<i>In situ</i> Study of Formation Kinetics of Au Nanoclusters during HCl and Dodecanethiol Etching

Citation: YANG Lina, HUANG Li, SONG Xueyang, HE Wenxue, JIANG Yong, SUN Zhihu, WEI Shiqiang. In situ Study of Formation Kinetics of Au Nanoclusters during HCl and Dodecanethiol Etching[J]. Acta Physico-Chimica Sinica, 2018, 34(7): 762-769. doi: 10.3866/PKU.WHXB201801084 shu

金纳米团簇在盐酸和十二硫醇刻蚀作用下的原位生长动力学研究

杨丽娜 ^1,2, ,
黄莉 ^1, ,
宋雪洋 ^1, ,
贺文雪 ^1, ,
姜泳 ^1, ,
孙治湖 ^{1,
,} ,
韦世强 ^{1,
,}

1.
中国科学技术大学国家同步辐射实验室，合肥 230029
2.
合肥工业大学食品科学与工程学院，合肥 230009

通讯作者: 孙治湖, zhsun@ustc.edu.cn
韦世强, sqwei@ustc.edu.cn

基金项目:
国家重点研究发展计划 2017YFA0402800

国家自然科学基金 11475176

国家自然科学基金 11621063

国家自然科学基金 21533007

国家自然科学基金 U1632263

国家重点研究发展计划(2017YFA0402800)和国家自然科学基金(11475176, U1632263, 21533007, 11621063)资助项目

摘要: 了解金属纳米团簇的形成机制对于进一步发展其化学制备方法是必要的。我们利用盐酸(HCl)和十二硫醇(RSH)共同刻蚀L₃ (L₃: 1, 3-双二苯基膦丙烷)包覆的多分散性的Au_n (15 ≤ n ≤ 60)团簇成功制备出单分散性的Au₁₃(L₃)₂(SR)₄Cl₄纳米团簇，并结合原位同步辐射X射线吸收谱、原位真空紫外-可见吸收光谱和质谱技术，研究了Au₁₃(L₃)₂(SR)₄Cl₄纳米团簇的动力学形成过程。结果表明，Au团簇从多分散到单分散的转变经历了3个明显不同的动力学步骤。首先，尺寸较大的多分散金属团簇Au_n主要在HCl刻蚀作用下，形成尺寸较小的亚稳的中间产物Au₈–Au₁₁团簇。然后，这些中间产物与反应溶液中已有的Au(Ⅰ)-Cl物种反应，并与SR发生部分配体交换，逐渐长大为由SR和L₃保护的Au₁₃团簇。最后，形成的Au₁₃团簇经过一个较缓慢的结构重组过程，最终形成稳定的Au₁₃(L₃)₂(SR)₄Cl₄的纳米团簇。

关键词:

English

In situ Study of Formation Kinetics of Au Nanoclusters during HCl and Dodecanethiol Etching

YANG Lina ^1,2, ,
HUANG Li ^1, ,
SONG Xueyang ^1, ,
HE Wenxue ^1, ,
JIANG Yong ^1, ,
SUN Zhihu ^{1,
,} ,
WEI Shiqiang ^{1,
,}

1.
National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, P. R. China
2.
School of Food Science and Engineering, Hefei University of Technology, Hefei 230009, P. R. China

Corresponding author: SUN Zhihu, zhsun@ustc.edu.cn WEI Shiqiang, sqwei@ustc.edu.cn

Received Date: 06 December 2017
Accepted Date: 02 January 2018
Revised Date: 30 December 2017
Available Online: 15 July 2018
Fund Project:

The project was supported by the National Key Research and Development Program of China (2017YFA0402800) and the National Natural Science Foundation of China (11475176, U1632263, 21533007, and 11621063)

Abstract: Gold nanoclusters are promising materials for a variety of applications because of their unique "superatom" structure, extraordinary stability, and discrete electronic energy levels. Controlled synthesis of well-defined Au nanoclusters strongly depends on rational design and implementation of their synthetic chemistry. Among the numerous approaches for the synthesis of monodisperse Au nanoclusters, etching of pre-formed polydisperse clusters has been widely employed as a top-down method. Understanding the formation mechanism of metal nanoclusters during the etching process is important. Herein, we synthesized monodisperse Au₁₃(L₃)₂(SR)₄Cl₄ nanoclusters via an etching reaction between polydisperse 1, 3-bis(diphenyl-phosphino)propane (L₃)-protected polydisperse Au_n (15 ≤ n ≤ 60) clusters and a mixed solution of HCl/dodecanethiol (SR). The Au₁₃ product, with a mean size of (1.1 ± 0.2) nm, shows pronounced step-like multiband absorption peaks centered at 327, 410, 433, and 700 nm. The synthetic protocol has a suitable reaction rate that allowss for real-time spectroscopic studies. We used a combination of in situ X-ray absorption fine structure (XAFS) spectroscopy, UV-Vis absorption spectroscopy, and matrix-assisted laser desorption ionization mass-spectrometry (MALDI-MS) to study the kinetic formation process of monodisperse Au₁₃ nanoclusters. Emphasis was given to the detection of reaction intermediates. The study revealed that the size-conversion of the Au₁₃ nanoclusters can be divided into three stages. In the first stage, the polydisperse Au₁₅–Au₆₀ clusters, covering a wide m/z range of 3000-13000, are prominently decomposed into smaller Au₈-Au₁₁ (within a m/z range of 3000–4000) species owing to the etching effect of HCl. They are immediately stabilized by the absorbed SR, L₃, and Cl^- ligands to form metastable intermediates, as indicated by the high intensity of the Au-ligand coordination peak at 0.190 nm as well as the low intensity of the Au–Au peaks (0.236 and 0.288 nm) in the Fourier-transform (FT) EXAFS spectra. In the second stage, these Au₈–Au₁₁ intermediates are grown into Au₁₃ cores. The experimental X-ray absorption near-edge spectra, totally different from that of Au(Ⅰ)-SR polymer, could be well reproduced by the calculated spectrum of the Au₁₃P₈Cl₄ cluster. The Au-ligand coordination number (1.0) obtained from the EXAFS fitting is much closer to the nominal values in Au₁₃(L₃)₂(SR)₄Cl₄ (0.92) than to that in Au(Ⅰ)-SR polymers (2.0), suggesting that majority of the Au atoms are in the form of Au₁₃ clusters. The driving force for this growth process is primarily the geometric factor to form a complete icosahedral Au₁₃ skeleton through the incorporation of Au(Ⅰ) ions or Au(Ⅰ)-Cl oligomers pre-existing in the solution. In the third stage, the composition of the clusters is nearly unchanged as indicated by the MALDI-MS and the UV-vis spectra; however, their atomic structure undergoes rearrangement to the energetically stable structure of Au₁₃(L₃)₂(SR)₄Cl₄. During this structural rearrangement, the central-peripheral and peripheral-peripheral Au–Au bond lengths (R_Au-Au(c-p) and R_Au-Au(p-p)) decrease from 0.272 to 0.267 nm and 0.295 to 0.289 nm, respectively, resulting in considerable structural distortion of the original icosahedral Au₁₃ skeleton. This distortion is also reflected by the slightly increased disorder degree of the Au-Au bonds from 0.00015 to 0.00017 nm². This work expands our understanding of the kinetic growth process of metal nanoclusters and promotes design and synthesis of metal nanomaterials in a controllable manner.

Key words:

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

金纳米团簇在盐酸和十二硫醇刻蚀作用下的原位生长动力学研究

通讯作者: 孙治湖, zhsun@ustc.edu.cn
韦世强, sqwei@ustc.edu.cn

English

In situ Study of Formation Kinetics of Au Nanoclusters during HCl and Dodecanethiol Etching

Corresponding author: SUN Zhihu, zhsun@ustc.edu.cn WEI Shiqiang, sqwei@ustc.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

金纳米团簇在盐酸和十二硫醇刻蚀作用下的原位生长动力学研究

通讯作者: 孙治湖, zhsun@ustc.edu.cn 韦世强, sqwei@ustc.edu.cn

English

In situ Study of Formation Kinetics of Au Nanoclusters during HCl and Dodecanethiol Etching

Corresponding author: SUN Zhihu, zhsun@ustc.edu.cn WEI Shiqiang, sqwei@ustc.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

通讯作者: 孙治湖, zhsun@ustc.edu.cn
韦世强, sqwei@ustc.edu.cn

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs