新型前过渡金属团簇光催化剂的设计与性能研究

Energy has become an urgent problem to be solved in the 21st century. Polyoxoniobates, polyoxotantalates, and polyoxotitanates are important early transition metal clusters. They are high performance photocatalytic water splitting materials due to their definite structures and clear energy levels. Therefore, it is expected that systematic synthesis and study of photocatalytic water splitting on the above-mentioned early transition metal clusters possess important theoretic and practical value. The applicants have obtained the current highest nuclear homopolyniobates, polyoxoniobate-vanadate and polyoxosilicon-niobates in their previous work, and have performed a preliminary study for these compounds in photocatalytic water splitting activity. Our project will be carried out from two aspects. One is to do synthetic investigation on polyoxoniobates, polyoxotantalates, and polyoxotitanates, so as to explore and summarize their synthesis law, as well as to look for the relations between structure and energy level. The other is to perform function-property characterization on these synthetic cluster compounds, and meanwhile to study their stability in different media, adsorption spectra and energy band structures, which in turn can help us to change their level structures by introducing transition metal ions so that they can generate adsorption in visible region, thereby enhancing their photocatalytic water splitting activities. By means of these experiments, photocatalytic water splitting materials having stable structures and excellent performance can be selected. It is believed that the work of this project will provide practical materials and valuable experimental data for polyoxometalates' application in the areas of materials and energy.

能源问题是21世纪全世界面临的最为重要和紧迫的问题，氢能是未来重要的二次能源，具有安全、高能、绿色、环保等优点。利用太阳能分解水制氢是目前氢能制备中最有前景的方法，其核心问题为光催化剂的研发。多金属铌酸盐、钽酸盐和钛酸盐作为一类重要的前过渡金属团簇化合物，是一类性能优异的光解水制氢催化材料，具有结构明确、能级清晰、性能优异等优点。关于该类前过渡金属团簇的合成及光解水制氢催化研究具有重要的理论和实际价值。本研究拟从两方面开展工作：一方面开展多金属铌酸盐、钽酸盐和钛酸盐的合成研究工作，探索和总结合成规律，寻找结构和能级之间的关系；另一方面对于所合成的团簇化合物进行功能性质表征，通过引入过渡金属离子改变簇合物的能级结构，使其在可见光区产生吸收，具备可见光照下光解水制氢的催化活性，从中筛选出结构稳定，性能优异的光解水制氢催化材料，为多金属氧酸盐化学在材料和能源领域的应用提供材料和实验数据。

能源问题是21世纪全世界面临的重要问题，氢能是未来重要的二次能源，具有安全、高能、绿色、环保等优点。利用太阳能分解水制氢是目前氢能制备中最有前景的方法，其核心问题为光催化剂的研发。多金属氧酸盐作为一类重要的前过渡金属团簇化合物，是一类性能优异的光解水制氢催化材料，具有结构明确、能级清晰、性能优异等优点。关于该类前过渡金属团簇的合成及光解水制氢催化研究具有重要的理论和实际价值。本课题开展以下研究工作：1. 基于多金属钨酸盐团簇光催化剂的设计，合成与光催化性能研究；2. 基于多金属铌酸盐，钽酸盐团簇光催化剂的设计、合成与光催化性能研究；3. 基于金属簇构筑的金属-有机框架化材料的设计、合成与性能研究。本课题共合成具有光催化活性的高核金属氧簇20余种，研究了所合成材料的各种理化性质和光催化性能，得到两个重要结论：1. 过渡金属掺杂可以有效调控光催化材料的能级结构，使其在可见光区产生吸收，提高太阳光利用率；2. 团簇光催化材料随着聚合度的增加，催化中心得到增加，提高光催化性能。在本项目资助下发表SCI研究论文26篇，其中由5篇论文被选为杂志的封面论文，为多金属氧酸盐化学在材料和能源领域的应用提供材料和实验数据。