Unlocking the Potential of Oxide‐Based Catalysts for CO2 Photo‐Hydrogenation: Oxygen Vacancies Promoted C─O Bond Cleavage in Key Intermediates

作者：Zhexing Lin, Zhengwei Yang, Jiajia Wang, Jun Wang, Huiting Huang, Jianyong Feng, Huihui Yan, Minyue Zhao, Xinyi Liu, Wangxi Liu, Zhaosheng Li, Zhigang Zou · 发表于：Advanced Materials · 年份：2025 · DOI：10.1002/adma.202408906 · 被引用次数：46 · 研究领域：Catalytic Processes in Materials Science、Carbon dioxide utilization in catalysis、CO2 Reduction Techniques and Catalysts

Abstract Oxygen vacancies are generally recognized to play significant roles in CO2 adsorption and activation during CO2 hydrogenation. However, by revisiting its structural/electronic affinity for a range of oxygen‐containing intermediates in CO2 hydrogenation processes, the additional roles of oxygen vacancies can be long overlooked and underestimated. Herein, using CO2 (photo‐)methanation as a model reaction, Co3O4 with abundant oxygen vacancies is employed to investigate the relationship between oxygen vacancies and the formation/conversion of oxygen‐containing intermediates. Combined analyses of in situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations reveal that the key intermediate is formate, whose C─O bond cleavage is inferred to be the rate‐limiting step during CO2 methanation on Co3O4. Remarkably, leveraging the oxygen vacancy‐mediated C─O bond scission to accelerate the conversion of formate, the CH4 production activity (1108.1 mmol g−1 h−1) and selectivity (93%) are improved significantly. This comprehensive study provides valuable insights into the multifaceted roles of oxygen vacancies in CO2 hydrogenation reactions, establishing a solid foundation toward the design and development of high‐performance oxide‐containing/‐based catalysts for the conversion of CO2 into various valuable chemicals.