VIII族双金属纳米结构的制备、催化偶联与依数性关系研究

This project to tend to develop a mild, non-hydrothermal, non-solvothemal solution synthetic route for the controllable preparation of group VIII bimetallic nanostructures including their solid solutions, and to investigate the growth mechanism of the nanoparticles and their catalytic performances in carbon-carbon cross-coupling reaction with colligative-like property in both oil and water systems. In the current proposal, the composition and structure of the biematallic nanoparticles will be tuned with the variation of reaction conditions, typically via kinetic controlling in the specific procedures, and the reaction and growth mechanisms will be revealed at the same time. In addition, the physical and chemical properties, especially the nanochemistry of catalytic activity of the biemetallic nanoparticles will be evaluated via performing catalysis of carbon-carbon cross-coupling reactions such as the ones of Suzuki, Ullmann and Stille ones. Through the intensive investigations, the highly catalytic performances of the catalysis and the relations between the properties with the composition and structure of the bimetallic nanoparticles, mainly the colligative-like property, will be achieved. This proposal will provide a feasible way to group VIII bimetallic nanoparticles, which is also available for various systems of bimetals, and the pre-proposal study has suggests that the bimetallic nanoparticles have obvious merits for the catalysis of organic reactions since that the bimetallic nanoparticles as catalyst can be easily performed in solutions without any surface modification and addition of phosphorus ligands. This work also presents a new space for the understanding of nanocatalysis and nanochemistry of bimetals, which may provide potential applications in techniques.

本申请旨在设计和发展一种非水热非溶剂热的VIII族双金属纳米材料的合成途径，实现其控制制备，并研究其催化偶联与依数性关系。着重利用动力学控制途径实现VIII族双金属纳米材料的温和制备与生长，并从微观动力学角度探明VIII族双金属在温和条件下的生长机理，实现VIII族双金属纳米材料组分分数在较大范围内(准)连续控制。通过研究所制备VIII族双金属纳米材料的磁性和纳米化学性质，探明其组成、结构与性质之间的关系，特别是研究和探明其催化碳-碳偶联反应与其依数性间的关系与规律，为VIII族双金属纳米材料的功能拓展和应用提供基础。

VIII族金属及其合金具有独特的原子结构与电子构型，其物理化学性能优异。在材料、能源、化工、凝聚态物理、固体化学、环境治理与保护、化学催化以及能量转换等众多学科领域都有着广泛的理论研究和应用研究价值。本项目在前期工作基础上，利用设计温和的液相合成方法，控制制备出NiPt、NiPd、CuPd、NiCoP、CuPdPt、CuPdPt/C和NiSe-MoSe2等多种VIII族双金属、多金属及VIII族金属化合物功能纳米材料，并详细研究了所制备纳米材料的组成、结构、微结构和形成过程与机理，以及其在催化偶联、电催化、光电探测等方面的性能。同时探讨了其纳米物理、化学性能与材料组成和结构之间的相互关系，探明了其内在关系和机理，取得了一些有意义的研究结果。本项目研究丰富了VIII族双金属、多金属及其相关化合物纳米材料的合成研究，为相关固溶体系纳米材料及其纳米复合结构的控制制备提供了有价值的借鉴，是对材料合成化学和功能纳米材料制备和性能研究的有益补充和拓展。在项目开展以来，部分研究结果已在Nano Letters等学术刊物上发表，目前已发表标注本基金项目资助的研究论文 28 篇。其中，以第一标注在Nano Letters、Chemistry of Materials、Journal of Materials Chemistry A （2篇）、Nanoscale（3篇）、APL Materials、Advanced Materials Interfaces、CrystEngComm、Electrochimica Acta和Dalton Transactions上发表研究论文12篇；以第二标注在Chemistry of Materials、Small、Nanoscale、Advanced Science、Journal of Power Sources、Journal of Materials Chemistry A、ACS Applied Materials & Interfaces和RSC Advances上发表研究论文8篇；以第三标注在Nano Letters等刊物上发表研究论文4篇；第四标注论文4篇；后续另有数篇关联研究工作将会陆续发表。获得授权发明专利1项。项目开展期间，培养毕业博士研究生 6 名，硕士研究生1名。