Oxygen vacancy-mediated dual active sites for highly selective photoreduction of atmospheric CO2 to CO

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The pursuit of value-added products via the photocatalytic reduction of atmospheric CO 2 is largely thwarted by the kinetically sluggish adsorption and activation of low-concentration CO 2 on conventional single active sites. Herein, we construct oxygen vacancies (OVs)-mediated Cu and W synergistic active sites within a CuWO 4 photocatalyst via a facile hydrothermal strategy to steer the efficient conversion of atmospheric CO 2 , which achieves an impressive CO production yield of 19.5 μmol g −1 and 100% CO selectivity under ambient air condition. Experimental characterizations and theoretical calculations unveil that Cu and W sites bridged by OVs play synergistic roles: Cu sites promote the adsorption of CO 2 and the rate-determining protonation step (*CO 2 → *COOH) via enhanced electron injection, while W sites further boost CO desorption by weakening *CO-surface interactions. This study not only elucidates the synergistic role of defect-induced dual metal sites but also provides a rational paradigm for designing highly active photocatalysts toward atmospheric CO 2 utilization.