镍/铜取代型钨-氧簇有机骨架的合成及其催化性质研究

Cluster Organic Frameworks (COFs), as a novel supramolecular structures, which were composed of metal-oxygen clusters as secondary structural units and organic molecule as pillars. The combination of metal-oxygen clusters and organic molecules offers endless possibilities for the structure and properties of cluster organic frameworks. COFs have been applied in gas adsorption/separation, sensing, catalysis, magnetism and other fields. .In this work, we plan to synthesize novel cluster organic frameworks which were formed by Ni6PW9/Cu6GeW9 as secondary structural unit. Firstly, we design and synthesize a series of polycyclic aromatic hydrocarbons and derivatives of thiophene as bridge molecules, and then use hydrothermal method to prepare cluster organic frameworks which were composed of metal oxygen clusters and organic rigid bridge molecules. Focusing on the study of their own properties, such as crystal structure, optical properties, magnetic properties; and the adsorption and separation properties of cluster organic frameworks, such as the separation of olefin/paraffin and methane storage. In addition, the COF which was composed of six-core copper would be explored as water oxidation catalysts in different solvents; and the COF which was composed of six-core nickel would be applied as the organic catalyst in Suzuki-Miyaura Reaction. These research results would help to expand the synthesis of cluster organic frameworks and their applications in energy field and industrial production.

氧合团簇有机骨架(Cluster Organic Frameworks)是由金属-氧簇为次级结构单元和有机分子为桥连分子构成的不同维度超分子结构。在气体选择性吸附/分离、传感、催化以及磁性等领域具有潜在的应用。本项目拟选取Ni6PW9/Cu6GeW9为次级结构单元制备新型氧合团簇有机骨架。设计、合成多环芳香烃类分子和噻吩衍生物，再采用水热法制备由有机刚性桥连分子与金属-氧簇组成的不同维度氧合团簇有机骨架。着重研究其物理化学性质，主要包括：晶体结构、光学性质、磁学性质等；研究氧合团簇有机骨架的吸附分离性能，如分离烯烃/石蜡和甲烷气体储存；此外研究由六核铜构成的氧合团簇有机骨架在不同溶剂条件下的电催化产氧性能和由六核镍构成的氧合团簇有机骨架在Suzuki-Miyaura反应中的催化性能。研究成果将有助于扩展氧合团簇有机骨架的合成，拓展其在能源领域和工业生产中的应用。

氧合团簇有机骨架(Cluster Organic Frameworks)是由金属-氧簇为次级结构单元和有机分子为桥连分子构成的不同维度超分子结构。在选择性吸附/分离、传感、催化以及磁性等领域具有潜在的应用。本项目实现了镍/铜取代的钨-氧簇作为次级结构单元为研究对象，设计、合成了多环芳香烃羧酸分子，再采用水热法制备由有机刚性桥连分子与金属-氧簇组成的不同维度的氧化团簇有机骨架。同时，实现了金属-氧簇和镍/铜取代型钨-氧簇有机骨架的光催化、电催化、磁性等领域的研究。此外，在完成项目工作外，还积极拓展金属-氧簇的应用和碳基材料的性能研究，包括金属-氧簇@石墨炔复合材料、石墨炔纳米墙、纳米氧化镍、铜基石墨烯等材料的合成及其电化学性质研究。本项目的完成对于氧合团簇有机骨架和金属-氧簇碳基复合材料的合成及其电化学性质研究提供了一定的指导意义。