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Journal of Solid State Chemistry 189 (2012) 108111

Contents lists available at SciVerse ScienceDirect

Journal of Solid State Chemistry


journal homepage: www.elsevier.com/locate/jssc

Biomolecule-assisted hydrothermal synthesis of silver bismuth sulde


with nanostructures
Sulawan Kaowphong a,b,n
a
Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
b
Materials Science Research Center, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand

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.

1. Introduction fabricate AgBiS2 nanoparticles. L-Cysteine is a common amino acid


and important biomolecule, which has been used in pharmaceu-
In recent years, ternary chalcogenide semiconducting nano- tical [10] and chemical synthesis [11]. L-Cysteine, a complexing
materials have received much attention due to their potential agent used to synthesize various metal suldes [1216], has also
applications in linear, nonlinear, optoelectronics, thermoelectric been employed as a sulfur source and is also benign to the
devices, and optical recording media [1]. AgBiS2, one of the environment. The hydrothermal method is one of the most promis-
semiconducting ternary suldes, has promising applications as a ing solution techniques for the synthesis of powders with controlled
novel semiconductor because of their unusual electronic and sizes and morphologies. This solution method has several other
magnetic properties [2]. It is well known that size, morphology, advantages, including accelerated interactions between the solid
and assembly behaviors have much inuence on their varying and uid species, and the formation of phase pure and homoge-
physical properties. These properties differ from those of the bulk neous materials [17]. In addition, the kinetics of the reactions can be
materials. The nanosized powders of semiconducting nanomater- accelerated due to the elevated temperatures.
ials have unusual physical properties due to the quantum con- In this work, the AgBiS2 nanoparticles were successfully pre-
nement effect [3]. Therefore, it is imperative to search for a pared by a simple biomolecule-assisted hydrothermal method. Up
simple, convenient and environmental friendly method for fabri- to the present time, the synthesis of AgBiS2 nanoparticles by using
cating nanostructured materials with controlled size, morphol- L-cysteine as the sulfur source has not been reported. Here, the
ogy, and assembly behaviors and, hence, tailoring their properties. proposed formation mechanism of the AgBiS2 nanoparticles was
Several routes have been developed for the preparation of presented, and the optical property of the AgBiS2 nanoparticles was
AgBiS2 such as microwave reux [2], ux techniques [46], examined.
solvothermal [7,8], and cyclic microwave techniques [9]. Never-
theless, these synthesis methods require toxic organic agents and
produce pungent H2S from sulfur sources used. To overcome this 2. Experimental procedure
problem, biomolecule-assisted method is the alternative way to
In a typical synthesis, 3 mmol AgNO3, 3 mmol Bi(NO3)3  5H2O,
and 6 mmol L-cysteine (C3H7NO2S) were separately dissolved
n
Correspondence address: Department of Chemistry, Faculty of Science, Chiang
in deionized water. The mixtures were transferred into 75 mL
Mai University, Chiang Mai 50200, Thailand. Fax: 6653 892277. Teon-lined stainless steel autoclave lled to 65% of its capacity.
E-mail address: sulawank@gmail.com The autoclave was sealed and maintained at 200 1C for 12, 48, and

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

Scheme 1. Schematic diagram used for preparation of AgBiS2.

72 h. After the autoclave had naturally cooled down to room


temperature, the products were separated from the mother liquor
by ltering, then they were washed with de-ionized water and
ethanol, respectively, and nally dried at 80 1C overnight. The
preparation is systematically shown in Scheme 1.
The crystallinity and phase purity of the samples were ana-
Fig. 1. XRD patterns of the AgBiS2 powders prepared at various hydrothermal
lyzed by X-ray diffractometer with CuKa radiation (wavelength: times.
0.15406 nm) operating at 20 kV15 mA in the 2y range of 10601.
The morphology and particle sizes of the samples were deter-
Table 1
mined by a eld emission-scanning electron microscopy (FE-SEM, XRD diffraction angle, FWHM, and crystallite size D of the AgBiS2 powders
JSM-6335F) operated at 15 kV accelerating voltage and transmis- prepared at various hydrothermal times.
sion electron microscopy (TEM, JEOL JEM-2010) operating at
200 kV. The chemical compositions were analyzed by energy Hydrothermal times/h 2y/deg. FWHM/radian D(2 0 0)/nm
dispersive X-ray spectroscopy (EDX) with the accelerating voltage
12 31.7063 0.2362 35
of 20 kV and inductively coupled plasma optical emission spec- 48 31.8699 0.1378 60
trophotometer (ICP-OES, Perkin Elmer 4300 DV, U.S.A.). The 72 31.7046 0.0984 84
optical property was examined by UVvis spectrometer (Lamda 25
Perkin Elmer, U.S.A.).
Fig. 2(ac) shows the SEM images of the AgBiS2 powders
prepared at different hydrothermal times. They are composed of
3. Results and discussion nearly spherical nanoparticles. The tendency of the particle size
changes, revealed by SEM observations, is in agreement with the
X-ray diffraction (XRD) patterns of the powders prepared at calculations of crystallite size from the XRD patterns as shown
various hydrothermal times are shown in Fig. 1. All of the in Table 1. The EDX spectrum of the powder prepared at 12 h in
diffraction patterns can be indexed as cubic AgBiS2 (JCPDS Fig. 2(d) presents the existence of Ag, Bi, S and Cu elements. The
database no. 04-0699) [18], without detection of any impurities. atomic ratio of Ag, Bi and S is 1:1.02:1.73, respectively, which
The patterns show a tendency of improvement in intensity from approximately respects to the stoichiometry of AgBiS2. It is noted
12 to 72 h, meaning that the holding time could be benecial to that the Cu element comes from the supporting copper holder. In
the crystallization of AgBiS2 crystallites. The broadening of the addition, the ICP-OES result provides the atomic ratio of Ag, Bi and
XRD lines is attributed to the nanocrystalline characteristics of S is 1.19:1:1.79, respectively, which is in agreement with the EDX
the powders, which indicates that the crystallite sizes are in analysis. These demonstrate that L-cysteine assisted method could
nanometer range. The crystallite sizes of the particles can be be an alternative way to synthesize stoichiometrical compounds.
estimated by applying the DebyeScherrer equation (Eq. (1)) Fig. 3 shows the transmission electron microscope (TEM)
images and selected area diffraction patterns (SAED) of the AgBiS2
0:9l
D 1 powders prepared at various hydrothermal times. They are all
B cos y composed of nanoparticles with a diameter range of about 2075 nm.
where D is the crystallite size in nanometers, l is the wavelength The TEM images show a smaller mean crystallite size that was
of CuKa (0.15406 nm), B is the full-width-at-half-maximum calculated from the XRD patterns. This deviation could be due to
(FWHM) in radians and y is the Bragg angle in degrees. The the fact that the crystallite size calculated by the DebyeScherrer
strongest peaks (2 0 0) were used to calculate the crystallite sizes. equation is a volume-averaged size, but analysis of TEM images
The calculated crystallite sizes of the powders prepared at various typically leads to a number average of the particles. Therefore,
hydrothermal times are summarized in Table 1. The results show a small number of large particles have a big contribution to
that the FWHM of the diffraction peaks decreased with the the diffraction measurement [20]. Obviously, the increase in the
prolonged reaction time. This proves that the crystallinity of the particle size of AgBiS2 nanoparticles was by increasing of the
particles improved and the crystallite sizes increased when the hydrothermal process reaction time. This may be due to its high
reaction times were prolonged. The calculated lattice constants surface energy and it is accompanied by increasing of aggregation
[19] are a bc 5.6546 A, which agree well with those of the to form larger nanoparticles. SAED patterns (inserted in TEM
JCPDS database (a bc 5.6546 A) [18]. images) of the nanoparticles show bright AgBiS2 concentric rings
110 S. Kaowphong / Journal of Solid State Chemistry 189 (2012) 108111

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

nanoparticles displayed a strong blue shift, caused by the quantum


connement effect. The proposed hydrothermal method using
L-cysteine as sulfur source provides an alternative approach to
prepare other binary and ternary semiconductor nanomaterials.

Acknowledgments

The author would like to thank the National Research Uni-


versity Project under Thailands Ofce of the Higher Education
Commission for nancial support.

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.

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