本文从光催化材料能带结构调控和光生载流子分离与传输两大关键科学问题出发，系统开展四项创新研究，成功构筑TCNQ-苝酰亚胺复合光催化剂（TCNQ-PTCDI）、自组装四羧基苯基卟啉超分子光催化剂（SA-TCPP）、苝酰亚胺聚合物光催化剂（Urea-PDI）等三大类新型全有机半导体光催化材料，并将其应用于环境污染物治理、分解水产氢和产氧、肿瘤治疗等重点领域，深刻揭示其中热力学、动力学等物理化学的普遍科学规律，系统研究有机分子偶极、半导体内建电场、自组装结构等因素与光催化剂性能的构效关系。成功构筑一系列TCNQ-苝酰亚胺（TCNQ-PTCDI）超分子光催化剂，其可见光催化性能较纯PTCDI超分子提升10倍以上，可以高效降解处理水中酚类污染物。机理研究证实，TCNQ与PTCDI分子间的π-π复合作用，为光生电子提供了快速转移的通道，而TCNQ强烈的电子受体作用进一步诱导光生载流子的分离，使得复合光催化剂的性能得以进一步提高。该工作为复合有机光催化剂的设计与性能调控提供了新思路。成功构筑基于四羧基苯基卟啉的自组装超分子光催化剂SA-TCPP，该超分子光催化剂实现了全光谱辐照下的双功能分解水产氢、产氧(40.8和36.1μmol g-1 h-1 )，亦可高效降解环境污染物，其性能是传统无机光催化剂的10倍以上。基于该SA-TCPP超分子光催化剂，探索研究光催化剂对于实体肿瘤的治疗效果，疗效显著。机理研究证实，TCPP合适的分子能级，为超分子半导体光催化剂贡献了恰当的能带结构，保证了该光催化剂的强氧化还原能力；而TCPP的大分子偶极为半导体光催化剂构筑了较大的内建电场，促进了光生载流子的快速分离和迁移，提高了光催化剂活性。该SA-TCPP超分子光催化剂可在细胞内部产生光生空穴，破坏细胞结构，将实体肿瘤快速彻底消除。该工作为设计合成新型有机超分子光催化剂及开发新性能提供了新思路。成功构筑高度结晶的尿素-苝酰亚胺（Urea-PDI）聚合物光催化剂，其在无助催化剂条件下实现超高效的分解水产氧（3223.9μmol g-1 h-1），性能较常规PDI超分子光催化剂提高106.5倍。机理研究证实，聚合物的深价带（+1.52 eV）能带结构提供了强氧化能力。此外，Urea-PDI的高结晶度和大分子偶极有助于形成强大的内建电场，从而促进光生载流子的分离和传输。此外，Urea-PDI结构非常稳定，连续照射100小时后性能不会降低。该工作提供光催化水氧化的新材料平台，为设计合成新型聚合物光催化材料提供思路。
Herein, starting from the two key scientific issues of regulating the band structure of photocatalytic materials and the separation and transport of photogenerated carriers in the photocatalytic process, four innovative studies have been systematically carried out. The three types of novel organic photocatalysts, TCNQ-PTCDI composite photocatalyst (TCNQ-PTCDI), self-assembled porphyrin (SA-TCPP), Urea-PDI polymer, have been successfully implemented. The applications of these novel photocatalysts in environmental pollutants treatment, water splitting, decomposition of aquatic oxygen production, tumor treatment and other important fields have been investigated. And the general scientific laws of thermodynamics and kinetics, such as organic molecular dipoles, built-in electric fields, self-assembled structures, have been deeply revealed.A series of TCNQ-PTCDI supramolecular photocatalysts have been successfully constructed, whose visible light photocatalytic performance is more than 10 times higher than that of PTCDI monomers, which can efficiently degrade and treat phenolic pollutants in water. Mechanism studies have confirmed that the π-π recombination between TCNQ and PTCDI molecules provides a fast transfer channel for photogenerated carriers, and the strong electron acceptor action of TCNQ further induces the separation of photo-generated carriers. This work provides new ideas for the design and performance regulation of composite organic photocatalysts.A self-assembled supramolecular tetracarboxyphenylporphyrin photocatalyst (SA-TCPP) has been successfully constructed. The SA-TCPP achieves dual functional evolution of hydrogen and oxygen under full spectrum (40.8 and 36.1μmol g-1 h-1). And several phonel poluutants can be efficiently degraded with the SA-TCPP, which is more than ten times that of traditional inorganic photocatalysts. Based on the SA-TCPP, the therapeutic effect on solid tumors has been explored and the effect is significant. Mechanism studies have confirmed that the appropriate molecular energy level of TCPP contributes an appropriate band structure for SA-TCPP, ensuring the strong redox capacity; and the large molecular dipole of SA-TCPP have built a strong built-in electric field in photocatalyst promoting the rapid separation and migration of photogenerated carriers. The SA-TCPP can destroy cell structures with photogenerated holes inside cancer cells, and quickly and completely eliminate solid tumors. This work provides new ideas for the design and synthesis of new organic supramolecular photocatalysts and its applications.A highly crystalline urea-perylene imide (Urea-PDI) polymer photocatalyst has been successfully built, which achieves super efficient oxygen evolution production (3223.9 μmol g-1 h-1) without cocatalysts. Its performance is 106.5 times higher than conventional PDI supramolecular photocatalyst. Mechanism studies have confirmed that the polymer has a deep valence band (+1.52 eV) structure, and thus has the strong oxidation ability. The high crystallinity and large molecular dipoles help Urea-PDI to form a strong built-in electric field, thereby promoting the separation and transmission of photogenerated carriers. In addition, Urea-PDI is very stable, and the performance did not decrease after continuous exposure for 100 hours. This work provides a new material platform for photocatalytic water oxidation and provides ideas for the design and synthesis of new polymer photocatalytic materials.
