硫掺杂π-共轭聚酰亚胺的助催化剂纳米构筑及其光催化机理研究

The solar energy resources of the Qinghai-Tibet Plateau are the second largest in the world, which is the most promising area for the utilization of solar energy in China. At present, the development and utilization of solar energy in Western China is mainly limited to photovoltaic and photothermal. However, the research and application of photocatalytic decomposition of water for hydrogen production and degradation of organic pollutants is still at the initial stage. This project aims at the high recombination rate of photoelectrons and holes of the conjugated polymers, which makes the quantum efficiency of photocatalytic reaction low and difficult to realize the efficient use of solar energy. Based on our study of π-conjugated polyimide (PI) semiconductor photocatalytic system, we found that: Sulfur (oxygen) doping or metal compounds can greatly improve the photocatalytic activity of PI, which is the first time to put sulfur doping and metal or non-metallic compounds into PI simultaneously, and design and prepare new PI based composite photocatalysts with high sunlight activity and stable performance. To characterize the morphology and photoelectric properties , chemical composition of surface and bulk, activity center, space structure and electronic configuration; To examine intrinsic relationship between the effects of different composition and morphology and photocatalytic activity; To explore the mechanism of cocatalyst action in the composite catalyst, the photogenerated electrons and holes in the migration and separation law of interface. It is of great theoretical and practical significance to construct a novel polymer composite photocatalytic material to promote the efficient use of solar energy to solve environmental pollution and energy shortage.

青藏高原太阳能资源居世界第二位，是我国太阳能利用最有前途的地区。目前，西部太阳能开发利用主要局限于光伏和光热，而光催化分解水制氢和降解有机污染物研究应用尚属起步阶段。本项目针对共轭聚合物光生电子和空穴复合率高，使得光催化反应量子效率低而难以实现太阳能高效利用的重大难题，基于我们对π-共轭聚酰亚胺（PI）半导体光催化体系研究发现：硫（氧）掺杂或金属化合物可极大改善PI光催化活性，率先提出把硫掺杂和金（非）属化合物组分修饰同时作用到PI，设计和制备具有高太阳光活性且性能稳定新型PI基复合光催化剂。表征其形貌、表面及体相化学组成、光电特性、活性中心空间结构和电子构型；考察不同组成及形貌与光催化活性之间内在关系；探究助催化剂在复合材料中的作用机制、光生电子-空穴在界面的迁移和分离规律，构建全新意义上的聚合物复合光催化材料，对促进高效利用太阳能解决环境污染和能源短缺问题具有重要的理论和实际意义。

青藏高原太阳能资源极为丰富，是我国太阳能利用最有前景的地区。近年来，西部太阳能开发利用主要局限于光伏和光热，而光催化分解水制氢和降解有机污染物研究应用尚属起步阶段。本项目选择具有极强电子传输特性的非金属和优异可见光光催化活性的金属硫（氧）化物及钴基产氧助催化剂材料，如 GO、α-Fe2O3、ZnO、SnS2、ZnS、WS2和Co3O4等，通过热聚合、水热、共沉淀及原位结晶生长等方法构筑了一系列GO/SPI、α-Fe2O3/SPI、ZnO/SPI、ZnS /SPI、SnS2/SPI、WS2/SPIS、Co3O4/SPI 复合纳米材料和硫掺杂聚酰亚胺纳米空心球（HSPI）光催化剂。充分利用 TEM、SEM、EDS、FTIR、BET、PXRD、DSC/TG、XPS、EPR、UV、PL、Photo-Current、EIS 等表征手段对复合材料样品的形貌、微观结构、比表面积、孔径大小与分布、晶体结构和结晶度、化学组成、各个元素的化学状态、共轭电子离域程度、光吸收特性、荧光性能、光电特性及载流子传输与分离效率等进行了详细表征和分析。对所制备样品的光催化降解有机污染物和分解水产氢活性进行了测试，发现其光催化活性和稳定性相对于基础材料SPI有了极大的提高和改善。还研究了SPI 基复合半导体光催化材料的形貌、微结构、结晶度和组装基元与光催化活性之间内在的关系，探究了助催化剂在复合材料中的作用机制、光生电子-空穴在界面的迁移和分离规律，为构建全新意义上的聚合物复合光催化材料提供了思路和实验依据，同时还对促进聚酰亚胺基聚合物光催化体系高效利用太阳能解决环境污染和能源短缺问题的新应用打下基础。. 合同任务完成，4年发表学术论文8篇，其中SCI论文5篇（包括ACS Omega二篇、polymers二篇、RSC Advances一篇），授权发明专利2件。. 培养硕士研究生2名（在读）。