Charge-ordered Cu+/Cu2+ pair regulated highly-selective electroreduction of carbon monoxide to acetate

Selective electrochemical reduction of CO 2 /CO to high-valuable C 2+ products is of great importance to alleviate the global warming and energy crisis problems, while the selective production of C 2 is severely limited by the C C coupling pathway on the catalyst interface. Herein, by employing a Cu + /Cu 2+ charge-ordered metal-organic framework (MOF) material (denoted to be Cu4BHT) as a CO electroreduction catalyst, a high acetate selectivity of 50.3% at 0.7 V versus reversible hydrogen electrode (RHE) has been achieved. An in-depth mechanism study reveals that the charge-ordered Cu + /Cu 2+ pair on Cu4BHT interface favors the C O bond activation, C C coupling, and proton-coupled electron transfer dynamics, which results in the selective formation of C 2+ products. This work illustrates the critical role of employing charge-ordered Cu + /Cu 2+ catalytic site pair for C C coupling, which paves the way for designing highly selective catalysts to promote the formation of the C 2 products.