Beruflich Dokumente
Kultur Dokumente
a r t i c l e i n f o a b s t r a c t
Available online 13 December 2011 Silver bismuth sulde (AgBiS2) nanostructures were successfully prepared via a simple biomolecule-
Keywords: assisted hydrothermal synthesis at 200 1C for 1272 h. Silver nitrate, bismuth nitrate and L-cysteine
AgBiS2 were used as starting materials. Here, the biomolecule, L-cysteine, was served as the sulde source and
Nanomaterial a complexing agent. The products, characterized by X-ray powder diffraction (XRD), scanning electron
Hydrothermal microscopy (SEM) and transmission electron microscopy (TEM), were cubic AgBiS2 nanoparticles with a
Biomolecule diameter range of about 2075 nm. It was found that their crystallinity and particle size increased with
Optical property increasing reaction time. The energy dispersive X-ray spectroscopy (EDX) and inductively coupled
plasma optical emission spectrophotometry (ICP-OES) analyses were used to conrm the stoichiometry
of AgBiS2. The optical band gap of the AgBiS2 nanoparticles, calculated from UVvis spectra, was 3.0 eV
which indicated a strong blue shift because of the quantum connement effect. A possible formation
mechanism of the AgBiS2 nanoparticles was also discussed.
& 2011 Elsevier Inc. All rights reserved.
0022-4596/$ - see front matter & 2011 Elsevier Inc. All rights reserved.
doi:10.1016/j.jssc.2011.12.010
S. Kaowphong / Journal of Solid State Chemistry 189 (2012) 108111 109
Fig. 2. SEM images of the AgBiS2 powders prepared at various hydrothermal times: (a) 12 h, (b) 48 h, (c) 72 h, and (d) the EDX spectrum of the AgBiS2 powders prepared at 12 h.
Fig. 3. TEM images and SAED patterns of the AgBiS2 powder prepared at hydrothermal times: (a) 12 h, (b) 48 h, and (c) 72 h.
corresponding to the (1 1 1), (2 0 0), (2 2 0), (3 1 1), (2 2 2) dif- reaction time increased. The L-cysteine-assisted ternary solution
fraction planes. The rings are diffuse and hollow implying that the system is quite complicated, and the formation of certain nanostruc-
powders were polycrystalline. ture is still obscure and needs in-depth understanding.
The literatures have reported that many metal ions can complex UVvisible absorption of AgBiS2 nanoparticles are shown in
with L-cysteine to form metalL-cysteine complexes [1216]. In this Fig. 4. For crystalline semiconductors, the UV absorption near band
work, a mechanism for the formation of AgBiS2 nanoparticles was edge follows the equation ahn (hnEg)n where a is the absor-
proposed. To produce AgBiS2, AgNO3, Bi(NO3)3 5H2O and L-cysteine bance, h is the Planck constant, n is the photon frequency, and Eg is
were mixed together in deionized water. Then, Ag and Bi3 ions the optical band gap, respectively. The parameter n is a pure
react with number associated with the different types of electronic transi-
L-cysteine at room temperature to form complexes [1,2]. tions: n1/2, 2, 3/2 or 3 for direct-allowed, indirect-allowed,
direct-forbidden and indirect-forbidden transitions, respectively
Ag nL-Cysteine-[Ag(L-Cysteine)n] (2)
[21]. It should be noted that the absorption is controlled by two
Bi3 nL-Cysteine-[Bi(L-Cysteine)n]3 (3) photon energy (hn) rangesthe high and low energies. When the
photon energy is greater than the energy band gap (Eg), the
[Ag(L-Cysteine)n] [Bi(L-Cysteine)n]3 -AgBiS2 (4) absorption is linearly increased with the increasing of photon
energy. For the photon energy which is less than Eg, the absorption
First, the formation of [Ag(L-Cysteine)n] and [Bi(L-Cysteine)n]3 becomes different from the linearity, which is caused by the
complexes prevent the formation of Ag2S and Bi2S3 because of dominant photonic absorption relating to the defect levels between
few free ions, Ag , Bi3 , and S2- in the solution. Second, at a given the valence and conduction bands of the product [2]. The direct
temperature, the [Ag(L-Cysteine)n] and [Bi(L-Cysteine)n]3 com- band gap of the AgBiS2 nanoparticles prepared at 12 h was
plexes undergo thermal decomposition to produce the AgBiS2 nuclei. calculated from its optical absorption spectrum by plotting (ahn)2
Then, these nuclei grow and form the AgBiS2 nanoparticles when the vs. hn curve and extrapolating the linear portion of the curve to
S. Kaowphong / Journal of Solid State Chemistry 189 (2012) 108111 111
Acknowledgments
References
[1] G. Shen, D. Chen, K. Tang, Y. Qian, J. Cryst. Growth 252 (2003) 199.
Fig. 4. UVvisible spectra of AgBiS2 nanoparticles prepared at hydrothermal time [2] D. Chen, G. Shen, K. Tang, X. Jiang, L. Huang, Y. Jin, Y. Qian, Inorg. Chem.
of 12 h. Commun. 6 (2003) 710.
[3] B. Pejova, I. Grozdanov, D. Nesheva, A. Petrova, Chem. Mater. 20 (2008) 2551.
[4] H.S.G. Kullerud, Econ. Geol. 54 (1959) 533.
[5] G.H. Moh, L.A. Taylor, Neues Jahrb. Mineral. H9 (1971) 405.
zero absorption (a 0), corresponding to 3.0 eV. This value displays [6] L.T. Bryndzia, O.J. Kleppa, Econ. Geol. 83 (1988) 174.
a strong blue shift compared with the band gap of bulk AgBiS2 [7] B. Xie, S. Yuan, Y. Jiang, J. Lu, Q. Li, Y. Wu, W. Yu, H. Zhang, Y. Qian, Chem. Lett.
(2002) 612.
(2.46 eV) [22]. Light absorption leads to an electron in the conduc- [8] T. Thongtem, N. Tipcompor, S. Thongtem, Mater. Lett. 64 (2010) 755.
tion band and a positive hole in the valence band. In nanoparticles, [9] T. Thongtem, J. Jaroenchaichana, S. Thongtem, Mater. Lett. 63 (2009) 2163.
they are conned to potential wells of small lateral dimension and [10] Y.J. Kim, L.K. Pannell, D.L. Sackett, Anal. Biochem. 332 (2004) 376.
[11] I.E. Gentle, D.P. De Souza, M. Baca, Bioconjugate Chem. 15 (2004) 376.
the energy difference between the position of the conduction band
[12] X. Chen, X. Zhang, C. Shi, J. Wan, Y. Qian, Mater. Chem. Phys. 98 (2006) 419.
and free electron, which leads to a quantization of their energy [13] X. Chen, X. Zhang, C. Shi, X. Li, Y. Qian, Solid State Commun. 134 (2005) 613.
levels. The phenomena when the size of the particles becomes [14] S.J. Bao, C.M. Li, C.X. Guo, Y. Qiao, J. Power Sources 180 (2008) 676.
[15] H. Gai, Y. Wu, L. Wu, Z. Wang, Y. Shi, M. Jing, K. Zou, Appl. Phys. A 91 (2008)
comparable to the de Broglie wavelength of a charge carrier. The
69.
increase in band gap of the as-prepared AgBiS2 nanoparticles is [16] B. Zhang, X. Ye, W. Dai, W. Hou, Y. Xie, Chem. Eur. J. 12 (2006) 2337.
attributed to the quantum connement effect [23]. [17] M. Yoshimura, K. Byrappa, J. Mater. Sci. 43 (2008) 2085.
[18] Powder Diffract, File, JCPDS Internat, Centre Diffract. Data, 12 Campus
Boulevard, Newtown Square, PA 19073-3273, U.S.A., 2001.
[19] C. Suryanarayana, M.G. Norton, X-ray Diffraction, A Practice Approach,
4. Conclusions
Plenum Press, New York, 1998.
[20] Y. Sun, H. Liu, X. Wang, X. Kong, H. Zhang, Chem. Mater. 18 (2006) 2726.
AgBiS2 nanoparticles were synthesized through a simple bio- [21] J.G. Speight, Langes Handbook of Chemistry, 16th ed, The McGraw-Hill
molecule-assisted hydrothermal method. The crystallinity, crystal- Companies, Inc., New York, 2005.
[22] I.I. Golovach, N.I. Dovgoshei, V.Y. Slivka, L.M. Suslikov, M.I. Golovei,
lite size of the nanopowders were highly dependent on the A.V. Bogdanova, Inorg. Mater. Des. 11 (1975) 820.
different hydrothermal times. The direct band gap of AgBiS2 [23] Y. Zhao, X.H. Liao, J.M. Hong, J.J. Zhu, Mater. Chem. Phys. 87 (2004) 149.