Recent advances in high-crystalline conjugated organic polymeric materials for photocatalytic CO conversion.

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.