Tuning the architectures of lead deposits on metal substrates by electrodeposition

Article abstract of DOI:10.1016/j.electacta.2008.08.005

Different morphologies of lead (Pb) deposited on different metal substrates have been prepared via electrochemical deposition in aqueous solution. The morphologies of as-deposited lead were determined by scanning electron microscope (SEM). It is found tha

Full text of DOI:10.1016/j.electacta.2008.08.005

Electrochimica Acta 54 (2008) 247–253
Contents lists available at ScienceDirect
Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta
Tuning the architectures of lead deposits on metal substrates by electrodeposition
a
a
a
a
a,b,c
d
a
Chen-Zhong Yao , Meng Liu , Peng Zhang , Xiao-Hui He , Gao-Ren Li
Ye-Xiang Tong
a
, Wen-Xia Zhao , Peng Liu ,
a,b,∗
MOE of Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China
Institute of Optoelectronic and Functional Composite Materials, Sun Yat-Sen University, Guangzhou 510275, China
State Key Lab of Rare Earth Materials Chemistry and Applications, Beijing 100871, China
b
c
d
Instrumental Analysis & Research Center, Sun Yat-Sen University, Guangzhou 510275, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 3 May 2008
Received in revised form 1 August 2008
Accepted 4 August 2008
Available online 9 August 2008
Different morphologies of lead (Pb) deposited on different metal substrates have been prepared via elec-
trochemical deposition in aqueous solution. The morphologies of as-deposited lead were determined by
scanning electron microscope (SEM). It is found that the various morphologies of the products are depen-
dent on the electrodeposition conditions, including the deposition current densities, concentration of
additives, substrates and deposition time. X-ray diffraction (XRD) and transmission electron microscope
(
TEM) results reveal that all these lead deposits with different morphologies can be assigned to the space
Keywords:
Electrodeposition
Lead
group Fm-3m (2 2 5).
©
2008 Elsevier Ltd. All rights reserved.
Octahedron
Zigzag nanowire
Nucleation
1
. Introduction
the systematical synthesis of various nanomaterials remains an
important research focus in the modern material chemistry [16].
Although different methods, such as template synthesis including
hard templates [17,18] or soft directing agents [19–25], chemical
vapor deposition, and colloidal synthesis, have been proved to be
successful in preparing diversified nanomaterials, self-organized
micro/nanostructures of metals at solid surfaces are attracting
much attention because it is possible to prepare stripes, dot arrays,
spiral patterns, etc. [26]. The solution phase approaches of metal
deposition have become a promising technique in the field of
nanostructure fabrication [27]. Among them, electrodeposition is
very attractive, for that the easy control of its parameters such as
deposition potential, time, and solution composition can be used
to adjust the growth rate, particle size and number density, with
precision and relatively low cost.
The preparation of micro/nanostructural materials has been a
research hotspot in recent years due to their inimitable properties
and potential applications in building blocks [1–4]. The properties
of nanomaterials, which strongly depend on size, size distribution,
shape, and chemical composition, vary widely [5–11]. In addi-
tion, the various nanostructures can offer fundamental scientific
opportunities for investigating the influence of size and dimen-
sionality with respect to their collective magnetic, optical, and
electronic properties and would provide possibilities to investi-
gate the novel properties and applications. Metallic nanoparticles
exhibit peculiar characteristics in quantized excitation coulomb
blockade, single-electron tunneling and metal–insulator transi-
tion, due to a combination of the large proportion of high-energy
surface atoms compared with the bulk solid and the nanometer-
scale mean free path of an electron [12–15]. However, four critical
challenges in the development of nanoscale science and technol-
ogy still exist: materials synthesis with controlled structures and
precision at the atomic/molecular scale, property characterization
of the structurally well understood components, nanodevice fab-
rication, and system manipulation and integration [3]. Hereinto,
Lead is an especially attractive element, due to its extremely
high reactivity and superconductivity [28]. The underpotential
deposition of Pb on some noble metal surfaces has been exten-
sively examined because monolayers and submonolayers of Pb can
enhance catalytic activity of the noble metal in a variety of elec-
troreduction processes, such as the reduction of H O2 to H O, the
2
2
reduction of O2 to H O in aqueous fuel cells, etc. [29,30]. Dubois
2
et al. [31,32] reported that lead nanowires grown in the nanopores
of porous track-etched polymer membranes via normal electrode-
position possess the characteristics of superconductivity. Single
crystal or polycrystalline Pb nanowires with diameter of about
∗ Corresponding author.
E-mail addresses: yaochzh1999@126.com, chedhx@mail.sysu.edu.cn (C.-Z. Yao).
0
013-4686/$ – see front matter © 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2008.08.005

248
C.-Z. Yao et al. / Electrochimica Acta 54 (2008) 247–253
1.0 mA cm 2. The architecture of the deposits is strongly depen-
dent on the electrolyte concentration. The best concentration range
for growing lead mesostructures with controlled architectures is
−
5
0 nm can be prepared by pulse electrodeposition in nanoporous
membrane [33]. However, these methods have a common disad-
vantage of removing the unwanted materials because the removal
of the template or directing agent from the surface of the nanoma-
terials requires harsh conditions or multiple washing procedures.
Moreover, the presence of residue may influence the properties and
increase the difficulty of analysis [15,34–36].
Electrodeposition without templates can provide versatility in
tailoring the architectures of nanostructures. In this paper, octa-
hedra, zigzag nanowires and nanoclusters on copper (Cu), hollow
cubic columns on aluminum (Al) and flowerlike architectures on
titanium (Ti) were synthesized by electrodeposition through sys-
tematically adjusting the parameters, such as the current density,
the concentration of boric acid, deposition time and the substrates.
The X-ray diffraction (XRD) and electron diffraction (ED) patterns
illustrate that face-centered cubic structure of lead is apt to be
formed.
−
1
from 0.001 to 0.01 mol L
out with a concentration of 0.005 mol L [38]. H BO is usually
and most experiments were carried
−
1
3
3
used as the additive and buffer agent. In our experiment, the elec-
trochemical deposition of Pb was carried out in aqueous solution
−
containing the following composition: 0.005 mol L Pb(CH CO ) ,
3 2 2
1
−
1
−1
0.2 mol L CH CO NH , and 0.5 mol L H BO with pH of about
3
2
4
3
3
4–5. An IM6e electrochemical workstation (Zahner, Elektrik) was
used for the electrochemical measurements. The electrodeposi-
tion experiments were carried out by galvanostatic electrolysis at
room temperature. The deposits were analyzed by X-ray diffraction
(PIGAKU, D/MAX 2200 VPC) to determine the film structures. The
surface morphologies of the as-deposited films were observed by
field emission scanning electron microscope (FE-SEM, JSM-6330F),
thermal field emission environment scanning electron microscope
(
(
TFE-SEM, FEI, Quanta 400), and transmission electron microscope
TEM, JEM-2010HR).
2. Experimental
Cyclic voltammetry (CV) and constant–current chronopotentio-
3. Results and discussion
metric (E–t) were employed to study Pb electrocrystallization onto
Cu, Al and Ti substrates, respectively. All of the electrochemical
experiments were carried out in a conventional three-electrode cell
system. Cu, Al and Ti wires were used as the working electrodes.
A graphite electrode was used as a counter electrode (spectral
grade). A saturated calomel electrode (SCE) was used as the ref-
erence electrode that was connected to the cell with a double salt
bridge system. All potential values determined in this study were
the values versus SCE.
3.1. Electrochemical measurements
Fig. 1(a) shows the CV of
a
Cu electrode in the solu-
−
1
−1
tion of 0.2 mol L
CH CO NH and 0.5 mol L
H BO as a
3 3
3
2
4
blank CV. Fig. 1(b) shows the CV of Cu electrode in the solu-
−
1
−1
tion of 0.005 mol L
Pb(CH CO ) , 0.2 mol L CH CO NH and
3
2
2
3
2
4
−
1
0.5 mol L H BO at different scan rates. A cathodic peak potential
3
3
(Epc) at around −0.52 V and an anodic peak (Epa) at around −0.39 V
−
1
Galvanostatic electrolysis was utilized in all electrochemi-
cal depositions under different current densities from 0.25 to
can be seen at a scan rate of 0.020 V s , corresponding to the reduc-
tion of Pb2+ to Pb, and anodic stripping of the electrode, respectively.
−
1
−1
−1
−1
Fig. 1. (a) CV of Cu electrode in the solution of 0.2 mol L CH3CO2NH4 and 0.5 mol L H3BO3 at a scan rate of 0.080 V s ; (b) CV of Cu electrode in the solution of 0.005 mol L
−1
−1
−1
Pb(CH3CO2)2, 0.2 mol L CH3CO2NH4 and 0.5 mol L H3BO3 at different scan rates (V s ): (a) 0.080, (b) 0.060, (c) 0.040 and (d) 0.020; (c) plot of Ep versus ln v; (d) plot of
jp versus v1
/2
.

C.-Z. Yao et al. / Electrochimica Acta 54 (2008) 247–253
249
The cathodic peak potential shifted negatively with the increase
of the sweep rate, the separation of the cathodic and anodic peak
potentials is large. The relation between the cathodic peak cur-
1
/2
rent density (jp) and the square root of sweep rate ꢀ
is linear.
It indicates that the reaction of Pb2 + 2e = Pb is irreversible. For
an irreversible charge-transfer electrodic process, the peak poten-
tial and the peak current density change can be explained by the
following equation [37]:
+
RT
˛Fv
RT
Ep = K −
ln
(1)
(2)
2˛F
jp = (2.99 × 10 )˛1/2n3/2C0D01/2v1/2
5
where Ep, K, ˛, ꢀ, jp, C and D stand for peak potential (for cathodic
0
0
peak), constant, electron-transfer coefficient, scan rate, peak cur-
rent density, ion concentration and diffusion coefficient. The Epc
moves to more negative potential linearly along with the natural
logarithm of ꢀ, and the jpc versus ꢀ1/2 exhibits a linear increase by
Fig. 2. Constant–current chronopotentiometric curves of Cu electrode in
−1
−1
−1
0.005 mol L Pb(CH CO ) , 0.2 mol L CH CO NH and 0.5 mol L H BO3 aque-
3
2
2
3
2
4
3
−
2
−2
degrees when the scan rate augments as shown in Fig. 1(c) and (d).
ous solution with different current densities: (1) 0.25 mA cm ; (2) 0.5 mA cm ;
(3) 0.75 mA cm ; (4) 0.85 mA cm ; (5) 1.0 mA cm ; (6) 1.5 mA cm .
−2
−2
−2
−2
This also indicates that the reduction of Pb2+ is an irreversible elec-
trodic process. According to Eq. (1), ˛ = 0.632 was calculated from
the slope of the plot of Epc versus ln ꢀ. The relationship between
jp and the potential sweep rate (ꢀ) is given by Eq. (2) at 298 K.
ior is similar to that at 0.5 mA cm 2, although the transition time
rapidly reduced to 2.5 s, and the electrode potential is steady at
−0.51 V (Fig. 2(2)). As can be seen in Fig. 2(3), the transition time
−
−9
2
−1
D = 1.75 × 10 m s can be calculated from the plot of jp versus
0
1
/2
−2
ꢀ
for the reduction peak shown in Fig. 1(d).
is 16 s under current density of 0.75 mA cm which is longer than
−
2
Fig. 2 shows E–t curves of the Cu electrode in the solu-
the value of 0.25 mA cm , and the electrode potential is −0.68 V
that is more negative than the cathodic potential of −0.52 V shown
in Fig. 1(b). Under this condition, a small amount of bubbles were
observed on the surface of the Cu electrode, which may be due to
the hydrogen evolution. The E–t curves at higher current densities,
−
1
−1
tion of 0.005 mol L
Pb(CH CO ) , 0.2 mol L CH CO NH and
3
2
2
3
2
4
−
1
0.5 mol L
H BO at different current densities. Along with
3 3
the time, the potentials become relatively stable under applied
current densities. Under the lowest applied current density of
−2
−2
0
.25 mA cm , there is a long transition time reaching about 12 s
such as 0.85, 1.0 and 1.5 mA cm , show that the transition time
(
Fig. 2(1)). Then the electrode potential reduces to −0.48 V and
becomes shorter and the electrode potential more negative.
The CV curves on Al and Ti electrodes in the solu-
holds at this potential. This current density meets the growth of Pb
nuclei which are sufficiently small and well separated. This behav-
−
1
−1
Pb(CH CO ) , 0.2 mol L CH CO NH and
tion of 0.005 mol L
3
2
2
3
2
4
−
1
−2
Fig. 3. (a) CV curve of Al electrode at 0.080 V s ; (b) constant–current chronopotentiometric curves of Al electrode with different current densities: (i) 0.75 mA cm , (ii)
−
2
−
2
−
1
0
.5 mA cm and (iii) 0.25 mA cm ; (c) CV curve of Ti electrode at 0.080 V s ; and (d) constant–current chronopotentiometric curves of Ti electrode with different current
densities: (i) 0.75 mA cm 2, (ii) 0.5 mA cm−2 and (iii) 0.25 mA cm in the solution of 0.005 mol L Pb(CH3CO2)2, 0.2 mol L CH3CO2NH4 and 0.5 mol L H3BO3.
−
−2
−1
−1
−1

2
50
C.-Z. Yao et al. / Electrochimica Acta 54 (2008) 247–253
−
1
−1
0
.5 mol L H BO at a scan rate of 0.020 V s are shown in Fig. 3(a)
the size distribution is wide. Moreover, there exist joined octahe-
dra in our experiment (inset in Fig. 4(a)). This may be explained
as follows. The reduction rate of Pb2+ is relatively slow under low
current density and the decrease of the Pb2+ concentration at the
Cu electrode interface can be sufficiently supplemented from the
3
3
and (c). The cathodic peaks appear at around −0.65 V and the anodic
peaks at about −0.35 V. Fig. 3(b) and (d) shows the E–t curves of
Al and Ti electrodes at different current densities. Under a current
density of 0.25 mA cm , the transition times are about 12 and 15 s,
and the electrode potentials hold at −0.67 and −0.58 V on Al and
Ti electrodes, respectively. With the current density increasing, the
transition times become longer and the electrode potentials shift
more negatively.
−2
2+
bulk solution (away from the electrode) by the transport of the Pb
ions. The abundant Pb2+ ions meet the feasibility of forming stable
Pb octahedra that can reduce the surface energy as small as possible
[34].
When the applied current density increases to 0.5 mA cm 2
−
,
3
.2. Synthesis, characterization, and formation mechanism of
dense and spherical crystals were obtained, which greatly con-
tributed to the reduction of the surface energy (Fig. 4(b)). Rod-like
lead deposits were obtained with the applied current density
multiform Pb architectures
−
2
Fig. 4 shows the different shapes of lead deposits, such
as octahedra, nonregular crystals, zigzag nanowires and nan-
oclusters, which grow on Cu electrodes under different current
increasing to 0.75 mA cm . Most of these nanorods are 5 ␮m long,
and the typical diameters are 1 ␮m as shown in Fig. 4(c). The lead
zigzag nanowires and nanoclusters were obtained, when the cur-
−2
−2
−2
densities in the range of (a) 0.25 mA cm , (b) 0.5 mA cm
,
rent density increased to 0.85 and 1.0 mA cm , as shown in Fig. 4(d)
−2
−2
−2
(
c) 0.75 mA cm , (d) 0.85 mA cm , and (e) 1.0 mA cm . When
and (e).
−2
deposited at 0.25 mA cm , the average edge length of the octa-
hedra is about 400 nm. The smallest one is about 100 nm and the
biggest one is about 1 ␮m. The obtained lead octahedra are reg-
ular without any disfigurement on the edges and the angles, and
The octahedral and spherical shapes of lead mesostructures
obtained at relatively low current densities can be explained
through the model based on a modified Wulff construction for
shape formation [36,38]. According to this model, the polyhedra
Fig. 4. SEM images of Pb deposits prepared in 0.005 mol L−1 Pb(CH3CO2)2, 0.2 mol L CH3CO2NH4 and 0.5 mol L H3BO3 aqueous solution by electrochemical deposition
−1
−1
−2
onto stationary Cu substrates with different current densities: (a) 0.25 mA cm 2; (b) 0.5 mA cm−2; (c) 0.75 mA cm ; (d) 0.85 mA cm ; (e) 1.0 mA cm . The insets in (a) and
−
−2
−2
(d) are the high-resolution (HR) images of octahedrons and nanowires, respectively.

C.-Z. Yao et al. / Electrochimica Acta 54 (2008) 247–253
251
−1
−1
−1
−1
Fig. 5. SEM images of Pb deposits prepared in solutions of (a) 0.005 mol L Pb(CH3COO)2, 0.2 mol L CH3CO2NH4 and 0.10 mol L H3BO3 and (b) 0.005 mol L Pb(CH3COO)2
and 0.2 mol L CH3CO2NH4 with current density of 0.25 mA cm .
−1
−2
−
1
−1
−1
Fig. 6. SEM images of Pb deposits prepared in 0.005 mol L Pb(CH3CO2)2, 0.2 mol L CH3CO2NH4, 0.5 mol L H3BO3 aqueous solution by electrochemical deposition onto
−
2
stationary Cu substrates with current density of 0.25 mA cm for different time: (a) 30 min; (b) 60 min; (c) 90 min.
can be described as a collection of single-crystal tetrahedra that
are twin-related at their adjoining faces. In our experiment, four
tetrahedra arranged symmetrically can form an octahedron and
sufficient tetrahedra in a three-dimensional configuration assem-
bled at a common vertex produce a spherical crystal. The formation
mechanisms for nanowires and nanoclusters are still under inves-
tigation.
In addition, we investigated the different time intervals for a
better understanding of the lead octahedra growth under the cur-
−
2
rent density of 0.25 mA cm on Cu substrate and the SEM images
are shown in Fig. 6. On the surface of the octahedral lead crys-
tals, a large number of particles with the size of much less than
100 nm can be observed along with the increase of the deposition
time. And the sizes of lead octahedral crystals become larger and
larger from nanoscale to microscale at the same time. The two
results confirm that the farther nucleation and growth of Pb is
inclined to reduce the surface energy of the crystals [34]. More-
over, nanoparticles with regular shape are difficult to be prepared
compared with multi-particle aggregates. These newly generated
nanocrystals are distributed on the whole surfaces of the bulk
octahedral Pb crystals. The possible mechanism is proposed as
follows. At the beginning of the growth of lead crystal, form-
ing octahedral crystals may be in favor of reducing the surface
energy of the crystals. Moreover, the surface energy is inclined to
be the minimum value. Thus the new nucleation of lead will be
The electrodeposition of Pb was carried out with 0.1 mol L−1
boric acid and without boric acid. As shown in Fig. 5, the per-
fect octahedral structures of Pb were not obtained compared with
Fig. 2(a). This clearly shows boric acid plays a crucial role in the for-
mation of the octahedral lead structures. The effect of boric acid on
the growth of Pb octahedral structures possibly may be attributed
to specific interactions between Pb nuclei and boric acid. In the syn-
thesis of materials, it is well known that some capping molecules
can block the crystal growth of certain directions and enhance that
of other directions [39,40]. The capping effect of boric acid may play
a key role for the growth of Pb octahedral structures.
−
1
−1
−1
Fig. 7. SEM images of Pb deposits prepared in 0.005 mol L Pb(CH3CO2)2, 0.2 mol L CH3CO2NH4 and 0.5 mol L H3BO3 aqueous solution for 30 min with current density
−2
of 0.25 mA cm on substrates of (a) Al and (b) Ti substrate.

2
52
C.-Z. Yao et al. / Electrochimica Acta 54 (2008) 247–253
first absorbed on the edge and corner due to its higher surface
energy.
Also, the substrates exert an obvious influence on the morpholo-
gies of the Pb deposits. The pattern of Pb deposited onto Al substrate
(
0
Fig. 7(a)) shows that the hollow cubic columns are shaped at
.25 mA cm . The thickness and width of the walls of the column
−
2
are about 100 nm and 1 ␮m, respectively. The center of the column
is filled with stacking square platform which is in-tangent with the
walls of the column. When Ti is used as electrodes, a high-resolution
SEM examination shows that the morphologies of lead deposits are
flowerlike architecture, which is composed of interlaced nanopetals
(Fig. 7(b)).
3.3. Structural analysis of lead octahedra and zigzag nanowires
Fig. 8(a) represents the XRD patterns of lead octahedra and
−
2
nanowires electrodeposited under 0.25 and 0.85 mA cm , respec-
tively, at room temperature. It is observed that as-deposited Pb
patterns of octahedra and nanowires are in excellent accordance
with a cubic structure that can be assigned to the space group
Fm-3m (2 2 5). The lattice parameters of the nanowires were
◦
a = b = c = 4.951 Å. The shifts of the nanowires were ꢁ (2ꢂ) = −0.144 ,
◦
◦
◦
−
0.131 , −0.127 and −0.140 for the (1 1 1), (2 0 0), (2 2 0) and (3 1 1)
◦
peaks, respectively, and the ꢁ (2ꢂ) shifts of the octahedra −0.021 ,
◦
◦
◦
−
0.029 , −0.004 and 0.032 . This can be explained as follows. It is
−1
Fig. 8. (a) XRD patterns of lead deposits prepared in 0.005 mol L Pb(CH3CO2)2,
−1
−1
0
.2 mol L CH3CO2NH4 and 0.5 mol L H3BO3 aqueous solution by electrochemical
deposition onto stationary Cu substrates at room temperature with different current
−
2
−2
densities: (i) 0.25 mA cm for 80 min and (ii) 0.85 mA cm for 20 min at a scan rate
◦
of 5 /min. (b) TEM image of an individual lead octahedron. The inset gives an ED
pattern obtained by the electron beam on the octahedron. (c) TEM image of single
lead zigzag nanowire. The inset gives an ED pattern recorded by focusing the electron
beam on the whole wire and high-resolution TEM image taken from the tip of lead
nanowire. The fringe spacing along the [1 1 1¯ ] axis is indicated.
−
1
Fig. 9. XRD patterns of lead deposits prepared in 0.005 mol L
Pb(CH3CO2)2,
−
1
−
1
0
.2 mol L CH3CO2NH4 and 0.5 mol L H3BO3 aqueous solution with current den-
sity of 0.25 mA cm onto substrates of (a) Al and (b) Ti at room temperature.
−2

C.-Z. Yao et al. / Electrochimica Acta 54 (2008) 247–253
253
well known that a nanowire form with a high aspect ratio experi-
ences more tensile stress along the c-axis direction on the surface
than the other forms, which leads to an increase in the c value [41].
In accord with this, c-axis-related peak shifts to lower angles of Pb
nanowires compared with the octahedra.
Fig. 8(b) shows the TEM image and the inset displays the typical
ED pattern of the selected octahedron. The ED pattern demonstrates
the whole lead octahedron is single crystal and the diffraction spots
can be indexed to the face-centered cubic phase of lead. The TEM
image of single zigzag lead nanowire is shown in Fig. 8(c). The ED
pattern was obtained when the beam direction was parallel to the
Potentially Important Natural Science Research and Young Teacher
Starting-up Research of Sun Yat-Sen University.
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We appreciated this work was supported by the Natural Sci-
ence Foundations of China (Grant Nos. 20603048 and 20573136),
the Natural Science Foundations of Guangdong Province (Grant
Nos. 06300070, 06023099, and 04205405), and the Foundations of
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