囊包多酸的金属-有机纳米笼的设计合成及催化电解水产氢研究

The hydrogen generation from electrolysis of water is the one of the most promising and cleanest ways to produce hydrogen. However, much energy is consumed during the electrolysis process, due to the overpotential of hydrogen evolution. Therefore, the exploitation of active non-noble-metal-based electrocatalysts to improve the cathodic hydrogen evolution reaction efficiency and reduce the costs is currently one of the most active research areas, which is highly desirable to hydrogen generation in large scale. Polyoxometalate-encapsulated metal organic nano-cages are a special kind of materials, which are composed of metal-organic framework hosts and polyoxometalate guests. These materials generally possess high surface area as well as excellent electro-catalysis and adsorption performance. Hence, design and preparation of this type of the materials is very promising. Although such compounds have potential electro-catalysis prosperity to produce hydrogen, the related studies have not been reported till now. Herein, we plan to design and prepare a series of new polyoxometalate-encapsulated metal organic nano-cages. Their hydrogen generation performance will be studied by the electrochemical testing techniques, such as linear cyclic voltammetry, electrochemical impedance spectroscopy and constant current electrolysis. Meanwhile, the influence factors on hydrogen generation efficiency, such as the composition and structures of polyoxometalate-encapsulated metal organic nano-cages, as well as the electrode modification method and modified electrode composition will be investigated in details. Further, the best catalytic performance of the modified electrode will be achieved by tunning the composition and structures of the catalysts. Obviously, this study can provide theoretical and experimental basis for development and exploitation of new type of active non-noble-metal-based electrocatalysts.

电解水制氢是最有前景，最清洁的制氢方法之一，但由于析氢过电位导致能耗增加，因此，开发高催化活性的非贵金属电催化剂，提高阴极析氢反应效率，降低成本，以实现大规模地制氢系当今的研究热点之一。囊包多酸金属-有机纳米笼是一类是由多孔的配位聚合物纳米笼囊包多酸客体分子构成的化合物，具有高的比表面积及优异的电催化和气体吸附性能，因此设计和制备新型此类配合物的研究方兴未艾。此类化合物具有潜在的电催化产氢性能，但相关研究尚未见报道。据此，本项目拟制备一系列新型囊包多酸金属-有机纳米笼化合物材料，利用线性循环伏安、交流阻抗谱、恒电流电解等电化学测试技术研究其催化析氢性能，探究囊包多酸金属-有机纳米笼的组成、结构及电极修饰方法和修饰电极组成等因素对催化产氢性能的影响，进而调控催化剂的组成和结构，优化修饰电极的催化性能。并进一步研究催化反应机理，为新型非贵金属电催化剂的开发和研制提供理论与实验依据。

电解水制氢是最有前景，最清洁的制氢方法之一，但由于析氢过电位导致能耗增加，因此，开发高催化活性的非贵金属电催化剂，提高阴极析氢反应效率，降低成本，以实现大规模地制氢系当今的研究热点之一。囊包多酸金属-有机纳米笼是一类是由多孔的配位聚合物主体框架和多酸客体分子构成的化合物，具有高的比表面积及优异的电催化和气体吸附性能，具有潜在的电催化产氢性能，因此，设计和制备新型此类囊包多酸金属-有机纳米笼具有十分重要的意义。本项目制备了一系列新型囊包多酸金属-有机纳米笼化合物材料，利用电化学测试技术研究了其催化析氢性能，探究了囊包多酸金属-有机纳米笼的组成、结构及电极修饰方法和修饰电极组成等因素对催化产氢性能的影响，通过调控催化剂的组成和结构，优化了修饰电极的催化性能，考察了结构和性能的关系。并进一步探究了材料的电化学传性及电容性，为新型多酸基材料的开发和利用提供了理论与实验依据。