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

REN Xiuqing ^1,2 ,
LIN Xinzhang ^1,3 ,
FU Xuemei ^1,3 ,
LIU Chao ^1,, ,
YAN Jinghui ² ,
HUANG Jiahui ^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

Corresponding author: LIU Chao, chaoliu@dicp.ac.cn HUANG Jiahui, jiahuihuang@dicp.ac.cn
Received Date: 27 October 2017
Revised Date: 22 November 2017
Accepted Date: 22 November 2017
Available Online: 1 July 2017
Fund Project: the National Natural Science Foundation of China 21601178the Young Thousand Talents Program of China, and the "Strategic Priority Research Program" of the Chinese Academy of Sciences XDA09030103The 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)the National Natural Science Foundation of China 21473186

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.
- Gold nanocluster,
- Au₂₁(S-Adam)₁₅,
- High-yield
1. [1]
  Jin, R.; Zeng, C.; Zhou, M.; Chen, Y. Chem. Rev. 2016, 116 (18), 10346. doi: 10.1021/acs.chemrev.5b00703 doi: 10.1021/acs.chemrev.5b00703
2. [2]
  Qian, H.; Zhu, M.; Wu, Z.; Jin, R. Acc. Chem. Res. 2012, 45 (9), 1470. doi: 10.1021/ar200331z doi: 10.1021/ar200331z
3. [3]
  Priecel, P.; Salami, H. A.; Padilla, R. H.; Zhong, Z. Y.; Lopez-Sanchez, J. A. Chin. J. Catal. 2016, 37 (10), 1619. doi: 10.1016/S1872-2067(16)62475-0 doi: 10.1016/S1872-2067(16)62475-0
4. [4]
  Rosi, N. L.; Mirkin, C. A. Chem. Rev. 2005, 105 (4), 1547. doi: 10.1021/cr030067f doi: 10.1021/cr030067f
5. [5]
  Dass, A.; Theivendran, S.; Nimmala, P. R.; Kumara, C.; Jupally, V. R.; Fortunelli, A.; Sementa, L.; Barcaro, G.; Zuo, X.; Noll, B. C. J. Am. Chem. Soc. 2015, 137 (14), 4610. doi: 10.1021/ja513152h doi: 10.1021/ja513152h
6. [6]
  Jin, R. Nanoscale 2010, 2 (3), 343. doi: 10.1039/b9nr00160c doi: 10.1039/b9nr00160c
7. [7]
  Zhu, M.; Aikens, C. M.; Hollander, F. J.; Schatz, G. C.; Jin, R. J. Am. Chem. Soc. 2008, 130 (18), 5883. doi: 10.1021/ja801173r doi: 10.1021/ja801173r
8. [8]
  Heaven, M. W.; Dass, A.; White, P. S.; Holt, K. M.; Murray, R. W. J. Am. Chem. Soc. 2008, 130 (12), 3754. doi: 10.1021/ja800561b doi: 10.1021/ja800561b
9. [9]
  Qian, H.; Eckenhoff, W. T.; Zhu, Y.; Pintauer, T.; Jin, R. J. Am. Chem. Soc. 2010, 132 (24), 8280. doi: 10.1021/ja103592z doi: 10.1021/ja103592z
10. [10]
  Liu, C.; Li, T.; Li, G.; Nobusada, K.; Zeng, C.; Pang, G.; Rosi, N. L.; Jin, R. Angew. Chem. Int. Ed. 2015, 54 (34), 9826. doi: 10.1021/ja103592z doi: 10.1021/ja103592z
11. [11]
  Song, Y.; Fu, F.; Zhang, J.; Chai, J.; Kang, X.; Li, P.; Li, S.; Zhou, H.; Zhu, M. Angew. Chem. Int. Ed. 2015, 54 (29), 8430. doi: 10.1002/anie.201501830 doi: 10.1002/anie.201501830
12. [12]
  Chen, Y.; Zeng, C.; Liu, C.; Kirschbaum, K.; Gayathri, C.; Gil, R. R.; Rosi, N. L.; Jin, R. J. Am. Chem. Soc. 2015, 137 (32), 10076. doi: 10.1021/jacs.5b05378 doi: 10.1021/jacs.5b05378
13. [13]
  Das, A.; Li, T.; Nobusada, K.; Zeng, Q.; Rosi, N. L.; Jin, R. J. Am. Chem. Soc. 2012, 134 (50), 20286. doi: 10.1021/ja3101566 doi: 10.1021/ja3101566
14. [14]
  Pei, Y.; Zeng, X. C. Nanoscale 2012, 4 (14), 4054. doi: 10.1039/c2nr30685a doi: 10.1039/c2nr30685a
15. [15]
  Philip, R.; Chantharasupawong, P.; Qian, H.; Jin, R.; Thomas, J. Nano Lett. 2012, 12 (9), 4661. doi: 10.1021/nl301988v doi: 10.1021/nl301988v
16. [16]
  Rosi, N. L.; Giljohann, D. A.; Thaxton, C. S.; Lytton-Jean, A. K.; Han, M. S.; Mirkin, C. A. Science 2006, 312 (5776), 1027. doi: 10.1126/science.1125559 doi: 10.1126/science.1125559
17. [17]
  Li, G.; Jin, R. J. Am. Chem. Soc. 2014, 136 (32), 11347. doi: 10.1021/ja503724j doi: 10.1021/ja503724j
18. [18]
  Yoskamtorn, T.; Yamazoe, S.; Takahata, R.; Nishigaki, J. I.; Thivasasith, A.; Limtrakul, J.; Tsukuda, T. ACS Catal. 2014, 4 (10), 3696. doi: 10.1021/cs501010x doi: 10.1021/cs501010x
19. [19]
  Fang, J.; Li, J.; Zhang, B.; Yuan, X.; Asakura, H.; Tanaka, T.; Teramura, K.; Xie, J.; Yan, N. Nanoscale 2015, 7 (14), 6325. doi: 10.1039/c5nr00549c doi: 10.1039/c5nr00549c
20. [20]
  Tan, Y.; Liu, X. Y.; Zhang, L.; Wang, A.; Li, L.; Pan, X.; Miao, S.; Haruta, M.; Wei, H.; Wang, H.; et al. Angew. Chem. Int. Ed. 2017, 56 (10), 2709. doi: 10.1002/anie.201610736 doi: 10.1002/anie.201610736
21. [21]
  Monnier, F.; Taillefer, M. Angew. Chem. Int. Ed. 2009, 48 (38), 6954. doi: 10.1002/anie.200804497 doi: 10.1002/anie.200804497
22. [22]
  Chen, H. J.; Liu, C.; Wang, M.; Zhang, C. F.; Li, G.; Wang, F. Chin. J. Catal. 2016, 37 (10), 1787. doi: 10.1016/S1872-2067(16)62478-6 doi: 10.1016/S1872-2067(16)62478-6
23. [23]
  Ishida, R.; Arii, S.; Kurashige, W.; Yamazoe, S.; Koyasu, K.; Negishi, Y.; Tsukuda, T. Chin. J. Catal. 2016, 37 (10), 1656. doi: 10.1016/S1872-2067(16)62501-9 doi: 10.1016/S1872-2067(16)62501-9
24. [24]
  Zhou, Y.; Li, G. Acta Phys. -Chim. Sin. 2017, 33(7), 1297. doi: 10.3866/PKU.WHXB201704101
25. [25]
  Zhu, M.; Aikens, C. M.; Hendrich, M. P.; Gupta, R.; Qian, H.; Schatz, G. C.; Jin, R.J. Am. Chem. Soc. 2009, 131 (7), 2490. doi: 10.1021/ja809157f doi: 10.1021/ja809157f
26. [26]
  Antonello, S.; Perera, N. V.; Ruzzi, M.; Gascon, J. A.; Maran, F. J. Am. Chem. Soc. 2013, 135 (41), 15585. doi: 10.1021/ja407887d doi: 10.1021/ja407887d
27. [27]
  Jin, R. C.; Qian, H. F.; Wu, Z. K.; Zhu, Y.; Zhu, M. Z.; Mohanty, A.; Garg, N. J. Phys. Chem. Lett. 2010, 1 (19), 2903. doi: 10.1021/jz100944k doi: 10.1021/jz100944k
28. [28]
  Si, S.; Gautier, C.; Boudon, J.; Taras, R.; Gladiali, S.; Bürgi, T. J. Phys. Chem. C 2009, 113 (30), 12966. doi: 10.1021/jp9044385 doi: 10.1021/jp9044385
29. [29]
  Zeng, C.; Qian, H.; Li, T.; Li, G.; Rosi, N. L.; Yoon, B.; Barnett, R. N.; Whetten, R. L.; Landman, U.; Jin, R. Angew. Chem. Int. Ed. 2012, 51 (52), 13114. doi: 10.1002/anie.201207098 doi: 10.1002/anie.201207098
30. [30]
  Nimmala, P. R.; Dass, A. J. Am. Chem. Soc. 2011, 133 (24), 9175. doi: 10.1021/ja201685f doi: 10.1021/ja201685f
31. [31]
  Liu, C.; Lin, J.; Shi, Y.; Li, G. Nanoscale 2015, 7 (14), 5987. doi: 10.1039/c5nr00543d doi: 10.1039/c5nr00543d
32. [32]
  Balasubramanian, R.; Guo, R.; Mills, A. J.; Murray, R. W. J. Am. Chem. Soc. 2005, 127 (22), 8126. doi: 10.1021/ja050793v doi: 10.1021/ja050793v
33. [33]
  Zeng, C.; Chen, Y.; Das, A.; Jin, R. J. Phys. Chem. Lett. 2015, 6 (15), 2976. doi: 10.1021/acs.jpclett.5b01150 doi: 10.1021/acs.jpclett.5b01150
34. [34]
  Chen, S.; Xiong, L.; Wang, S.; Ma, Z.; Jin, S.; Sheng, H.; Pei, Y.; Zhu, M. J. Am. Chem. Soc. 2016, 138 (34), 10754. doi: 10.1021/jacs.6b06004 doi: 10.1021/jacs.6b06004
35. [35]
  Dass, A.; Stevenson, A.; Dubay, G. R.; Tracy, J. B.; Murray, R. W. J. Am. Chem. Soc. 2008, 130 (18), 5940. doi: 10.1021/ja710323t doi: 10.1021/ja710323t
36. [36]
  Das, A.; Li, T.; Nobusada, K.; Zeng, C.; Rosi, N. L.; Jin, R. J. Am. Chem. Soc. 2013, 135 (49), 18264. doi: 10.1021/ja409177s doi: 10.1021/ja409177s
1. [1]
  Min Huang , Ru Cheng , Shuai Wen , Liangtong Li , Jie Gao , Xiaohui Zhao , Chunmei Li , Hongyan Zou , Jian Wang . Ultrasensitive detection of microRNA-21 in human serum based on the confinement effect enhanced chemical etching of gold nanorods. Chinese Chemical Letters, 2024, 35(9): 109379-. doi: 10.1016/j.cclet.2023.109379
2. [2]
  Leichen Wang , Anqing Mei , Na Li , Xiaohong Ruan , Xu Sun , Yu Cai , Jinjun Shao , Xiaochen Dong . Aza-BODIPY dye with unexpected bromination and high singlet oxygen quantum yield for photoacoustic imaging-guided synergetic photodynamic/photothermal therapy. Chinese Chemical Letters, 2024, 35(6): 108974-. doi: 10.1016/j.cclet.2023.108974
3. [3]
  Shaonan Tian , Yu Zhang , Qing Zeng , Junyu Zhong , Hui Liu , Lin Xu , Jun Yang . Core-shell gold-copper nanoparticles: Evolution of copper shells on gold cores at different gold/copper precursor ratios. Chinese Journal of Structural Chemistry, 2023, 42(11): 100160-100160. doi: 10.1016/j.cjsc.2023.100160
4. [4]
  Zhi Li , Wenpei Li , Shaoping Jiang , Chuan Hu , Yuanyu Huang , Maxim Shevtsov , Huile Gao , Shaobo Ruan . Legumain-triggered aggregable gold nanoparticles for enhanced intratumoral retention. Chinese Chemical Letters, 2024, 35(7): 109150-. doi: 10.1016/j.cclet.2023.109150
5. [5]
  Xiangqian Cao , Chenkai Yang , Xiaodong Zhu , Mengxin Zhao , Yilin Yan , Zhengnan Huang , Jinming Cai , Jingming Zhuang , Shengzhou Li , Wei Li , Bing Shen . Synergistic enhancement of chemotherapy for bladder cancer by photothermal dual-sensitive nanosystem with gold nanoparticles and PNIPAM. Chinese Chemical Letters, 2024, 35(8): 109199-. doi: 10.1016/j.cclet.2023.109199
6. [6]
  Ji Liu , Dongsheng He , Tianjiao Hao , Yumin Hu , Yan Zhao , Zhen Li , Chang Liu , Daquan Chen , Qiyue Wang , Xiaofei Xin , Yan Shen . Gold mineralized "hybrid nanozyme bomb" for NIR-II triggered tumor effective permeation and cocktail therapy. Chinese Chemical Letters, 2024, 35(9): 109296-. doi: 10.1016/j.cclet.2023.109296
7. [7]
  Ya-Wen Zhang , Ming-Ming Gan , Li-Ying Sun , Ying-Feng Han . Supramolecular dinuclear silver(I) and gold(I) tetracarbene metallacycles and fluorescence sensing of penicillamine. Chinese Journal of Structural Chemistry, 2024, 43(9): 100356-100356. doi: 10.1016/j.cjsc.2024.100356
8. [8]
  Yu ZHANG , Fangfang ZHAO , Cong PAN , Peng WANG , Liangming WEI . Application of double-side modified separator with hollow carbon material in high-performance Li-S battery. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1218-1232. doi: 10.11862/CJIC.20230412
9. [9]
  Junmei FAN , Wei LIU , Ruitao ZHU , Chenxi QIN , Xiaoling LEI , Haotian WANG , Jiao WANG , Hongfei HAN . High sensitivity detection of baicalein by N, S co-doped carbon dots and their application in biofluids. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 2009-2020. doi: 10.11862/CJIC.20240120
10. [10]
  Xiaoxiao Huang , Zhi-Long He , Yangpeng Chen , Lei Li , Zhenyu Yang , Chunyang Zhai , Mingshan Zhu . Novel P-doping-tuned Pd nanoflowers/S,N-GQDs photo-electrocatalyst for high-efficient ethylene glycol oxidation. Chinese Chemical Letters, 2024, 35(6): 109271-. doi: 10.1016/j.cclet.2023.109271
11. [11]
  Tao LIU , Yuting TIAN , Ke GAO , Xuwei HAN , Ru'nan MIN , Wenjing ZHAO , Xueyi SUN , Caixia YIN . A photothermal agent with high photothermal conversion efficiency and high stability for tumor therapy. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1622-1632. doi: 10.11862/CJIC.20240107
12. [12]
  Wen LUO , Lin JIN , Palanisamy Kannan , Jinle HOU , Peng HUO , Jinzhong YAO , Peng WANG . Preparation of high-performance supercapacitor based on bimetallic high nuclearity titanium-oxo-cluster based electrodes. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 782-790. doi: 10.11862/CJIC.20230418
13. [13]
  Feng Wu , Xuemin Kong , Yixuan Liu , Shuli Wang , Zhong Chen , Xu Hou . Microfluidic-based isolation of circulating tumor cells with high-efficiency and high-purity. Chinese Chemical Letters, 2024, 35(8): 109754-. doi: 10.1016/j.cclet.2024.109754
14. [14]
  Zhe Wang , Li-Peng Hou , Qian-Kui Zhang , Nan Yao , Aibing Chen , Jia-Qi Huang , Xue-Qiang Zhang . High-performance localized high-concentration electrolytes by diluent design for long-cycling lithium metal batteries. Chinese Chemical Letters, 2024, 35(4): 108570-. doi: 10.1016/j.cclet.2023.108570
15. [15]
  Qijun Tang , Wenguang Tu , Yong Zhou , Zhigang Zou . High efficiency and selectivity catalyst for photocatalytic oxidative coupling of methane. Chinese Journal of Structural Chemistry, 2023, 42(12): 100170-100170. doi: 10.1016/j.cjsc.2023.100170
16. [16]
  Qiangwei Wang , Huijiao Liu , Mengjie Wang , Haojie Zhang , Jianda Xie , Xuanwei Hu , Shiming Zhou , Weitai Wu . Observation of high ionic conductivity of polyelectrolyte microgels in salt-free solutions. Chinese Chemical Letters, 2024, 35(4): 108743-. doi: 10.1016/j.cclet.2023.108743
17. [17]
  Changzhu Huang , Wei Dai , Shimao Deng , Yixin Tian , Xiaolin Liu , Jia Lin , Hong Chen . A self-cleaning window for high-efficiency photodegradation of indoor formaldehyde. Chinese Chemical Letters, 2024, 35(9): 109429-. doi: 10.1016/j.cclet.2023.109429
18. [18]
  Kunsong Hu , Yulong Zhang , Jiayi Zhu , Jinhua Mai , Gang Liu , Manoj Krishna Sugumar , Xinhua Liu , Feng Zhan , Rui Tan . Nano-engineered catalysts for high-performance oxygen reduction reaction. Chinese Chemical Letters, 2024, 35(10): 109423-. doi: 10.1016/j.cclet.2023.109423
19. [19]
  Hai-Ling Wang , Zhong-Hong Zhu , Hua-Hong Zou . Structure and assembly mechanism of high-nuclear lanthanide-oxo clusters. Chinese Journal of Structural Chemistry, 2024, 43(9): 100372-100372. doi: 10.1016/j.cjsc.2024.100372
20. [20]
  Ningning Gao , Yue Zhang , Zhenhao Yang , Lijing Xu , Kongyin Zhao , Qingping Xin , Junkui Gao , Junjun Shi , Jin Zhong , Huiguo Wang . Ba²⁺/Ca²⁺ co-crosslinked alginate hydrogel filtration membrane with high strength, high flux and stability for dye/salt separation. Chinese Chemical Letters, 2024, 35(5): 108820-. doi: 10.1016/j.cclet.2023.108820

Get Citation

PDF

XML

Metrics

PDF Downloads(13)
Abstract views(383)
HTML views(26)

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

Synthesis of High Yield Au21(SR)15 Nanoclusters

Metrics

通讯作者: 陈斌, bchen63@163.com

Synthesis of High Yield Au₂₁(SR)₁₅ Nanoclusters