Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
권호 표지

Preparation of Copper Nanoparticles Protected by Chemisorption via Thiol Group

Thiol기의 화학흡착을 이용한 구리 나노입자의 제조

  • Kim, Jung-Teag (Division of Applied Chemical Engineering, Pukyong National University) ;
  • Ju, Chang-Sik (Division of Applied Chemical Engineering, Pukyong National University)
  • 김정택 (부경대학교 응용화학공학부) ;
  • 주창식 (부경대학교 응용화학공학부)
  • Received : 2008.10.30
  • Accepted : 2008.11.26
  • Published : 2008.12.31
Download PDF
⟨ Previous Next ⟩

Abstract

In this work, we made a study for the 3D SAM formation of octanethiol, decanethiol, and dodecanethiol on copper nanoparticles and we verified stability of the copper particle depending on the ratio of dodecanethiol to copper. The reaction was performed in a one-phase system under nitrogen atmosphere and the thiolated copper particles could be obtained by centrifugation. We could confirm that the nanoparticles consisted of a spherical shape of 3~6 nm from TEM images. FT-IR, XPS and TGA results showed that alkanethiols were chemisorbed via thiol group and the packing density of the alkanethiols on copper surface increased with the alkyl chain lengths. XRD patterns gave us useful information about superlattice formations. Finally, $Cu_2O$ was formed when the molar ratio of dodecanethiol to copper is less than unity and copper nanoparticles formed more compact 3D SAMs when the molar ratio of dodecanethiol to copper was 1.25.

구리 나노입자의 표면에 화학흡착한 octanethiol, decanethiol 및 dodecanethiol의 3D SAMs를 연구하였고, dodecanethiol의 투입량 변화에 따른 구리 나노입자의 산화 안정성을 고찰하였다. 제조 공정은 산소로부터 보호하기 위해 질소 분위기에서 수행하였고, 합성된 입자는 원심분리를 통하여 획득하였다. 구리 전구체는 Copper(II) nitrate, 환원제는 sodium borohydride를 사용하였으며, 반응은 단일상에서 진행하였다. 나노 크기의 구리입자는 TEM 분석을 통하여 확인하였고, 그 크기는 약 3~6 nm였다. FT-IR, XPS와 열중량분석(TGA) 결과 alkanethiol의 thiol기가 구리 표면에 화학흡착 한다는 것과 alkyl기의 사슬이 길수록 alkanethiol의 흡착양이 증가한다는 것을 확인하였고, XRD 패턴으로부터 구리 나노입자의 거대격자회절(superlattice diffraction)을 관측할 수 있었다. 그리고 dodecanethiol의 투입양이 구리의 투입양보다 적을 경우 구리는 $Cu_2O$의 형태로 산화되었으며, 구리보다 1.25배 많이 투입할 경우 더욱 조밀한 SAMs를 형성하였다.

Keywords

References

  1. Chen, L., Zhang, D., Chen, J., Zhou, H. and Wan, H., 'The Use of CTAB to Control the Size of Copper Nanoparticles and the Concentration of Alkylthiols on Their Surfaces,' Mater. Sci. Eng., A, 415, 156-161(2006) https://doi.org/10.1016/j.msea.2005.09.060
  2. Chen, T. Y., Chen, S. F., Sheu, H. S. and Yeh, C. S., 'Reactivity of Laser-Prepared Copper Nanoparticles : Oxidation of Thiols to Disulfides,' J. Phys. Chem. B, 106, 9717-9722(2002) https://doi.org/10.1021/jp0205822
  3. Casella, I. G., Cataldi, T. R. I., Guerrieri, A. and Desimoni, E., 'Copper Dispersed into Polyaniline Films as an Amperometric Sensor in Alkaline Solutions of Amino Acids and Polyhydric Compounds,' Anal. Chem. Acta., 335, 217-225(1996) https://doi.org/10.1016/S0003-2670(96)00351-0
  4. Ang, T. P., Wee, T. S. A. and Chin, W. S., 'Three-Dimensional Self-Assembled Monolayer (3D SAM) of n-alkanethiols on Copper Nanoclusters,' J. Phys. Chem. B, 108, 11001-11010(2004) https://doi.org/10.1021/jp049006r
  5. Brust, M., Walker, M., Bethell, D., Schiffrin, D. J. and Whyman, R., 'Synthesis of Thiol-derivatised Gold Nanoparticles in a Two- Phase Liquid-Liquid System,' J. Chem. Soc., Chem. Cummun., 801-802(1994)
  6. 6. Porter, M. D., Bright, T. B., Allara, D. L. and Chidsey, C. E. D., 'Spontaneously Organized Molecular Assembles. 4. Structural Characterization of n-alkyl Thiol Monolayers on Gold by Optical Ellipsometry, Infrared Spectroscopy, and Electrochemistry,' J. Am. Chem. Soc., 109, 3559-3568(1987) https://doi.org/10.1021/ja00246a011
  7. Ulman, A., Eilers, J. E. and Tillman, N., 'Packing and Molecular Orientation of Alkanethiol Monolayers on Gold Surfaces,' Langmuir, 5, 1147-1152(1989) https://doi.org/10.1021/la00089a003
  8. Laibinis, P. E., Whitesides, G. M., Allara, D. L., Tao, Y. T., Parikh, A. N. and Nuzzo, R. G., 'Comparison of the Structures and Wetting Properties of Self-Assembled Monolayers of n-Alkanethiols on the Coinage Metal Surfaces, Cu, Ag, $Au^1$,' J. Am. Chem. Soc., 113, 7152-7167(1991) https://doi.org/10.1021/ja00019a011
  9. Hostetler, M. J., Stokes, J. J. and Murray, R. W., 'Infrared Spectroscopy of three-Dimensional Self-Assembled Monolayers : N-Alkanethiolate Monolayers on Gold Cluster Compounds,' Langmuir, 12, 3604-3612(1996) https://doi.org/10.1021/la960249n
  10. Murthy, S., Bigioni, T. P., Wang, Z. L., Khoury, J. T. and Whetten, R. L., 'Liquid-Phase Synthesis of Thiol-derivatized Silver Nanocrystals,' Mater. Lett., 30, 321-325(1997) https://doi.org/10.1016/S0167-577X(96)00274-1
  11. Brundle, C. R., Evans, C. A. and Wilson, S., Encyclopedia of Materials Characterization, Butterworth-Heinemann; Manning, Boston(1992)
  12. Vensebaa, F., Zhou, Y., Deslandes, Y., Kruus, E. and Ellis, T. H., 'XPS Study of Metal-sulfur Bonds in Metal-alkanethiolate Materials,' Surf. Sci., 405, L472-L476(1998) https://doi.org/10.1016/S0039-6028(98)00097-1
  13. Snyder, R. G. and Strauss, H. L., 'C-H Stretching Modes and the Structure of n-Alkyl Chains. 1. Long, Disordered Chains,' J. Phys. Chem., 86, 5145-5150(1982) https://doi.org/10.1021/j100223a018
  14. Synder, R. G., Maroncelli, M., Strauss, H. L. and Hallmark, V. M., 'Temperature and Phase Behavior of Infrared Intensities : The Poly(methylene) Chain,' J. Phys. Chem., 90, 5623-5630(1986) https://doi.org/10.1021/j100280a030
  15. Lee, Y. I., Choi, J. R., Lee, K. J., Stott, N. E. and Kim, D. H., 'Large-scale Synthesis of Copper Nanoparticles by Chemically Controlled Reduction for Applications of Inkjet-printed Electronics,' Nanotechnology, 19, 415604-415610(2008) https://doi.org/10.1088/0957-4484/19/41/415604
  16. Tung, C. C., Chou, Y. I., Lin, P. J., Lin, S. D. and Chen, H. I., 'Preparation of Self-Assembled Alkanethiol-modified Au/GaAs Ethanol Vapor Sensors,' Proceedings(CD-ROM) of 2008 Taiwan/ Korea/Japan ChE Conference and 55th TwIChE Annual Conference(2008)