Materials Research Bulletin 44 (2009) 220–223

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Materials Research Bulletin

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Short communication

A facile water-based process for preparation of stabilized Bi nanoparticles

Yi Wang a,c, Jingzhe Zhao b,*, Xu Zhao a, Lanqin Tang a, Yunling Li a, Zichen Wang a
a
College of Chemistry, Jilin University, Changchun 130023, China
b
Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China
c
Department of Chemistry, Yanbian University, Yanji 133000, China

A R T I C L E I N F O A B S T R A C T

Article history: Stabilized bismuth nanoparticles have been prepared by reducing bismuth chloride with hydrazine
Received 19 December 2007 hydrate in the presence of sodium oleate under a facile water-based process. The obtained samples are
Received in revised form 5 March 2008 investigated by X-ray diffraction, transmission electron microscopy (TEM) and differential thermal
Accepted 26 March 2008
analysis and thermogravimetry (DTA/TG). The present results indicate that the bismuth nanoparticles are
Available online 8 April 2008
spherical, small diameter and in a high purity. In addition, measurement of water contact angle indicates
that Bi samples are hydrophobic, which gives defense to samples from further oxidation, samples are
Keywords:
steady in 6 months without obvious oxidation.
A. Metals
B. Chemical synthesis ß 2008 Elsevier Ltd. All rights reserved.
C. X-ray diffraction
C. Electron microscopy
D. Microstructure

1. Introduction [15]. Wang group reported a hydrofluoric acid-free hydrothermal

The nanoscaled particles have attracted much attention for
their special physical and chemical properties distinct from those
of the bulk [1,2]. As a semimetal with unusual properties that
result from its very small carrier effective masses, large mean free
path (a millimeter at 4.2 K), highly anisotropy Fermi surface, and
small energy overlap (about 38 meV at 77 K) [3], bismuth exhibits
excellent thermoelectric properties, unique electronic transport
properties, and very large magnetoresistance (MR) [4–7]. As the
crystallite size decreases (<70 nm), the transition from semimetal
to a semiconductor in bismuth is possible [8].
Some works have been done to prepare nanosized bismuth
[9,10]. Most of them were usually performed in organic phase
[11,12], such as Kim group synthesized bismuth nanoparticles
(diameters in the range 6–13 nm) in N,N-dimethylformamide
(DMF) by reducing bismuth chloride with sodium borohydride
[13]. Li group synthesized single-crystalline bismuth nanowires
and nanospheres by reducing sodium bismuthate in ethylene
glycol phase with the presence of poly(vinylpyrrolidone) (PVP) or
acetone [14]. Fang group reported a high-temperature organic
solution (dioctyl ether [CH3(CH2)7]2O) reduction method to
produce bismuth nanoparticles with diameters about 15 nm
* Corresponding author. Tel.: +86 731 8809278; fax: +86 731 8809278.
E-mail address: zhaojz@mail.jlu.edu.cn (J. Zhao).
etching method to produce bismuth nanospheres [16], while high
pressure is indispensable by their method. Nanosized bismuth
prepared in water phase under normal pressure is reported rarely.
Because bismuth salts dissolve easily in organic phase such as
ethylene glycol, otherwise, in water phase, they form generally
suspension for their hydrolyzation. In this work, we introduced
sodium oleate as dispersant, morphology controller and stabilizer,
prepared successfully spherical bismuth nanoparticles with size of
about 25–40 nm in an aqueous solution with low temperature and
normal pressure. The compositions, crystal structure, morphology
of samples together with the effects of stabilizer were analyzed.
2. Experimental
Bismuth (III) chloride (BiCl3) was used as precursors of Bi
nanoparticles, hydrazine hydrate (N2H4H2O) was used as both a
reductant and a controller of pH value. Distilled water and sodium
oleate were used as solvent and stabilizer, respectively. All of these
high-grade chemicals were used without further purification.
The typical bismuth nanoparticles were synthesized according
to the following procedure: 0.002 mol of BiCl3, 0.0315 g sodium
oleate (the weight ratio of sodium oleate to BiCl3 is about 1:20),
and 8 mol/L hydrazine hydrate 20 ml were mixed under rapid
stirring for 30 min, the mixture was transferred into a water bath
with a temperature of 80 8C, stirred for 60 min, ripened for 10 min.
When the reaction was finished, the black-solid were filtered and

0025-5408/$ – see front matter ß 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2008.03.026
 Y. Wang et al. / Materials Research Bulletin 44 (2009) 220–223 221

washed several times to remove excessive ions with distilled water

and residual water on the surfaces of the obtained products with
acetone. After being dried for 20 h, the obtained dark powders
were kept for further characterization.
The crystal structure of the samples was characterized by X-ray
powder diffraction (XRD), performed at room temperature with a
Cu Ka X-ray source using an XRD-6000 instrument (SHIMADZU,
Japan). Energy-dispersive X-ray (EDX) analysis was carried out by
using a SSX-550 scanning electron microscope equipped with an
energy-dispersive X-ray detector (SHIMADZU, Japan). The Fourier
transform infrared (FTIR) spectra of the samples were measured by
a FTIR-8400s (SHIMADZU, Japan) instrument in the wavenumber
range of 400–4000 cm1. Transmission electron microscopy (TEM)
was carried out on samples with a JEM-3010 (JEOL, Japan)
instrument using standard techniques. Differential thermal
analysis and thermogravimetry (DTA/TG) (DTG-60AH SHIMADZU,
Japan) were conducted on the samples in the 20–550 8C
Fig. 2. EDX pattern of the as-prepared bismuth nanoparticles.
temperature range, with a heating rate of 10 8C/min and in
dynamic air. The purity of samples was determined by ICP (Agilent
7500a, USA) and CHN element analysis (PE-2400, USA). Water
contact angle was obtained by FT Å200. are generated from the glue under the sample and the surfactant
(sodium oleate).
3. Results and discussions In our system, the thermodynamic feasibility of the chemical
reaction we employed for the synthesis of Bi nanoparticles can be
3.1. Composition and crystal structure of bismuth nanoparticles explained as

4BiCl3 þ 12N2 H4 H2 O Ð 4Bi þ 6N2 þ 12H2 O þ 12NH4 Cl: (1)

To determine the chemical composition and crystal structure of
the samples, representative X-ray diffraction patterns are given.
Fig. 1a and b shows X-ray diffraction patterns of as-prepared Bi
nanoparticles and the same sample after being preserved for 6
months, respectively. All of the diffraction peaks can be readily
indexed to pure rhombohedral phase of Bi. The calculated lattice
constants a = 4.547 Å, c = 11.856 Å from XRD data, are consistent
with the standard values of a = 4.546 Å and c = 11.860 Å (JCPDS 05-
0519). The sharp and strong peaks reveal that the products
crystallize well. Furthermore, the XRD pattern of bismuth
nanoparticles after being preserved for 6 months (Fig. 1b) is
completely consistent as those as-prepared bismuth nanoparticles,
which indicates a good stability of the as-prepared bismuth
nanoparticles.
Thorough elementary composition analysis of the resultant
powders was performed by energy-dispersive X-ray analysis. The
typical EDX analysis (Fig. 2) demonstrates that the obtained
bismuth nanoparticles are pure and the carbon and oxygen peaks
The above reaction comprises two half reactions:
N2 þ 4H2 O þ 4e ! N2 H4 þ 4OH ðE0 ¼ 1:15 VÞ (2)
BiðOHÞ3 þ 3e ! Bi þ 3OH ðE0 ¼ 0:46 VÞ (3)
0
According to the E values of the half-reactions (2) and (3), the
standard Gibbs free energy change DG8 of the total reaction (1)
could be estimated to be about 799 kJ mol1, which indicates
that hydrazine hydrate can reduce bismuth (III) to bismuth (0).
Besides, the byproducts (NH4Cl, N2) can easily be removed and
pure bismuth will be obtained.
3.2. Thermal stability and the purity of bismuth nanoparticles
Fig. 3 displays the thermal stability of Bi nanoparticles, which is
studied by DTA/TG. It is apparent that the sample shows an

Fig. 1. XRD patterns of spherical bismuth nanoparticles: as-prepared bismuth

nanoparticles (a), the same sample after being preserved for 6 months (b). Fig. 3. DTA/TG curves of bismuth nanoparticles.
222 Y. Wang et al. / Materials Research Bulletin 44 (2009) 220–223

endothermic region on the DTA curve located around 275.8 8C, and
the corresponding large mass increase, evidenced by the TG curve,
are due to the oxidation of Bi nanoparticles in the sample above
240 8C. Below 200 8C, a little mass increase is found (about 1.87%),
which indicates that the nanoparticles are relatively steady in a
wide temperature range.
The corresponding thermogravimetric curve indicates that total
mass increase of product is ca. 10%. The metallic purity of the
sample can be calculated from the weight gain (10%) in the
thermobalance as ca. 100%, and leads to the conclusion that pure
bismuth nanoparticles have been prepared. At the same time, we
use ICP and CHN element analysis to examine the purity of the
sample. Table 1 presents the element analysis of the sample, which
shows little hydrogen, carbon and nitrogen in the final sample. The
result of the ICP shows that the weight percentage of bismuth in
the sample is 99.93%. All these measurements indicate the high
purity of the sample.

Fig. 4. TEM image of spherical bismuth nanoparticles prepared in the present of

3.3. Morphology of bismuth nanoparticles
sodium oleate.

The morphology of the sample was examined by transmission

electron microscopy. Fig. 4 shows a typical TEM image of the as-
prepared Bi nanoparticles. The nanoparticles formed in the
presence of sodium oleate are found to be spherical, and the size
distribution calculated from several TEM images indicates that the
average particle diameter is in the range of 25–40 nm. In addition,
a few small size particles of 15 nm and large size particles of about
50 nm in diameter are also found.
3.4. Influence of reaction parameters
To find the influence of reaction temperature, several reduction
experiments were performed at different temperature. If the
reactive temperature is below 60 8C, the reduction reaction is so
slowly that the pure bismuth cannot be obtained. The precipitates
we get are a grey mixture. Above 90 8C, the bulk bismuth with
metallic lustre is obtained, no bismuth nanoparticles exist in
samples.
In addition, concentration dependent experiments were carried
out by varying the concentration of reductant. When the
concentration of reductant (N2H4H2O) changes from 8 mol/L to
16 mol/L, there are of no obvious effect upon the size and
morphology of samples. But as the concentrations are below 8 mol/
L, the precursor (bismuth (III)) in the suspension cannot transform
completely to bismuth (0).
decreased and the dispersion of bismuth nanoparticles is
improved, which prevent the agglomeration of the nanoparticles.
In contrast to samples prepared without sodium oleate, the
samples prepared in the presence of sodium oleate are spherical
nanoparticles of 25–40 nm (Fig. 4). We also find that the quantity
of sodium oleate (the weight ratio of sodium oleate to BiCl3: from
1:20 to 1:1) has little impact on the size of bismuth nanoparticles
in the given range.
It is well known that the nanosized bismuth could easily be
oxidized, and it generally needs to be preserved in some organic
solvent (such as hexane) or under inert gas [10,17]. For the bismuth
nanoparticles prepared by this method, they can be randomly
preserved in common sealed pocket for at least 6 months without
obvious oxidation (as can be seen from Fig. 1b). FTIR analysis is also
carried out. In IR spectra (Fig. 6), the peak at 1098 cm1 can be
attributed to infrared absorption of nanosized bismuth [18], two
peaks at 2847 cm1 and 2916 cm1 can be attributed to methylene
(C–H) of sodium oleate, the band position at about 1740 cm1 is
due to the –COO– groups of sodium oleate. It is interesting to
detect that the as-prepared bismuth nanospheres are able to float
on the surface of water and water contact angle of the sample is
about 1258 (Fig. 6 inset). It can be concluded that there is a layer of
an organic group of sodium oleate stayed on the surface of bismuth

3.5. Effects of sodium oleate

In the reaction system, sodium oleate was added at the initial

stage of the reaction. According to the results of the experiments,
sodium oleate plays important roles as dispersant, morphology
controller and stabilizer. If sodium oleate is absent, the reaction
completes quickly in only about 10 min, the samples are bismuth
nanoplates and a few nanorobs as shown in Fig. 5. While in the
presence of sodium oleate, the rate of the reduction reaction is

Table 1
The C, H, N element analysis of sample

Weight of sample (mg) Percentage

H N C

1.7713 0.23 0.00 1.76

1.8317 0.21 0.00 1.53
Fig. 5. TEM image of bismuth nanoplates and nanorobs prepared without sodium
Average 0.22 0.00 1.64
oleate.
 Y. Wang et al. / Materials Research Bulletin 44 (2009) 220–223
Fig. 6. FTIR spectra of different samples: (a) pure sodium oleate (b) bismuth
nanoparticles prepared by 5% sodium oleate and its water contact angle (the inset).
nanospheres (the layer can be removed by ultrasonic cleaning with
absolute ethanol). The hydrophobic surface may effectively avoid
the incursion of water and oxygen that improves the anti-oxidated
ability of the samples.
4. Conclusion
In this work, spherical bismuth nanoparticles have been
synthesized using a facile chemical reduction method in water
phase at 80 8C, in which sodium oleate was used as the dispersant,
morphology controller and stabilizer. The XRD analysis proves that
the Bi nanoparticles are rhombohedral phase. The TEM image
shows that the as-prepared bismuth nanoparticles are spherical
with diameters of 25–40 nm. The presence of sodium oleate
prevents the agglomeration and oxidation of the sample, controls
223
morphology of the sample. The stabilized bismuth nanoparticles
can be kept for at least 6 months without obvious oxidation.
Compare with other methods for the synthesis of bismuth
nanoparticles, the present method shows more merits, such as
water-based process, low reaction temperature, normal pressure
and a small size of the bismuth nanospheres.
Acknowledgements
This work was supported by the Scientific Research Foundation
for the Returned Overseas Chinese Scholars, State Education
Ministry (SRF for ROCS, SEM) and the Natural Science Foundation
of Jilin Province for Excellent Young Scholars (Grant No.
20040117).
References
[1] Z.Y. Tang, N.A. Kotov, M. Giersig, Science 297 (2002) 237.
[2] T. Ould-Ely, J.H. Thurston, A. Kumar, M. Respaud, W.H. Guo, C. Weidenthaler, K.H.
Whitmire, Chem. Mater. 17 (2005) 4750.
[3] F.Y. Yang, K. Liu, K. Hong, D.H. Reich, P.C. Searson, C.L. Chien, Science 284 (1999)
1335.
[4] S. Park, K. Kang, W.Q. Han, T. Vogt, J. Alloy Comp. 400 (2005) 88.
[5] J.P. Heremans, C.M. Thrush, D.T. Morelli, M.C. Wu, Phys. Rev. Lett. 88 (2002)
216801.
[6] G. Bhimarasetti, M.K. Sunkara, J. Phys. Chem. B 109 (2005) 16219.
[7] P. Chiu, I. Shih, Nanotechnology 15 (2004) 1489.
[8] A. Nikolaeva, D. Gitsu, T. Huber, L. Konopko, Phys. B 346–347 (2004) 282.
[9] T.E. Huber, K. Celestine, M.J. Graf, Phys. Rev. B 67 (2003) 245317.
[10] M. Motoyama, Y. Fukunaka, S. Kikuchi, Electrochim. Acta 51 (2005) 897.
[11] E.E. Foos, R.M. Stroud, A.D. Berry, A.W. Snow, J.P. Armistead, J. Am. Chem. Soc. 122
(2000) 7114.
[12] Y.B. Zhao, Z.J. Zhang, H.G. Danga, Mater. Lett. 58 (2004) 790.
[13] Y.W. Wang, B.H. Hong, K.S. Kim, J. Phys. Chem. B 109 (2005) 7067.
[14] J.W. Wang, X. Wang, Q. Peng, Y.D. Li, Inorg. Chem. 43 (2004) 7552.
[15] J.Y. Fang, K.L. Stokes, W.L. Zhou, W.D. Wang, J. Lin, Chem. Commun. (2001)
1872.
[16] H. Liu, Z.L. Wang, J. Am. Chem. Soc. 127 (2005) 15322.
[17] Y.D. Li, J.W. Wang, Z.X. Deng, Y.Y. Wu, X.M. Sun, D.P. Yu, P.D. Yang, J. Am. Chem.
Soc. 123 (2001) 9904.
[18] M.R. Black, Y.-M. Lin, S.B. Cronin, O. Rabin, M.S. Dresselhaus, Phys. Rev. B 65 (2002)
195417.