Yang Fengyi, Qu Jiafu, Zheng Yang, Cai Yahui, Yang Xiaogang, Li Chang Ming, Hu Jundie
School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou 215009, China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.
Nanoscale. 2022 Oct 27;14(41):15217-15241. doi: 10.1039/d2nr04727f.
The photocatalytic conversion of carbon dioxide (CO) to high-value-added fuels is a meaningful strategy to achieve carbon neutrality and alleviate the energy crisis. However, the low efficiency, poor selectivity, and insufficient product variety greatly limit its practical applications. In this regard, conjugated organic polymeric materials including carbon nitride (g-CN), covalent organic frameworks (COFs), and covalent triazine frameworks (CTFs) exhibit enormous potential owing to their structural diversity and functional tunability. Nevertheless, their catalytic activities are largely suppressed by the traditional amorphous or weakly crystalline structures. Therefore, constructing relevant high-crystalline materials to ameliorate their inherent drawbacks is an efficient strategy to enhance the photocatalytic performance of conjugated organic polymeric materials. In this review, the advantages of high-crystalline organic polymeric materials including reducing the concentration of defects, enhancing the built-in electric field, reducing the interlayer hydrogen bonding, and crystal plane regulation are highlighted. Furthermore, the strategies for their synthesis such as molten-salt, solid salt template, and microwave-assisted methods are comprehensively summarized, while the modification strategies including defect engineering, element doping, surface loading, and heterojunction construction are elaborated for enhancing their photocatalytic activities. Ultimately, the challenges and opportunities of high-crystalline conjugated organic polymeric materials in photocatalytic CO conversion are prospected to give some inspiration and guidance for researchers.
将二氧化碳（CO₂）光催化转化为高附加值燃料是实现碳中和和缓解能源危机的一项有意义的策略。然而，低效率、差的选择性和不足的产品种类极大地限制了其实际应用。在这方面，包括氮化碳（g-C₃N₄）、共价有机框架（COFs）和共价三嗪框架（CTFs）在内的共轭有机聚合物材料由于其结构多样性和功能可调性而展现出巨大潜力。然而，它们的催化活性在很大程度上受到传统无定形或弱结晶结构的抑制。因此，构建相关的高结晶材料以改善其固有缺点是提高共轭有机聚合物材料光催化性能的有效策略。在这篇综述中，强调了高结晶有机聚合物材料的优势，包括降低缺陷浓度、增强内建电场、减少层间氢键和晶面调控。此外，全面总结了它们的合成策略，如熔盐法、固体盐模板法和微波辅助法，同时阐述了包括缺陷工程、元素掺杂、表面负载和异质结构建在内的改性策略以提高其光催化活性。最后，展望了高结晶共轭有机聚合物材料在光催化CO₂转化中的挑战和机遇，为研究人员提供一些启发和指导。
