Materials Science and Engineering B 131 (2006) 200–202

A novel electrochemical preparation of PbS nanoparticles

Yu Jun Yang ∗
Zhuzhou Institute of Technology, Zhuzhou, 412008 Hunan, PR China
Received 3 December 2004; accepted 19 April 2006

Abstract
A simple one-step anodic sonoelectrochemical method to synthesize PbS nanoparticles has been developed. With the lead foil as the sacrificing
anode, Pb(II) was anodically dissolved from the lead electrode into the aqueous solution of sodium sulfide, supporting electrolyte (potassium
nitrate) and capping agent (PVA) at a constant potential, and then the produced Pb(II) reacted with the sulfide anion to form PbS nanoparticles
under ultrasonic irradiation. The effects of the applied potential, capping agent and ultrasound in the formation of PbS nanoparticles are discussed,
and the results suggest that the anodic sonoelectrochemical method may be a general and convenient way to prepare metal sulfide nanoparticles.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Electrochemistry; Nanoparticles; Lead sulfide; Anodic electrolysis; Ultrasonic irradiation

1. Introduction been done on the electrochemical preparation of semiconductor

Semiconductor nanocrystals have electronic properties
between those of molecular entities and macrocrystalline solids
and there has been much interest in the synthesis and char-
acterization of sulfide semiconductor nanocrystals in the past
decade. Various new methods for the preparation of metal sulfide
nanoparticles such as ultraviolet irradiation [1], X-ray irradiation
[2], solvothermal method [3] and microwave assisted heating [4]
have been reported recently.
The combination of sonochemistry and electrochemistry is a
new technique used to generate novel materials. Silver nanopar-
ticles [5], nanowire [6] and nanorods [7] were prepared by
reducing the Ag+ at the cathode surface from AgNO3 aqueous
solution in an ultrasonic bath. Metal selenides nanoparticles have
also been successfully synthesized with sonoelectrochemical
method, which combines the existing cathodic electrodeposi-
tion techniques of metal selenides and ultrasonic irradiation.
CdSe and PbSe nanoparticles were fabricated by reductively
co-depositing Cd/Pb and selenium at negative potential on the
cathode which also acted as the ultrasound emitter from the
aqueous solution of CdSO4 /Pb(Ac)2 and Na2 SeSO3 [8,9].
Although metal sulfide thin films can be electrodeposited on
the cathode surface [10,11], however, until now no research has
∗ Tel.: +86 733 8182953; fax: +86 733 8182953.
E-mail address: yangyujun@yahoo.com.
sulfide nanomaterials. It is due to the fact that the cathodic elec-
trodeposition of semiconductor sulfide was usually carried out in
an acidic bath (pH 3.00–4.00) containing metals ion and sodium
thiosulfate (Na2 S2 O3 ). Under ultrasonic irradiation, pure lead
sulfide nanoparticles cannot be produced because it is inevitable
for the colloidal sulfur to form in the acidic solution.
In this report, we take a different approach to electrochemi-
cally synthesize metal sulfide nanoparticles. With the lead foil
used as the sacrificing anode, PVA capped lead sulfide nanoparti-
cles were successfully synthesized in the sodium sulfide aqueous
solution under ultrasonic irradiation. Our further study sug-
gests that this novel anodic sonoelectrochemical method may
be a general and convenient way to prepare other metal sulfide
nanoparticles.
2. Experimental
All the chemical reagents except lead foil were of pure grade.
The experiment was performed in a one-compartment cell. Elec-
trolysis was carried out with a PGSTAT 30 (Eco. Chemie,
Netherlands) electrochemical system. The reference electrode
was Ag/AgCl (saturated KCl) and the counter electrode was
a platinum grid. A 3 cm2 lead foil (AR, Ajax Chemicals, Aus-
tralia) was used as sacrificing anode. PVA of 2.5 g was dissolved
into 250 mL 0.04 M KNO3 and 0.04 M Na2 S solution. Work-
ing, reference and counter electrodes were immersed into the
prepared solution. The distance between working electrode and

0921-5107/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2006.04.014
 Y.J. Yang / Materials Science and Engineering B 131 (2006) 200–202 201

counter electrode was kept at 5 cm. High purity nitrogen gas

was bubbled into the solution to remove the dissolved oxygen
from the system. The electrolysis cells were put into an operat-
ing ultrasonic bath (ZQ25-2A Subminiature Ultrasonic Cleaning
Machine, Gang Xing Ultrasonic Co. Ltd., China) and the elec-
trolysis was carried out in the presence of an ultrasonic field
(25 kHz, 100 W) under N2 atmosphere. The temperature during
the reactions was controlled at ca. 25 ◦ C. PbS nanonanoparticles
were prepared via electrochemical oxidation with controlled-
potential at 0.8, 1.0 and 1.2 V at ambient temperature. Black
colloid solution was obtained after 15 min of electrolysis. Cen-
trifuge the solution and wash the precipitate with distilled water
and absolute ethanol for several times. The black powder was
dried in vacuum oven at room temperature for 4 h.
The products were characterized by using ultraviolet spec-
troscopy (UV), powder X-ray diffraction (XRD) and trans-
mission electron microscopy (TEM). Powder X-ray diffraction Fig. 1. UV–vis absorption spectrum of PbS nanoparticles synthesized in 0.04 M
data were collected using a Siemens X-ray diffractometer at a KNO3 , 0.04 M Na2 S and 1 wt.% PVA aqueous solution with 0.8, 1.0 and 1.2 V
scanning rate of 4◦ /min in the 2θ range from 10 to 90◦ , with applied on the lead electrode under 25 kHz ultrasonic irradiation.
graphite monochromatized Cu K␣ radiation (λ = 0.15418 nm).
TEM experiments were carried out employing Philips CM 10 The purity and composition of the product were further ana-
transmission electron microscope, using an accelerating voltage lyzed using powder X-ray diffraction. The XRD pattern of the
of 100 kV. The samples used for TEM were prepared by dispers- as-prepared PbS nanoparticles (Fig. 2) shows the presence of
ing some products in ethanol followed by ultrasonic vibration for broad peaks corresponding to the cubic crystal structure. The
30 min. One drop of the suspension was placed on a copper net, positions and intensities of the peaks are in good agreement
which was dried carefully in vacuum oven. Absorption spectrum with the JCPDS values for cubic phase PbS. The broadening of
was recorded using a Shimadzu UV–vis 265 spectrophotometer the peaks indicates the nanocrystallite nature of the product.
in the wavelength range of 300–900 nm at room temperature. The dimensions and morphologies of the PbS nanoparticles
are shown in the TEM image (Fig. 3). It is apparent that the
3. Results and discussion as-prepared PbS nanoparticles present spherical morphologies,
although some very large particles exist. The average size of
During the experiment, black product was formed immedi- these nanoparticles is 9 nm, which is less than the excitonic Bohr
ately once upon the beginning of electrolysis in the ultrasonic radius of the bulk PbS (ca. 18 nm). The average size of PbS
bath. This indicates that the chemical reaction rate of the reactive nanoparticles calculated from the measurements of nanopar-
system is very fast at room temperature (25 ◦ C). It can be con- ticles on the TEM image is consistent with the result calcu-
cluded from the experimental phenomenon that the nucleation lated for the half-width of diffraction peaks using the Scherrer’s
rate is far excess the growth rate of the particles. So this reactive formula.
mechanism favors the formation of nanoparticles.
The UV–vis absorption spectrum of the as-prepared PbS
nanoparticles is shown in Fig. 1. It can be seen that the UV–vis
absorption edge is in the 370 nm, and shows a very significant
blue shift from the bulk PbS crystals [12]. This is an indica-
tion of quantum confinement, because the average size of PbS
nanoparticles is smaller than the excitonic Bohr radius of the
bulk PbS (ca. 18 nm).
The applied potential is an important factor affecting the reac-
tion. The higher the applied potential, the higher the anodic
current is. And a higher current will definitely leads to a faster
dissolution rate of Pb2+ from the lead electrode surface. As
shown in Fig. 1, with constant reaction time (15 min), the absorp-
tion peak increased as the potential applied on the working
electrode was increased while no obvious peak shift can be
observed. However, the large amount of hydrogen gas evolved
when the potential higher than 0.8 V was applied on the work-
ing electrode. The pH value of the solution dropped very quickly
Fig. 2. The powder XRD patterns of PbS nanoparticles synthesized in 0.04 M
and caused the evolution of toxic H2 S. So 0.8 V is the optimum KNO3 , 0.04 M Na2 S and 1 wt.% PVA aqueous solution with 0.8 V applied on
potential in this experiment. the lead electrode under 25 kHz ultrasonic irradiation.
202 Y.J. Yang / Materials Science and Engineering B 131 (2006) 200–202
Fig. 3. The TEM images of PbS nanoparticles synthesized in 0.04 M KNO3 ,
0.04 M Na2 S and 1 wt.% PVA aqueous solution with 0.8 V applied on the lead
electrode under 25 kHz ultrasonic irradiation.
The basis of this novel sonoelectrochemical technique to syn-
thesize PbS nanoparticles is massive nucleation using high cur-
rent density electrolysis, followed by the removal of the deposit
from the electrode by the ultrasonic pulse. The electrolysis
of lead produces Pb2+ in the ultrasonic bath, which immedi-
ately reacts with the S2− . The high-density burst of ultrasound
removes the PbS particles from the anode, clean the electrode
surface and replenishes the double layer with S2− by stirring the
solution [9]. If ultrasonic irradiation was not employed, it was
observed that PbS was deposited on the lead electrode surface.
As a result, PbS nanoparticles cannot be obtained. The con-
centration of the PVA is another factor affecting the formation
of PbS nanoparticles. In the absence of PVA, PbS aggregated
into micron-sized particles. Lower concentration of PVA cannot
prevent the aggregation of the PbS nanoparticles. However, as
indicated by the XRD study of the products, a mixture of PbS and
metal lead nanoparticles was obtained when the concentration
of PVA was higher than 1.5 wt.%.
4. Conclusion
We have demonstrated a novel sonoelectrochemical method
for the preparation of nanoparticles of PbS. With lead electrode
as sacrificing anode and the application of a positive poten-
tial, PVA capped PbS nanoparticles with average size of 9 nm
were produced in the aqueous solution of sodium sulfide under
ultrasonic irradiation. This method is also applicable for the
preparation of other sulfide semiconductor nanoparticles such
as CdS and ZnS.
References
[1] C.Y. Wang, X. Mo, Y. Zhou, Y.R. Zhu, H.T. Liu, Z.Y. Chen, J. Mater.
Chem. 10 (2000) 607–608.
[2] Y.D. Yin, X.L. Xu, Chem. Commun. 16 (1998) 1641–1642.
[3] S.H. Yu, Y.S. Wu, J. Yang, Z.H. Han, Y. Xie, Y.T. Qian, X.M. Liu,
Chem. Mater. 10 (1998) 2309–2312.
[4] H. Wang, J.R. Zhang, J.J. Zhu, J. Cryst. Growth 233 (2001) 829–836.
[5] A. Gedanken, Y. Koltypin, O. Palchik, S. Liu, J. Zhu, Langmuir 16
(2000) 6396–6399.
[6] J.J. Zhu, Q.F. Qiu, H. Wang, J.R. Zhang, J.M. Zhu, Z.Q. Chen, Inorg.
Chem. Commun. 5 (2002) 242–244.
[7] Y.J. Xiong, Y. Xie, G.O. Du, X.M. Liu, X.B. Tian, Chem. Lett. 1 (2002)
98–99.
[8] J.J. Zhu, S.T. Aruna, Y. Koltypin, A. Gedanken, Chem. Mater. 12 (2000)
143–147.
[9] G. Hodes, A. Gedanken, Y. Koltypin, R. Polsky, Y. Mastai, J. Am.
Chem. Soc. 121 (1999) 10047–10052.
[10] M. Sharon, K.S. Ramaiah, M. Kumar, M. Neumann-Spallart, C. Levy-
Clement, J. Electroanal. Chem. 436 (1997) 49–52.
[11] G. Sasikala, R. Dhanasekaran, C. Subramanian, Thin Solid Films 302
(1997) 71–76.
[12] R.S. Kane, R.E. Cohen, R. Silbery, Chem. Mater. 8 (1996) 1919–
1924.