多酸分子电催化剂的设计合成与高效析氢性能研究

探索高效低廉的电解水析氢（HER）催化剂是解决氢能绿色生产的关键难题。问题核心是如何提升催化剂的本征活性及活性位点数目。一条理想途径是在分子水平上实现催化材料的定向构建。多酸作为结构明确的无机金属氧簇，在电化学环境下具有同时富集质子和电子的特殊能力，是理想的分子催化剂设计平台。目前，多酸与铂、石墨碳、硫化钼簇等材料复合已展现出良好的HER性能。但是何种组成、结构及还原程度的多酸才能发挥作用？其催化机理与活性位点是什么？又如何保证多酸催化体系的稳定性？这些关键问题依然没有确切答案。因此，本课题拟将HER优势催化活性组分引入多酸分子体系，设计合成多酸基贵金属簇、过渡金属簇和硫化物簇三个系列化合物，并构建基于多酸团簇分子的电催化剂体系；利用上述分子模型揭示催化剂组成、结构、活性中心键连方式以及催化剂与载体界面相互作用等因素对HER性能的影响，为开发高效低廉产氢电催化剂提供有重要学科价值的新理论。

The key problem to solve the green production of hydrogen energy is to explore efficient and low-cost catalysts for hydrogen evolution reaction (HER) from electrolytic water. The central task is how to improve the intrinsic activity and the active sites of the target electrocatalysts. An ideal way is to realize the directional construction of catalytic materials at the molecular level. Polyoxometalates (POMs), as a kind of inorganic metal-oxo cluster compounds with clear structures, possess the special ability of enriching protons and electrons at the same time under electrochemical environment, which can be an ideal platform for molecular catalyst design. At present, POMs can form composite materials with platinum, graphite carbon, or molybdenum sulfide clusters, exhibiting good HER performance. However, what composition, structure and reducing degree of POMs truly play an important role? What is its catalytic mechanism and active site? And how to ensure the stability of POM-based electrocatalytic system? The above key questions remain unanswered. Therefore, this project plans to introduce HER dominant catalytic active components into the POM molecular system, synthesize three series of compounds, that is, POM-based noble metal clusters, transition metal clusters and sulfide clusters. Furthermore, we will attempt to construct POM-based single molecular electrocatalyst system. The above molecular model will be used to reveal the influence of catalyst composition, structure, active center bonding mode and catalyst/support interface on HER performance and its regulation mechanism. Finally, this project will provide a new theory with important scientific significance and subject value for the development of high efficient and low-cost hydrogen production electrocatalysts.