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

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: 6 December 2017
Revised Date: 30 December 2017
Accepted Date: 2 January 2018
Available Online: 8 July 2018
Fund Project: The project was supported by the National Key Research and Development Program of China 2017YFA0402800the National Natural Science Foundation of China 11475176the National Natural Science Foundation of China 11621063the National Natural Science Foundation of China 21533007the National Natural Science Foundation of China U1632263The 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)

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.
- Au nanoclusters,
- Size-convergence,
- Kinetic process,
- In situ spectroscopy,
- Etching,
- HCl,
- Dodecanethiol
1. [1]
  Jin, R. C. Nanoscale 2010, 2, 343. doi: 10.1039/b9nr00160c doi: 10.1039/b9nr00160c
2. [2]
  Li, G.; Jin, R. C. Acc. Chem. Res. 2013, 46, 1749. doi: 10.1021/Ar300213z doi: 10.1021/Ar300213z
3. [3]
  Yau, S. H.; Varnavski, O.; Goodson, T. Acc. Chem. Res. 2013, 46, 1506. doi: 10.1021/Ar300280w doi: 10.1021/Ar300280w
4. [4]
  Lu, Y. Z.; Chen, W. Chem. Soc. Rev. 2012, 41, 3594. doi: 10.1039/c2cs15325d doi: 10.1039/c2cs15325d
5. [5]
  Wang, C.; Yao, Y.; Song, Q. J. Mater. Chem. C 2015, 3, 5910. doi: 10.1039/c5tc00290g doi: 10.1039/c5tc00290g
6. [6]
  Jiang, D. E. Acta Phys. -Chim. Sin. 2010, 26, 999. doi: 10.3866/PKU.WHXB20100414
7. [7]
  Jin, R. C.; Zeng, C. J.; Zhou, M.; Chen, Y. X. Chem. Rev. 2016, 116, 10346. doi: 10.1021/acs.chemrev.5b00703 doi: 10.1021/acs.chemrev.5b00703
8. [8]
  Sun, J.; Jin, Y. D. J. Mater. Chem. C2014, 2, 8000. doi: 10.1039/c4tc01489h doi: 10.1039/c4tc01489h
9. [9]
  Zhou, Y.; Li, G. Acta Phys. -Chim. Sin.2017, 33, 1297. doi: 10.3866/PKU.WHXB201704101
10. [10]
  Zhu, M.; Lanni, E.; Garg, N.; Bier, M. E.; Jin, R. J. Am. Chem. Soc. 2008, 130, 1138. doi: 10.1021/ja0782448 doi: 10.1021/ja0782448
11. [11]
  Wu, Z. K.; MacDonald, M. A.; Chen, J.; Zhang, P.; Jin, R. C. J. Am. Chem. Soc. 2011, 133, 9670. doi: 10.1021/ja2028102 doi: 10.1021/ja2028102
12. [12]
  Qian, H. F.; Zhu, Y.; Jin, R. C. Proc. Natl. Acad. Sci. USA 2012, 109, 696. doi: 10.1073/pnas.1115307109 doi: 10.1073/pnas.1115307109
13. [13]
  Qian, H. F.; Zhu, Y.; Jin, R. C. ACS Nano2009, 3, 3795. doi: 10.1021/Nn901137h doi: 10.1021/Nn901137h
14. [14]
  Qian, H. F.; Zhu, M. Z.; Lanni, E.; Zhu, Y.; Bier, M. E.; Jin, R. C. J. Phys. Chem. C 2009, 113, 17599. doi: 10.1021/jp9073152 doi: 10.1021/jp9073152
15. [15]
  Qian, H. F.; Eckenhoff, W. T.; Bier, M. E.; Pintauer, T.; Jin, R. C. Inorg. Chem. 2011, 50, 10735. doi: 10.1021/Ic2012292 doi: 10.1021/Ic2012292
16. [16]
  Qian, H. F.; Zhu, M. Z.; Andersen, U. N.; Jin, R. C. J. Phys. Chem. A 2009, 113, 4281. doi: 10.1021/Jp810893w doi: 10.1021/Jp810893w
17. [17]
  Shichibu, Y.; Konishi, K. Small 2010, 6, 1216. doi: 10.1002/smll.200902398 doi: 10.1002/smll.200902398
18. [18]
  Shichibu, Y.; Suzuki, K.; Konishi, K. Nanoscale 2012, 4, 4125. doi: 10.1039/C2nr30675a doi: 10.1039/C2nr30675a
19. [19]
  Woehrle, G. H.; Brown, L. O.; Hutchison, J. E. J. Am. Chem. Soc. 2005, 127, 2172. doi: 10.1021/ja0457718 doi: 10.1021/ja0457718
20. [20]
  Shichibu, Y.; Negishi, Y.; Tsunoyama, H.; Kanehara, M.; Teranishi, T.; Tsukuda, T. Small 2007, 3, 835. doi: 10.1002/smll.200600611 doi: 10.1002/smll.200600611
21. [21]
  Duan, H. W.; Nie, S. M. J. Am. Chem. Soc.2007, 129, 2412. doi: 10.1021/Ja067727t doi: 10.1021/Ja067727t
22. [22]
  Yang, L. N.; Cheng, H.; Jiang, Y.; Huang, T.; Bao, J.; Sun, Z. H.; Jiang, Z.; Ma, J. Y.; Sun, F. F.; Liu, Q. H.; et al.Nanoscale 2015, 7, 14452. doi: 10.1039/c5nr03711e doi: 10.1039/c5nr03711e
23. [23]
  Jin, R. C.; Qian, H. F.; Wu, Z. K.; Zhu, Y.; Zhu, M. Z.; Mohanty, A.; Garg, N. J. Phys. Chem. Lett. 2010, 1, 2903. doi: 10.1021/jz100944k doi: 10.1021/jz100944k
24. [24]
  Yu, Y.; Yao, Q. F.; Luo, Z. T.; Yuan, X.; Lee, J. Y.; Xie, J. P. Nanoscale 2013, 5, 4606. doi: 10.1039/C3nr00464c doi: 10.1039/C3nr00464c
25. [25]
  Zhang, J. W.; Zhou, Y.; Zheng, K.; Abroshan, H.; Kauffman, D. R.; Sun, J. L.; Li, G. Nano Res. 2017, doi: 10.1007/s12274-017-1935-2 doi: 10.1007/s12274-017-1935-2
26. [26]
  Sun, Z. H.; Oyanagi, H.; Nakamura, H.; Jiang, Y.; Zhang, L.; Uehara, M.; Yamashita, K.; Fukano, A.; Maeda, H. J. Phys. Chem. C 2010, 114, 10126. doi: 10.1021/Jp101345n doi: 10.1021/Jp101345n
27. [27]
  Yao, T.; Sun, Z. H.; Li, Y. Y.; Pan, Z. Y.; Wei, H.; Xie, Y.; Nomura, M.; Niwa, Y.; Yan, W. S.; Wu, Z. Y.; et al. J. Am. Chem. Soc. 2010, 132, 7696. doi: 10.1021/Ja101101d doi: 10.1021/Ja101101d
28. [28]
  Yao, T.; Liu, S. J.; Sun, Z. H.; Li, Y. Y.; He, S.; Cheng, H.; Xie, Y.; Liu, Q. H.; Jiang, Y.; Wu, Z. Y.; et al. J. Am. Chem. Soc. 2012, 134, 9410. doi: 10.1021/Ja302642x doi: 10.1021/Ja302642x
29. [29]
  Li, Y. Y.; Cheng, H.; Yao, T.; Sun, Z. H.; Yan, W. S.; Jiang, Y.; Xie, Y.; Sun, Y. F.; Huang, Y. Y.; Liu, S. J.; et al.J. Am. Chem. Soc. 2012, 134, 17997. doi: 10.1021/Ja306923a doi: 10.1021/Ja306923a
30. [30]
  Sun, Z. H.; Liu, Q. H.; Yao, T.; Yan, W. S.; Wei, S. Q. Sci. China-Mater. 2015, 58, 313. doi: 10.1007/s40843-015-0043-4 doi: 10.1007/s40843-015-0043-4
31. [31]
  Nimmala, P. R.; Dass, A. J. Am. Chem. Soc. 2011, 133, 9175. doi: 10.1021/ja201685f doi: 10.1021/ja201685f
32. [32]
  Meng, X.; Xu, Q.; Wang, S.; Zhu, M. Nanoscale 2012, 4, 4161.doi: 10.1039/c2nr30272a doi: 10.1039/c2nr30272a
33. [33]
  Zeng, C. J.; Liu, C. Y.; Pei, Y.; Jin, R. C.ACS Nano 2013, 7, 6138. doi: 10.1021/Nn401971g doi: 10.1021/Nn401971g
34. [34]
  Hall, K. P.; Mingos, D. M. P. Prog. Inorg. Chem. 1984, 32, 237. doi: 10.1002/9780470166338.Ch3 doi: 10.1002/9780470166338.Ch3
35. [35]
  Zhang, P.; Sham, T. K. Phys. Rev. Lett.2003, 90, 245502. doi: 10.1103/PhysRevLett.90.245502 doi: 10.1103/PhysRevLett.90.245502
36. [36]
  Jin, R. C.; Zhu, Y.; Qian, H. F. Chem.-Eur. J. 2011, 17, 6584. doi: 10.1002/chem.201002390 doi: 10.1002/chem.201002390
37. [37]
  Ravel, B.; Newville, M. J. Synchrotron Rad. 2005, 12, 537. doi: 10.1107/S0909049505012719 doi: 10.1107/S0909049505012719
38. [38]
  Newville, M. J. Synchrotron Rad. 2001, 8, 322. doi: 10.1107/S0909049500016964 doi: 10.1107/S0909049500016964
39. [39]
  Briant, C. E.; Theobald, B. R. C.; White, J. W.; Bell, L. K.; Mingos, D. M. P. J. Chem. Soc. -Chem. Commun. 1981, 201. doi: 10.1039/C39810000201 doi: 10.1039/C39810000201
40. [40]
  Menard, L. D.; Xu, H. P.; Gao, S. P.; Twesten, R. D.; Harper, A. S.; Song, Y.; Wang, G. L.; Douglas, A. D.; Yang, J. C.; Frenkel, A. I.; et al. J. Phys. Chem. B 2006, 110, 14564. doi: 10.1021/Jp060740f doi: 10.1021/Jp060740f
41. [41]
  Ankudinov, A. L.; Ravel, B.; Rehr, J. J.; Conradson, S. D. Phys. Rev. B 1998, 58, 7565. doi: 10.1103/PhysRevB.58.756 doi: 10.1103/PhysRevB.58.756
1. [1]
  Lian Sun , Honglei Wang , Ming Ma , Tingting Cao , Leilei Zhang , Xingui Zhou . Shape and composition evolution of Pt and Pt₃M nanocrystals under HCl chemical etching. Chinese Chemical Letters, 2024, 35(9): 109188-. doi: 10.1016/j.cclet.2023.109188
2. [2]
  Ruotong Wei , Aokun Liu , Jian Kuang , Zhiwen Wang , Lu Yu , Changlin Tian . Probing the dynamic properties in the LLPS process via site-directed spin labeling-electron paramagnetic resonance (SDSL-EPR) spectroscopy. Chinese Chemical Letters, 2025, 36(4): 110029-. doi: 10.1016/j.cclet.2024.110029
3. [3]
  Chang LIU , Chao ZHANG , Tongbu LU . Small-size Au nanoparticles anchored on pyrenyl-graphdiyne for N₂ electroreduction. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 174-182. doi: 10.11862/CJIC.20240305
4. [4]
  Xiangdong Lai , Tengfei Liu , Zengchao Guo , Yihan Wang , Jiang Xiao , Qingxiu Xia , Xiaohui Liu , Hui Jiang , Xuemei Wang . In situ formed fluorescent gold nanoclusters inhibit hair follicle regeneration in oxidative stress microenvironment via suppressing NFκB signal pathway. Chinese Chemical Letters, 2025, 36(2): 109762-. doi: 10.1016/j.cclet.2024.109762
5. [5]
  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
6. [6]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
7. [7]
  Dan-Ying Xing , Xiao-Dan Zhao , Chuan-Shu He , Bo Lai . Kinetic study and DFT calculation on the tetracycline abatement by peracetic acid. Chinese Chemical Letters, 2024, 35(9): 109436-. doi: 10.1016/j.cclet.2023.109436
8. [8]
  Wenya Jiang , Jianyu Wei , Kuan-Guan Liu . Atomically precise superatomic silver nanoclusters stabilized by O-donor ligands. Chinese Journal of Structural Chemistry, 2024, 43(9): 100371-100371. doi: 10.1016/j.cjsc.2024.100371
9. [9]
  Luyao Lu , Chen Zhu , Fei Li , Pu Wang , Xi Kang , Yong Pei , Manzhou Zhu . Ligand effects on geometric structures and catalytic activities of atomically precise copper nanoclusters. Chinese Journal of Structural Chemistry, 2024, 43(10): 100411-100411. doi: 10.1016/j.cjsc.2024.100411
10. [10]
  Rakesh Kumar Gupta , Zhi Wang , Di Sun . Shining bright: Revolutionary near-unity NIR phosphorescent metal nanoclusters. Chinese Journal of Structural Chemistry, 2024, 43(11): 100417-100417. doi: 10.1016/j.cjsc.2024.100417
11. [11]
  Ling-Hao Zhao , Hai-Wei Yan , Jian-Shuang Jiang , Xu Zhang , Xiang Yuan , Ya-Nan Yang , Pei-Cheng Zhang . Effective assignment of positional isomers in dimeric shikonin and its analogs by ¹H NMR spectroscopy. Chinese Chemical Letters, 2024, 35(5): 108863-. doi: 10.1016/j.cclet.2023.108863
12. [12]
  Chengde Wang , Liping Huang , Shanshan Wang , Lihao Wu , Yi Wang , Jun Dong . A distinction of gliomas at cellular and tissue level by surface-enhanced Raman scattering spectroscopy. Chinese Chemical Letters, 2024, 35(5): 109383-. doi: 10.1016/j.cclet.2023.109383
13. [13]
  Manyu Zhu , Fei Liang , Lie Wu , Zihao Li , Chen Wang , Shule Liu , Xiue Jiang . Revealing the difference of Stark tuning rate between interface and bulk by surface-enhanced infrared absorption spectroscopy. Chinese Chemical Letters, 2025, 36(2): 109962-. doi: 10.1016/j.cclet.2024.109962
14. [14]
  Ruilong Geng , Lingzi Peng , Chang Guo . Dynamic kinetic stereodivergent transformations of propargylic ammonium salts via dual nickel and copper catalysis. Chinese Chemical Letters, 2024, 35(8): 109433-. doi: 10.1016/j.cclet.2023.109433
15. [15]
  Ling Tang , Yan Wan , Yangming Lin . Lowering the kinetic barrier via enhancing electrophilicity of surface oxygen to boost acidic oxygen evolution reaction. Chinese Journal of Structural Chemistry, 2024, 43(11): 100345-100345. doi: 10.1016/j.cjsc.2024.100345
16. [16]
  Meng Shan , Yongmei Yu , Mengli Sun , Shuping Yang , Mengqi Wang , Bo Zhu , Junbiao Chang . Bifunctional organocatalyst-catalyzed dynamic kinetic resolution of hemiketals for synthesis of chiral ketals via hydrogen bonding control. Chinese Chemical Letters, 2025, 36(1): 109781-. doi: 10.1016/j.cclet.2024.109781
17. [17]
  Ping Wang , Tianbao Zhang , Zhenxing Li . Reconstruction mechanism of Cu surface in CO2 reduction process. Chinese Journal of Structural Chemistry, 2024, 43(8): 100328-100328. doi: 10.1016/j.cjsc.2024.100328
18. [18]
  Yuchen Wang , Yaoyu Liu , Xiongfei Huang , Guanjie He , Kai Yan . Fe nanoclusters anchored in biomass waste-derived porous carbon nanosheets for high-performance supercapacitor. Chinese Chemical Letters, 2024, 35(8): 109301-. doi: 10.1016/j.cclet.2023.109301
19. [19]
  Mengli Xu , Zhenmin Xu , Zhenfeng Bian . Achieving Ullmann coupling reaction via photothermal synergy with ultrafine Pd nanoclusters supported on mesoporous TiO2. Chinese Journal of Structural Chemistry, 2024, 43(7): 100305-100305. doi: 10.1016/j.cjsc.2024.100305
20. [20]
  Ziyi Liu , Xunying Liu , Lubing Qin , Haozheng Chen , Ruikai Li , Zhenghua Tang . Alkynyl ligand for preparing atomically precise metal nanoclusters: Structure enrichment, property regulation, and functionality enhancement. Chinese Journal of Structural Chemistry, 2024, 43(11): 100405-100405. doi: 10.1016/j.cjsc.2024.100405

Get Citation

PDF

XML

Metrics

PDF Downloads(6)
Abstract views(552)
HTML views(104)

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