物理化学学报 >> 2018, Vol. 34 >> Issue (7): 825-829.doi: 10.3866/PKU.WHXB201712013

所属专题: 原子水平上精确控制纳米簇和纳米粒子

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合成高产率的Au21(SR)15纳米簇

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. 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
  • 收稿日期:2017-10-27 发布日期:2018-03-26
  • 通讯作者: 刘超,黄家辉 E-mail:chaoliu@dicp.ac.cn;jiahuihuang@dicp.ac.cn
  • 基金资助:
    国家自然科学基金(21601178);国家自然科学基金(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)

Synthesis of High Yield Au21(SR)15 Nanoclusters

Xiuqing REN1,2,Xinzhang LIN1,3,Xuemei FU1,3,Chao LIU1,*(),Jinghui YAN2,Jiahui HUANG1,*()   

  1. 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
  • Received:2017-10-27 Published:2018-03-26
  • Contact: Chao LIU,Jiahui HUANG E-mail:chaoliu@dicp.ac.cn;jiahuihuang@dicp.ac.cn
  • Supported by:
    the National Natural Science Foundation of China(21601178);the National Natural Science Foundation of China(21473186);the Young Thousand Talents Program of China, and the "Strategic Priority Research Program" of the Chinese Academy of Sciences(XDA09030103)

摘要:

近年来,精确原子个数的金纳米簇因其在催化、生物医药、传感等领域具有潜在应用而备受关注。本研究中使用金刚烷硫醇(HS-Adam)作为配体制备了Au23(S-Adam)16纳米簇。在室温条件下,通过HS-Adam刻蚀Au23(S-Adam)16纳米簇,得到了纯度较高的Au21(S-Adam)15,其转换率可达20% (根据金原子计算)。并通过紫外可见吸收光谱(UV-Vis),电喷雾(ESI)和基质辅助激光解析飞行时间(MALDI)质谱以及热重分析(TGA)对合成的金纳米簇进行表征。

关键词: 金纳米簇, Au21(S-Adam)15, 高产率

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: Gold nanocluster, Au21(S-Adam)15, High-yield

MSC2000: 

  • O641