Engineering of oxygen vacancy and bismuth cluster assisted ultrathin Bi₁₂O₁₇Cl₂ nanosheets with efficient and selective photoreduction of CO₂ to CO

Abstract

The photocatalytic conversion of CO2 into solar‐powered fuels is viewed as a forward‐looking strategy to address energy scarcity and global warming. This work demonstrated the selective photoreduction of CO2 to CO using ultrathin Bi12O17Cl2 nanosheets decorated with hydrothermally synthesized bismuth clusters and oxygen vacancies (OVs). The characterizations revealed that the coexistences of OVs and Bi clusters generated in situ contributed to the high efficiency of CO2–CO conversion (64.3 μmol g−1 h−1) and perfect selectivity. The OVs on the facet (001) of the ultrathin Bi12O17Cl2 nanosheets serve as sites for CO2 adsorption and activation sites, capturing photoexcited electrons and prolonging light absorption due to defect states. In addition, the Bi‐cluster generated in situ offers the ability to trap holes and the surface plasmonic resonance effect. This study offers great potential for the construction of semiconductor hybrids as multiphotocatalysts, capable of being used for the elimination and conversion of CO2 in terms of energy and environment.

Time-averaged atomic volume spectrum: locating and identifying vacancies

“…1–3 The concept of vacancy engineering, which has recently emerged in several fields, 4–6 is a direct manifestation of this crucial importance. For example, vacancy engineering is one of the core issues in the design and application of energy materials, such as oxygen vacancies in photocatalytic materials 7 and hydrogen storage materials, 8 vacancy creation in water electrolysis catalysts, 9 and cation vacancies in energy-related 2D nanosheets. 10 Since Frenkel 11 in 1926 and Wagner and Schottky 12 in 1930 independently proposed the mechanisms of vacancy formation, significant progress has been made in various areas related to vacancies.…”