Efficient C-N coupling for urea electrosynthesis on defective Co3O4 with dual-functional sites.

Abstract

Urea electrosynthesis under ambient conditions is emerging as a promising alternative to conventional synthetic protocols. However, the weak binding of reactants/intermediates on the catalyst surface induces multiple competing pathways, hindering efficient urea production. Herein, we report the synthesis of defective Co3O4 catalysts that integrate dual-functional sites for urea production from CO2 and nitrite. Regulating the reactant adsorption capacity on defective Co3O4 catalysts can efficiently control the competing reaction pathways. The urea yield rate of 3361 mg h-1 gcat-1 was achieved with a corresponding faradaic efficiency (FE) of 26.3% and 100% carbon selectivity at a potential of -0.7 V vs. the reversible hydrogen electrode. Both experimental and theoretical investigations reveal that the introduction of oxygen vacancies efficiently triggers the formation of well-matched adsorption/activation sites, optimizing the adsorption of reactants/intermediates while decreasing the C-N coupling reaction energy. This work offers new insights into the development of dual-functional catalysts based on non-noble transition metal oxides with oxygen vacancies, enabling the efficient electrosynthesis of essential C-N fine chemicals.