Electrochimica Acta 45 (2000) 4151– 4158

www.elsevier.nl/locate/electacta

Kinetic analysis of hydrogen evolution at Ni–Mo alloy

electrodes
J.M. Jakšić a,*, M.V. Vojnović b, N.V. Krstajić b
a
Faculty of Agriculture, Uni6ersity of Belgrade, Karnegie6a 4, 11000 Belgrade, Yugosla6ia
b
Faculty of Technology and Metallurgy, Uni6ersity of Belgrade, Karnegie6a 4, 11000 Belgrade, Yugosla6ia

Received 2 December 1999; received in revised form 30 March 2000

Abstract

The hydrogen evolution reaction (HER) on Ni, Mo and MoNi intermetallic compound was investigated with ac
impedance and dc polarization measurements in 1.0 mol dm − 3 NaOH solution at 25°C. The rate constants of the
forward and backward reactions of Volmer, Heyrovsky and Tafel steps were estimated by a nonlinear fitting method.
MoNi alloy electrode provides a much lower overpotential for the HER than Ni and Mo electrodes, sometimes which
exhibit similar catalytic activity. The main pathway for the HER at above mentioned electrode materials is
Volmer–Heyrovsky with Heyrovsky as the rate determining step. © 2000 Elsevier Science Ltd. All rights reserved.

Keywords: Hydrogen evolution reation; Mehanism Mo–Ni alloys; ac Impedance

1. Introduction with optimized adsorption characteristics.

The hydrogen evolution reaction (HER) is one of the
most frequently investigated reactions. The reason is
that the reaction proceeds through a limited number of
steps with only one type of intermediate. The kinetics
of H2 evolution from bases have been widely investi-
gated at Ni [1–3], owing to the relatively good catalytic
activity and high corrosion stability.
From the theory of electrocatalysis [4] the electrocat-
alytic acivity depends on the heat of adsorption of the
intermediate on the electrode surface, in a way giving
arise to the well known ‘vulcano’ curve. It is clear that
beside the precious metals, there is no way to find new
materials among pure metals, which would possess a
high catalytic activity for HER.
Practically there are two possibility to enhance the
activity of bare Ni, (i) to increase the surface area by
various methods or (ii) from a catalytic point of view,
to combine Ni with other pure metals to obtain alloys
* Corresponding author.
Miles [5] suggested that a combination of two metals
from the two brunches of vulcano curve could results in
enhanced activity. Jaksic [6] showed that a combination
of Ni or Co with Mo could result in a substantial
enhancement of HER.
Numerous studies thoroughly investigated the kinet-
ics and mechanism of HER at Ni– Mo [7 – 16] alloys of
various compositions, obtained by electrodeposition
from suitable baths. All these electrodes are character-
ized by having a high roughness factor. Chialvo et al.
[17] investigated the dependence of the electrocatalytic
activity of bulk Ni– Mo alloys on composition for
HER, varying atomic percentage from 0 to 25% in
molybdenum.
In this study, we report the results regarding the
HER on some metallurgically prepared Ni– Mo alloy
electrodes. The electrodes were mechanically polished
to avoid the problem of ‘geometric’ effect and to find
out eventually presented true catalytic effect for HER.
The general mechanism of HER in alkaline solution
is based on the following three steps:

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4152 J.M. Jakšić et al. / Electrochimica Acta 45 (2000) 4151–4158
k1
M+ H2O+e ? MHads +OH− (rate 61) (1)
k−1
k2
MHads +H2O+e ? H2 +M+ OH− (rate 62) (2)
k−2
k3
MHads +MHads ? H2 +2M (rate 63) (3)
k−3

HER starts with the proton discharge electrosorption

(Volmer reaction, Eq. (1), and follows either or both
electrodesorption step (Heyrovsky reaction, Eq. (2)),
and/or H recombination step (Tafel reaction, Eq.
(3)).
The relation between the coverage ([H) of the ad-
sorbed H intermediate and cathodic overpotential for
HER was investigated on Mo, Ni and MoNi inter-
metallic compounds especially. The rate constants for
forward and backward reactions in the three steps of
HER were calculated from dc current densities, charge
transfer resistance (Rct) and relaxation elements (Rp and
Cp) obtained from impedance spectra, based on the
analysis of Armstrong and Hendersons [18].

  
The reaction rates of three steps are given by

61 =k1(1− [)exp −
iFp
−k − 1[ exp
(1−iFp) n
RT RT

  
=61 =k%1(1−[) −k%− 1[ (4a)

62 =k2[ exp −
iFp
−k − 2(1−[)exp
(1−i)Fp n
RT RT
=62 =k%2[−k%− 2(1−[) (4b)
63 =k3[ −k − 3(1− [)
2 2
(4c)
where, ki and k − i are the rate constants of the forward
and backward reactions. For convenience, the rate con-
stant values have nominally been written also to include
the OH−, H2O and H2 pressure.
The charge balance (r0) under a constant current
density ( j ), and the mass balance (r1) of the fractional
surface coverage ([) are given by the following
equations:
j
r0 = = −(61 +62) (5)

  
F
q ([
r1 = =61 −62 −263 (6)
F (t

Fig. 2. X-ray diffraction patterns of some Mo– Ni alloys.

Compositions indicated in the figure.

where, j is the current density for HER and q is the

maximum surface charge corresponding to a surface [
equal to 1.
Fig. 1. Equivalent circuit for single-adsorbate mechanism The steady-state H coverage, [, is given by setting
(Armstrong’s electric circuit). r1 = 0, then
 J.M. Jakšić et al. / Electrochimica Acta 45 (2000) 4151–4158 4153

Fig. 3. Tafel polarization curves on Mo–Ni electrodes in 1.0

mol dm − 3 NaOH at 25°C.

Fig. 4. Effect of Ni content on the current density for HER at

−(k%1 +k%− 1 +k%2)+[(k%1 +k%− 1 +k%2)2 +8k%1k3]1/2 overpotential, p = −0.4 V, for Mo– Ni alloys measured in 1.0
[=
4k3 mol dm − 3 NaOH at 25°C.
(7)
The rate constants k − 2 and k − 3 for the backward 2. Experimental
reactions are not included in Eq. (7), because they have
no significant influence on the reaction rates of the Mo– Ni alloy compounds with the following nominal
second (Eq. (4b)) and third step (Eq. (4c)). composition, MoNi; MoNi2; MoNi3; and MoNi4 were
At the equilibrium condition (61 =62 =63 =0), the metallurgically prepared by arc melting of the pure
relationship between ki values can be represented by components (Ni, Mo) under argon atmosphere
k1k2 k 21k3 (Philips). The phase structure of the alloys was ana-
k−2 = , k−3 = 2
(8) lyzed by X-ray diffraction method. Typical X-ray pat-
k−1 k− 1
terns for some Mo– Ni alloys are presented in Fig. 2.
Eq. (8) allows us to reduce the number of indepen- The results of X-ray analysis show that except MoNi4
dent parameters in the ki values from six to four. compound all other alloys have a multiphase structure.
In the impedance studies, HER mechanism is esti- For example, MoNi3 sample beside MoNi3 phase con-
mated by using the electric circuit of Armstrong [18], tains also Mo and MoNi4 phases. X-ray diagram for
given in Fig. 1, which contains the ac impedance ele- MoNi intermetallic compound was not analyzed in
ments, R, Rp and Cp.
detail, since the reference diagram does not exist in the
Rp opened literature, but some peaks have been analyzed
Zf =R +
(1+j…~p)
The double-layer capacitance (Cdl) is used as a circuit
element of the smooth electrodes.
The rate constants for forward and backward reac-
tions in the three steps of the HER were calculated
from dc current densities, charge transfer resistance
(Rct) and relaxation elements (Rp and Cp) obtained
from impedance spectra, based on Armstrong and Hen-
dersons analysis [17,18].
(9)
with reference to the other patterns. These analyze
pointed out that MoNi sample contains MoNi and
MoNi4 as separated phases.
The polished Mo– Ni electrodes (0.05 mm finished)
were mounted in Teflon.
The electrochemical experiments were performed at
25°C in solutions of 1.0 mol dm − 3 NaOH. Solutions
were made with spectrograde NaOH (Merck) and
deionized water.

Table 1
Kinetic parameters of the HER for Mo–Ni electrodes in 1.0 mol dm−3 NaOH at 25°C (from the Tafel curves)

Electrode Ni Mo MoNi MoNi2 MoNi3 MoNi4

−b (mV) 121 126 132 142 148 138

j0×106 (A cm−2) 3.3 5.4 79 70 32 13
4154 J.M. Jakšić et al. / Electrochimica Acta 45 (2000) 4151–4158
A conventional three-compartment glass cell was
used. A saturated calomel electrode (SCE) in the same
solution as that of the working electrode was used as
the reference electrode. Platinum gauze, spot-welded
onto a platinum wire sealed into a glass tube, was
used as a counter electrode.
Tafel curves were recorded potentiostatically in the
current range of : 1 mA cm − 2 to 100 mA cm − 2,
using a PAR273 potentiostat. The resistance of the
solution was determined by ac impedance spec-
troscopy. The ac impedance measurements were car-
ried out with the same potentiostat connected to a
PAR5301 lock-in amplifier, controlled by a computer
through a GPBI PC2A interface. The impedance mea-
surements were carried out in the frequency region of
50 mHz to 80 kHz. There were ten frequency points
per decade above 5 Hz. The fast Fourier transforma-
tion (FFT) technique was used in the impedance mea-
surements in the frequency region below 5 Hz. The
real (Z%) and imaginary (Z¦) components of the
impedance spectra in the complex plane were analyzed
using the nonlinear least squares (NLS) fitting pro-
Fig. 5. Experimental (circled points) and solid lines calculated
from the evaluated ki values complex plane diagrams for HER
on Ni (S=3.45 cm2, p= − 0.272 V), Mo (S =1.65 cm2,
p= − 0.345 V) and MoNi (S =0.84 cm2, p= −0.180 V) in
1.0 mol dm − 3 NaOH at 25°C.
gram to estimate the parameters of R, Rp and Cp.
The rate constants were calculated by minimizing the
residual (S) of the sum of each experimental datum
(the dc polarization measurement and ac impedance
results).
3. Results and discussion
Polarization curves for the HER, obtained by the
polarization measurements are presented in Fig. 3. Po-
larization curves were recorded after holding the elec-
trodes at a constant cathodic current density of 100
mA cm − 2 for about 1 h. A single-valued Tafel slope is
observed at all electrodes. The values for Tafel slopes
at Mo– Ni alloy electrodes are somewhat higher than
− 0.12 V, probably due to the presence of the oxide
films on the electrode surfaces, which causes additional
potential drop. Table 1 presents the main kinetic
parameters, the exchange current density for an appar-
ent surface area of 1 cm2 and Tafel slope, b for those
electrodes.
All investigated Mo– Ni alloys possess higher cata-
lytic activity of either Ni or Mo. For example, MoNi2
and MoNi4 have about three times the activity of base
components. The highest activity for HER exhibits
MoNi electrode, which is illustrated in Fig. 4.
Conway et al. [7] obtained somewhat lower catalytic
activity for the HER at bulk Ni(40)Mo(60) in the
same solution and temperature (at j = 0.1 A cm − 2,
p = 0.48 V) than MoNi electrode (at j = 0.1 A cm − 2,
p = 0.42 V) in this study. In the same time, the cata-
lytic activity of bulk Ni1 − x Mox (05 x 50.25) alloys,
investigated by Chialvo [17] were much lower.
The impedance analyzes were carried out only at
Ni, Mo and MoNi electrodes, because the other Mo–
 J.M. Jakšić et al. / Electrochimica Acta 45 (2000) 4151–4158 4155

Table 2
The fitted parameter values of the equivalent circuit for HER at Ni, Mo and MoNi in 1.0 mol dm−3 NaOH at 25°C

Electrode −p (V) R (V cm2) Rp (V cm2) Cp (mF cm−2) Cdl (mF cm−2)

Ni 0.184 567 1476 129 62

0.272 80.7 111 99 62
0.364 13.7 13.6 94 61
0.440 4.20 3.10 109 53
0.494 2.10 0.09 87 58
Mo 0.233 37.5 340 495 64
0.345 13.1 17.2 474 65
0.393 5.62 5.2 434 63
0.472 1.56 1.6 435 62
0.516 1.14 0.59 266 60
MoNi 0.112 46.2 408 248 66
0.180 8.90 35.9 206 64
0.227 2.43 5.94 267 63
0.315 0.93 0.75 327 65
0.382 0.51 0.02 357 64

Ni alloys did not exhibit significantly better catalytic
activity then Ni and Mo for the HER. Fig. 5 shows
typical complex-plane impedance diagrams at certain
overpotentials, p on Ni, Mo and MoNi electrodes. The
experimental data are represented by the circled points.
The impedance spectra consist of two overlapping
semicircles. The experimental data are treated through
the NLS fitting to estimate the elements of Arm-
strong’s equivalent circuit given in Fig. 1. The values
of the impedance parameters, which are necessary to
calculate the rate constants in the mechanism at Ni,
Mo and MoNi electrodes, are listed in Table 2.
The rate for HER was estimated from dc current
density and fitted parameters values of Armstrong’s
equivalent circuit using factorial fitting.
The estimated values of the rate constants are pre-
sented in the Table 3, for the apparent surface area of
1 cm2.
The complex-plane impedance diagrams calculated
from the evaluated ki values are presented by the solid
lines in Fig. 5. The potential dependence of the current
density is illustrated in Fig. 6. The corresponding solid
lines are obtained from the evaluated rate constants.
The fit of polarization curve at low overpotential val-
ues (near the reversible hydrogen potential) is worst. In
our opinion the positive deviation of the experimental
curves from the calculated Tafel plots is probably
caused by the presence of some other electrochemical
reactions such as the reduction of the oxide eventually
presented at the surface and/or electrochemical absorp-
tion of the hydrogen.
Now, it is also possible to evaluate the reaction rates
of the three steps, and the surface coverage of atomic
hydrogen from the estimated rate constants.
The surface coverage, [, of adsorbed hydrogen
atoms as function of overpotential for the investigated
electrodes are illustrated in Fig. 7. In all cases, the
value of [ increases at more negative potentials and
reaches its saturation value ([ “ 1) at higher overpo-
tentials.
The reaction rates of the Volmer, Heyrovsky and
Tafel processes in the hydrogen evolution mechanism
and the resulting total current value are all indepen-
dently shown in Fig. 8, as calculated from the esti-
mated ki values, in a wide potential region. In this
figure, all the rate values, 6i (mol cm − 2 s − 1) are shown
in terms of current, F×6i (A cm − 2).

Table 3
The estimated values for the rate constant for HER at Ni, Mo and MoNi electrodes in 1.0 mol dm−3 NaOH solution at 25°C (ki,
mol cm−2 s−1)

k1 k−1 k2 k−2 k3 k−3

Ni 5×10−10 6×10−9 1.5×10−11 4.2×10−12 3×10−10 6.2×10−12

Mo 8×10−10 9×10−9 1.3×10−11 1.2×10−12 4×10−10 3.2×10−12
MoNi 3×10−9 1.5×10−7 1.5×10−10 3×10−12 2.2×10−10 8.8×10−13
4156 J.M. Jakšić et al. / Electrochimica Acta 45 (2000) 4151–4158
From Fig. 8, one can see that at overpotentials
lower than approximately −0.15 V, the reaction
mechanism is a consecutive combination of Volmer
step and parallel Tafel and Heyrovsky steps. At Ni
electrode Heyrovsky step prevails over Tafel step, at
Mo electrode prevails the Tafel step and at MoNi
Fig. 6. Tafel polarization curves on Ni, Mo and MoNi elec-
trodes in 1.0 mol dm − 3 NaOH at 25°C. The continuous lines
were calculated from the evaluated ki values.
Fig. 7. Potential dependence of the calculated values of the
surface coverage by adsorbed hydrogen ([) on Ni, Mo and
MoNi electrodes in 1.0 mol dm − 3 NaOH at 25°C.
electrode, these two steps are of equal rates. At over-
potentials more negative of approximately − 0.25 V,
at almost full coverage of electrodes with Hads, the
mechanism of the HER is consecutive combination of
Volmer and Heyrovsky steps of equal rates and rate of
Tafel step negligible, at all investigated electrode mate-
rials. The reaction rate is controlled by the Heyrovsky
reaction because of the much smaller k2 value as com-
pared with the k1 and k3 values.
The evaluated ki values correspond to apparent sur-
face area of 1 cm2, but if we take into consideration
the fact that corresponding values for the double-layer
capacity of Ni, Mo and MoNi electrodes are very
similar (see Table 1), which means that the roughness
factors are also similar; one can conclude that true
catalytic effect is obtained at MoNi electrode for
HER.
4. Conclusions
Among investigated Mo– Ni alloys, such as MoNi,
MoNi2, MoNi3 and MoNi4 intermetallic compounds
only MoNi exhibits considerably higher true catalytic
activity then Mo and Ni electrodes for HER in 1.0
mol dm − 3 NaOH solution at 25°C.
The rate constants of the forward and backward
reactions of Volmer, Heyrovsky and Tafel steps were
estimated by a nonlinear fitting method.
The main pathway is Volmer– Heyrovsky with rate-
determining step of Heyrovsky at all investigated
electrodes.
 J.M. Jakšić et al. / Electrochimica Acta 45 (2000) 4151–4158 4157

Fig. 8. Potential dependence of the current density ( j ) and the reaction rates for HER on Ni, Mo and MoNi electrodes in 1.0 mol
dm − 3 NaOH at 25°C.
4158 J.M. Jakšić et al. / Electrochimica Acta 45 (2000) 4151–4158
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