can increase the C−C coupling effect, and thus achieve high FE of CO₂–to–ethanol. In addition, density functional theory (DFT) calculation and operando attenuated total reflectance surface-enhanced infrared absorption spectroscopy further confirmed the reaction path and mechanism of CO₂–to–EtOH.