Predesign of Catalytically Active Sites via Stable Coordination Cluster Model System for Electroreduction of CO to Ethylene.

Purposefully designing the well-defined catalysts for the selective electroreduction of CO to C H is an extremely important but challenging work. In this work, three crystalline trinuclear copper clusters (Cu -X, X=Cl , Br , NO ) have been designed, containing three active Cu sites with the identical coordination environment and appropriate spatial distance, delivering high selectivity for the electrocatalytic reduction of CO to C H . The highest faradaic efficiency of Cu -X for CO -to-C H conversion can be adjusted from 31.90 % to 55.01 % by simply replacing the counter anions (NO , Cl , Br ). The DFT calculation results verify that Cu -X can facilitate the C-C coupling of identical *CHO intermediates, subsequently forming molecular symmetrical C H product. This work provides an important molecular model system and a new design perspective for electroreduction of CO to C products with symmetrical molecular structure.