Photoinduced Defect Engineering: Enhanced Photothermal Catalytic Performance of 2D Black In2O3−x Nanosheets with Bifunctional Oxygen Vacancies

Abstract Photothermal CO2 reduction technology has attracted tremendous interest as a solution for the greenhouse effect and energy crisis, and thereby it plays a critical role in solving environmental problems and generating economic benefits. In2O3−x has emerged as a potential photothermal catalyst for CO2 conversion into CO via the light‐driven reverse water gas shift reaction. However, it is still a challenge to modulate the structural and electronic characteristics of In2O3 to enhance photothermocatalytic activity synergistically. In this work, a novel route to activate inert In(OH)3 into 2D black In2O3−x nanosheets via photoinduced defect engineering is proposed. Theoretical calculations and experimental results verify the existence of bifunctional oxygen vacancies in the 2D black In2O3−x nanosheets host, which enhances light harvesting and chemical adsorption of CO2 molecules dramatically, achieving 103.21 mmol gcat−1 h−1 with near‐unity selectivity for CO generation and meanwhile excellent stability. This study reveals an exciting phenomenon that light is an ideal external stimulus on the layered In2O3 system, and its electronic structure can be adjusted efficiently through photoinduced defect engineering; it can be anticipated that this synthesis strategy can be extended to wider application fields.