光催化技术为解决环境、能源问题提供了新思路。本论文围绕共轭光催化材料的三维复合结构设计和自组装过程调控开展了四项研究工作。在三维复合结构设计方面，成功构筑了g-C3N4/TiO2、PDI/rGO光催化材料，建立起吸附富集-光催化去除的协同策略，实现了对流动废水长时间、免分离的高效净化，为水环境中污染物的控制提供了新思路。在苝酰亚胺超分子自组装的研究中，通过设计酰胺侧链基团来调控氢键、π-π相互作用，成功构筑PDI-4-氨基邻苯二甲酸和高结晶PDI-NH超分子光催化剂，并系统研究其自组装结构与光催化性能之间的构效关系。通过一步煅烧法成功制备了g-C3N4/TiO2三维光催化材料，具有优异的吸附富集-光催化协同性能。该光催化剂实现了在流动体系中苯酚的连续去除，反应90小时去除率保持在16.0%，同时还具有免分离的优势。一方面，三维结构可以增强对污染物的吸附富集能力，并提供多维度的物质、电子传输通道；另一方面，g-C3N4和TiO2之间的异质结构可以实现光生载流子的高效分离与迁移。通过电化学沉积-浸渍负载的方法，可控制备了PDI纳米棒锚定在rGO表面的PDI/rGO三维催化材料，其具有高效的吸附富集-光电协同降解有机污染物的性能。PDI/rGO适合于流动体系中免分离的污水处理，连续反应55小时，亚甲基蓝的去除率稳定在88.3%。一方面，通过π-π作用构筑的PDI/rGO三维结构，比表面积大，具有优异的吸附富集性能；另一方面，外加偏压可以有效促进光生载流子的分离与传输，发挥光电协同催化优势，显著提高降解效率。通过调控PDI分子酰胺侧链的氢键作用，成功构筑了短程π-π堆积的PDI-4-氨基邻苯二甲酸超分子光催化材料。其可见光降解苯酚的速率是商业PDI、g-C3N4的16.1和29.0倍，同时具有高效的光催化产氢性能（1.1 mmolg-1h-1）。邻位双羧基的氢键作用较强，PDI分子沿氢键平面优势组装，并在π-π方向上形成短程有序的堆积结构，缩短了光生电荷的传输距离，进而有效提高了载流子的分离效率。以咪唑为溶剂可控制备了高结晶PDI-NH光催化材料，其光催化产氧性能突破到40.6 mmolg-1h-1，是普通PDI超分子的1353.0倍，亦可高效降解有机污染物。PDI-NH的高结晶性来源于在高温咪唑溶剂中，基于氢键和π-π相互作用的自组装过程。PDI-NH的高度有序堆积结构有利于构筑内建电场，从而驱动光生载流子的高效分离，进而促进光催化氧化反应。此外，高结晶PDI-NH光催化材料结构稳定，在可见光下连续反应50小时，产氧性能保持不变。

Photocatalysis provides new ideas for solving environmental and energy problems. Herein, based on the conjugated photocatalysts, four innovative studies have been carried out, aiming at the design of three-dimensional structure and the regulation of self-assembly process. On the one hand, the three-dimensional g-C3N4/TiO2, PDI/rGO photocatalysts are successfully constructed, and a new strategy of adsorption enrichment-photocatalysis synergy is established. Especially, the degradation process in the long-term flow system without separation is realized, which provides new ideas for the pollutant removal in wastewater treatment. On the other hand, the PDI-4-aminophthalic acid and high crystalline PDI-NH supramolecular photocatalysts are constructed via the π-π and hydrogen bonding interaction in the self-assembly process. Further, the relation between self-assembly structure and photocatalytic performance is systematically studied.The three-dimensional g-C3N4/TiO2 photocatalyst is successfully prepared by a one-step calcination method, which has excellent adsorption enrichment-photocatalysis synergy performance. The photocatalyst realizes the continuous degradation of organic pollutants in the flow system without separation, and the removal rate is maintained at 16% after 90 hour’s reaction. On the one hand, the three-dimensional structure can enhance the adsorption enrichment performance and provide multi-dimensional channels for mass and charge carrier transport. On the other hand, the g-C3N4/TiO2 heterojunction can effectively improve the separation and migration of photogenerated carriers.The PDI anchored rGO (PDI/rGO) three-dimensional photocatalyst is synthesized by an electrodeposition-impregnation method. The catalyst has an enhanced adsorption enrichment photo-electrocatalysis synergy performance. In particular, PDI/rGO is suitable for wastewater treatment in the flow system with separation free. The stability is very high, and the removal ratio is 88.3% for over 55 hours. On the one hand, the three-dimensional structure constructed by π-π interaction has a large surface area and enables the adsorption-enrichment ability. On the other hand, the electrocatalysis can not only promote the separation and transport of carriers, but also cooperates with photocatalysis to improve the degradation performance.The sheet-layered PDI-4-aminophthalic acid (ortho-carboxyl PDI) supramolecular photocatalyst is successfully constructed by adjusting the orientation of hydrogen bonding. The visible light degradation rate of the ortho-carboxyl PDI is 36.3 or 7.3 times that of meta- or para- carboxyl PDI, respectively. Besides, the ortho-carboxyl PDI has an efficient photocatalytic hydrogen evolution rate (1.1 mmolg-1h-1). The ortho carboxyl group has a strong hydrogen bonding, then PDI molecules are assembled along the hydrogen bonding direction. Further the sheet-layer stacking morphology is constructed through short-range π-π interaction. The short-range π-π stacking can shorten the transmission distance of photogenerated carriers and then effectively promote the separation and migration of carriers.The highly crystalline perylene imide supramolecular (PDI-NH) photocatalyst is prepared by a high temperature imidazole solvent method. The catalyst possesses a breakthrough photocatalytic oxygen performance (40.6 mmolg-1h-1), which is 1353 times than the ordinary supramolecular PDI. The high crystallinity of PDI-NH comes from the self-assembly process based on hydrogen bonding and π-π interaction in a high-temperature imidazole environment. The highly ordered arrangement of PDI molecules contributes to the construction of the built-in electric field, which can effectively promote the separation of photo-generated carriers and efficiently drive the photocatalytic oxidation reaction. In addition, the crystalline PDI-NH is very stable and its oxygen production remains unchanged for over 50 hours.