Regulating Cu Oxidation State for Electrocatalytic CO2 Conversion into CO with Near-Unity Selectivity via Oxygen Spillover.

ABSTRACT

Cu-based catalysts are the most intensively studied in the field of electrocatalytic CO2 reduction reaction (CO2RR), demonstrating the capacity to yield diverse C1 and C2+ products albeit with unsatisfactory selectivity. Manipulation of the oxidation state of Cu sites during CO2RR process proves advantageous in modulating the selectivity of productions, but poses a formidable challenge. Here, an oxygen spillover strategy is proposed to enhance the oxidation state of Cu during CO2RR by incorporating the oxygen donor Sb2O4. The Cu-Sb bimetallic oxide catalyst attains a remarkable CO2-to-CO selectivity approaching unity, in stark contrast to the diverse product distribution observed with bare CuO. The exceptional Faradaic efficiency of CO can be maintained across a wide range of potential windows of ≈700 mV in 1 m KOH, and remains independent of the Cu/Sb ratio (ranging from 0.11 to 101). Correlative calculations and experimental results reveal that oxygen spillover from Sb2O4 to Cu sites maintains the relatively high valence state of Cu during CO2RR, which diminishes the binding strength of *CO, thereby achieving heightened selectivity in CO production. These findings propose the role of oxygen spillover in CO2RR over Cu-based catalysts, and shed light on the rational design of highly selective CO2 reduction catalysts.