Sun Kang, Qian Yunyang, Li Dandan, Jiang Hai-Long
Hefei National Research Center for Physical Sciences at the Microscale, Department of Chemistry, University of Science and Technology of China, Hefei, Anhui, 230026, P. R. China.
Institutes of Physical Science and Information Technology, Key Laboratory of Structure and Functional Regulation of Hybrid Materials, Ministry of Education, Anhui University, Hefei, Anhui, 230601, P. R. China.
Adv Mater. 2024 Nov 27:e2411118. doi: 10.1002/adma.202411118.
Photocatalysis leverages solar energy to overcome the thermodynamic barrier, enabling efficient chemical reactions under mild conditions. It can greatly reduce reliance on traditional energy sources and has attracted significant research interest. Reticular materials, including metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), represent a class of crystalline materials constructed from molecular building blocks linked by coordination and covalent bonds, respectively. Reticular materials function as heterogeneous catalysts, combining well-defined structures and high tailorability akin to homogeneous catalysts. In this review, the regulation of light absorption, charge separation, and surface reactions in the photocatalytic process through precise molecular-level design based on the features of reticular materials is elaborated. Notably, for MOFsmicroenvironment modulation around catalytic sites affects photocatalytic performance is delved, with emphasis on their unique dynamic and flexible microenvironments. For COFs, the inherent excitonic effects due to their fully organic nature is discussed and highlight the strategies to regulate excitonic effects for charge- and/or energy-transfer-mediated photocatalysis. Finally, the current challenges and future directions in this field, aiming to provide a comprehensive understanding of how reticular materials can be optimized for enhanced photocatalysis is discussed.
光催化利用太阳能克服热力学障碍,从而在温和条件下实现高效化学反应。它可以大大减少对传统能源的依赖,并引起了广泛的研究兴趣。网状材料,包括金属有机框架(MOF)和共价有机框架(COF),是一类分别由通过配位键和共价键连接的分子构建单元构成的晶体材料。网状材料作为多相催化剂,兼具结构明确和可高度定制的特点,类似于均相催化剂。在这篇综述中,基于网状材料的特性,通过精确的分子水平设计阐述了光催化过程中光吸收、电荷分离和表面反应的调控。值得注意的是,深入探讨了MOF催化位点周围的微环境调节对光催化性能的影响,重点关注其独特的动态和灵活微环境。对于COF,讨论了由于其完全有机性质而产生的固有激子效应,并强调了调节激子效应以实现电荷和/或能量转移介导的光催化的策略。最后,讨论了该领域当前的挑战和未来方向,旨在全面了解如何优化网状材料以增强光催化性能。