Ekcrrochim~ca Acto. Vol. 40. No. I I. pp.1653-1662.

1995
Copyright G 1995 Elsevier Science Ltd.
j Pergamon Printed in Great Britain. All rights nerved
0013~4686/95 $9.50 + 0.00
0013-4686(95)oWJ3-3

NICKEL DEPOSITION FROM UNBUFFERED NEUTRAL

CHLORIDE SOLUTIONS IN THE PRESENCE OF OXYGEN

C. Q. GUI* and JIM Y. LEE

Department of Chemical Engineering, National University of Singapore. IO Kent Ridge Crescenl,
Singapore 05 I 1

(Receioed I6 Junuary 1995)

Abstract-A comparison is made between depositions from neutral unbuffered chloride solutions of
nickel with and without the presence of oxygen. In the presence of oxygen, a poorly conductive layer of
Ni(OH), is formed early because of oxygen reduction which occurs prior to nickel deposition. The surface
Ni(OH), inhibits the first charge transfer reaction of Ni” to active intermediate (categorically represent-
ed by Ni(OH),,,), and subsequently diminishes the nucleation and growth of nickel. The effect is more
pronounced in region with little hydrogen evolution. Surface flakes characteristic of uninhibited nickel
deposition are clearly absent in the scanning electron micrographs of deposits. The current efficiency of
nickel deposition is slightly increased in the presence of oxygen. It is also found that the oxygen effect is
more effective in 0.1 M NiCI,, This is due to the fact that uninhibited deposition of nickel and hydrogen
evolution. which are promoted by high and low Ni” concentration respectively. are less efficient than
oxygen effect at an intermediate concentration level.

Key words: nickel deposition, oxygen reduction, unbuffered solution, electrodeposition, chloride.

INTRODUCTION and

Porous nickel deposits and nickel powders are Ni(OH),,, + Ni2’ + 2e + Ni + Ni(OH),,, (3)
important industrial materials that find applications Ni(OH),,, + e -+ Ni + OH (4)
in many diverse production activities such as manu-
facturing of alkaline batteries, anti-corrosion paints, where Ni(OH),,, is used categorically to represent
catalysts and magnetic storage media[l-41. In our the active intermediates which may also be chloride
previous investigation on the effects of oxygen containing complexes. In the absence of oxygen, the
reduction on nickel deposition from aqueous morphology of nickel deposits was found to relate
unbuffered chloride solutions[5], it was found that a well with the relative prominence of the two
poorly conductive Ni(OH), phase was deposited on reduction peaks for a given deposition potential[12].
the electrode by the chemical reactions between In the presence of oxygen, precipitation of Ni(OH),
Ni’+ and the products of oxygen reduction, which at the electrode due to increase in local pH from
occurred at a more positive potential. The dynamic oxygen reduction could substantially lower the effec-
stability of this Ni(OH), phase is much higher than tive adsorption of reactive intermediate Ni(OH),,, .
the colloidal Co(OH), formed in the reactive deposi- The first reduction process corresponding to
tion of cobalt. As a result, a porous metal deposit reaction[2] is suppressed as a result. The deposition
was not obtained. The presence of a highly stable of nickel in the presence of oxygen subsequently
Ni(OH), phase suppresses the adsorption of reactive follows a different reaction pathway. It is therefore of
intermediate for metal deposition, and also inhibits interest to find out how this would affect the struc-
the nucleation and crystal growth of nickel. The ture and morphology of nickel deposited at various
overall deposition process is rendered more irrevers- potentials. The results would also enhance the
ible as a result. understanding of electrodeposition and electro-
In aqueous unbuffered solutions of simple nickel plating of bulk nickel in the presence of dissolved
ions, two one-electron metal reduction reactions take oxygen.
place in succession. giving rise to two clearly identi-
fiable peaks in the cyclic voltammograms[6-I I].
Hydrogen evolution also occurs to various extent in EXPERIMENTAL
the same potential region.
Electrochemical measurements made use of a con-
Ni’+ + H,O = NitOH)’ + H’ (1) ventional three-electrode cell and an automated
Ni(OH) + + e + Ni(OH),,, EG&G model 273 potentiostat galvanostat. For
(2)
voltammetric measurements. a rotating glassy
carbon (GC) disk electrode 5 mm in diameter
* Author 10 Hhom correspondence should be addressed. (0.196cm2) was used as the working electrode. The

1653
1654 C. Q. GUI and J. Y. LEI!
counter and reference electrodes were a large area
nickel foril (BDH) and a saturated calomel reference
electrode (.w), respectively. Particular care was
taken before every experiment to polish the GC disk
electrode with diamond paste, followed by thorough
cleansing with deionised water in an ultrasonic bath.
The electrode after drying on a tissue was imme-
diately used in the experiments. The reproducibility
of experimental results was greatly improved by such
pretreatment. All controlled potential electrochemi-
cal techniques for nickel deposition were started at
0 V in the cathodic direction.
All chemicals used were of the AR grade. I M KCI
was added to the electrolyte to reduce the ohmic
drop between the Luggin capillary of the reference
electrode and the working electrode. The pH of
unbuffered chloride solutions was approximately
6.24. The voltammetric characteristics of nickel
deposition in the presence of oxygen was studied
using dissolved oxygen in order to avoid the stirring
and shielding interference resulting from bubbling
oxygen through the electrolyte during electrochemi-
cal measurements. To this effect pure 0, was passed
through the electrolyte for about IOmin before the
start of the measurements. For comparative mea-
surements requiring O,-free solutions, the electrolyte
was purged by flowing N, for IOmin. The gas was
fed through a sintered glass plug directed onto the
working electrode, with its flow rate regulated by a
rotameter. All experiments were carried out at room
temperature.
Striping voltammetry was used for the analysis of
deposit structure and the determination of current
efficiency in deposition. To this effect Ni was depos-
ited on I cm’ 100 mesh stainless steel screens. The
pretreatment procedure of stainless steel was exactly
the same as that for the GC disk electrode. The
deposit was carefully rinsed with deionized water
after deposition. Stripping was carried out in a solu-
tion containing 1 M KCI and I M H,BO, at pH = I.
The stripping solution was buffered to prevent any
changes in pH during the experiments. The potential
was scanned from -0.7 to OV at IOOmVs- in
order to ascertain full dissolution of the deposits and
5.500 I I I I
4.500
3.500
';
.
':
E 2.500
a
::
B 1.500
2
B
0.500
Fig. I. Voltammograms of nickel deposition from unbutlered 0.1 M NiC12 + I M KCI (pH = 6.24) at
IOmVs- ’ in the presence or absence of dissolved oxygen. Electrode area was 0.196cm’.
to identity the various metallurgical phases in the
deposits. On the other hand, surface morphology of
nickel deposited on stainless steel under different
conditions was examined by a Hitachi JSM-T330A
scanning electron microscope.
RESULTS AND DISCUSSIONS
Cyclic voltammetry ofnickel electrodeposition
The voltammograms in Fig. I show the effects of
dissolved oxygen on nickel deposition from 0.1 M
NiCI, in I M KCI (pH = 6.24) at IOmVs-‘. In
agreement with previous reports, deposition in the
absence of dissolved oxygen is characterized by two
clearly identifiable reduction peaks in the cathodic
scan. It was suggestedC7, 93 that nickel deposition
passed through the formation of adsorbed interme-
diate complexes, based on the fact that the differen-
tial capacity decreased proportionately with
increasing Ni’ + concentration. As a result, in this
paper the participation of one-electron charge trans-
fer reactions (2)-(4) and the formation of nickel
complex intermediate Ni(OH),,, are recommended
to proceed in nickel deposition. As described in Ref.
[ 12, 133, the first reduction peak is very sensitive to
the presence of any kind of inhibitors. Therefore, the
presence of the first reduction peak may reflect
nickel deposition with little inhibition. The second
reduction process occurred oia nickel deposition
among hydrogen evolution which commonly inhibits
nickel deposition. Its appearance as a shoulder in the
region of hydrogen evolution is consistent with the
low current efficiency inherent in nickel depositions.
In the reverse scan where the potential was swept
anodically, oxidation of nickel occurred at -0.64V
but with an intensity much smaller than nickel depo-
sition. The incomplete oxidation of nickel could be
attributed to the facile formation of passivating
Ni(OH), in neutral to alkaline solutions:
Ni + 2H,O - 2e = Ni(OH), + 2H’ (5)
The metal was passivated by the presence of
Ni(OH), on its surface and further oxidation could
I I I I
 Unbulrered neutral chloride solutions I655

not take place easily. Voltammetric studies have even under electrode rotation. This conforms the
indicated that reversal of potential after the second early finding that the Ni(OH), surface layer formed
peak would lead to a decline in the anodic current upon oxygen reduction is highly stable, and cannot
for nickel oxidation[ 12, 131. Passivation of nickel be removed by mechanical rotation of the electrode.
oxidation is even more severe if the metal is depos- Subsequently electrode rotation promotes mostly
ited in the region of vigorous hydrogen evolution hydrogen evolution. Agitation of the solution is
(H, passivation). Hydrogen may passivate nickel oxi- therefore deleterious to nickel deposition regardless
dation directly, and/or indirectly as a result of the of the absence or presence of dissolved oxygen. Such
increase in pH due to hydrogen evolution, which action promotes greater hydrogen evolution and
makes the electrode vicinity an environment conduc- subsequently reduces the current efficiency of nickel
ive to Ni(OH), formation. deposition.
When electrodeposition was carried out in the
presence of dissolved oxygen, some Ni(OH), was Current transients in potentiostatic deposition
deposited on the electrode prior to nickel deposition
because of the increase in interfacial pH from oxygen Figure 3 shows the current-time response curves in
reduction, which occurred much easily and persisted the potentiostatic depositions of nickel from 0.25 M
throughout nickel deposition[4]. This early presence NiCI, in 1 M KCI solution with and without flowing
of Ni(OH), on the electrode suppresses the adsorp- oxygen (50cm’ min- ‘) at various deposition poten-
tion of reactive complex Ni(OH),,,, and subse- tials. In support of our previous findings[5], the elec-
quently the nucleation of nickel. The two trocystallization of nickel in aqueous solutions,
one-electron charge transfer reactions are no longer regardless of the presence or absence of oxygen,
differentiable in the voltammogram, and the exhibited characteristics of three dimensional pro-
reduction of Ni*+ is displaced cathodically because gressive nucleation and crystal growth which was
of the inhibition effect from the early deposition of rate limited by interfacial charge transfer reactions.
Ni(OH), Nickel deposition in this case is practically The deposition current approached a steady state
indiscernible from hydrogen evolution (Fig. 1). The value after a sufficiently long time when the surface
dearth of nickel also decreased the current due to was fully covered by nickel deposit. The nickel
hydrogen evolution, a reaction catalyzed by nickel. deposit is expected to be densely structured, as was
Nickel passivation is again evident in the anodic confirmed by scanning electron microscopic
scan. As will be elaborated later, the increased irre- examination[5]. In the initial stage of deposition.
versibility of nickel deposition in the presence of dis- however, the current reached a maximum value
before its decline to the steady state. The rising
solved oxygen does not necessarily lead to a decrease
in current efficiency. current response is due mainly to the nucleation and
crystal growth of nickel whereas the decline after the
Figure 2 shows the voltammograms of nickel
deposition on a rotating electrode from 0.05 M maximum is due partly to the passivation of nickel
by hydrogen evolution. As has been emphasized
NiCI, in I M KCI at 1OmVs ’ in the absence of
dissolved oxygen. The intensity of peak A increases earlier, hydrogen passivation is always in effect with
with the rotation rate, indicating that nickel deposi- or without the presence oxygen in electrodeposition.
tion is rate limited at least in part by transport of When potentiostatic depositions under different
Ni2’ ions to the electrode. When the potential was conditions are compared in Fig. 3. the deposition
swept further in the cathodic direction, however, current is clearly lower in the presence of oxygen.
hydrogen evolution was benefited by electrode rota- The decrease in the deposition current is due to the
tion. On the other hand, the conspicuous absence of early formation of poorly conductive Ni(OH): from
peak A in the presence of dissolved oxygen persists oxygen reduction. which inhibits the nucleation and
growth of nickel. For depositions at - 1.2 V or more
negative where hydrogen evolution is rampant, the
oscillations in current may be attributed to the inter-
ference from gas bubbles and to the accelerated pre-
cipitation of Ni(OH), due to pH increase from
hydrogen evolution. The effect of oxygen reduction
on steady state nickel deposition is most succinctly
illustrated by the plot of deposition current against
NiCI, concentration (Fig. 4). As the deposition
current steadied itself rather quickly, its value at
3 min in potentiostatic depositions at - 1.0 V was
taken as the steady state value. It is obvious from
Fig. 4 that deposition current in the presence of
oxygen is always lower. The promotional effect of
oxygen reduction on Ni(OH), formation. which inhi-
: bits nickel deposition, is again to blame. More
1 I I I I I I
-1.2 -7 .o -0.8
importantly, Fig. 4 shows that the difference in
-0.6 -0.4 -0.2 0
current between depositions with and without
oxygen is most pronounced at 0.1 M NiCI,. That a
Fig. 2. Voltammograms of nickel deposition from 0.05 M moderate concentration of NiCI, exercises the great-
NiCI, + I M KCI at IOmVs~’ with electrode rotation and est inhibition on nickel deposition can be rational-
without dissolved oxygen. Electrode area was 0.196cm’. ised as follows: According to a previous report[5].
1656 C. Q. GUI and J. Y. LEE

-0.100 -
I I I 1 I I l

0.000 0.100 0.200 0.300 0.400 0.500

Tine / kS

Fig, 3. Effect of deposition potential on the current-time response in potentiostatic depositions from
0.25M NiCI, + I M KCI. The deposition was carried out either in the absence or presence of flowing
oxygen (50cm3 min-‘). Electrode area was 0.196cm2.

at 5 mV/s. Nickel was earlier deposited on stainless

steel substrates by potentiostatic deposition at
- 1.OV for 15 min. from 0.05 M NiCI, in 1 M KCI
with or without the presence of oxygen. The two
stripping peaks appearing at - -0.03 V and 0.045 V
respectively correspond probably to two different
structures in the nickel deposits. It is known that
nickel deposits often contain the z- and p-phase solid
solutions of Ni-H[6, 11, 131. The peak at the more
positive potential (peak 11) is likely the low hydrogen
content r-Ni phase. The continual increase in anodic
current after peak II was confirmed to be due to sub-
strate oxidation. In addition, no oxidation of nickel
was found in the second cycle, indicating that strip-
021
00 01 02 03 04 05 06
ping of nickel was complete in the first cycle. In
addition, no residual nickel or nickelous oxides on
NICIZ Concentrct~on / mol.dmeH the substrates could be detected visually. The anodic
Fig. 4. Dependence of deposition current on NiClz concen- dissolution of nickel can be categorically represented
tration for nickel deposition in the presence of either by the reaction :
flowing N, or Oz. The deposition current was measured
Ni - 2e = Ni*’ (6)
from potentiostatic deposition at - 1.0V at 3 min when the
deposition was considered at the steady state. Electrode Hence, the current efficiency of nickel deposition
area was 0.196 cm’. can be approximated by the ratio QJQp, where Q,
and Q, are respectively the anodic charge of nickel
the negative effect of oxygen reduction on nickel dissolution in stripping voltammetry and the
deposition diminishes at high NiCI, concentrations cathodic charge in potentiostatic deposition. The
because of a more competitive adsorption of variations in current efficiency with NiCl, concentra-
Ni(OH),,, relative to Ni(OH), formation. At the tion for depositions with and without oxygen are
other extreme, hydrogen evolution is more efficient given in Table I. Increase in NiCI, concentration is
at low Ni’+ concentration. The passivating Ni(OH)2 found to increase the current efficiency, irrespective
is formed in the latter case primarily from hydrogen of the presence or absence of oxygen. This arises pri-
evolution, with contributions from oxygen reduction marily from the increase in the rate for nickel deposi-
playing a relatively minor part. The difference tion at high nickel concentrations. The current
between depositions with and without oxygen is efficiency is also improved slightly in deposition with
therefore less apparent. In conclusions, the effects of oxygen, although the total deposition charge may be
oxygen on nickel electrodeposition are not substan- smaller. As a consequence of an early formation of
tial at both high and low ends of Ni’+ concentra- Ni(OH), attributable to oxygen reduction, hydrogen
tion. The greatest impact is shown only at moderate evolution is curtailed because of the lack of catalytic
concentrations. nickel metal. This leads to a proportionate increase
in hydrogen inhibition and the current efficiency of
Striping voltammetr~ nickel deposition is increased as a result.
Figure 5 shows the stripping voltammograms of Parallel to the change in deposition current with
nickel deposits in I M KCI + I M H,BO, (pH = I) NiClz concentration (Fig. 4). the difference in current
 Unbult‘ered neutral chloride solutmns 1657

3.000

~~~~~~~

: -7.000 - . --_‘c_ Uithout O*

P 1st Cycle
e
: ,,,,.‘c.UirhO*
-9.000 -
:
-11.00 - :
‘.

I I 1 I 1 I I
-13.00 -
0.250 0.150 0.050 -0.050 -0.150 -0.250 -0.350 -0.450 -0.550

Fig. 5. Stripping voltammograms of nickel oxidation in 1M KCI + I M H,BO, (pH = I) at SmVs-I.

The deposits were obtained from a I5 min potentiostatic deposition from 0.05 M NiCI, + I M KCI at
- I .O V in the presence of either flowing 0, or flowing N, Electrode area was O.l96cm*.

efficiency for depositions with and without oxygen is presence of flowing 0,. This is again demonstrative
greatest at a moderate concentration of 0.1 M. Depo- of the effect of an early formation of Ni(OH), (by
sition at low NiCI, concentration is accompanied by oxygen reduction) on hydrogen evolution and the
considerable hydrogen evolution. Passivation by resulting increase in current efficiency. This effect
hydrogen surpasses the effects of oxygen to a great loses its significance at - I.0 V and beyond where
extent. At the other extreme of high NiC1, concen- hydrogen evolution predominates, and overwhelms
tration, nickel deposition is promoted by the increas- the effect of oxygen reduction. There is, therefore, no
ing competitiveness of nickel complex Ni(OH),,, apparent difference between depositions with and
adsorption relative to Ni(OH), precipitation. As a without oxygen in the second reaction regime.
result, the effects of oxygen on nickel deposition are
diminished at both ends of the concentration spec-
trum, leading to a peak in current efficiency at some 1 I
intermediate value. Under the experimental condi-
tion, 0.1 M NiC1, was most effective in suppressing 0 Wlthout 02
0
hydrogen evolution using the effects of oxygen in 0 With 02
r-i
nickel deposition. ,’
f ‘$5,
The dependence of current efficiency on deposition :

potential in 0.25 M NiCI, with and without 0, is

given in Fig. 6. Although hydrogen evolution
occurred to a large extent in the potential range of
interest. the deposition process can be clearly classi-
fied into two reaction regimes. At deposition poten-
tials below - l.OV, the current efliciency generally
increases with the cathodic shift in potential, irre-
spective of the presence or absence of oxygen. On the
contrary, current efficiency decreases with cathodic
potential at - l.OV and beyond and is virtually zero
at - 1.2V. It is doubtless that hydrogen evolution
has increased its domination in this regime, and Deposltlon
Potent~ol/ V vs SCE

nickel deposition is inhibited primarily by Ni(OH), Fig. 6. Dependence of current efficiency of nickel deposi-
arising from hydrogen evolution. The first reaction tion on deposition potential for 0.25 M NiClz in the pres-
regime also finds the current efficiency higher in the ence of either flowing Nz or flowing 0,.

Table 1. Current efficiency of nickel deposition from NiCl, in 1 M KCI at

- 1.0 V for 5 min in the presence of either flowing N, or flowing 0,

Current efficiency (QJQ,), %

NiCI, concentration Difference, %
mol*dm-3 Bubbling N, Bubbling 0, A

0.05 14.5 15.8 1.3

0.10 15.2 20.6 5.4
0.25 21.6 24.3 2.7
0.50 29.0 29. I nl
1658 C. Q. GUI and J. Y. LEE

Examination of surface morphology tial of -0.9V corresponding to the start of

Scanning electron microscopy was used to
examine the morphology of nickel deposits. Figure 7
shows the micrographs of nickel deposits from 1 min
potentiostatic depositions from 0.25 M NiCl, in 1 M
KC1 at different potentials in the presence of flowing
0,. Cracks are prominent on all of the surfaces
examined, indicating that the deposits were highly
stressed due to the precipitation of nickel hydroxides
and hydrogen evolution during deposition. The
cracked surface structure is also obtained from depo-
sition without oxygen (Fig. 8). At a deposition poten-
deposition, however, intersecting flakes alere found
sporadically on some parts of the SUI rface. The
surface morphology from deposition at -0.9V in
the presence of flowing nitrogen in drama tically dif-
ferent, showing a loose, but near completme coverage
of the surface by the flakes. According to Gomez et
aI.[12], the flakes are attributed to nickel deposition
with little inhibition at low potentials. The low
surface coverage by active nickel complex WOW,,,
in deposition with oxygen shows that reac tions (1) to
(4) are inhibited, primarily through an ea.rly forma-

(a) -0.9V

(b) -1.OV

Fig. 7. Scanning electron micrographs of nickel deposited from 0.25M NiCl, + 1 M KCI at various
deposition potentials. Deposition was carried out for one min in the presence of flowing 0,.
 Unbuffered neutral chloride solutions 1659

(c) -1.2v
Fig. 7. (continued)

tion of Ni(OH), which covers a large fraction of the depositions with oxygen[5]. This again indicates
depositing surface. Highly stable Ni(OH), formed that nickel deposition in the presence of oxygen is
from oxygen reduction is not uniformly distributed inhibited, not only in nucleation, but growth of crys-
on the surface. The intersecting flakes therefore only tallites as well.
exercise limited inhibition on deposition. When the The morphology of nickel from potentiostatic
deposition potential was increased beyond - 1.0 V, depositions of longer time was also examined for the
aggregates of hemispherical crystal grains of variable effects of oxygen (Fig. 9). A dense and bright deposit
size were found atop the underlying cracked layer was obtained in the presence of 0, at - 1.0 V, the
(Figs. 7b and 7~). In addition, the size of crystal same appearance as deposition without 0, at
grains was found to decrease with increase in deposi- - 1.1 V. In comparison deposition at - l.OV without
tion potential. The crystal grains, which are rem- oxygen shows again a surface populated by intersec-
nants of growth sites. are less abundant in ting flakes, formed in the early stage of deposition. It

Fig. 8. Scanning electron micrograph of a nickel deposited from 0.25 M NiCI, t 1 M KC1 at -0.9 V for
15 min in the presence of flowing N,
1660 C. Q. Cur and J. Y. LEE

can therefore be concluded that deposition in the CONCLUSIONS

presence of 0, proceeds with a greater inhibition
because of the increased occupation of the surface by
Ni(OH), , which was formed earlier as a consequence
of oxygen reduction. When the potential was
increased to - 1.1 V where hydrogen evolution is
vigorous, mass deposition of nickel occurred. The
deposit had a rather poor adhesion to the substrate.
It is speculated the nickel crystals in this case was
imbued with Ni(OH), from hydrogen evolution
along the intergranular boundaries.
Nickel deposition from aqueous neutral chloride
solutions was studied in the presence and absence of
oxygen. In the presence of oxygen, a poorly conduc-
tive Ni(OH), layer formed upon oxygen reduction is
deposited on the electrode surface prior to nickel
deposition. This Ni(OH), layer inhibits the forma-
tion of surface active nickel complex Ni(OH),,,, and
diminishes both the nucleation and growth of nickel.
Scanning electron microscopic examination of the

(a) - l.OV without 0,

(b) - l.OV with 0,

Fig. 9. Scanning electron micrographs of nickel deposited from 0.25 M NiCI, + 1 M KC1 at various
potentials for 15 min in the presence of either flowing 0, or flowing N,
 Unbuffered neutral chloride solutions 1661

(c) - 1.1 V without 0,

(d) -l.lVwithO,

Fig. 9. (continued)

deposit surface shows that, for depositions where is, however, no Increase in current efficiency when
hydrogen evolution is more subdued, the surface is deposition is predominated by hydrogen evolution.
covered by intersecting flakes characteristic of unin- Here massive amount of Ni(OH), is formed through
hibited nickel depositions without oxygen. On the hydrogen evolution, surpassing the effect of oxygen,
contrary, deposition in the presence of oxygen shows which occurs earlier. In addition, it is found that the
only the characteristic cracks of nickel due to great effect of oxygen is more noticeable in an interme-
inhibition of Ni(OH), on deposition. diate concentration of 0.1 M NiCl, . Nickel deposi-
In the potential range where hydrogen evolution is tion is not inhibited by oxygen at high Ni2+
not excessive, deposition in the presence of oxygen concentration due to increased adsorption of active
results in a small but noticeable increase in current nickel complex Ni(OH),,,. On the other hand,
efficiency of nickel deposition. Suppression of hydro- hydrogen evolution predominates in the low Ni*+
gen evolution in this case comes mainly from the concentration range, effectively nullifying the effects
Ni(OH), layer formed upon oxygen reduction. There of oxygen.
1662 C. Q. GUI and J. Y. LEE

Acknowledgements-The authors would like to express 6. A. Saraby-Reintjes and M. Fleischmann, Elccrrochim.

their gratitude to Mr. S. T. Tung for the sem examination Acra 29.557 (1984).
of nickel deposits. The work is financially supported by a 7. I. Epelboin, M. Joussellin and R. Wiart. J. e/ec~rroctnu/.
research grant (RP 920616) from the National University of Chem. 119,61 (1981).
Singapore. 8. W. G. Proud and C. Muller, Electrochim. Acfcr js, 405
(1993).
9. E. Chassaing. M. Joussellin and R. Wiart, J. decrro-
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