Enhancing Photocatalytic CO2 Conversion through Oxygen‐Vacancy‐Mediated Topological Phase Transition

Abstract Weak adsorption of gas reactants and strong binding of intermediates present a significant challenge for most transition metal oxides, particularly in the realm of CO 2 photoreduction. Herein, we demonstrate that the adsorption can be fine‐tuned by phase engineering of oxide catalysts. An oxygen vacancy mediated topological phase transition in Ni‐Co oxide nanowires, supported on a hierarchical graphene aerogel (GA), is observed from a spinel phase to a rock‐salt phase. Such in situ phase transition empowers the Ni‐Co oxide catalyst with a strong internal electric field and the attainment of abundant oxygen vacancies. Among a series of catalysts, the in situ transformed spinel/rock‐salt heterojunction supported on GA stands out for an exceptional photocatalytic CO 2 reduction activity and selectivity, yielding an impressive CO production rate of 12.5 mmol g −1 h −1 and high selectivity of 96.5 %. This remarkable performance is a result of the robust interfacial coupling between two topological phases that optimizes the electronic structures through directional charge transfer across interfaces. The phase transition process induces more Co 2+ in octahedral site, which can effectively enhance the Co‐O covalency. This synergistic effect balances the surface activation of CO 2 molecules and desorption of reaction intermediates, thereby lowering the energetic barrier of the rate‐limiting step.