高效光电催化2e氧还原反应复合电极的构筑及其在燃料电池产能-原位制备H2O2体系中的性能研究

An integrated system based on fuel cell to generate electricity-in situ synthesize hydrogen peroxide is that using fuel cell as reactor, hydrogen peroxide can be in-situ prepared by cathodic 2e ORR, simultaneously outputting electric energy. The key to its development and real application lies on the research and development of high-efficient catalytic materials of 2e ORR . The present proposal focuses on the development of novel, high-efficient photoelectrocatalytic 2e ORR electrode materials, choosing p-type semiconductor polyterthiophene (pTTh) with visible light response as the basement, adopting “pTTh design and synthesis-doping control-cocatalyst complex” as technical route, improving the charge separation efficiency and conductivity of pTTh by adjusting the compositions and configurations of doped N, P, O elements, accelerating the charge transfer process of pTTh surface by reuniting with carbon quantum dots cocatalysts, further enhancing the catalytic kinetics, deeply exploring the charge transfer process on the electrode surface via innovatively adopting ultrafast time-resolved transient adsorption spectroscopy technology, revealing the intrinsic relationships between the compositions and structures of the electrode and its photoelectrocatalytic performance, elucidating the mechanism of photoelectrocatalytic reaction, aiming at obtaining the photoelectrical cathodic material with outstanding performance. Through the project, it is expected to provide both key materials and technical support for the integrated system with electricity and H2O2 co-generation.

燃料电池产能-原位制备H2O2一体化系统利用燃料电池作为反应器，通过阴极2e氧还原反应（ORR）原位制备H2O2，同时对外输出电能，其发展和实际应用的瓶颈在于高效催化2eORR材料的研发。本项目围绕开发新型、高效光电催化2eORR电极材料而展开研究，拟以具有可见光响应的p型半导体聚三噻吩（pTTh）材料为基体，采用“pTTh设计合成-掺杂调控-助催化剂复合”的技术路线，通过调控掺杂元素N、P、O的组分及构型改善pTTh的电荷分离效率和导电性，进而复合碳量子点（CQDs）助催化剂加速电荷转移以改善催化动力学过程；创新采用超快时间分辨瞬态吸收光谱技术，深入探究电极表面的电荷转移过程；揭示电极的组成、结构与其光电催化性能的内在关联，阐明光电催化反应机理，以期获得高性能的光电阴极材料。本项目成果为一体化电能与H2O2共生系统提供关键材料支撑和技术支持。

燃料电池产能-原位制备H2O2一体化系统是利用燃料电池作为反应器，通过阴极2e-氧还原反应（ORR）原位制备H2O2，同时对外输出电能，其发展和实际应用的瓶颈在于高效催化2e- ORR材料的研发。本项目围绕光电催化2e- ORR电极材料的设计、制备与调控，光电催化活性机制，以及一体化电能与H2O2共生系统搭建等方面开展了一系列研究工作，取得了一些有特色的研究成果：1）开发了光电催化2e- ORR原位制备H2O2的聚三噻吩（Poly Terthiophene, pTTh）一体化电极，并通过构筑异质结构（CuOx@pTTh），改善了电极的电荷分离效率和导电性，提高了其降解有机废水的效率，最后设计并搭建了基于光增强锌空电池的电能与H2O2共生及污水处理器件联用一体化系统，为新能源转换与废水处理技术的耦合应用提供了概念证明；2）创新采用NH3活化技术，定向调控了有序介孔碳（OMC）的氧还原反应（ORR）电子选择性，搭建了锌-空气电池驱动H2O2原位制备及污水处理功能化器件，为非金属N掺杂炭基材料的设计与应用提供理论支持和技术指导。.其次，我们在高效Pt基合金4e- ORR催化剂可控制备方面进行了拓展研究，具体如下：利用碳分子筛（有序介孔碳，OMC）刚性骨架的空间限域作用，有效解决了高温热还原技术制备Pt基合金催化剂中金属颗粒易烧结、团聚等问题，并通过精细去合金化处理，实现了结晶性好、粒径小（~4.3 nm）的表面富Pt的PtNi3合金嵌入OMC阵列复合材料的可控制备，展示了优异的ORR活性和高稳定性。该工作为利用分子筛模板限域合成Pt基合金纳米颗粒并用于高效电催化4e- ORR反应提供了坚实基础。.通过本项目的实施，完成了研究计划。已发表高水平SCI期刊论文7篇；培养硕士研究生3名。