多金属氧簇与共价三嗪框架杂化结构的设计组装及光/电催化性能

多金属氧簇（POMs）化学组成和电子结构高度可控，在光/电催化领域具有重要应用。针对POMs在光/电催化中遇到的问题：（1）在光解水体系中需要使用贵金属光敏化剂且POMs难以循环使用，（2）电催化过程中POMs易流失、电子传输效率低，本项目将具有光/电活性的POMs与共价三嗪框架（CTFs）进行组装，构筑POM@CTFs杂化结构，研究POM@CTFs的组装策略及其光解水产氢与醇电催化氧化的催化活性。在水还原反应中，将活性POMs直接“锚定”在光敏材料CTFs上，这种组合在替代贵金属光敏化剂的同时实现POMs的固载；在电催化方面，将POM@CTFs用于催化醇的选择性氧化，建立醇分子高效、绿色转化的新途径。本研究旨在揭示POM@CTFs组成、结构与催化性能间的构效关系规律，阐明其催化作用机理。POMs与CTFs间的杂化，将丰富和发展POMs合成化学与催化化学，为其工业化应用奠定理论基础。

Polyoxometalates (POMs), with highly tunable chemical composition and electronic structures, have shown important applications in photo/electro-catalysis areas. To resolve common challenges faced in POMs-based photo/electro-catalysis, that is, (1) the use of noble-metal-containing photosensitizers and the difficulty of recycling POMs in the light-driven water splitting systems, (2) the low electron transport efficiency and leaching of POMs catalysts during electrocatalytic process; in this project, we propose to prepare POM@CTFs hybrids by assembling light-/electro-active POMs with Covalent Triazine Frameworks (CTFs) and to investigate the assembly strategies as well as their catalytic activities for light-driven water splitting or electrocatalytic alcohol oxidation. For the water reduction part, the active POMs will be anchored onto light-absorbing CTFs with the goal of replacing traditional noble-metal-containing photosensitizers and immobilizing POMs catalysts; for the electrocatalysis part, the electrode will be modified by POM@CTFs for selectively catalyzing alcohol oxidation to develop an effective and green route. The goal of this project is to establish the structure-activity correlation between the structural composition of POM@CTFs and their catalytic activities in proposed reactions, and at the same time to systematically investigate the catalytic mechanism. In addition, the preparation of POM@CTFs composites will not only enrich and expand the POM-based synthetic/catalytic chemistry, also lay a theoretical foundation for future potential industrial applications.