异种金属原子掺杂Au纳米团簇的HOMO-LUMO能隙以及电催化性质研究

The novel optical, catalysis and electrical properties of Au nanolusters have attracted intense attention of many research teams. Recently, the HOMO-LUMO energy gap and electrocatalysis properties of Au nanoclusters are a hotspot in current research. At present most of the reports are focus on the properties of the single elemental Au nanoclusters, but the research of HOMO-LUMO energy gap and electrocatalysis properties of Au nanoclusters doped by dissimilar metals atom is rarely studied. What kind of impact in the HOMO-LUMO energy gap structure will be found when the dissimilar metal atoms doped into the Au nanoclusters. Do the electrocatalic performances of alloyed Au nanoclusters improve? In order to solve these scientific problems and pave a new study direction for the Au nanoclusters, we will carry out a system work in three aspects. (1) Developing some method to synthesis the Au nanclusters doped with dissimilar metal atoms and using a variety of characterization methods to determine the compositions and structure of alloyed Au nanoclusters; (2) Using the method of differential pulse voltammetry to study the HOMO-LUMO energy gap of alloyed Au nanoclusters, and getting the influencing mechanism based on the theoretical calculation; (3) Selecting a superior performance catalyst for oxygen reduction reaction. To complete these work, it can not only improve the level of the basic research but also have a certain application value.

具有新颖光学、催化和电学性质的Au纳米团簇吸引了很多研究组关注, Au纳米团簇的HOMO-LUMO能隙以及电催化性质是当前的研究热点。然而大部分的报道是以单质Au纳米团簇的性质研究为主，研究异种金属掺杂的Au纳米团簇的HOMO-LUMO能隙以及电催化性质报道还较少。异种金属原子掺杂会对Au纳米团簇的HOMO-LUMO的能隙产生何种影响？异种金属的掺杂是否会提升团簇的电催化性能？为了解答这些科学问题和开拓新的研究方向，我们将开展三个方面工作：(1)发展异种金属掺杂Au纳米团簇的合成方法，并且通过多种表征手段确定其结构和组成；(2)利用电化学微分脉冲伏安方法研究异种金属掺杂Au纳米团簇的HOMO-LUMO能隙结构，结合理论计算探讨其影响机制；(3)筛选出性能优越氧还原电催化剂。完成这些工作，不仅对基础研究有促进，同时具备一定的应用价值。

针对单质Au纳米团簇经过异种金属元素掺杂后对HOMO-LUMO能带以及电催化性质研究较少的现状，发展了一种简单高效的Cu掺杂Au纳米团簇的方法，获得了多种掺杂个数不同的纳米团簇。虽然获得此类合金团簇的晶体结构，但是Cu掺杂的Au纳米团簇的个数不确定，导致单晶解析较为困难。因此在项目的执行过程中将研究方向改进为纯Au纳米团簇的合成与分离提纯、结构解析以及HOMO-LUMO能隙等性质的研究。项目执行中获得了多个具有新颖结构的Au纳米团簇，比如合成和解析出Au56(TBBT)34团簇结构，发现了Au纳米团簇的极性和荧光性质与团簇内核的层数有关，表现出特殊的奇-偶层数相关性；另外合成和解析出Au49(2,4-DMBT)27结构，发现此团簇的内核由fcc和非fcc单元组合而成，并且此结构影响了团簇的HOMO-LUMO能带。项目负责人以第一作者身份发表了4篇研究论文：包括了2篇Angew. Chem., Int. Ed.，1篇Anal. Chem., 以及1篇Chem. Commun.。这些工作将有助于人们进一步认识金属纳米团簇的特殊性质，并且有可能在相关领域获得较大的应用。

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