Creating Cation Vacancies in BiOCl Nanosheets Toward Exceptional Visible‐Light‐Driven Photocatalytic CO₂ Reduction

BiOCl-based materials have emerged as promising photocatalysts for converting CO₂ into valuable products and fuels. However, challenges such as low light absorption and inefficient charge carrier separation require effective solutions, with vacancy engineering offering a promising approach. Current research primarily focuses on anion vacancies, leaving cation vacancies less explored. In contrast, this study presents a novel method to enhance visible-light-driven photocatalysts by Bi cation vacancies in ultrathin BiOCl nanosheets through a straightforward hydrochloric acid etching process (HAE-BiOCl). These introduced Bi vacancies not only expand the light absorption range and enhance carrier separation, but also serve as active sites for CO₂ adsorption. Additionally, Bi vacancies can effectively lower the activation energy of COOH^- species and thereby enhance overall reaction activity. As a result, the HAE-BiOCl catalyst exhibits exceptional photocatalytic CO₂ reduction performance without the need for co-catalysts or sacrificial agents. It achieves high CO generation rates of 68.39 and 17.43 µmol g^-1 h^-1 under 300 W Xe lamp and visible light irradiation, respectively. These rates are significantly higher compared to counterparts without vacancy creation and surpass those of most reported Bi-based photocatalysts. This study underscores the potential of inducing cation vacancies via acid etching as a valuable strategy for advancing photocatalysis.