结构精确的铜（0）纳米团簇的可控合成与性能研究

Investigating the structure-property correlations as well as the growth mechanism of Cu(0) nanoclusters will shed lights on more scientific advances. In this project, a series of bi-dentate ligands containing both P and S/Se bonding sites are to be designed, synthesized, and used to controllably prepared mono-disperse Cu(0) nanoclusters in the existence of specific reducing agent. A battery of advanced analytical methods will performed to separate, purify, and identify the resultant Cu(0) nanoclusters. Based on the atomically precise structures of Cu(0) nanoclusters, not only the growth mechanism of the nanoclusters can be captured using several in-situ tracking techniques, but the stability and optical, electrochemical, chiral and magnetic properties of these nanoclusters can also be fully investigated. In addition, the combination of experimental and theoretical outcomes enable us to research the ligand effect such as substituent or steric hindrance effect on the chemic-physical properties of Cu(0) nanoclusters. The relationship between geometric/electronic structures and properties can also be determined. Furthermore, the crystal structures of Cu(0) nanoclusters and relevant theoretical calculations will establish the catalysis-structure correlations as well as the mechanism of catalysis on the model reaction of CO electrochemical reduction which using Cu(0) nanoclusters as catalytic agents.

研究铜（0）纳米团簇结构与性能之间的关系，阐明其生长机制，将有可能带来重要的科学发现。本项目拟设计合成一系列具有膦与硫/硒的双配位基配体，筛选合适的强还原剂，发展可控高产率合成铜（0）纳米团簇的方法，合成一系列原子数精确的铜（0）纳米团簇。综合应用各种现代分析方法分离、纯化、鉴定所合成的铜（0）纳米团簇，寻求其晶体结构。应用各种原位跟踪技术研究团簇生长过程。基于精确结构的基础上，应用现代分析方法研究所合成的铜（0）团簇的稳定性、光学、电化学、手性、磁性等。结合理论计算，研究配体对铜（0）纳米团簇的物理化学性质的影响、金属核与配体的表/界面性质的变化、 团簇的几何/电子结构与其性能之间的关系，揭示团簇的前线分子轨道与其理化性质之间的量子化学规律。以铜（0）纳米团簇为催化剂，CO电还原反应为模型反应，借助理论计算模拟反应过程，研究结构与催化性能之间的关系，探究催化反应的机理。

铜具有较强的表面等离子共振与良好的催化性能。合成铜及铜基团簇，研究铜及铜基团簇结构与性能之间的关系，阐明其生长机制，将有可能带来重要的科学发现。本项目通过调控配体的电子性能、设计合成一系列具有膦与硫/硒的双配位基配体，筛选合适的强还原剂，优化合成策略，建立可控高产率合成铜及铜基纳米团簇的方法。应用原位跟踪技术研究团簇生长过程，通过考察反应条件的调控与产物团簇结构之间的对应关系，确定铜基团簇的稳定性影响因素，借助铜的多价态特点重点考察了铜的加入对团簇结构转化演化的影响，阐明铜的价态、浓度（摩尔量）与团簇结构转变的相关性。本项目实施以来（1）通过对铜团簇可控合成的探索，我们获取了30余个具有新颖结构且原子精确的铜及铜基合金团簇，并突破了铜团簇的大尺度合成；（2）基于铜的多价态特点，实现了铜诱导下的转化演化，阐明了铜团簇大小与稳定性的影响因素，谱绘出团簇转化演化的生长路径；（3）实现了催化与导电功能导向性的铜团簇的设计与合成，通过捕获催化反应中间体，发现了铜基团簇催化末端炔烃与内炔的叠氮化炔烃环加成等新反应机理。