钌参与构筑的多金属氧簇的设计、合成、结构及其光催化性能研究

In the given research work, Ruthenium trichloride and polyoxometalates cluster has been used as raw materials, and by controlling reaction conditions and raw materials ratios, ruthenium was combined with anion of polyoxometalates cluster to prepare novel type of ruthenium-containing polyoxometalates.. Ruthenium trichloride and heteroatom-oxyacid radical of polyoxometalates clusters were used as raw materials and ruthenium ions were combined with heteroatom-oxyacid radical to prepare novel type of ruthenium and oxyacid radical-containing polyoxometalates.. Functional organic molecules were used to react with the obtained new type of ruthenium-containing polyoxometalates and coordinated water molecules in polyoxometalates cluster were displaced by the functional organic molecules to get functional organic molecule ruthenium-containing polyoxometalates cluster.. Systematic characterization and determination of structure as well as investigation of physical and chemical properties of the ruthenium-containing polyoxometalates cluster will be made. It’s catalytic activity to catalyse photochemical reactions for oxygen-production by photolysis of water and oxidation of alkene with molecular oxygen or hydrogen peroxide under light and photo-degradation of organic pollutant in water were studied.. The effects of the composition and structure of ruthenium-containing polyoxometalates cluster acting as catalyst with various kinds of reactions were investigated.. The ruthenium-containing polyoxometalates cluster could be expected to have vast application prospect by adjusting its structure and optimizing the photocatalysis activation.. The research on synthesis and photocatalytic activation of the ruthenium-containing polyoxometalates cluster can lead to explore various kinds of connection patterns of ruthenium with polyoxometalates cluster or oxyacid radical to get novel structure type and to enrich the research content of them, so it is theoretically significant. At the same time, the research has important guidelines significance and application prospects at the aspects of preparation and selection and novel catalyst, will certainly break the dependence on consumption of fossil energy and will lead to reduce environmental pollution and discharge of greenhouse gases as well.

用三氯化钌和多金属氧簇反应，制备钌参与构筑的新型多金属氧簇；以三氯化钌（或其他钌化合物）和杂原子含氧酸根反应，制备钌与含氧酸根构成的新型多金属氧簇; 以功能有机分子与新型钌多金属氧簇反应, 制备有机分子功能化的钌构筑的新型多金属氧簇。对所制得的多金属氧簇进行系统的表征，测定化合物的结构并研究其性质。探索制得的新型多金属氧簇对光解水制氧、光作用下分子氧或双氧水氧化烯烃、光降解水中有机污染物等反应的催化活性。考察多金属氧簇的组成、结构对不同反应类型催化活性的影响。通过调整多金属氧簇的结构，优化多金属氧簇的光催化性质，以期得到具有应用前景的钌构筑的多金属氧簇。开展本项目的研究，不仅可以探索钌与多金属氧簇及含氧酸根的结合方式，丰富钌和多金属氧簇的结构类型和研究内容，具有重要的理论意义；同时，在新型催化剂的设计、制备和选择等方面也具有重要的指导意义和应用前景。

多金属氧簇由于其特有的组成、独特的结构和优良的物理化学性质，在催化、材料以药物等领域具有重要应用价值和应用前景。由钌构成的化合物，由于钌本身的特性，在光化学领域表现出明显的优势。如何将多金属氧簇的催化性能与钌化合物的光化学性能结合起来形成具有优良光催化活性的化合物，是多金属氧簇化学领域一个具有重要意义的研究课题。. 虽然目前化学工作者在钌构筑的多金属氧簇化学领域已开展了多方面的研究工作，但文献调研发现，该类研究工作主要集中在国外，而我国的研究工作要少得多；已报道的该类化合物中，新颖结构类型偏少，催化研究的反应类型以及催化剂种类也不多。因此，开展钌参与构筑的多金属氧簇的设计合成及其催化性质研究非常有必要。. 在基金资助下，开展了以简单含钌化合物为原料，采用不同的合成方法, 在一定条件下，分别与多金属氧簇前驱体或Mo、W、Se、As、V等含氧酸根反应，通过钌与多金属氧簇阴离子或含氧酸根结合，成功制备了多例新颖结构的纯无机As-W-Ru、Se-W-Ru簇和Mo-Ru簇化合物；向反应体系中引入有机分子，通过钌离子与有机分子配位，成功得到数十例具有新型结构的有机-无机杂化的Mo(W, Se, V)-Ru簇、As-W-Ru簇、Se-W(Mo, V)-Ru簇等化合物，对所得化合物进行了系统表征，测定了化合物的晶体结构，研究了化合物的热稳定性、在溶液中的稳定性、电化学性质等，初步探讨了部分化合物的电催化活性、对硫醚氧化和醇类氧化反应的催化活性，取得了一些有意义的结果。这些新颖结构化合物的成功制得，创新了钌参与构筑的多金属氧簇化合物的合成方法，丰富了含钌多金属氧簇的结构化学，具有重要的理论意义。同时，对所合成化合物催化活性的研究，在新型催化剂的制备和选择等方面具有重要的指导意义和应用前景。