配体修饰的贵金属原子簇+多金属氧簇纳米复合团簇的制备，结构及其催化性能研究

In this project, multidentate functional thiolate(SR) and phenylphosphine(PPhXR3-X) ligands and their related derivatives were applied to functionalize the surface of the precursor including Au(PPh3)Cl and [Pd(Ph2P(CH2)2PPh2)Cl2] which contained noble metal elements, with suitable reducing agents such as NaBH4 and solvent, atomically precise noble metal nanoclusters with different topology structure could be formed through nuclearity convergence and sever as cationic clusters. Then a serial of polyoxometalates(POMs) clusters with diverse topologic structure and charge including Keggin，Anderson and Waugh type POMs, especially Anderson type clusters that can incorporate the transition metal elements(Fe, Co, Ni, Cu, Zn ) as central heteroatom were designed and synthesized as anionic clusters. Through electrostatic interaction and charge balance, the corresponding cationic clusters and anionic clusters would be effectively combined forming bi-nanocluster multi-metal based complex nanocluster. We intended to develop a stepwise and controllable method to obtain novel organic-inorganic hybrid complex nanocluster materials. Their structure will be characterized by proper characterization including single-crystal X-ray diffraction to investigate the self-assemble law between these cationic clusters and anionic clusters with different topologic structure and charge .The influence of different surface ligands to induce cluster with specific core number will be explored. Finally, under the mediation of POMs anionic clusters, the multifunctional catalysis property of these complex clusters including the selective oxidation of benzenemethanol and cyclohexane will be further investigated. Combined with quantum calculation, the relationship of crystal structures and properties will also be explored. The project will enrich the structural chemistry of noble metal nanoclusters and POMs，promote the development of ligand covalent functionalization chemistry of clusters, lay down the foundation for developing ligand functionalized, stable and effective nanocluster catalytic organic-inorganic hybrid materials and the correlated applications.

本项目拟选用硫醇和苯基膦类有机配体，对贵金属（Au，Pd）前驱体表面进行共价修饰，在NaBH4等还原剂和不同溶剂的诱导下形成原子精确的贵金属团簇阳离子。然后选用和制备多种多酸阴离子簇包括Keggin，Anderson和Waugh型多酸，特别是中心可以引入过渡金属杂原子（Fe，Co，Ni，Cu，Zn）Anderson多酸，通过阴阳离子之间静电作用进行有效的复合，发展一种分步可控制备新颖的有机-无机杂化多金属复合团簇材料的方法。对其结构进行包括单晶衍射方面的表征，考察不同拓扑结构及带电荷数的阴/阳离子簇之间复合组装的规律，团簇表面有机配体对其成核规律的影响, 进一步探索考察复合团簇在多酸调控下催化氧化方面的性能，包括苯甲醇，环己烷选择性氧化方面的性能，并结合理论计算研究其晶体结构与功能性质之间的构效关系。本项目的研究将丰富团簇的结构化学，为构筑稳定，高效的复合团簇催化剂及其应用奠定基础。

本项目以精准合成的金属原子簇主要包括贵金属团簇、多金属氧簇及其相应的复合团簇以及部分衍生单原子催化剂作为一类原子级结构明确研究载体，利用大科学装置同步辐射发展单晶衍射、粉末衍射从头法结构解析、XASF、PDF等先进精准结构探测手段实现对多层级复杂材料精准结构探测解析,并建立相应精准构效关系。深刻理解催化反应相关机制为特定性能高效新型催化材料精准合成起到指导设计作用。在本项目资助下，以通讯作者共发表论文24篇主要包括： Angew. Chem. Int. Ed.（1篇）; Adv. Energy Mater.（1篇）; Nano Energy（3篇）; J. Mater. Chem. A(1篇); Chem. Sci.( 1篇); Acs Appl. Mater. Interfaces(2篇); Nanoscale (2篇); J.Mater.Chem.C. (1篇); Inorg. Chem. Front. (1篇); Nanoscale Adv. (1篇); Dalton. Trans. (2篇); CrystEngComm (1篇)；Ind. Eng. Chem. Res. (1篇)；Catalysts (1篇); New J. Chem. (2篇); Chin. Sci. Bull. (1篇); Chin. J. Inorg. Chem(2篇)。以第一作者共发表论文8篇主要包括：Nat. Commun. (1篇); Coord. Chem. Rev.(1篇); Nano Res.(3篇) ;Chem. Commun.（2篇）; Phys. Sci. Rev. (1篇); 成果目前申请美国专利1项，中国专利4项。第一作者撰写英文专著Chemistry of Nanomaterials - A Practical Guide的相关章节，出版国内首部基于olex2晶体结构解析与可视化中文专著1部。