Materials Research Bulletin 49 (2014) 172–175

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Materials Research Bulletin

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

Nanostructured hydrocerussite compound (Pb3(CO3)2(OH)2) prepared

by laser ablation technique in liquid environment
D.L. da Cunha a,*, G.F.C. Pereira b, J.F. Felix c, J. Albino Aguiar a,b, W.M. de Azevedo a,d
a
Programa de Pós Graduação em Ciência de Materiais, Universidade Federal de Pernambuco, Avenida Prof. Moraes Rego, 1235, Cidade Universitária, Recife,
PE, 50670-901, Brazil
b
Departamento de Fı´sica, Universidade Federal de Pernambuco, Avenida Prof. Moraes Rego, 1235, Cidade Universitária, Recife, PE, 50670-901, Brazil
c
Departamento de Fı´sica Universidade Federal de Viçosa. Av. P H Rolfs, s/n, Campus Universitário, Viçosa, MG, 36570-000, Brazil
d
Departamento de Quı´mica Fundamental, Universidade Federal de Pernambuco, Avenida Prof. Moraes Rego, 1235, Cidade Universitária, Recife, PE, 50670-
901, Brazil

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

Article history: This article presents a chemical bottom-up synthesis of highly crystalline and nanostructured
Received 10 March 2013 hydrocerussite (Pb3(CO3)2(OH)2) with hexagonal morphology prepared by laser ablation in liquid. The
Received in revised form 30 June 2013 results demonstrate that is possible to use laser ablation in liquid to prepare complex chemical
Accepted 18 August 2013
compounds. The experiment consisted of a high power second harmonic of an Nd:YAG laser incidence on
Available online 4 September 2013
the surface of a Pb target immersed in primary alcohols. Three different values of fluency and four
different primary alcohols were used in order to investigate the influence of fluency delivered to the
Keywords:
target surface and the chemical composition of the liquid environment on the properties of the prepared
A. Inorganic compound
A. Nanostructures
materials. Crystalline and nanostructured hexagonal particles of hydrocerussite, with average widths of
B. Chemical synthesis 1.0  0.3 mm and average thickness of 80  20 nm, were obtained when laser ablation was done in methanol
C. X-ray diffraction and ethanol whereas hydrocerussite and metallic lead were obtained when 1-propanol or 1-butanol were
D. Microstructure used. Additionally, it was shown that the values of the laser fluency used in this study do not modify the
sample morphology and composition. In order to explain the observed results a photochemical reaction
model induced by laser ablation of a metallic Pb surface immersed in alcohol solution is presented.
ß 2013 Elsevier Ltd. All rights reserved.

1. Introduction in the literature, it can be observed that this methodology has been
used to obtain materials such as: metal oxides, metal colloids,
Laser ablation of solid targets in liquid medium has been semiconductor, and nitrites [3–10]. Few examples of more
extensively used in the past two decades, at the beginning as a complex compounds obtained by laser ablation can be found in
technique to produce a colloidal solution of nanoparticles, and the literature: it was developed a catalyst free electrochemistry-
subsequently as a successful material fabrication technique that is assisted pulsed laser ablation in liquid route to fabricate
able to quickly prepare nanostructured materials of various polyoxometalate nanostructures Cu3(OH)2(MoO4)2 [11]; also it
compositions, morphologies and phases [1,2]. The reason for that was presented a surfactant-assisted preparation method to obtain
choice seems to be the fact that laser ablation in liquid can be layered silver bromide-based inorganic/organic nanosheets by
considered as a chemically clean and a one-pot synthetic route that pulsed laser ablation in aqueous media [12]. Additionally, the size
are able to prepare a variety of functionalized new nanostructures, and morphology of nanoparticles has been modified [13,14] by
where the final product is usually obtained without by-products adjusting the variables that control the composition and the
and no need for further purification. Also it is a low cost structure of nanomaterials generated by laser ablation in liquid
experimental technique, which presents few controlled param- environment [15].
eters and provides extreme confined conditions of high tempera- Aiming to contribute to the development of this area, we
ture and pressure that favor the formation of unusual metastable present a chemical bottom up synthesis of nanostructured and
phases. However, over the majority of laser ablation results found highly crystalline hydrocerussite (Pb3(CO3)2(OH)2) compound
with hexagonal morphology, prepared exclusively by laser
ablation technique in a liquid environment.
Hydrocerussite Pb3(CO3)2(OH)2 is quite a rare mineral in nature
* Corresponding author. Tel.: +55 81 9755 2072; fax: +55 81 2126 8442.
that is found in small quantities in soil only. It consists of basic lead
E-mail addresses: diegolcunha@gmail.com (D.L. da Cunha), gp91@df.ufpe.br
(G.F.C. Pereira), jorlandiof@gmail.com (J.F. Felix), albino@df.ufpe.br carbonate with a trigonal crystalline structure. Its hexagonal
(J. Albino Aguiar), wma@ufpe.br (W.M. de Azevedo). atomic layers overlap along the direction (0 0 1) which promotes

0025-5408/$ – see front matter ß 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.materresbull.2013.08.030
 D.L. da Cunha et al. / Materials Research Bulletin 49 (2014) 172–175 173

the growth of hexagonal structures, where layer A consists of Pb Electron. The UV–vis spectra where recorded using an Ocean
and CO3, and layer B of Pb and OH, with a stacking sequence of the Optics CHEM2000-UV-VIS spectrometer, whereas the crystal
type BAABAA [16]. Although hydrocerussite is rare in nature and it structure and the infrared analysis were obtained using Siemens
has been playing a significant role in geology and in environmental X-ray diffraction analyze model D5000 with Cu Ka radiation and a
issues [17], it has also been applied as a polymer stabilizer [18] and Bruker FTIR spectroscope model IFS 66, respectively.
it has been extensively investigated in the lead acid battery
industry [19]. The literature shows that experimental crystalliza- 3. Results and discussions
tion and thermodynamic data on Pb carbonates are limited, and
the characterization of these properties requires an adequate It is already known that the ablation of a surface of a solid target
amount of samples but unfortunately the mineral is rare and never immersed in a liquid environment causes the ejection of a plasma
occurs in a sizeable amount. Regarding to the synthesis of plume containing atomic neutral and ionized specimens of both
hydrocerussite, most methods found in the literature are awkward liquid and ablated solid [1,2]. Inside the plasma plume, heated by
and time consuming [20,21]. To overcome these difficulties and to the laser beam and confined by the liquid environment, the
present an example of more complex inorganic compound pressures and temperatures reach values of about 106 Pa and 103 K
synthesis using laser ablation technique, we present in this paper [22]. These critical conditions added to the rapid cooling caused by
the laser ablation technique in the liquid environment as a the liquid environment favors the occurrence of chemical
straightforward synthetic route for the preparation of nanostruc- processes in non-equilibrium conditions and the formation of
tured hydrocerussite Pb3(CO3)2(OH)2 compound. materials with metastable configurations [23]. Using this non-
conventional synthetic route, the ablation of the Pb target
2. Experimental produces Pb atoms, ions and Pb particles that became dispersed
in the liquid environment and subsequently interacted with
Fig. 1 shows the experimental scheme used to synthesize the adsorbed O2 to form the lead oxide, PbO. This statement can be
nanostructured Pb carbonate compound, where a metal plate of Pb confirmed by the result presented in Fig. 2 that shows the UV–vis
(99.5%, America Elements) used as target material was placed on spectra of the irradiated solutions taken immediately after the
the bottom of a glass vessel filled up with 10 cm3 of alcohol ablation process. The spectra of all samples shows two absorption
solution. The target was irradiated for 10 min with the second bands around 210 and 250 nm which can be assigned to Pb and
harmonic of a pulsed Nd:YAG laser (Spectra-Physics Quanta-Ray PbO nanoparticles absorption bands [24,25]. During the experi-
GCR-170) operating at 532 nm and 10 Hz, with 8 ns of pulse width, ment this rich environment of ions and particles assisted by the
which was focused on the target with a spot size of about 1 mm in laser radiation may behave as a catalyst surface for the oxidation of
diameter using a 100 mm focal length lens. the alcohol molecule resulting in a complete decomposition of
Finally, the products were centrifuged and collected. The methanol into CO2 and H2O, which subsequently reacts with PbO
solutions obtained including sediments were dropped and dried on resulting in the hydrocerussite compound. The synthesis may
glass substrates for sample characterization. For comparison of the occur according to the scheme below:
results, three different laser fluencies on the solid target were used
0.5 J/cm2, 2.0 J/cm2 and 4.0 J/cm2, and in order to establish the PbðsolidÞ þ hn þ O2 ! nPb þ Pbþm þ PbO
mechanism for preparing the sample, the ablation reaction was
performed in methanol (Merck PA), ethanol (Kinetics PA), 1- hn þ nPb0 catalyst
propanol (Merck PA) and 1-butanol (Merck PA), for which the
experimental setup is summarized in Table 1. CH3 OH þ O2 ! CO2 þ H2 þ H2 O
The morphology of the samples was analyzed by scanning
electron microscope using a Jeol microscope model JSM-5900, 3PbO þ CO2 þ H2 ! Pb3 ðCO3 ÞðOHÞ2
where the samples were previously metalized with 10 nm of Au
thin film by sputtering, model SC-701 Quick Coater form Sanyu This assumption is supported by the experimental results
already published in the literature on the photochemistry of
methanol [26], the decomposition of methanol on metallic surfaces
[27] and the results of photo decomposition of alcohols with metal
ions in solution induced by radiation [28].
A few hours after the ablation procedure finished a whitish
powder precipitate was obtained when methanol and ethanol
were used as liquid environments, while a grayish color solution
was obtained when 1-propanol or 1-butanol was used. In order to

Fig. 1. Schematic diagram of the experimental setup for nanoparticle production.

Table 1
Experimental parameters used for the laser ablation of the Pb target in this work.

Sample Solid Liquid Liquid Fluency Repetition Ablation

Name Target Environment Volume Rate Time

PbMet-A Pb Plate Methanol 10 cm3 2.0 J/cm2 10 Hz 10 min

PbMet-B Pb Plate Methanol 10 cm3 0.5 J/cm2 10 Hz 10 min
PbMet-C Pb Plate Methanol 10 cm3 4.0 J/cm2 10 Hz 10 min
PbEtha Pb Plate Ethanol 10 cm3 2.0 J/cm2 10 Hz 10 min
PbPro Pb Plate 1-Propanol 10 cm3 2.0 J/cm2 10 Hz 10 min
Fig. 2. Pb and PbO absorption bands on the UV–vis spectra of the irradiated
PbBut Pb Plate 1-Butanol 10 cm3 2.0 J/cm2 10 Hz 10 min
solutions.
174 D.L. da Cunha et al. / Materials Research Bulletin 49 (2014) 172–175

Fig. 3. XRD patterns recorded for the samples PbMet-A, PbEtha, PbPro, PbBut. The
crystalline phases and main crystalline planes associated with each phase are also
shown.

characterize their crystalline nature and to find out the right

structure and morphology of the synthesized materials, XRD, FTIR
and SEM analysis of the precipitated powders was performed.
Fig. 3 shows the X-ray diffraction analysis for the samples
prepared in methanol, ethanol, 1-propanol and 1-butanol; this
figure also identifies the crystalline phases and diffraction planes for
each sample. The diffraction pattern of the samples prepared in
methanol and ethanol exhibits 17 distinct diffraction peaks at 2u,
which correspond to the crystalline planes of the trigonal crystalline Fig. 5. (a) SEM image for PbMet-A as made. (b) SEM image for PbMet-A sample after
structure of the hydrocerussite reported on JCPDS card 130131. On sonication.

the other hand, when the Pb target is ablated in 1-propanol and 1-

butanol it is observed that, besides the 17 diffraction peaks mode), which can be assigned as the modes belonging to the
belonging to the hydrocerussite phase, 5 extra diffraction peaks hydrocerussite compound, which is in agreement with our X-ray
appear. These correspond to the crystalline planes of the cubic fcc of results and those from literature [20].
metallic lead structure, which is reported on JCPDS card 040686. The Fig. 5a and b shows the SEM characterization for the sample
metallic lead became the major phase for the Pb target ablated in 1- prepared in the methanol and deposited on a glass substrate.
butanol. These results can be explained if we use the reduction Fig. 5a shows the sample as made and Fig. 5b shows the same
mechanism for metallic ions in alcohols [26–30]. sample, but after it has been treated in ultrasound for 10 min
In conclusion, only hydrocerussite is obtained when the Pb before deposition on glass substrate. A nice crystalline structure of
target is ablated in ethanol and methanol solution whereas a hexagonal shape was observed, with average widths of
combination of hydrocerussite and Pb metal particles are obtained 1.0  0.3 mm and an average thickness of 80  20 nm. The results
for the solvent 1-propanol and 1-butanol, and the metallic phase is of this study are in agreement with the literature, which show that the
more intense in 1-butanol. The Pb metallic phase obtained can be crystalline structure of hydrocerussite has a trigonal crystal structure,
explained due to the reducing character of the alcohol used as a
solvent medium. In effect, several metal nanoparticles such as
cobalt, nickel, silver copper, palladium and semiconductor
quantum dots [29–33] have been obtained using the reducing
power of alcohols with large carbon chains.
The presence of the hydrocerussite in the samples and the
influence of the chemical composition of the solvent used for the
preparation process can also be confirmed by the FTIR spectra of
the samples. Fig. 4 shows that all samples present absorption peaks
at 3531 cm1 (OH stretching), 1736 cm1 (CO3 v3 mode),
1629 cm1 (CO3 v1 mode), 1396 cm1 (CO3 v3 mode), 1044 cm1
(OH libration), 783 cm1 (CO3 v2 mode) and 681 cm1 (CO3 v4

Fig. 4. The FTIR spectra and principal infrared absorption modes for the samples Fig. 6. (a) SEM image for PbMet-B sample as made.(b) SEM image for PbMet-C
PbMet-A, PbEtha, PbPro, PbBut. sample as made.
 D.L. da Cunha et al. / Materials Research Bulletin 49 (2014) 172–175 175

starts to grow and becomes the most predominant phase in 1-

butanol.

4. Conclusions

The laser ablation of a lead target in solutions of primary alcohols

such as methanol and ethanol with a second harmonic of a Nd:YAG
laser showed that it is possible to obtain highly crystalline and
nanostructured hydrocerussite with a hexagonal morphology having
average widths of 1.0  0.3 mm and an average thickness of 80  20 nm.
On the other hand when the solvent is changed to 1-propanol or 1-
butanol besides hydrocerussite, a second phase is observed which
Fig. 7. SEM image for sample PbEtha as made. corresponds to the metallic lead. Also it was shown that the values of the
laser fluency used in this study do not modify the sample morphology and
composition. The mechanism proposed to explain the compound
formation was based on the ablation technique which consists of
producing excited specimens of the target and solvent. The photodecom-
position of the solvent assisted or catalyzed by the metallic particle in the
reaction medium produces CO2 that reacts with PbO yielding
Pb3(CO3)2(OH)2. However, due to the reducing power of the alcohol
used, metallic lead can be obtained concomitantly with hydrocerussite.

Acknowledgments

The authors would like to thank CNPQ contract No. 305587/

2003-0 and No. 473.144/03-4 CAPES, FACEPE contract No. APQ-
0589-1.05/08 and No. APQ-0468-1.06/10 1.06/10 and INCT-INAME
Fig. 8. SEM image for sample PbPro as made. for the financial support received during this research.

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