通过盐酸刻蚀和生长作用来选择性合成不同尺寸大小的金纳米团簇（英文）

Selective Synthesis of Different-Sized Gold Nanoclusters through HCI-Etching and-Growth Effect

本文在两个Auss的合成反应过程中，在不同的反应时间加入盐酸调控反应路径，分别能合成Au7和Au13团簇．用原位质谱和原位紫外可见光吸收谱监测这两个盐酸加入后的反应过程，发现盐酸在Au7和Au13团簇的合成反应中分别起着刻蚀剂和生长剂的作用．分别用H^＋和Cl^-代替盐酸来重复上述的反应，发现盐酸中的H^＋和Cl^-分别起着刻蚀和生长作用．构建了盐酸对团簇的刻蚀和生长作用机理即盐酸中的H^＋可以使团簇表面的Au（I）-PPha键断裂，从而实现团簇的刻蚀；盐酸中的Cl^-能促使溶液中产生含Au-Cl键的前驱物，这些前驱物通过化学吸附作用吸附在团簇表面，从而使团簇长大．

Controllable syntheses of different-sized gold nanoclusters are of great significance for their fundamental science and practical applications. In this work, we achieve the controllable and selective syntheses of Au7 and Au13 clusters through adding HCl to the traditional Aull synthetic route at different reaction time. Time-dependent mass spectra and UV- Vis spectra were ernployed to monitor these two HCl-directed processes, and revealed the distinct roles of HCl as an etchant or a growth prornotor, respectively. Furthermore, parallel experiments on independent synthetic routes involving only non-chlorine H＋ （acetic acid） or Cl （tetraethy larnrnoniurn chloride） instead of HCl were perforrned, which illustrated the main role of H^＋-etching and Cl^ -assisted growth in HCl-directed cluster synthetic routes. We propose the HCl-etching is mainly achieved via the H＋ action to break the Au（I）-PPh3 part of clusters, while the HCl-prornoted growth is realized via the attachment of Au-Cl species to the pre-forrned clusters.