超薄二维材料负载磁性金属纳米团簇的表/界面组装、反应机理及电催化性能研究

Ultrathin 2D nanomaterials are sheet-like structures with single- or few-layer thickness (typically less than 5 nm), but lateral size larger than 100nm or even up to tens of micrometres. Owing to the ultrahigh specific surface area and strong quantum confinement of electrons in two dimensions, these ultrathin 2D nanomaterials display many unconventional optical, electronic and catalytic performances. Magnetic metal nanoclusters are ultra-small particles protected by functional groups or monolayer ligands. They often have defined compositions and structures with the sizes of less than 3 nm, they show special magnetic property and catalytic activities. In this project, based on the preparation of magnetic metal nanoclusters by our research group and mastered liquid-phase exfoliation method of ultrathin non-carbon two-dimensional materials, Through the bonding effects between the surface ligands of metal nanoclusters and the interface functional groups of two dimensional materials, design and synthesize the metal nanoclusters grown on the two dimensional layered materials, utilize the first principles methods to study the status of support and the change of the interfacial properties of metal nanoclusters on the two-dimensional materials, fully embody the cooperative effects of metal nanoclusters and the two-dimensional materials, investigate the mechanism of the catalytic reaction and then explore the association between the surface/interface structure of metal nanoclusters and two-dimensional materials with the catalytic performance. Our research in this project will help to in-depth understanding the basic scientific issues of catalytic reaction of metal nanoclusters, revealing the structure-activity relationship of the structures of two-dimensional materials and catalytic performance and provide technical support for the development of efficient composite catalysts.

超薄二维纳米材料为单层或几层原子厚度（一般小于5 nm）的片状材料。由于其超大的比表面积和量子效应，表现出超常的光、电及催化性能。磁性金属纳米团簇是一类以表面官能团或配体保护的具有特定结构，尺寸小于3 nm的超微粒子，呈现出独特的磁性质和催化性能。本项目拟以课题组发现的磁性金属纳米团簇制备方法和已经掌握的超薄非碳二维材料的液相剥离途径为基础，通过金属团簇表面的配体与二维材料界面的官能团的键合作用进行表界面设计合成二维层状材料负载的磁性金属纳米团簇复合材料，用第一原理方法研究金属团簇在二维材料表面上的支撑情况和界面性质变化，充分体现金属纳米团簇与超薄二维材料的协同作用，研究催化反应机理，继而探索金属纳米团簇与片状基底的表/界面结构与催化性能之间的关联。本项目的开展将有助于深入理解金属团簇催化反应的一些规律，揭示二维材料的组成结构与催化性能之间的构效关系，为开发高效的复合催化剂提供技术支持。

基于项目研究计划，研究了系列超薄二维材料（MXenes、MOFs、过渡金属硫化物、单或双金属氢氧化物）、超薄二维材料/磁性纳米团簇的制备和表界面性质，建立了新型超薄二维材料、超薄二维材料/磁性纳米团簇复合的组装机制，丰富了新型超薄二维材料及其复合材料的制备方法学。拓展了超薄二维材料与磁性金属、合金纳米团簇、氧化物纳米团簇、磷化物团簇的应用领域，围绕电化学功能导向（包括锂空气电池、锂硫电池、锂离子电池、锌空气电池、电催化等），聚焦于超薄二维材料、复合结构与性能间的构效关系，建立了不同电化学能量转换与存储器件、电磁器件中高性能关键材料的设计策略，实现了长寿命锂空气电池体系、自催化锂空气电池体系、长寿命锂硫电池体系、低电压高效全解水产氢体系、高功率锌空气电池体系和中低频、宽带吸收的电磁器件开发。此外，本项目还开展了部分氧空位型材料、层状稀土氢氧化物纳米片与有机物杂化材料、正电基质材料与多硫化物的主客体复合结构、静电纺丝碳纤维负载磁性纳米团簇/铁氧体纳米团簇的制备及相关性能研究，为开展纳米化学传感器、重金属离子分离、电池中贵金属回收、电磁波吸收等领域的研究积累了重要的实验数据，奠定了理论与实践基础。