Citation: Liu Danye, Chen Dong, Liu Hui, Yang Jun. Inside-Out Migration of Noble Metals in Ag₂S Nanoparticles[J]. Acta Physico-Chimica Sinica, ;2020, 36(7): 190606. doi: 10.3866/PKU.WHXB201906069 shu

Inside-Out Migration of Noble Metals in Ag₂S Nanoparticles

Liu Danye ^1,2 ,
Chen Dong ¹ ,
Liu Hui ^1,, ,
Yang Jun ^1,2,,

1.
State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, P. R. China
2.
University of Chinese Academy of Sciences, Beijing 100049, P. R. China

Corresponding author: Liu Hui, liuhui@ipe.ac.cn Yang Jun, jyang@ipe.ac.cn
Received Date: 24 June 2019
Revised Date: 25 July 2019
Accepted Date: 26 July 2019
Available Online: 31 July 2019
Fund Project: the National Natural Science Foundation of China 21573240The project was supported by the National Natural Science Foundation of China (21506225, 21573240, 21706265)the National Natural Science Foundation of China 21506225the National Natural Science Foundation of China 21706265

Materials such as metals, semiconductors, and oxides are attractive at nanometer scales due to the physical and chemical property differences with their bulk counterparts as induced by the quantum confinement effect and large surface-to-volume ratios. In particular, heterogeneous nanostructures consisting of semiconductors and noble metals are extremely important because of the synergistic effects occurring at the interfaces between their noble metal and semiconductor domains; these often equip the heterogeneous nanostructures with improved properties compared to those of isolated individual components. Thus far, heterogeneous nanostructures have garnered a considerable research interest, and tremendous development in achieving high degree control over these nanostructures with respect to their domain size, morphology, and composition has been realized. Their immense application potential in optics, catalysis, imaging, and biomedicine render them a field full of original innovation possibilities. Herein, we demonstrate a phenomenon observed in core-shell nanostructures composed of noble metals and silver sulfide (Ag₂S): the inside-out migration of noble metals in Ag₂S nanoparticles. We prepare core-shell nanostructures with noble metals and Ag₂S residing at the core and shell regions, respectively, through various synthetic strategies including seed-mediated growth and galvanic replacement reactions followed by sulfidation. We then characterize the core-shell nanostructures before and after aging them in toluene at room temperature (e.g. 25 ℃) for a period of time up to 72 h. In contrast to the reported diffusion of Au from the outside to the inside of InAs or PbTe nanoparticles, which results in an Au core encapsulated by an amorphous InAs or PbTe shell, the noble metals (Au, Ag, Pd, or Pt) in core-shell nanostructures with noble metals and Ag₂S residing at the core and shell regions, respectively, are found to diffuse from the inside to the outside through the Ag₂S shell. Thus, heterogeneous nanodimers consisting of the corresponding noble metal and Ag₂S are formed. Observations using an electron transmission microscope confirm that the inside-out migration of noble metals in Ag₂S is carried out in a holistic manner. Due to the apparent interface mismatch between face-centered cubic noble metals and monoclinic Ag₂S crystal phases, defects such as vacancies must exist at these interfaces. This makes the migration of noble metals in Ag₂S possible by either a vacancy/substitutional mechanism or by the self-purification mechanism that occurs intrinsically in nanoscale semiconductors. As the migration rate of noble metals in Ag₂S increases with the decrease in the size of the noble metal core and the radius of noble metal atoms, the inside-out migration rates of Ag, Pd, and Pt in Ag₂S are found to be much higher than that of Au because of their smaller particle sizes or atom radii. This scientific phenomenon can be effective in the development of synthetic routes for heterogeneous nanostructures that might not be obtained by conventional methods.
- Nanoparticle,
- Noble metal,
- Silver sulfide,
- Core-shell structure,
- Migration
1. [1]
  He, P.; Yuan, F. L.; Wang, Z. F.; Tan, Z. A.; Fan, L. Z. Acta Phys. -Chim. Sin. 2018, 34, 1250. doi: 10.3866/PKU.WHXB201804041
2. [2]
  Soltani, S.; Diep, V. M.; Zeto, R.; Armani, A. M. ACS Photonics 2018, 5, 3550. doi: 10.1021/acsphonotics.8b00296 doi: 10.1021/acsphonotics.8b00296
3. [3]
  Hashiyada, S.; Narushima, T.; Okamoto, H. ACS Photonics 2019, 6, 677. doi: 10.1021/acsphonotics.8b01500 doi: 10.1021/acsphonotics.8b01500
4. [4]
  Zhao, Q.; Ji, M.; Qian, H.; Dai, B.; Weng, L.; Cui, J.; Zhang, J.; Ouyang, M.; Zhu, H. Adv. Mater. 2014, 26, 1387. doi: 10.1002/adma.201304652 doi: 10.1002/adma.201304652
5. [5]
  Sun, Y.; Duan, J.; Zhu, J.; Chen, S.; Antonietti, M. ACS Appl. Nano Mater. 2018, 1, 6649. doi: 10.1021/acsanm.8b01470 doi: 10.1021/acsanm.8b01470
6. [6]
  Liu, Y. F.; Hu, B.; Yin, Y. Z.; Liu, G. L.; Hong, X. L. Acta Phys. -Chim. Sin. 2019, 35, 223. doi: 10.3866/PKU.WHXB201802263
7. [7]
  Munir, A.; Joya, K. S.; Ulhaq, T.; Babar, N. U. A.; Hussain, S. Z.; Qurashi, A.; Ullah, N.; Hussain, I. ChemSusChem 2019, 12, 1517. doi: 10.1002/cssc.201802069 doi: 10.1002/cssc.201802069
8. [8]
  Yang, J. Noble Metal-based Nanocomposites: Preparation and Applications. Wiley-VCH: Weinheim, German, 2019; pp. 1-33.
9. [9]
  Lei, G.; He, Y. Acta Phys. -Chim. Sin. 2018, 34, 11. doi: 10.3866/PKU.WHXB201706301
10. [10]
  Zhang, Y.; Wu, M.; Wu, M.; Zhu, J.; Zhang, X. ACS Omega 2018, 3, 9126. doi: 10.1021/acsomega.8b01071 doi: 10.1021/acsomega.8b01071
11. [11]
  Xuan, Y.; Yang, X. Q.; Song, Z. Y.; Zhang, R. Y.; Zhao, D. H.; Hou, X. L.; Song, X. L.; Liu, B.; Zhao, Y. D.; Chen, W. Adv. Funct. Mater. 2019, 29, 1900017. doi: 10.1002/adfm.201900017 doi: 10.1002/adfm.201900017
12. [12]
  Gong, L. J.; Xie, J. N.; Zhu, S.; Gu, Z. J.; Zhao, Y. L. Acta Phys. -Chim. Sin. 2018, 34, 140. doi: 10.3866/PKU.WHXB201707174
13. [13]
  Bai, H. R.; Fan, H. H.; Zhang, X. B.; Chen, Z.; Tan, W. H. Acta Phys. -Chim. Sin. 2018, 34, 348. doi: 10.3866/PKU.WHXB201708311
14. [14]
  Liu, Y.; Jiang, Y.; Zhang, M.; Tang, Z.; He, M.; Bu, W. Acc. Chem. Res. 2018, 51, 2502. doi: 10.1021/acsaccounts.8b00214 doi: 10.1021/acsaccounts.8b00214
15. [15]
  Jin, N.; Zhang, Q.; Yang, M.; Yang, M. Microsc. Res. Tech. 2019, 82, 670. doi: 10.1002/jemet.23213 doi: 10.1002/jemet.23213
16. [16]
  Grouchko, M.; Popov, I.; Uvarov, V.; Magdassi, S.; Kamyshny, A. Langmuir 2009, 25, 2501. doi: 10.1021/la803843k doi: 10.1021/la803843k
17. [17]
  Radziuk, D. V.; Zhang, W.; Shchukin, D.; Möhwald, H. Small, 2010, 6, 545. doi: 10.1002/smll.200901623 doi: 10.1002/smll.200901623
18. [18]
  Qu, J.; Liu, H.; Wei, Y.; Wu, X.; Yue, R.; Chen, Y.; Yang, J. J. Mater. Chem. 2011, 21, 11750. doi: 10.1039/c1jm12358k doi: 10.1039/c1jm12358k
19. [19]
  Mokari, T.; Aharoni, A.; Popov, I.; Banin, U. Angew. Chem. Int. Ed. 2006, 45, 8001. doi: 10.1002/anie.200602559 doi: 10.1002/anie.200602559
20. [20]
  Franchini, I. R.; Bertoni, G.; Falqui, A.; Giannini, C.; Wang, L. W.; Manna, L. J. Mater. Chem. 2010, 20, 1357. doi: 10.1039/b915687a doi: 10.1039/b915687a
21. [21]
  Liu, H.; Ye, F.; Cao, H.; Ji, G.; Lee, J. Y.; Yang, J. Nanoscale 2013, 5, 6901. doi: 10.1039/c3nr01949g doi: 10.1039/c3nr01949g
22. [22]
  Mokari, T.; Sztrum, C. G.; Salant, A.; Rabani, E.; Banin, U. Nat. Mater. 2005, 4, 855. doi: 10.1038/nmat1505 doi: 10.1038/nmat1505
23. [23]
  Hu, W.; Liu, H.; Ye, F.; Ding, Y.; Yang, J. CrystEngComm 2012, 14, 7049. doi: 10.1039/c2ce25594d doi: 10.1039/c2ce25594d
24. [24]
  Yang, J.; Ying, J. Y. J. Am. Chem. Soc. 2010, 132, 2114. doi: 10.1021/ja909078p doi: 10.1021/ja909078p
25. [25]
  Efros, A. L.; Rosen, M. Annu. Rev. Mater. Sci. 2000, 30, 475. doi: 10.1146/annurev.matsci.30.1.475 doi: 10.1146/annurev.matsci.30.1.475
26. [26]
  Erwin, S. C.; Zu, L.; Haftel, M. I.; Efros, A. L.; Kennedy, T. A.; Norris, D. J. Nature 2005, 436, 91. doi: 10.1038/nature03832 doi: 10.1038/nature03832
27. [27]
  Turnbull, D. J. Appl. Phys. 1950, 21, 1022. doi: 10.1063/1.1699435 doi: 10.1063/1.1699435
28. [28]
  Dalpian, G. M.; Chelikowsky, J. R. Phys. Rev. Lett. 2006, 96, 226802. doi: 10.1103/PhysRevLett.96.226802 doi: 10.1103/PhysRevLett.96.226802
29. [29]
  Yang, J.; Ying, J. Y. Angew. Chem. Int. Ed. 2011, 50, 5637. doi: 10.1002/anie.201101213 doi: 10.1002/anie.201101213
30. [30]
  Feng, Y.; Liu, H.; Yang, J. Sci. Adv. 2017, 3, e1700580. doi: 10.1126/sciadv.1700580 doi: 10.1126/sciadv.1700580
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Inside-Out Migration of Noble Metals in Ag₂S Nanoparticles