English

Synthesis and Characterization of Small Size Gold-Graphitic Nanocapsules

• LIU Fang ,
• ZHANG Lufeng ,
• DONG Qian ,
• CHEN Zhuo ^,

• State Key Laboratory of Cheme/Biosensing and Chemometric, Hunan University, Changsha 410082, P. R. China

Corresponding author: CHEN Zhuo, zhuochen@hnu.edu.cn

• Received Date: 15 May 2018
  Accepted Date: 22 June 2018
  Revised Date: 13 June 2018
  Available Online: 15 June 2019
• Fund Project:

  The project was supported by the National Natural Science Foundation of China (21522501, 21521063) and the Hunan Provincial Natural Science Foundation, China (2018JJ1007)

Abstract: The preparation of plasmonic metal-based substrates has been a hot research topic during the past decades in the area of surface-enhanced Raman spectroscopy (SERS). The localized surface plasmon resonance effect of plasmonic metal nanostructures enhances the electromagnetic field for SERS analysis, thereby making SERS an extremely sensitive detection technique. However, commonly developed plasmonic metal substrates exhibit poor stability and reproducibility. Since the separation of graphene from graphite, graphene has been widely used in various fields because of its unique physical, chemical, electronic, and optical properties. In the field of SERS, graphene has been used for graphene-enhanced Raman scattering, which makes use of the chemical enhancement mechanism in SERS. In addition, it has capabilities of surface molecular enrichment, quenching fluorescence, surface homogenization, and has strong chemical stability. Due to these characteristics of graphene, SERS substrates based on graphene-metal nanocapsules have attracted the attention of researchers. In this work, a small size gold-graphitic nanocapsules (Au@G) was prepared by chemical vapor deposition (CVD). The material exhibits a core-shell structure consisting of a graphitized carbon layer coated on Au nanoparticles (Au NPs). The Au NP core of the Au@G provides a major enhancement factor for Raman analysis, and the external graphitized carbon shell ensures strong chemical stability of the material. The Au@G exhibits a uniform particle size with diameter ~17 nm. In order to control the size of the Au@G, tetraethyl orthosilicate (TEOS) and tetraethylorthotrimethylammonium bromide were used as the raw material and template, respectively, a 45 nm-thick layer of mesoporous silica was coated on the synthesized Au NPs. The presence of the mesoporous silica capping layer prevented aggregation and particle size growth of the Au NPs during high-temperature CVD. At the same time, we studied the effect of TEOS concentration on the growth of the graphitized carbon layer during CVD. The results revealed that a decrease of the TEOS concentration is conducive for obtaining a high graphitic Au@G, and the concentration of TEOS does not affect the particle size of the Au@G. Raman detection of crystal violet molecules using Au@G demonstrated the latter's good Raman enhancement effect. The Au@G prepared by high-temperature CVD exhibits a clean surface with no impurities. It is an SERS substrate with both physical and chemical enhancement. The unique Raman spectral peaks and small size of Au@G ensure its great potential for use in the fields of molecular detection and cell imaging analysis.

Key words:
• Gold-graphitic nanocapsues
•  /  Chemical vapor deposition
•  /  Surface-enhanced Raman spectroscopy
•  /  Mesoporous silica
•  /  Au nanoparticles

• 1. [1]

     Cortes, E.; Etchegoin, P. G.; Le Ru, E. C.; Fainstein, A.; Vela, M. E.; Salvarezzaet, R. C. J. Am. Chem. Soc. 2010, 132, 18034. doi: 10.1021/ja108989b

  2. [2]

     Sun, M.; Zhang, Z.; Zheng, H.; Xu, H. Sci. Rep. 2012, 2, 647. doi: 10.1038/srep00647

  3. [3]

     Hudson, S. D.; Chumanov, G. Anal. Bioanal. Chem. 2009, 394, 679. doi: 10.1007/s00216-009-2756-2

  4. [4]

     Tripp, R. A.; Dluhy, R. A.; Zhao, Y. Nano Today 2008, 3, 31. doi: 10.1016/S1748-0132(08)70042-2

  5. [5]

     Quang, L. X.; Lim, C.; Seong, G. H.; Choo, J.; Do, K. J.; Yoo, S. Lab. Chip. 2008, 8, 2214. doi: 10.1039/B808835G

  6. [6]

     Golightly, R. S.; Doering, W. E.; Natan, M. J. ACS Nano 2009, 3 (10), 2859. doi: 10.1021/nn9013593

  7. [7]

     Willets, K. A.; Duyne, R. P. V. Annu. Rev. Phys. Chem. 2007, 58, 267. doi: 10.1146/annurev.physchem.58.032806.104607

  8. [8]

     Henry, A.; Sharma, B.; Cardinal, M. F.; Kurouski, D.; Duyne, R. P. V. Anal. Chem. 2016, 88: 6638. doi: 10.1021/acs.analchem.6b01597

  9. [9]

     Zhang, B.; Xu, P.; Xie, X.; Wei, H.; Li, Z.; Mack, N. H.; Han, X.; Xu, H.; Wang, H. J. Mater. Chem. 2011, 21, 2495. doi: 10.1039/C0JM02837A

  10. [10]

      Cecchini, M. P.; Turek, V. A.; Paget, J.; Kornyshev, A. A.; Edel, J. B. Nat. Mater. 2013, 12, 165. doi: 10.1038/nmat3488

  11. [11]

      Wang, J.; Zhou, F.; Duan, G.; Li, Y.; Liu, G.; Su, F.; Cai, W. RSC Adv. 2014, 4, 8758. doi: 10.1039/C3RA47882C

  12. [12]

      Xu, P.; Han, X.; Zhang, B.; Du, Y.; Wang, H. Chem. Soc. Rev. 2014, 43, 1349. doi: 10.1039/C3CS60380F

  13. [13]

      Hakonen, A.; Svedendahl, M.; Ogier, R.; Yang, Z.; Lodewijks, K.; Verre, R.; Shegai, T.; Andersson, P. O.; K ll, M. Nanoscale 2015, 7, 9405. doi: 10.1039/C5NR01654A

  14. [14]

      Kang, L.; Xu, P.; Chen, D.; Zhang, B.; Han, X.; Li, Q.; Wang, H. J. Phys. Chem. C 2013, 117, 10007. doi: 10.1021/jp400572z

  15. [15]

      Schluecker, S. Angew. Chem. Int. Ed. 2014, 53, 4756. doi: 10.1002/anie.201205748

  16. [16]

      Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V. Science 2004, 306, 666. doi: 10.1126/science.1102896

  17. [17]

      Somani, P. R.; Somani, S. P.; Umeno, M. P. Chem. Phys. Lett. 2006, 430, 56. doi: 10.1016/j.cplett.2006.06.081

  18. [18]

      刘忠范.物理化学学报, 2016, 32 (4), 810. doi: 10.3866/PKU.WHXB201603012Liu, Z. F. Acta. Phys. -Chim. Sin. 2016, 32 (4), 810. doi: 10.3866/PKU.WHXB201603012

  19. [19]

      Allen, M. J.; Tung, V. C.; Kaner, R. B. Chem. Rev. 2010, 110, 132. doi: 10.1021/cr900070d

  20. [20]

      Dreyer, D. R.; Todd, A. D.; Bielawski, C. W. Chem. Soc. Rev. 2014, 43, 5288. doi: 10.1039/C4CS00060A

  21. [21]

      Ling, X.; Xie, L.; Fang, Y.; Xu, H.; Zhang, H.; Kong, J.; Mildred, S.; Dresselhaus, M. S.; Zhang, J.; Liu, Z. Nano Lett. 2010, 10, 553. doi: 10.1021/nl903414x

  22. [22]

      Kang, L.; Chu, J.; Zhao, H.; Xu, P.; Sun, M. J. Mater. Chem. A 2015, 3, 9024. doi: 10.1039/C5TC01759A

  23. [23]

      Li, X.; Li, J.; Zhou, X.; Ma, Y.; Zheng, Z.; Duan, X. Carbon 2014, 66, 713. doi: 10.1016/j.carbon.2013.09.076

  24. [24]

      Gong, T.; Zhu, Y.; Zhang, J.; Ren, W.; Quan, J.; Wang, N. Carbon 2015, 87, 385. doi: 10.1016/j.carbon.2015.02.055

  25. [25]

      Zhao, Y.; Xie, Y.; Bao, Z.; Tsang, Y. H.; Xie, L.; Chai, Y. J. Phys. Chem. C 2014, 118, 11827. doi: 10.1021/jp503487a

  26. [26]

      Wu, C.; Lim, Z.; Zhou, C.; Guo, W. W.; Zhou, S.; Zhu, Y. Chem. Commun. 2013, 49, 3215. doi: 10.1039/c3cc39202c

•