Surface modification of Cu_(2)O with stabilized Cu^(+) for highly efficient and stable CO_(2) electroreduction to C_(2+) chemicals

摘要

Copper(Cu)-based materials are known as the most attractive catalysts for electrochemical carbon dioxide reduction reaction(CO_(2)RR),especially the Cu^(+) species(e.g.,Cu_(2)O),which show excellent capability for catalyzing CO_(2) to C_(2+) chemicals because of their unique electronic structure.However,the active Cu^(+) species are prone to be reduced to metallic Cu under an electroreduction environment,thus resulting in fast deactivation and poor selectivity.Here,we developed an advanced surface modification strategy to maintain the active Cu^(+) species via assembling a protective layer of metal-organic framework(copper benzenetricarboxylate,CuBTC) on the surface of Cu_(2)O octahedron(Cu_(2)O@CuBTC).It's encouraging to see that the Cu_(2)O@CuBTC heterostructure outperforms the bare Cu_(2)O octahedron in catalyzing CO_(2) to C_(2+) chemicals and dramatically enhances the ratio of C_(2)H_(4)/CH_(4) products.A systematic study reveals that the introduced CuBTC shell plays a critical role in maintaining the active Cu^(+) species in Cu_(2)O@CuBTC heterostructure under reductive conditions.This work offers a practical strategy for improving the catalytic performance of CO_(2)RR over copper oxides and also establishes a route to maintain the state of valence-sensitive catalysts.