Abstract
Energy crisis and environmental problems urgently drive the proposal of new strategies to improve human wellbeing and assist sustainable development. To this end, scientists have explored many metal oxides-based photocatalysts with high stability, low cost, earth abundance, and potentially high catalytic activity relevant for key applications such as H2O splitting, CO2 reduction, N2 fixation, and advanced oxidation of pollutants. In these metal oxides, oxygen vacancies (OVs) are ubiquitous and intrinsic defects with pronounced impacts on the physicochemical properties of the catalysts, which may open new opportunities for obtaining efficient metal oxides. The thorough understanding of the structural and electronic nature of OVs is necessary to determine how they serve as catalytically active sites. In this review, we summarize the origin of OVs, the strategies to introduce OVs, as well as the fundamental structure-activity relationships to relate these crystal defects to catalyst properties including light absorption, charge separation, etc. We emphasize the mechanism of OVs formation and their effects on the intrinsic catalytic characteristics of the metal oxides. We also present some multicomponent catalytic platforms where OVs contribute to catalysis via synergy. Finally, opportunities and challenges on engineering defects in photocatalysts are summarized to highlight the future directions of this research field.
摘要
高效、 稳定的催化材料有望解决日益严峻的环境污染和能源危机问题. 金属氧化物具有高稳定性、 低成本以及高催化活性等优点, 在能源转换和环境净化等领域有广阔的应用前景, 已广泛应用于H2O裂解、 CO2还原、 固氮以及污染物的高级氧化等催化领域中. 氧空位作为金属氧化物中普遍存在的一种内在缺陷, 被证实可显著影响甚至改变材料的物理化学性质, 是调控催化剂结构和催化性能的有效手段. 深入了解催化材料氧空位的调节以及氧空位对催化性能的作用机制, 为设计出高效金属氧化物催化剂提供重要理论基础. 本文综述了近年来调控氧空位的基本原理和控制因素, 介绍了氧空位的结构与催化活性的基本关系, 包括如何影响材料的光吸收、 电荷分离和反应物的吸附活化等, 着重介绍了氧空位的形成机制及其对金属氧化物催化特性的影响. 同时, 我们还对多组分催化过程中, 氧空位与其他类型催化组分间的协同催化机制进行了总结. 最后, 本文提出了材料缺陷工程在催化领域面临的机遇和挑战.
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Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (U1905215, 51772053 and 51672046).
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Author contributions Zhuang Z and Yu Y conceptualized the work, and wrote and revised the manuscript. Zhuang G and Chen Y collected and summarized the literatures, and contributed to the manuscript writing. Yu J revised the manuscript and offered creative proposal for improving the depth and coverage of the review. All authors contributed to the general discussion.
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Guoxin Zhuang received his BSc in materials science and engineering from Fuzhou University. He is currently pursuing his PhD degree at Fuzhou University under the supervision of Prof. Yu and Prof. Zhuang. His research focuses on the design of MOFs and catalysts for CO2 photoreduction.
Zanyong Zhuang received his BSc in chemistry from Xiamen University, and his PhD in 2011 from Fujian Institute of Research on the Structure of Matter (FJIRSM), Chinese Academy of Sciences (CAS). He became an associate researcher in FJIRSM, CAS in 2014. Currently he is an associate professor at Fuzhou University. His research interests include the design of lowdimensional nanostructures, nanocrystals growth and assembly, comprehensive utilization of solid waste, and the related catalytic topics.
Yan Yu received her BSc, MSc and PhD degrees from Fuzhou University. She was a postdoctoral fellow in FJIRSM, CAS, and became a Professor at Fuzhou University in 2011. Her research interests include semiconductors, photocatalysis, environmental purification materials, comprehensive utilization of solid waste, and the related topics.
Jiaguo Yu received his BSc and MSc degrees in chemistry from the Central China Normal University and Xi'an Jiaotong University, respectively, and his PhD in materials science in 2000 from Wuhan University of Technology. In 2000, he became a Professor at Wuhan University of Technology. He was a postdoctoral fellow at the Chinese University of Hong Kong from 2001 to 2004, a visiting scientist from 2005 to 2006 at the University of Bristol, and a visiting scholar from 2007 to 2008 at the University of Texas, Austin. His research interests include semiconductors, photocatalysis, photocatalytic hydrogen production, solar fuels, dye-sensitized solar cells, adsorption, CO2 capture, graphene, and the related topics.
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Zhuang, G., Chen, Y., Zhuang, Z. et al. Oxygen vacancies in metal oxides: recent progress towards advanced catalyst design. Sci. China Mater. 63, 2089–2118 (2020). https://doi.org/10.1007/s40843-020-1305-6
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DOI: https://doi.org/10.1007/s40843-020-1305-6