Article

pubs.acs.org/JPCC

Eect of Ammonia on Pt, Ru, Rh, and Ni Cathodes During the

Alkaline Hydrogen Evolution Reaction
Ramasamy Palaniappan and Gerardine G. Botte*
Center for Electrochemical Engineering Research, Chemical and Biomolecular Engineering Department, 165 Stocker Center, Ohio
University, Athens, Ohio 45701, United States
S Supporting Information
*

ABSTRACT: The eects of ammonia on the hydrogen evolution reaction (HER) with Pt,
Rh, Ru, and Ni have been investigated using electrochemical methods. The activity of the
catalysts for HER, in the presence of ammonia follows the trend Rh > Pt > Ru > Ni. Pt and
Ru exhibit a decrease in the activity toward HER. Cyclic voltammetric (CV) studies show
that the presence of ammonia results in weaker metalhydrogen underpotential
deposition (MHupd) bonds. In addition, the activity of HER on Pt and Ru is retarded
in the presence of ammonia, supporting the theory that the activity for HER is higher on
the metal surface with Hupd than on the bare metal. On the contrary, the activity for HER
on Rh surface in the presence of ammonia is enhanced, suggesting the MHupd bond is a
barrier to the HER. CV for Ni in the presence of ammonia shows a Ni(OH)2 reduction
peak. However, the overpotentials for HER on Ni are very high such that no signicant
dierence is observed in the activity of HER.
eciencies at such voltages. Previous studies have reported the
operation of an ammonia electrolyzer stack in a divided cell
mode, where the anolyte containing ammonia and ammoniafree catholyte are fed in separate compartments.15,16 However,
during the electrolysis of ammonia, traces of ammonia can
diuse into the cathodic compartment at the rate of 6.33
108 mol cm2 s1.17 It has also been noticed that the pH of the
anode compartment drops while that at the cathode compartment is found to increase during a single pass in an ammonia
electrolyzer.16
Operating the electrolytic cell in a continuous stirred tank
type mode would help alleviate the problems associated with
the divided-cell electrolyzer. Therefore, it is critical that the
presence of ammonia does not provide any detrimental eect
on the stability of the catalyst and its activity toward HER. An
understanding of HER kinetics on the electrocatalyst is vital to
comprehend the eect of ammonia on the HER for that
material. HER has been a subject of interest for over two
centuries, since the invention of water electrolysis. Ever since
Horiuti published on the matter,18,19 numerous researchers
have independently studied the reaction and have made
signicant contributions to the mechanism of HER.2025
HER has played an important role in the development of
electrochemical principles, including the famous Butler
Volmer equation in 1924.26
A wide range of materials has been tested for their ecacy as
electrocatalysts for the HER in alkaline media, of which the
group IV metals in the periodic table and their alloys have

1. INTRODUCTION
The history of ammonia oxidation dates back to 1836 and
possibly beyond that.1 Recent developments in electrocatalysts
for ammonia electro-oxidation have led to the recognition of
ammonia as a safe and clean hydrogen carrier for distributed
power generation.27 It facilitates a robust and economical
method to produce hydrogen as opposed to the traditional high
temperature cracking of ammonia and high-energy consuming
water electrolysis processes. The reactions for an ammonia
electrolytic cell comprise of ammonia electro-oxidation at the
anode and alkaline water reduction at the cathode as shown in
eqs 13.8 Pt and PtIr alloys have been identied as the most
suitable electrocatalysts for the oxidation of ammonia.912 The
anodic electro-oxidation of ammonia has been identied as the
limiting reaction for this process, as it reaches a maximum at 0.6
to 0.8 V versus reversible hydrogen electrode (RHE) on
polycrystalline Pt.1214 On the other hand, the cathodic
hydrogen evolution reaction (HER), shown in eq 2, is known
for its facile kinetics.
Anode:

2NH3 + 6OH N2 + 6H 2O + 6e

E 0 = 0.77 V vs SHE
Cathode:

(1)

6H 2O + 6e 3H 2 + 6OH

E 0 = 0.82 V vs SHE
Overall:

(2)

2NH3 N2 + 3H 2

E 0 = 0.059 V

(3)

In order to realize higher eciencies it is required to operate

the electrolytic cell at voltages, such that the potential at the
anode is maintained below its limiting value. It is desired that
cathode electrocatalysts facilitate high hydrogen production
XXXX American Chemical Society

Received: May 26, 2013

Revised: July 30, 2013

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Table 1. Electroplating Solution Composition, Operating Conditions, and Results for Constant Potential Electrodeposition of
Pt, Rh, Ru, and Ni on Untreated Carbon Fiber Paper (Toray TGP-H-30) Substratea
material

electrodeposition solution composition

temp (C)

potential (V)
vs Ag/AgCl

average current density

(mA cm2)

total deposition time (s)

loading
(0.1 mg)

Pt
Rh
Ru
Ni

HCl - 1M; H2PtCl6 - 3 g l1

RhCl3 - 3 g l1
HCl - 1M; RuCl3 - 3 gl1
NiSO46H2O 280 g l1;
NiCl26H2O - 40 g l1;
H3BO3 - 30 g l1

78
78
78
40

0.100
0.01
0.200
0.800

4.328
1.879
3.472
7.537

1000
2500
4000
240

5.1
5.5
5.8
5.3

Electrodeposition was carried out for all catalysts until a loading of 5 mg was achieved, except iridium for which there was no appreciable mass gain
after 2 h.

received predominant attention.2741 They are preferred to

noble metal based cathodes for the HER due to their relative
low-cost. Nevertheless, they have drawbacks owing to their ease
of deactivation, high overpotentials, and low activity toward
HER.42,43 A wide variety of noble metals (including Pt, Ir, Rh,
Ru, Pd) and their alloys,27,4450 oxides25,51 and perovskites
have been evaluated for activity toward HER. Studies range
from theoretical modeling, such as quasi steady state
calculations,52 density functional theory studies,24 and volcano
plot (exchange current density for hydrogen evolution versus
enthalpy of formation of M-H bond) simulations,21 to
experiments utilizing cyclic voltammetry (CV), linear sweep
voltammetry (LSV),27,53 constant potential, and electrochemical impedance spectroscopy (EIS).54,55 In addition, it
has been reported that the HER is sensitive to the
electrocatalyst crystal structures.56,57
The HER proceeds through VolmerHeyrovskyTafel
(VHT) mechanism in both acidic and alkaline environments.26,27,55 The mechanism in the alkaline medium is
shown in eqs 46. The Heyrovsky (or electrochemical
desorption) step and the Tafel (or chemical recombination)
step are parallel and competing reactions. It is important to
know which of these steps will be rate-determining, as it
determines the stability of the electrode. The extent of the
reaction proceeding through one of the two steps should be
directly related to the resistance of the other (i.e., the reaction
will proceed via the step with a lower resistance or a higher rate
constant), which can be evaluated by potential decay and EIS.
Volmer:

M + H 2O + e MH + OH

Heyrovsky:

density (i0), and rate constant, in the presence and absence of

ammonia. Based on an extensive theoretical study, Greeley et
al., concluded that Pt, Ir, Rh, Ru, Pd, Ni, and Co displayed high
activities for HER.24 In addition, Pt, Rh, Ru, and Ni continued
to show high activities for HER, when alloyed with q wide
range of transition materials.54,62
Within this context, the objective of this paper is to
determine the eect of ammonia on the alkaline HER kinetics
on Pt, Ru, Rh, and Ni electrocatalysts using voltammetric,
alternating current (AC) impedance, and current transient
techniques.24 It has been shown that potassium hydroxide
(KOH) solution exhibits maximum ammonia electro-oxidation
rate at a concentration of 5 M, therefore it was chosen for our
studies. Carbon ber paper (CFP) substrates were used for
electrodeposition of the catalysts as they demonstrated a better
performance for the electrolysis in alkaline medium.4,9 In order
to address the main objective, the following tasks were
performed:
1. Pt, Rh, Ru, and Ni electrodes were prepared by
electrodeposition onto CFP substrates. The electrodes
were then characterized using scanning electron
microscopy (SEM), energy dispersive X-ray (EDX)
spectroscopy, and X-ray diraction (XRD) while the
electrochemical active surface area (EASA) was determined using CV.
2. The kinetic parameters of the electrodes for HER in
aqueous 5 M KOH were determined in the presence and
absence of ammonia using LSV and EIS techniques.
3. The eects of ammonia on long-term stability of the
electrocatalysts were evaluated using constant potential
experiments.

(4)

MH + H 2O + e M + H 2 + OH
(5)

Tafel:

2MH + 2M + H 2

2. MATERIALS AND METHODS

All of the chemicals used in this study were of analytical grade
and were obtained from Alfa Aesar. All the experiments were
repeated in order to check for reproducibility, and the errors
reported in the paper were calculated through error
propagation, taking into account the instrumental error and
standard deviations in the measurements. All electrochemical
experiments were performed with a potentiostat (Solartron
1287) coupled with a frequency response analyzer (Solartron
1252A) with an electrochemical interface. Hg/HgO saturated
with KOH (20% by weight), purchased from Koslow Scientic,
was used as the reference electrode for measurements in
alkaline solution, whereas an Ag/AgCl electrode saturated with
KCl, purchased from Fisher Scientic, was used in acidic
solutions. A glass-body luggin capillary was used to house the
reference electrode in order to reduce the solution resistance
and avoid contamination of the solution.

(6)

EIS is one of the standard techniques to estimate the

impedance of various components of an electrochemical
reaction and, therefore, rate constants for the steps involved
in the mechanism.54,55,5860 Armstrong and Henderson derived
the equivalent circuits for a two-step electrochemical reaction
with one intermediate in the absence of diusion control by
evaluating the impedance from their corresponding rate
equations.61 Harrington and Conway extended this procedure
to derive the impedance equations for the three-step HER and
subsequently veried the validity of the equations using
complex plane plots obtained from EIS experiments using Pt
electrodes in 0.5 M sodium hydroxide solution.54,62
However, the eect of ammonia on HER has not been
reported. This can be better understood by evaluating the
kinetic parameters such as Tafel slope (TS), exchange current
B

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Figure 1. EDX for metals Pt, Rh, Ru, and Ni are labeled A, B, C, and D respectively. The SEM images of the corresponding metals at 2500 are
placed exactly below the EDX images. It can be observed that the plating occurs in a globule-type fashion occurring uniformly along the lengths of
the carbon bers for all but Ru, where the deposition occurred in a more layered structure.

measurement. Choice of a pretreatment procedure is dependent upon the nature of the electrocatalyst and the substrate and
is crucial to obtaining reproducible results. The pretreatment
was performed in two stages: rst by performing a CV in 1 M
KOH solution at 50 mV s1 in the region where there is no
oxide formation, until a sustained periodic state for the
voltammogram was achieved, so that any impurity that might
hinder the electrochemical measurement in the potential range
would be removed. Second, the electrode was subjected to a
potential of 1.42 V versus Hg/HgO in 1 M KOH for 1 h in
order to remove any surface oxides that might have formed on
the electrode, during the previous step or while drying.35 Steps
1 and 2 were repeated until a reproducible surface was
obtained.
The electrodes were then subjected to EASA measurements
followed by the CV, LSV, and EIS studies. The EASA for Pt
and Rh were evaluated by measuring the hydrogen adsorption
charge in 0.5 M sulfuric acid,6366 while the EASA for Ni was
evaluated by the charge required to produce -Ni(OH)2 in 1 M
KOH using CV.67 The solution was deaerated by bubbling
argon gas (99.999% purity, from Praxair) at 15 mL min1 for 15
min prior to the measurements.
Carbon monoxide (CO) stripping voltammetry was used to
measure the EASA for Ru and to verify the EASA for Pt
obtained via hydrogen adsorption.68,6970The CO stripping
voltammetry was carried out under a fume hood. The test
solution (1 M KOH for Pt and 0.5 M H2SO4 for Ru) was
saturated with carbon monoxide, of purity 99.9% from Praxair,
which is evident from the open circuit voltage reaching steady
state. The electrode was held at a constant potential of 25 mV
versus RHE in the respective test solution. The solution was
then purged with argon gas for 15 min, while continuing to
hold the electrode at the same potential. Thereafter, CV tests
were carried out on the working electrode in the CO electrooxidation region. The CV for EASA measurement was carried
out with a 5 cm 5 cm Pt foil auxiliary electrode at a scan rate

2.1. Electrode Preparation and Physical Characterization. The electrocatalysts used in this study were prepared
by electrodeposition onto two untreated Toray TGP-H-30
CFP, purchased from Electrochem Inc., of size 2 cm 2 cm
sandwiched on either side of an 18-mesh titanium gauze
substrate of purity 99.9% (Alfa Aesar) as reported by Boggs and
Botte.9 The substrate was then degreased with acetone and
rinsed with deionized water, dried in an oven at 80 C and
weighed using a microbalance with an accuracy of 0.1 mg, prior
to and after the electrodeposition. The electrodepositions were
conducted at constant potentials that were chosen based on
metal ion reduction peaks in the CV as described in the
Supporting Information available online. The conditions for Pt,
Rh, Ru, and Ni electrodeposition are detailed in Table 1. The
electrodeposition experiments were conducted in a 250 mL
Pyrex glass beaker on a stirring hot plate with a built-in
thermocouple and a glass-ceramic surface from Corning. The
potentials are provided in Table 1. The contents of the beaker
were stirred at 100 rpm using a magnetic stirrer bar to maintain
uniform temperature and minimize mass transfer limitations;
the temperature was maintained using the thermocouple builtin with the hot plate. A 5 cm 5 cm Pt foil of thickness 0.01
cm and purity 99.999% (ESPI Metals) and an Ag/AgCl
electrode saturated with KCl were used as the auxiliary and
reference electrodes, respectively. The electrodepositions were
carried out until a loading of 1.25 mg cm2 was obtained. The
CFP on one side of the sandwich was cut for physical
characterization of the electrode, which was used for surface
morphology by SEM and elemental analysis by EDX studies
using a JEOL JSM 6390 scanning electron microscope. The
signature crystallographic orientation of the synthesized
electrodes were studied using XRD on a Rigaku Ultima IV
using Cu K (1.54 ) radiation generated with 40 kV and 30
mA, at a scan rate of 0.5 min1.
2.2. Pretreatment and EASA Measurements. All the
electrodes were pretreated, prior to the electrochemical
C

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Table 2. Electrochemical Active Surface Area for Pt, Rh, Ru, and Ni Electrodeposited on Carbon Fiber Papera
material

method

charge
(7 C)

specic charge
(C cm2)

surface area
(1.01 cm2)

roughness factor
(0.04)

specic area 103

(0.02 cm2 g1 catalyst)

Pt
Pt
Rh
Ru
Ni

CO stripping
hydrogen adsorption
hydrogen adsorption
CO stripping
NiNi2+

68643.4
37261.9
92959.3
289529.0
116833.5

420
210
221
420
514

181.60
177.44
420.63
689.35
227.30

45.40
44.36
105.16
172.34
56.83

35.61
34.79
76.48
118.85
47.35

Errors reported were calculated through error propagation using instrumental errors for current and voltage. Ru had the highest surface area among
the electrodes prepared.

normalize the current obtained for the material with its EASA
(the area of the electrode material that is active to an
electrochemical reaction). The EASA for the catalysts were
evaluated as mentioned in the Supporting Information available
online. Table 2 provides the results of the EASA, the specic
area of the catalysts, and the method adopted to evaluate the
EASA. The EASA for Pt obtained using CO stripping
voltammetry agreed with that obtained using the hydrogen
adsorption method, providing credence to the technique used.
It can be observed that Ni exhibits an EASA similar to that of
Pt. However, Ru displayed the highest EASA and roughness,
consistent with the SEM images, which indicate a rough layer
type deposition that is equally prevalent in the gaps between
the carbon bers. The high EASA for Rh is attributed to the
smaller particle size of the deposits. The results reported in this
study, unless mentioned otherwise, have been normalized with
respect to the EASA.
3.2. Voltammetry Studies. Figure 2 illustrates the Tafel
plots for the catalysts under investigation in 5 M KOH in the

of 50 mV s1. The sustained periodic state for the voltammograms was obtained after 5 cycles.
2.3. Electrochemical Characterization. The CV, LSV,
EIS, and constant potential experiments were carried out with a
3-electrode setup in 5 M KOH solution in the presence and
absence of 1 M ammonia. A 5 cm 5 cm Ni gauze (10 mesh
woven from 0.1 mm diameter wire, Alfa Aesar) was used as the
counter electrode for each experiment. The Ni gauze was
sandblasted using a micro sand blaster (Swam Blaster, Crystal
Mark, Inc.) with alumina (size 27.5 m, purchased from Crystal
Mark, Inc.) for 2 min, then degreased with acetone and rinsed
with deionized water.
The CV tests were carried out by scanning the potential from
1.1 to 0.1 V versus Hg/HgO and back at 10 mV s1. While
the LSV experiments were carried out by scanning the potential
between 0.9 V to 1.3 V versus Hg/HgO at 1 mV s1. The
low scan rate of 1 mV s1 was sucient to maintain the reaction
under kinetic-control by allowing enough time for the diusion
of fresh reacting species to the electrode surface. Sustained
periodic results were obtained for both CV and LSV after the
fth scan.
The EIS experiments were performed by applying an AC
amplitude of 10 mA with a frequency range between 10 kHz
and 0.1 Hz superimposed over a DC potential 1.1 V versus
Hg/HgO in the HER region. The electrodes were polarized at
the DC potential for 15 min prior to the EIS measurements.
Constant potential experiments were carried out in a solution
of 5 M KOH in the presence and absence of ammonia at a
potential of 1.1 V versus Hg/HgO for 3 h.

3. RESULTS AND DISCUSSION

3.1. Electrodeposition and Physical Characterization.
Pt, Rh, Ru, and Ni were successfully deposited on the CFP
electrodes and veried by an increase in the electrode mass as
well as by SEM and EDX studies. The results for the
electrodeposition (average current and catalyst loading) are
reported along with the electrodeposition solutions and
conditions in Table 1. SEM and EDX results for the electrodes
after electrodeposition are reported in Figure 1. The SEM
images for Pt, Rh, and Ni show globule type deposition with
the size of each globule in the range 10 to 100 nm and
pertaining to carbon bers in the rst two layers, consistent
with the literature. On the other hand, the SEM image for Ru
shows a layer type deposition. The EDX images show that the
electrodes are predominantly comprised of respective metal
along with carbon from the substrate and trace amounts of
oxygen that occurred as a result of exposure to atmosphere.
The slightly higher oxygen content on the nickel electrode
could be attributed to the existence of hydroxides.
In order to eectively compare the intrinsic electrochemical
activity of an electrocatalyst for a reaction, it is crucial to

Figure 2. Tafel plots for steady state linear sweep voltammograms for
Pt, Rh, Ru, and Ni in 5 M KOH in the presence and absence of 1 M
ammonia. Voltammograms without ammonia are shown by dashed
lines (--) while solid lines () represent the presence of ammonia.
Inset to gure represents the data in the region of interest 110 mV to
250 mV for enhanced clarity. Current densities (ireal) were evaluated
based on the electrochemical active surface area. Voltammograms were
carried out at a potential scan rate of 1 mV s1.

presence and absence of 1 M ammonia. It can be observed from

Figure 2 that the noble metals exhibit two dierent TSs in the
region below and above 200 mV. However, for Ni, two
dierent TSs were measured in regions below and above 240
mV. This is in agreement to that observed by Vilekar et al.,
based on quasi-steady state theory.52 The TS in the low
D

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overpotential (<200 mV) region has been attributed to the

reaction proceeding through the VolmerTafel pathway, while
the TS at high overpotential (>200 mV) is due to the Volmer
Heyrovsky path.52 The Tafel constants were estimated by
tting the LSV data to the Tafel equation after correcting for
the IR drop using linear regression with a 95% condence level.
The HER kinetics at the low overpotential region is of
particular interest to ammonia electrolysis as one tries to
achieve maximum hydrogen production at low cell voltages and
prevent the anode of the electrolytic cell from reaching its
limiting potential. In addition, it was observed that at high
overpotentials the diculty for hydrogen to escape the wet
surface of the untreated CFP electrode was enhanced.
Consequently, it is also observed that the high TS that
accompanies the high i0 at high overpotentials, implying that
the HER currents in this region is masked by diusion.
Therefore, only the Tafel parameters (TS and i0) calculated at
the lower overpotential region (between 118 mV and 200
mV) will be used in this study.
The Tafel constants along with the overpotentials at current
density of 0.25 mA cm2 (corresponding to a hydrogen
evolution rate of 1.73 l h1 for an electrode with EASA 1 m2)
are reported in Table 3. The overpotential at 0.25 mA cm2,

The existence of hydroxides results in a high activity for the

electrochemical dissociation of water. However, it also exhibits
a considerably low activity for the desorption steps, resulting in
the formation of hydrides thereby leading to the deactivation of
Ni.
It can also be observed from Figure 2 that, in the presence of
ammonia, the overpotential-log i behavior for the catalysts
continue to exhibit a low TS in the low overpotential region,
and a high TS in the high overpotential region. This behavior is
similar to that without ammonia, implying that the VHT
mechanism still applies to the HER in the presence of 1 M
ammonia. It can be noticed that the overpotentials for Pt, Ru
(inset to Figure 2) and Ni (Figure 2) are higher due to a partial
surface deactivation reaction in the presence of ammonia.71
However, the overpotentials observed for Rh with 1 M
ammonia is lower than that observed without ammonia; this
could be attributed to surface activation thereby increasing the
HER on Rh. From Table 3 it can be noted that the
overpotentials for HER at 0.25 mA cm2 in 5 M KOH with
1 M ammonia follows the trend: Rh < Pt < Ru < Ni.
The cyclic voltammograms for Pt, Rh, Ru, and Ni in 5 M
KOH with 1 M ammonia and ammonia-free solutions in the
region preceding the HER, shown in Figures 3A through 3D,
provide a deeper insight to the surface process. It is known that
catalyst utilization and the kinetics for HER are dependent
upon the surface coverage of the overpotential deposited
hydrogen (Hopd) which is weakly bonded to the catalyst surface
and is considered to be the actual intermediate for the
HER.23,54,55 Hopd is in turn dependent upon the potential for
the hydrogen underpotential deposition (Hupd), i.e., the
hydrogen that is adsorbed at potentials lower than equilibrium
potential (E0) as shown in eq 7. It is agreed upon that the Hupd
is strongly bound to the catalyst surface.23,54

Table 3. Tafel Parameters Obtained from Linear Sweep

Voltammetric Studies for Pt, Rh, Ru, and Ni Electrodes in 5
M KOH in the Presence and Absence of Ammoniaa

material
Pt
Rh
Ru
Ni

ammonia
concentration
(M)

Tafel slope
(3 mV
decade1)

exchange current
density (0.002
mA cm2)

overpotential,
, iesa = 0.25
mA cm2
(1 mV)

0
1
0
1
0
1
0
1

157
171
220
219
140
222
95
108

0.043
0.031
0.040
0.069
0.021
0.047
0.0005
0.001

125
152
162
125
147
159
255
260

M + H 2O + e MH upd + OH

E < E0

(7)

where, E0 = 0 V versus SHE. The potential of occurrence for

the Hupd is indicative of the strength of the MHupd bond, i.e.,
the more positive it is, relative to the HER, the stronger the
MHupd bond will be.23,73,74 However, the role of the Hupd on
HER is a controversial subject, with opposing views: Markovic
et al.,23 reported that the strong Hupd hinders the HER, while
Conway et al. claims that the presence of Hupd enhances the
rate of HER.20,73,74 Coincidentally, by evaluating the shift in the
Hupd peaks that arises due to the addition of ammonia and
relating the shifts in potential for Hupd formation to the changes
in HER kinetics provides important information to understand
the role of Hupd.
In the absence of ammonia, the CV for Pt (Figure 3A) shows
three reversible peaks A01, A02, and A03 associated with Hupd
in the Pt (111), Pt (100) planes and the reduction of the
surface oxide or OH ion desorption for Pt, respectively.23,75
However the CV for Rh and Ru, in the absence of ammonia
were similar.45,69 The cathodic peaks B01, B02 (Figure 3B) for
Rh and peaks C01, C02 (Figure 3C) for Ru can be attributed to
the Hupd and the reduction of the metal-oxide that was formed
during the forward scan, thereby implying that the overpotential for Hupd follows the trend Pt > Rh > Ru. On the other
hand, the CV for Ni indicates a small plateau type feature at
D01, attributed to the reduction of the Ni(OH)2.76,77 However,
the absence of a distinct reduction peak indicates the
transformation of Ni(OH)2 from the reversible -phase to a
irreversible -phase. The presence of oxides for Ni at such low

The Tafel slope and exchange current density were calculated for
cathodic HER at the low and high overpotential regions separately.
The exchange current density and the overpotentials at 0.25 mA cm2
were evaluated based on the EASA of the catalyst.

without ammonia, follows the order Pt < Ru < Rh < Ni,

whereas the exchange current densities followed the trend Pt >
Rh > Ru > Ni in this region. In the absence of ammonia, Pt
displayed the least overpotential and highest i0 among the
catalysts studied, conrming the highest activity of Pt for HER
as seen from the volcano plots.
The TS obtained for the catalysts in 5 M KOH in the
absence of ammonia in the low overpotential region increased
in the order Ni < Ru < Pt < Rh. The TS for the noble metal
catalysts follow the trend observed by Fournier et al., for the
same catalysts embedded in a porous LaPO4 matrix in 1 M
KOH.71 Lower TS indicate higher hydrogen evolution rate for
an increase in overpotential. Although Ni has the lowest TS, it
also has the highest overpotential at a current density of 0.25
mA cm2 as well as an i0 at least 100 times lower than the other
catalysts. The higher overpotentials exhibited by Ni electrodes
could be due to the existence of hydroxides even at potentials
as low as 1.0 V versus Hg/HgO conrmed by Silverman in
the revised EMF-pH diagrams for the NickelWater system.72
E

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Figure 3. Cyclic voltammograms for (A) Pt, (B) Rh, (C) Ru, and (D) Ni in 5 M KOH with the presence and absence of 1 M ammonia. () Solid
lines indicates presence of ammonia while the (--) dashed lines indicate the absence of it. The voltammograms shown above are representative of the
steady state cycle achieved at the 5th cycle and at a potential scan rate of 10 mVs1. It can be seen that in the presence of ammonia all the Hupd peak
is more pronounced and occurs at a slightly more negative potential for all the catalysts.

surface blockage by intermediates from chemical or a minor

electrochemical oxidation of ammonia along with the OH ions
that were adsorbed at considerably lower potentials.12 This can
be veried by the presence of an additional reduction peaks
B12 and C12 for Rh and Ru, respectively. The additional
reduction peaks B12 and C12 and larger Hupd peaks B11 and
C11 could be attributed to either the ammonia desorption or a
shift in the surface-oxide reduction peak in the negative
direction or both. In addition, the presence of ammonia
indicates no metal-oxide reduction peaks for Rh and Ru.
In addition, it could be observed that the Hupd peaks for Pt
A01 and A02 appear to have slightly shifted by 120 mV to 180
mV in the negative direction, implying a weaker PtHupd bond.
The shift in the Hupd to a more negative potential could be a
result of adsorbed ammonia or intermediates for ammonia
electro-oxidation. Similarly, the presence of ammonia causes
the Hupd peaks B01 for Rh and C01 for Ru, to be shifted in the
negative direction by 40 mV and 30 mV, respectively, implying
a slightly weaker MHupd bond. The extent of the shift appears
to be caused by the sensitivity of electrocatalyst surface to
ammonia.
The CV for Ni Figure 3D in the presence of ammonia
indicates peak D11 corresponding to the reduction of Ni(OH)2
to Ni.76,79 This suggests a reversible nature of the hydroxide
and could in turn imply that the presence of ammonia prevents

potentials can be veried by the Pourbaix diagram and obviates

the existence of Hupd.72
The voltammograms in the presence of ammonia display
three distinctive features: (1) the absence of the metal-oxide
reduction, (2) the signicantly larger cathodic currents in the
Hupd region between 0.4 V to 0.9 V, and (3) the presence of
an additional reduction peak. The absence of the metal oxide
desorption peak indicates the removal of oxides by taking part
in the ammonia electro-oxidation reaction or its masking by the
signicantly larger ammonia electro-oxidation currents.
For Pt, the potential scan in the positive direction shows a
peak A14 corresponding to the adsorption of ammonia and
another at 0.25 V corresponding to the onset of ammonia
electro-oxidation. Upon evaluating the charges under the
reversible peak A11A11, after accounting for the double
layer and desorption of ammonia, this agrees with the charge
required for Hupd in the absence of ammonia, implying that the
peak A11 is due to Hupd. The additional reduction peaks A12
and A13 can be attributed to the reduction of the intermediates
of ammonia oxidation and ammonia desorption as veried by
stripping studies by de Vooys et al.12 and dierential
electrochemical mass spectroscopy studies by Wasmus et al.78
In the presence of ammonia, Rh and Ru did not exhibit any
distinct ammonia electro-oxidation peaks during the potential
scan in the positive direction. This has been attributed to
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estimating the best equivalent circuit for the impedance data is

explained in the Supporting Information to this article (found
online).
3.3.1. Eect of Ammonia on Equivalent Circuit Parameters for HER. A list of equivalent circuit models that were
evaluated for HER is described in Figure 4AE. The
ArmstrongHenderson model61 (Figure 4A) describes a
typical case for HER, the model is usually used in a scenario
where the Nyquist plots indicate the presence of two time
constants. The constant phase element (CPE) model (Figure
4B) is an extension to the Randles circuit and a simplied
version of the ArmstrongHenderson model, where the
impedance of the parallel RpCp branch is eliminated due to
the considerably low pseudocapacitance. The CPE model is
designed to t systems with one time constant and frequency
dispersion.80 Additionally, in the derived circuits (Figure 4C
through 4E), a CPE element replaced the capacitor in the
ArmstrongHenderson model, were evaluated.
The EIS results for Pt, Rh, Ru, and Ni are presented in
Figures 5A through 5D, in the form of Nyquist (or) ColeCole
(or) complex-plane plots along with its equivalent circuit t and
the t obtained from the rate constants derived for the VHT
mechanism (Section 3.4). As a rule of thumb, the high
frequency intercept in the Nyquist plot represents the solution
resistance, while the diameter of the semicircle represents the
Faradaic resistance. Harrington and Driessche81 give an
excellent description on how to decipher an impedance spectra
and the signicance of the equivalent circuit elements for
specic cases. The Nyquist plots indicate the presence of only
one time constant and no Warburg-type feature at the lower
frequency range, indicating that the HER is charge transfer
controlled. Nevertheless, due to its practical signicance to
HER, the ArmstrongHenderson model was evaluated to t
the impedance spectra. Figures 5A to 5C show that the CPE
model oered the best possible t for HER on the noble metals.
The CPE accounts for the capacitance dispersion with
frequency as a result of the inhomogeneity of the electrode
surface,58,71,80 while Figure 5D shows that the Armstrong
Henderson model oered the best t for the Ni electrodes,
conrming that found in the literature.58,61 The derived circuits
did not oer any signicant improvement in the t when
compared with the CPE model, suggesting a faster recombination reaction. The total impedance for all the models in
Figure 4 obeys the equation:

the conversion of the hydroxide from the reversible phase to

its irreversible phase. The Figure also shows that the
ammonia adsorption or electro-oxidation peaks are absent,
since they do not occur until considerably higher potentials
through a direct electron transfer reaction with the NiOOH
catalyst.76
Upon adding ammonia and by correlating the shift in the
Hupd with the change in the overpotential of the catalyst, the
role of Hupd on the HER could be understood. The addition of
ammonia results in weaker MHupd bonds for Pt, Rh, and Ru.
The weaker MH upd bond (Figures 3A and 3C) is
accompanied by a decrease in the HER activity on Pt and Ru
in the presence of ammonia, thereby implying that the activity
for HER is higher on a surface with Hupd than on the bare
metal.20,73,74 This hypothesis can also be conrmed from the
shift in Hupd (i.e., an Hupd of 140 mV results in an
overpotential decrease of 27 mV for Pt, whereas a Hupd shift
of 40 mV results in an overpotential decrease of 11 mV).
Thereby validating the hypothesis by Conway et al. that the
activity of HER is thermodynamically more favorable on the
surface with the stronger Hupd, rather than on the bare metal
itself.74 However for Rh, an increase in activity toward HER is
observed with the weaker MHupd bonds. The addition of
ammonia hinders the formation of the Hupd bonds on Rh
thereby leaving room for the formation of Hopd, which is
reported to enhance the HER on the Rh surface. This suggests
that a HER on Rh could follow a dierent mechanism. A
possible mechanism for HER on Rh might consist of the a
surface where Hupd bonds act as a barrier to HER and Hopd
being the actual intermediate for HER, as proposed by
Markovic et al.23
3.3. EIS Studies. The EIS technique can be used to identify
the rate constants for each step in the reaction mechanism.
Figure 4 shows the various equivalent circuit models that were
evaluated to describe the HER.58,59,71 The procedure for

1 1
Z T = R s + (Zf1 + ZCPE
)

(8)

where Rs is solution resistance, Zf is faradaic impedance, and

ZCPE is impedance due to the CPE. Since, all of the models are
based on the ArmstrongHenderson equivalent circuit, the
Faradaic impedance can be expressed as
Zf = R ct + 1/(jCp + (1/R p))
Figure 4. Equivalent circuit models evaluated for the representation of
HER impedance spectra at E = 1.161 V vs Hg/HgO. Figures A
through E depict: ArmstrongHenderson model (A-H), Modied
Randles circuit (CPE model), A-H model with capacitance dispersion
at a high frequency, A-H model with capacitance dispersion at low
frequency, and A-H model with capacitance dispersion at low and high
frequency domains, respectively. Rs solution resistance, Cdl double
layer capacitance, Rf Faradaic resistance, Rct charge transfer
resistance, Rp polarization resistance or pseudoresistance, Cp
pseudocapacitance. Constant phase element (CPE), CPEdl and CPEp
accounts for frequency dispersion in double layer capacitance and
pseudocapacitance, respectively.

(9)

where Rct is charge transfer resistance, Rp is polarization

resistance, Cp is pseudocapacitance, and is angular frequency.
The equation for the impedance of the CPE element is given by
ZCPE = 1/[T (j) ]

(10a)

T = Cdl [R s1 + R ct1](1 )

(10b)

where Cdl is the double layer capacitance, and is the angle

that describes the extent of frequency dispersion of the double
layer capacitance. The equivalent circuit tting suggests that the
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Figure 5. Nyquist (or) complex-plane plot for the experimental impedance spectra for HER obtained with electrocatalysts: Pt (A), Rh (B), Ru (C),
and Ni (D) at E = 1.102 V vs Hg/HgO ( = 166 mV) in the presence and absence of ammonia. In addition, the spectra for equivalent circuit
models (described in inset to Supplemental Figure S4 to this paper found online) that best t the experimental values are shown along with the
spectra obtained by using the rate constants evaluated for the VHT mechanism. The experimental data for HER in the absence and presence of
ammonia are represented by clear (red) and lled (blue) square markers, respectively.

Table 4. Circuit Parameters for the Equivalent Circuit Fit to the Impedance Spectra for the HER on Pt, Rh, Ru, and Ni in the
Presence and Absence of Ammonia at an Overpotential of 166 mVa
Goodness of Fit
Material

Ammonia Concentration (M)

Chi-Square

Sum-Square

Rs ()

CPEdl- T

CPEdl- P

Cdl (mF cm2)

Rf ( cm2)

CP (mF)

Pt

0
1
0
1
0
1
0
1

0.012
0.006
0.005
0.003
0.007
0.012
0.012
0.012

1.211
0.602
0.412
0.286
0.549
0.831
0.837
1.000

0.039
0.046
0.065
0.054
0.050
0.039
0.023
0.022

0.136
0.108
0.108
0.129
0.174
0.192
0.005
0.006

0.663
0.671
0.810
0.793
0.755
0.722
1.000
1.000

50
42
70
74
44
36
20
28

31.06
44.07
35.82
36.30
37.68
51.50
498.75
553.43

15.69
16.81

Rh
Ru
Ni
a

The CPE model oered the best t the impedance data for Pt, Rh, and Ru. However the ArmstrongHenderson model oered the best t for the
impedance data for the Ni electrode. It can be observed that Pt oered the least Faradaic resistance in the absence of ammonia, while Rh oered the
least resistance in the presence of ammonia. The trend in the Faradaic resistance follows the trend in overpotentials in accordance with the LSV
studies in the presence and absence of ammonia.

pseudocapacitance oers signicant impedance toward the

HER, thereby following the Armstrong Henderson model. The
procedure adopted for optimal equivalent circuit tting is
described in the Supporting Information and supplemental
gure (Figure S4) to this paper that is found online.

pseudocapacitance term is negligible for the noble metals and

obeys the CPE model, thereby implying that the H adsorption
formed as a result of the Volmer step quickly recombined to
form hydrogen, and in turn suggesting that the water
dissociation step is the slow step. However for Ni, the
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Table 5. Rate Constants and Surface Coverage Were Estimated for the Catalysts in the Presence and Absence of Ammonia at an
Overpotential of 166 mVa
Rate Constant (mol cm2 s1)
Material
Pt
Rh
Ru
Ni

Ammonia Concentration
(M)

k1
(x1010)

k1
(x106)

k2
(x108)

k3
(x106)

kav
(x1010)

Surface Coverage
q
(C cm2 )

Fractional Coverage
(monolayers)

0
1
0
1
0
1
0
1

3.22
2.26
2.64
2.76
2.77
2.02
30.67
32.74

2.47
2.10
0.98
0.50
0.24
0.19
3.73
3.28

0.42
0.35
1.29
1.16
1.33
1.13
0.0002
0.0001

0.25
0.25
1.71
0.80
0.45
0.42
0.0029
0.0022

9.89
7.01
8.54
8.91
8.96
6.57
0.06
0.05

9.05
7.58
4.99
5.50
4.41
3.78
28.69
34.43

0.043
0.036
0.023
0.025
0.021
0.018
0.112
0.134

Rate constants and surface coverage were derived for the catalysts using the equivalent circuit parameters shown in Table 4 by the Levenberg
Marquardt algorithm for the VolmerHeyrovskyTafel mechanism. The addition of ammonia leads to a decrease in the rate constant for the slowest
step, k1 for Pt and Ru, and k2 for Ni. However, for Rh, the addition of ammonia results in an increase in the rate constant for the Volmer step (k1).

The values for the circuit elements for the equivalent circuit
t for the impedance spectra at 166 mV, along with the
goodness of t (2 and sum squared values) are reported in
Table 4. The maximum average error for the t, estimated from
the sum squared values for 45 data points, for the noble metal is
0.016 obtained using the CPE model, whereas the average
error for Ni is 0.043 obtained using the Armstrong
Henderson model. The results for other models exhibited
higher errors and therefore were not reported. From Table 4, it
could be observed that there is no signicant dierence in the
solution resistance, whereas the double layer capacitance per
unit area decreased in the order Rh > Pt > Ru > Ni in the
absence and presence of ammonia. In addition, it is noticed that
the double layer capacitance is greater than the expected 20 mF
cm2, for all the noble metals. The higher Cdl values is specic
to the alkaline medium and specically to the coadsorption of
the OH anion in the double layer region.23 On the other hand,
the Faradaic resistance per unit area increased in the order Pt <
Ru < Rh < Ni, as observed for the trend in overpotentials
obtained from LSV results. The addition of ammonia did not
result in any change in the trend for the double layer
capacitance per unit area. Meanwhile the Faradaic resistance
(Rf) increased for Pt, Ru, and Ni, altering the trend in Rf to Rh
< Pt < Ru < Ni. The results are consistent with the LSV studies,
conrming their validity. The higher activity on Rh can be
attributed to (1) the weakening of the surface hindering Rh
Hupd bonds,23 or (2) the high tendency to adsorb OH ions
and therefore its reduced activity for Hupd formation45 or (3) its
selectivity of reducing nitrates and its intermediates, or a
combination of the three. Further study is required to explain
the higher activity for Rh toward HER in the presence of
ammonia. Evaluating the variation in the Hopd surface coverage
and rate constants for the Volmer, Heyrovsky, and Tafel steps
in the presence of ammonia could oer a deeper understanding
to the eect of ammonia on the HER.
3.3.2. Eect of Ammonia on Kinetic Rate Constants for
HER and Hopd Surface Coverage. Upon assuming Langmurian
adsorption, and neglecting the backward reactions for the
Heyrovsky and Tafel steps, the nal expression for the rate
equations for reactions in eqs 46 is given by:

(11b)

3 = k 3 2

(11c)

where k1, k1, k2, and k3 are the potential independent rate
constants; is the overpotential; is the fractional surface
coverage of Hopd species; 1 and 2 are the transfer coecients.
r0 = i/F = (1 + 2)

(12a)

r1 = (q/F )(d /dt ) = (1 2 23)

(12b)

where r0 is the rate of electron consumption, r1 is the rate of

surface coverage, and q is the charge required for the formation
of a monolayer of Hopd. The expression for fractional surface
coverage at a steady state can be obtained by solving the
quadratic equation, from eq 11b, for
= [(k1 + k 1 + k 2 )
+

(k1 + k 1 + k 2 )2 + 8k1 + k 3 ]/4k 3

(13)

Upon linearizing eqs 12a and 12b; applying the phasors to

introduce the AC component and eliminating , one obtains
Yf = 1/Zf = A + B /(j + C)

(14)

where

A = F(r0/)

(14a)

B = (F 2/q)(r0/) (r1/)

(14b)

C = (F /q)(r1/)

(14c)

The expressions for the equivalent circuit elements from the

EIS experiments in relation to the HER can be obtained by
comparing eqs 14 with 9,54

R ct = 1/A

(15a)

R p = 1/((A2 C /B) + A)

(15B)

Cp = A2 /B

(15c)

The HER kinetics is usually described by four independent

kinetic parameters (k1, k1, k2, k3) and the fractional surface
coverage as described in eqs 11a11c and eq 13 respectively.
1, and 2 was assumed to be 0.5. However, EIS experiments
yield only 3 values for Rct, Rp, and Cp for eqs 15a15c. The

1 = k1(1 ) exp(1f) k 1 exp((1 1)f)

= k1 (1 ) k 1

2 = k 2 exp( 2f) = k 2

(11a)
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value for i0 obtained from LSV studies was used in the

expression for the average rate constant described in eq 16. The
solutions to the rate constants were obtained by maintaining
constant.
1

kav = 1/(k11 + k 21) = i0/2F = exp(f)/k1

+ k 2

(16)

The potential independent rate constants for the reactions

46 were estimated, by tting the circuit elements from
impedance measurements to eqs 15a15c, derived from the
impedance equation for the VHT mechanism. The Levenberg
Marquardt algorithm was used for the nonlinear tting with a
tolerance level of 1 1014. The estimated rate constants were
then used in the impedance eq 14 to re-evaluate the impedance
spectra in the interested frequency range. The surface coverage
was varied until the rate constants were able to closely predict
the impedance spectra. These potential independent rate
constants and surface coverage are reported in Table 5.
From Table 5, at an overpotential of 166 mV, the trends in
the average rate constants (kav) in the absence and presence of
1 M ammonia agreed with the results obtained using the LSV
studies. In addition, for all the noble metals the rate constant
for the Volmer or the water dissociation step (k1) is lower than
that of the desorption steps. However, the rate constant for the
water dissociation step (k1) for the Ni electrode is higher than
that of the desorption steps, as expected, thereby causing a low
surface coverage for the noble metal electrodes, and a higher
surface coverage for Ni as mentioned in Table 5. Among
desorption steps, the rate constant for the nonelectrochemical
Tafel step was higher than the electrochemical Heyrovsky step
for all the catalysts at 166 mV. In addition, Pt presents the
highest rate constant for the slow Volmer step, explaining its
superior activity.
The addition of ammonia results in a decrease in the average
rate constant (kav) for HER, which is observed for Pt, Ru, and
Ni (a schematic representation of the mechanism is provided in
Figure S5). Moreover, the presence of ammonia results in the
reduction of the rate constant k1 for the slow Volmer step for Pt
and Ru, accompanied by a drop in the rate constant for the
desorption steps thereby resulting in a lower Hopd surface
coverage. This is evident for Pt and Ru, which in turn cause a
decline in the average rate constant and activity for HER. On
the other hand, an increase in k1 was observed for Rh, which
explains the rise in the Hopd surface coverage and therefore the
increase in the average rate constant and activity for HER.
For Ni, although an increase in k1 and Hopd surface coverage
is observed with the addition of ammonia, this results in a
reduction in the rate of the slow rate-determining Tafel step.
This decrease in the rate constant of the rate determining Tafel
step explains the Hopd higher surface coverage and lower
activity toward HER for Ni.
3.4. Constant Potential Studies. Figure 6 shows the
current densitytime plots at a potential of 1.1 V versus Hg/
HgO for the CFP based Pt, Rh, Ru, and Ni electrocatalysts in 5
M KOH, in the presence and absence of ammonia. A high
surface area Ni gauze was used as the auxiliary in place of a Pt
foil counter to avoid the depletion of ammonia through electrooxidation. The current densities shown were evaluated based
on the EASA. All four catalysts present sucient stability at the
applied potential in the presence and absence of ammonia.
From Figure 6, Ni has the lowest cathodic current density
irrespective of the presence of ammonia. In addition, it is also
observed that Pt continued to display the highest current

Figure 6. Current density-time plot for constant potential studies for

Pt, Rh, Ru, and Ni in 5 M KOH in the presence and absence of
ammonia at 1.1 V versus Hg/HgO for a period of 3 h. It can be
observed that the addition of ammonia resulted in lower reduction
current densities for all materials except Rh. Rh also displayed the
most stable and highest activity toward HER in the presence of
ammonia.

density in the absence of ammonia despite losing 0.38 mA cm2

after 3 h, conrming to the LSV and EIS studies. Although, the
addition of ammonia resulted in a minimum current loss of 0.1
mA cm2 for Pt and Ru, the catalysts appear to be stable. On
the contrary, an increase in the current density with time is
observed for Rh. This performance is very similar to the
performance of a deactivated Rh electrode in 1 M KOH.82
Wrona et al. attribute this deactivation to traces of unknown
metal impurities on the electrode. The authors also reported
that the surface of Rh electrodes can be puried (remove
surface blockage species) during HER in alkaline media by
cycling the potential of the electrode between 1.0 and 0.3 V vs
a Hg/HgO reference electrode. On the contrary, an increase in
the current density with time is observed for the Rh electrode
in the presence of ammonia. This means that the presence of
ammonia in the electrolyte causes a self-purication of the
surface of the Rh electrode. It is hypothesized that the
deactivation of the surface of the Rh electrode is due to the
formation of a Hupd layer on Rh, which acts as a barrier to
HER. In addition, the higher HER current in the presence of
ammonia could be attributed to the weaker RhHupd bond
formation, evident from CV measurements (as seen in Figure
3B), which tends to easily break o from the surface thereby
creating fresh active sites for HER. The rather slow reactivation
could be due to the constant competition from Hupd formation
at 1.1 V, specic only to HER sites, resulting in a delay in
reaching the steady state. The studies conrm highest activity
toward HER on Rh in the presence of ammonia as expected
from the LSV and EIS results.

4. CONCLUSION
A study of the eect of ammonia on the HER on Pt, Rh, Ru,
and Ni electrodes was performed. The following conclusions
were made based on the results obtained:
1. The LSV, EIS, and chronoamperometric results for HER
in ammonia free alkaline solutions were similar to that
reported in the review on HER. The activity of the
catalysts for HER followed the order Pt > Ru > Rh > Ni.
2. The presence of ammonia results in a slight loss in the
HER activity for Pt, Ru, and Ni. However Rh displayed a
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higher activity toward HER in the presence of ammonia,

resulting in the trend in activity Rh > Pt > Ru > Ni.
3. EIS results conrm that the noble metal catalysts have a
slow water dissociation step and a fast recombination
step, while the vice versa was observed for Ni. The
addition of ammonia resulted in a decrease in the average
rate constant of the slow step for Pt, Ru, and Ni.
However, the opposite behavior was observed for Rh.
4. EIS results also indicate that the presence of ammonia
causes a decrease in the rate constant k1 of the ratedetermining Volmer step for Pt and Ru and k3 for Ni,
thereby explaining the decrease in their activity toward
HER. Whereas, the addition of ammonia results in the
increase in k1 substantiating the increase in Hopd surface
coverage and in-turn the HER activity on Rh.
5. The addition of ammonia resulted in the weakening of
the metal Hupd bond accompanied by a decrease in the
activity of the catalysts toward HER for Pt and Ru.
Thereby supporting the hypothesis that HER is more
active on the surface with hydrogen than the surface
containing the bare metal. On the other hand, an
increase in the activity toward HER was observed for Rh,
suggesting that the HER on Rh is higher on the bare
metal surface.
In conclusion, Rh oers the highest activity toward HER in
the presence of ammonia among the catalysts evaluated.
Further studies need to be performed to evaluate the eect of
ammonia on the activity of HER for bimetallic alloys.

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49.

ASSOCIATED CONTENT

S Supporting Information
*

A full description of the procedure used to determine the

electrodeposition potential, EASA, along with the estimation of
rate constant mechanism by evaluating the equivalent circuit
parameters to represent the impedance spectra for the HER in
the presence and absence of ammonia is given. The CVs used
to determine the electrodeposition potential and EASA, XRD
patterns for the synthesized electrocatalysts, and owchart used
for estimating the rate constants are provided. Finally, a cartoon
depicting the proposed mechanism of HER in the presence and
absence of ammonia on Pt, Ru, and Ni is given. This
information is available free of charge via the Internet at
http://pubs.acs.org.

REFERENCES

AUTHOR INFORMATION

Corresponding Author

*Tel.: +1 740 593 9670; fax: +1 740 593 0873. E-mail address:
botte@ohio.edu.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
The authors would like to acknowledge the nancial support of
the Center for Electrochemical Engineering Research (CEER)
at Ohio University and the Department of Defense through the
U.S. Army Construction Engineering Research Laboratory
(W9132T-09-10001). The content of the information does not
reect the position or the policy of the U.S. government. XRD
measurements were performed at CEER. The authors would
also like to thank Dr. Howard Dewald and Dr. Madhivanan
Muthuvel for their feedback and valuable discussions.

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