Synthesis of High Yield Au<sub>21</sub>(SR)<sub>15</sub> Nanoclusters

Citation: REN Xiuqing, LIN Xinzhang, FU Xuemei, LIU Chao, YAN Jinghui, HUANG Jiahui. Synthesis of High Yield Au₂₁(SR)₁₅ Nanoclusters[J]. Acta Physico-Chimica Sinica, 2018, 34(7): 825-829. doi: 10.3866/PKU.WHXB201712013 shu

Synthesis of High Yield Au₂₁(SR)₁₅ Nanoclusters

任秀清 ^1,2, ,
林欣章 ^1,3, ,
付雪梅 ^1,3, ,
刘超 ^{1,
,} ,
闫景辉 ^2, ,
黄家辉 ^{1,
,}

1.
中国科学院大连化学物理研究所，催化基础国家重点实验室，金催化研究中心，辽宁大连 116023
2.
长春理工大学化学与环境工程学院，长春 130022
3.
中国科学院大学，北京 100049

通讯作者: 刘超, chaoliu@dicp.ac.cn
黄家辉, jiahuihuang@dicp.ac.cn

基金项目:
国家自然科学基金 21601178

国家青年千人计划和中国科学院“战略性先导科技专项” XDA09030103

国家自然科学基金(21601178, 21473186)，国家青年千人计划和中国科学院“战略性先导科技专项”(XDA09030103)资助项目

国家自然科学基金 21473186

摘要: In recent years, Au nanoclusters have attracted much attention as new nanomaterials, which contain several to two hundred Au atoms and are protected by ligands. The structures and properties of Au nanoclusters are usually sensitive to the particle size due to quantum confinement effect. Au nanoclusters have been applied to different fields, such as optical properties, catalysis, and biology. There are two common methods for the synthesis of atomically precise Au nanoclusters: "size focusing" and "ligand exchange". Although a series of Au nanocluster have been obtained via "size focusing" and "ligand exchange", obtaining high yield of such Au nanoclusters is a challenge. Au₂₁(S-Adam)₁₅ was previously synthesized via etching Au₁₈ nanoclusters with excess thiols, and its crystal structure was determined by X-ray diffraction crystallography; however, the yield of Au nanoclusters was low. In this study, we prepared Au₂₁(S-Adam)₁₅ in high yield via conversion of Au₂₃(S-Adam)₁₆ to Au₂₁(S-Adam)₁₅. Firstly, Au₂₃(S-Adam)₁₆ nanoclusters were synthesized using adamantanethiols(HS-Adam) as the protecting ligand and HAuCl₄ as the gold resource in ethyl acetate solvent. Au₂₃(S-Adam)₁₆ were further etched with excess thiols at room temperature. After reacting for 30 min, highly pure Au₂₁(S-Adam)₁₅, with high yield of ~20% based on HAuCl₄ precursor, were successfully prepared. Au₂₃(S-Adam)₁₆ and Au₂₁(S-Adam)₁₅ were characterized by electrospray ionization (ESI), UV-Vis absorption spectroscopy, matrix-assisted laser desorption ionization (MALDI) mass spectrometry, and thermogravimetric analysis (TGA). ESI-MS and UV-Vis spectra confirm the high purity of the Au₂₃(S-Adam)₁₆. After conversion, UV-Vis spectra show the absorption peaks of Au₂₁(S-Adam)₁₅ at 700, 540, 435 and 380 nm. The MALDI-MS of Au₂₁(S-Adam)₁₅ shows several peaks at 6502, 6471, 6106, 5411, and 5048, assigned to Au₂₁(S-Adam)₁₄S, Au₂₁(S-Adam)₁₄, Au₂₀(S-Adam)₁₃, Au₁₉(S-Adam)₁₀, and Au₁₈(S-Adam)₉, respectively. The fragments of Au nanoclusters were produced by the strong laser intensity, which easily removes carbon tails from HS-Adam. Thermogravimetric analysis (TGA) was also performed to check the purity of Au₂₁(S-Adam)₁₅ nanoclusters. The TGA curve shows a weight loss of 42% (expected value, 38%). UV-Vis absorption spectroscopy was performed to track the conversion of Au₂₃(S-Adam)₁₆ to Au₂₁(S-Adam)₁₅. It was found that Au₂₃(S-Adam)₁₆ can convert to Au₂₁(S-Adam)₁₅ with a conversion efficiency of up to 97%, using excess thiols at room temperature within 30 min. In general, we successfully synthesized highly pure Au₂₁(S-Adam)₁₅ nanoclusters, with high yield of ∼20% based on HAuCl₄, by etching Au₂₃(S-Adam)₁₆ with excess thiols at room temperature.

关键词:

English

Synthesis of High Yield Au₂₁(SR)₁₅ Nanoclusters

1.
Gold Catalysis Research Center, State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, P. R. China
2.
School of Chemistry & Environmental Engineering, Changchun University of Science and Technology, Changchun 130022, P. R. China
3.
University of Chinese Academy of Sciences, Beijing 100049, P. R. China

Corresponding author: LIU Chao, chaoliu@dicp.ac.cn HUANG Jiahui, jiahuihuang@dicp.ac.cn

Received Date: 27 October 2017
Accepted Date: 22 November 2017
Revised Date: 22 November 2017
Available Online: 15 July 2018
Fund Project:

The project was supported by the National Natural Science Foundation of China (21601178, 21473186), the Young Thousand Talents Program of China, and the "Strategic Priority Research Program" of the Chinese Academy of Sciences (XDA09030103)

Abstract: In recent years, Au nanoclusters have attracted much attention as new nanomaterials, which contain several to two hundred Au atoms and are protected by ligands. The structures and properties of Au nanoclusters are usually sensitive to the particle size due to quantum confinement effect. Au nanoclusters have been applied to different fields, such as optical properties, catalysis, and biology. There are two common methods for the synthesis of atomically precise Au nanoclusters: "size focusing" and "ligand exchange". Although a series of Au nanocluster have been obtained via "size focusing" and "ligand exchange", obtaining high yield of such Au nanoclusters is a challenge. Au₂₁(S-Adam)₁₅ was previously synthesized via etching Au₁₈ nanoclusters with excess thiols, and its crystal structure was determined by X-ray diffraction crystallography; however, the yield of Au nanoclusters was low. In this study, we prepared Au₂₁(S-Adam)₁₅ in high yield via conversion of Au₂₃(S-Adam)₁₆ to Au₂₁(S-Adam)₁₅. Firstly, Au₂₃(S-Adam)₁₆ nanoclusters were synthesized using adamantanethiols(HS-Adam) as the protecting ligand and HAuCl₄ as the gold resource in ethyl acetate solvent. Au₂₃(S-Adam)₁₆ were further etched with excess thiols at room temperature. After reacting for 30 min, highly pure Au₂₁(S-Adam)₁₅, with high yield of ~20% based on HAuCl₄ precursor, were successfully prepared. Au₂₃(S-Adam)₁₆ and Au₂₁(S-Adam)₁₅ were characterized by electrospray ionization (ESI), UV-Vis absorption spectroscopy, matrix-assisted laser desorption ionization (MALDI) mass spectrometry, and thermogravimetric analysis (TGA). ESI-MS and UV-Vis spectra confirm the high purity of the Au₂₃(S-Adam)₁₆. After conversion, UV-Vis spectra show the absorption peaks of Au₂₁(S-Adam)₁₅ at 700, 540, 435 and 380 nm. The MALDI-MS of Au₂₁(S-Adam)₁₅ shows several peaks at 6502, 6471, 6106, 5411, and 5048, assigned to Au₂₁(S-Adam)₁₄S, Au₂₁(S-Adam)₁₄, Au₂₀(S-Adam)₁₃, Au₁₉(S-Adam)₁₀, and Au₁₈(S-Adam)₉, respectively. The fragments of Au nanoclusters were produced by the strong laser intensity, which easily removes carbon tails from HS-Adam. Thermogravimetric analysis (TGA) was also performed to check the purity of Au₂₁(S-Adam)₁₅ nanoclusters. The TGA curve shows a weight loss of 42% (expected value, 38%). UV-Vis absorption spectroscopy was performed to track the conversion of Au₂₃(S-Adam)₁₆ to Au₂₁(S-Adam)₁₅. It was found that Au₂₃(S-Adam)₁₆ can convert to Au₂₁(S-Adam)₁₅ with a conversion efficiency of up to 97%, using excess thiols at room temperature within 30 min. In general, we successfully synthesized highly pure Au₂₁(S-Adam)₁₅ nanoclusters, with high yield of ∼20% based on HAuCl₄, by etching Au₂₃(S-Adam)₁₆ with excess thiols at room temperature.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

Synthesis of High Yield Au₂₁(SR)₁₅ Nanoclusters

通讯作者: 刘超, chaoliu@dicp.ac.cn
黄家辉, jiahuihuang@dicp.ac.cn

English

Synthesis of High Yield Au₂₁(SR)₁₅ Nanoclusters

Corresponding author: LIU Chao, chaoliu@dicp.ac.cn HUANG Jiahui, jiahuihuang@dicp.ac.cn

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Synthesis of High Yield Au21(SR)15 Nanoclusters

通讯作者: 刘超, chaoliu@dicp.ac.cn 黄家辉, jiahuihuang@dicp.ac.cn

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Synthesis of High Yield Au21(SR)15 Nanoclusters

Corresponding author: LIU Chao, chaoliu@dicp.ac.cn HUANG Jiahui, jiahuihuang@dicp.ac.cn

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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