Electrochemistry Communications 82 (2017) 61–65

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Electrochemistry Communications
journal homepage: www.elsevier.com/locate/elecom

Electrochemical synthesis of Au-Ni(OH)2-nanocomposite on glassy carbon MARK

electrode as highly active bifunctional electrocatalyst for oxygen evolution
and oxygen reduction reactions
Pandiyaraj Kanagavalli, Rajagopal Sudha, Sidhureddy Boopathi, Shanmugam Senthil Kumar⁎
Electrodics and Electrocatalysis Division, CSIR - Central Electrochemical Research Institute, Karaikudi, India

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

Keywords: In this work, we demonstrated an electrochemical method to prepare Au-Ni(OH)2-nanocomposite on a glassy

Au-NiHCF carbon substrate (Au-Ni(OH)2-NC/GCE). This modified nanocomposite showed high electrocatalytic activity
Au-Ni(OH)2 towards oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) compared to similarly prepared
Nanocomposite Au free Ni(OH)2-NC/GCE. The above nanocomposite was prepared through two step processes; first gold‑nickel
Oxygen evolution reaction
hexacyanoferrate nanocomposite film on GCE (Au-NiHCF-NC/GCE) was synthesized by single step electro-
Oxygen reduction reaction
chemical cycling approach. Later, the Au-NiHCF-NC/GCE was treated electrochemically in alkaline solution to
Bifunctional electrode
produce Au-Ni(OH)2-NC/GCE. The as-formed Au-Ni(OH)2-NC/GCE was used as a bifunctional electrode to study
the OER and ORR in alkaline solution. The resulting nanocomposite exhibits high electrocatalytic activity and
fast electron transfer kinetics due to the synergic effect of the formation of more active β-Ni(OH)2 phase and Au
nanoparticles (AuNPs) during the electrochemical cycling process.

1. Introduction activity of non-noble metal hydroxide could be improved by doping or

Ni(OH)2 has been considered as important hydrous metal oxides
among the other transition metal hydroxides due to its diverse applic-
ability in the electrochromic device, batteries, electrocatalysis, elec-
trochemical sensors etc. [1–5]. In specific, Ni based metal oxides are
critical towards water splitting reaction because of its catalytic activity
and high stability in severe alkaline conditions [6–7]. In general, phy-
sicochemical and electrochemical properties of Ni(OH)2 towards
oxygen evolution reactions (OER) depends highly on its surface mor-
phology, synthetic methodology and activation procedure [7–9]. OER is
the sluggish reaction in water electrolysis, and the use of tailor made
anode electrocatalyst with high electrocatalytic activity are imperative
for the growth of green technologies [7,9–11]. Significant research ef-
fort has been made in the development of Ni based anode materials
[12–14]; however, reducing the large over potential and preparing a
more active form of β-Ni(OH)2 for OER still remains a challenge.
Electrochemical surface derivatization of Ni(OH)2 from the mixed
valence‑nickel hexacyanoferrate is a facile, binder free and two-step
electrochemical approach [15]. In this process, a cyano complex of
metal hexacyanoferrate leach out from the electrode and leads to the
formation of metal hydroxide on electrode surface during electro-
chemical cycling in alkaline solution. In general, electrochemical
aging process [12,13,16–18]. Yeo et al. reported that few monolayer
thick β-Ni(OH)2 formed on the gold substrate could enhance the elec-
trocatalytic activity of OER [8]. Hence, a facile synthetic methodology
for the preparation of AuNPs incorporated Ni(OH)2 is highly desirable
for OER applications, rather than using a bulk gold electrode as a
substrate and controlling the thickness of Ni(OH)2 over the substrate. In
the present study, Au-Ni(OH)2-NC/GCE is directly derived from Au-
NiHCF-NC/GC for the first time using electrochemical approach. The
fabricated Au-Ni(OH)2-NC/GCE is utilized for OER and ORR and the
results are compared with Au free Ni(OH)2-NC/GCE.
2. Experimental procedure
The following chemicals were purchased from Merck and Alfa Asear
and used as received without further purifications. Analytical grade
NiCl2, K3[Fe(CN)6], KNO3 and KOH were purchased from Merck and
HAuCl4 was purchased from Alfa Asear. Aqueous solutions of the re-
agents were prepared using water (18.2 MΩ·cm) from Milli-Q water
purification system.
All the electrochemical experiments were carried out using BASi
potentiostat. For voltammetric studies, two types of glassy carbon
working electrodes (BASi GCE area-0.07 cm2 & Pine instruments

⁎
Corresponding author.
E-mail addresses: ssenthilmugam@gmail.com, ssenthilkumar@cecri.res.in (S.S. Kumar).

http://dx.doi.org/10.1016/j.elecom.2017.07.024
Received 26 May 2017; Received in revised form 19 July 2017; Accepted 26 July 2017
Available online 27 July 2017
1388-2481/ © 2017 Elsevier B.V. All rights reserved.
P. Kanagavalli et al. Electrochemistry Communications 82 (2017) 61–65

rotating disk electrode (RDE)-0.2472 cm2), a platinum foil counter
electrode and an Ag/AgCl-(3 M NaCl) reference electrode were used. In
the present study, all the measured potentials were converted to re-
versible hydrogen electrodes using the following equation.
ERHE = EAg AgCl + 0.059(pH ) + 0.197
Before starting any electrochemical experiments, the glassy carbon
electrode (working electrode) was well polished with alumina slurry
followed by sonication for 5 min towards the pre-cleaning process.
Aqueous solutions of the reagents were taken in the appropriate
ratio to electrodeposit Au-NiHCF nanocomposite film on GCE. The de-
position of Au-NiHCF nanocomposite is carried out using 0.25 mM
NiCl2 + 0.25 mM K3[Fe(CN)6] + 0.1 mM HAuCl4. The concentration
of the supporting electrolyte is fixed at 0.1 M KNO3. Under these op-
timum conditions, only more NiHCF grows on GCE and further yields
maximum redox current charge corresponding to Ni(OH)2. The elec-
trochemical cycling experiments were carried out for 10 cycles in the
potential ranging from 1.617 to 0.617 V with the scan rate of 0.1 V s− 1.
The as prepared nanocomposite was then washed with Milli-Q water.
The control system NiHCF on GCE was prepared in the same manner
without the use of HAuCl4. Both the control NiHCF/GCE and Au-
NiHCF/GCE nanocomposites were cycled in 0.1 M KOH solution
(25 cycles) in the potential window of 0.477 to 1.577 V with the scan
rate of 0.1 V s− 1 leading to the formation of Ni(OH)2/GCE and Au-Ni
(OH)2-NC/GCE respectively.
These Ni(OH)2/GCE and Au-Ni(OH)2-NC/GCE were utilized for OER
and ORR using cyclic voltammetry (CV) and rotating disk electrode
(RDE) experiments. The number of electrons involved during ORR was
calculated using the Koutecky-Levich (K-L) eq. [19].
1 1 1 1 1 electrolyte. Fig. 1C shows the comparison of typical cyclic voltammetric
= + = + redox responses of NiHCF/GCE and its analogs Au-NiHCF-NC/GCE in
i ik il ik Bω1 2
where, ik and il are the kinetic and limiting current density respectively;
B is the Levich constant and is given by
B = 0.2nFD 2 3ϑ−1 6Co
where, n is the number of electrons, F is the Faraday constant
(96,487 C mol− 1), D is the diffusion coefficient of oxygen
(1.75 × 10− 5 cm2 s− 1), ϑ is the kinematic viscosity of the water
(0.01 cm2 s− 1), and Co is the dissolved oxygen concentration
(1.14 ×10− 6 mol cm− 3).
3. Results and discussions
Fig. 1A & B shows the typical formation of the electrochemically
deposited NiHCF/GCE and its hybrid Au-NiHCF-NC/GCE. A sharp peak
at 1.27 V and a shoulder peak ~ at 1.087 V increases with increasing
number of cycles, indicating the formation of two different stoichio-
metric NiHCF on GCE as follows [20].
K2NiII [FeII (CN)6] ⇋ KNiII [FeIII (CN)6] + K+ + e− (1)
II II
K Ni1.5 [FeII (CN)6] ⇋ Ni1.5 [FeIII (CN)]6 + K+ + e− (2)
In contrast, during the formation of Au-NiHCF/GCE, the deposition
ratio of the above two stoichiomers differs compared to pure NiHCF
deposition, as shown in the Fig. 1B. During the electrochemical cycling,
Au3 + ions are reduced to Au0 and are deposited on GCE while two
different stoichiometric of NiHCF also deposited at the same time.
Though the deposition of NiHCF on GCE is independent under the
present experimental condition, the simultaneous depositions of Au
nuclei serve as an active site for the formation of Prussian blue (PB).
The PB is formed as the result of decomposition of the ferricyanide
during electrochemical cycling hence, may influence the reaction ki-
netics of the formation of NiHCF film on GCE [19]. However, the sta-
bility of the Au-PB nanocomposite film depends on the pH, the con-
centrations of K3[Fe(CN)6] and HAuCl4 in the potassium salt
0.1 M KNO3. The redox peaks at 1.017 V and 1.217 V corresponds to
two different stoichiometric of NiHCF as explained in Eqs. (1) and (2)
respectively. Fig. 1C, shows typical cyclic voltammetric behavior cor-
responding to the formation of pure NiHCF. However, the ratio of two
different stoichiometric of NiHCF was varied in pure and hybrid films
due to the presence of AuNPs.

A B
Fig. 1. Nanocomposites formation on GCE by cyclic vol-
0.3
tammetric (CV) experiments using A) 0.25 mM
0.2 NiCl2 + 0.25 mM K3[Fe(CN)6] B) 0.25 mM
0.2
NiCl2 + 0.25 mM K3[Fe(CN)6] + 0.1 mM HAuCl4 - con-
−1
0.1 taining 0.1 M KNO3 at scan rate of 0.1 V s for 10 cycles.
0.1
j/ mA cm -2

C) Typical redox responses of the NiHCF/GCE and Au-

j/mA cm -2

NiHCF-NC/GCE in 0.1 M KNO3 solution at the scan rate of

0.0 0.0 0.1 V s− 1. D) CV responses of the Ni(OH)2/GCE and Au-Ni
(OH)2-NC/GCE solution in 0.1 M KOH at the scan rate of
-0.1 0.1 V s− 1.
-0.1

-0.2
-0.2
-0.3
0.6 0.8 1.0 1.2 1.4 1.6 0.6 0.8 1.0 1.2 1.4 1.6

E/V vs. RHE E/V vs. RHE

C 0.3 D 3 Ni(OH)2
NiHCF
Au-Ni(OH)2
Au-NiHCF
0.2
2
j/mA cm -2

j/mA cm -2

0.1

0.0 1

-0.1
0
-0.2

-0.3 -1
0.6 0.8 1.0 1.2 1.4 1.6 0.6 0.8 1.0 1.2 1.4 1.6

E/V vs. RHE E/V vs. RHE

62
P. Kanagavalli et al. Electrochemistry Communications 82 (2017) 61–65

A A’

B B’

C 0
Au -4f7/2
0
Au -4f5/2 D 2+
Ni -2p3/2 2+
Ni -2p1/2
Ni(OH) 2

Ni(OH)2 854.4 eV satellite satellite

Intensity (a.u.,)

Intensity (a.u.,)

853.9 eV

Au-Ni(OH)2

Au-Ni(OH) 2

80 85 90 95 845 850 855 860 865 870 875 880 885

Binding energy/eV Binding energy/eV
Fig. 2. FE-SEM images of (A) NiHCF/GCE and (B) Au-NiHCF-NC/GCE and its corresponding (A’) Ni(OH)2/GC and (B’) Au-Ni(OH)2-NC/GCE. (C) XPS spectra of Au-4f and (D) Ni-2p.

In order to fabricate Ni(OH)2/GCE and Au-Ni(OH)2-NC/GCE, the
NiHCF and Au-NiHCF-NC deposited GCE were electrochemically cycled
continuously in a 0.1 M KOH solution in the potential range between
0.477 and 1.577 V at the scan rate of 0.1 V s− 1 for 25 cycles. Since the
redox characteristics of Prussian blue analogs are not stable in alkaline
solutions, the electrodes undergo profound chemical change leading to
the formation of an insoluble form of metal hydroxides [20,21]. After
the electrochemical cycling, CV was recorded in the fresh 0.1 M KOH
solution. From Fig. 1D it is evident that the bare Ni(OH)2/GCE showed
the typical characteristic redox response corresponding to the forma-
tion of intermediate NiOOH/Ni(OH)2 at 1.467 V/1.407 V. In the case of
Au-Ni(OH)2-NC/GCE the redox behavior corresponding to the forma-
tion of NiOOH/Ni(OH)2 is observed at 1.487 V/1.407 V. The positive
shift in anodic peak (0.02 V) is attributed to the β-Ni(OH)2 formation in
the hybrid Au-Ni(OH)2. Interestingly, during the formation of Au-Ni
(OH)2-NC/GCE the OER current density was observed at ~2.5 mA/cm2
whereas no OER current density was observed in the case of Au free Ni
(OH)2-NC/GCE. In general, the electrochemical formation of Ni(OH)2
often leads to α & γ-Ni(OH)2 [14,22,23] is known to be a poor elec-
trocatalyst for OER. After continuous electrochemical aging for several
hours, the α & γ-Ni(OH)2 convert to more active β & γ-Ni(OH)2. In
contrast, electrochemical cycling of Au-NiHCF-NC/GCE in alkaline so-
lution clearly confirms the formation of more active OER catalyst i.e. β-
Ni(OH)2. Au nanoparticles assist the formation of β-Ni(OH)2 rather than
α & γ-Ni(OH)2.
The morphology of the hexacyanoferrate modified electrodes was
characterized using FESEM both before and after electrochemical cy-
cling in 0.1 M KOH solution. The FESEM micrographs of Au-NiHCF,
NiHCF, Au-Ni(OH)2 and Ni(OH)2 is shown in Fig. 2. From Fig. 2A it is
evident that the NiHCF shows a spongy nanoporous type morphology
while the corresponding Ni(OH)2 on GC shows similar (spongy nano-
porous) morphology with more aggregation, Fig. 2A′. This is because of
the electrochemical cycling in alkali solution ruptures the cyanide
bridging between Ni and Fe in the complex leading to the formation of
Ni(OH)2 aggregate on GCE. In the case of Au-NiHCF, spongy kind of
nanoporous structure along with uniformly distributed gold nano-
particles (AuNPs) of size ~10 nm was observed as shown in Fig. 2B.
This reveals that the nucleation of gold and NiHCF particles occurs si-
multaneously during electrochemical cycling. Later, the electro-
chemical treatment of Au-NiHCF in 0.1 M KOH leads to formation of

63
P. Kanagavalli et al. Electrochemistry Communications 82 (2017) 61–65

A 14 0.2
Ni(OH)2 B 1.66 Ni(OH)2
Fig. 3. (A) CVs response of Ni(OH)2/GCE and Au-Ni(OH)2-
NC/GCE recorded in 0.1 M KOH solutions with the scan
Au-Ni(OH)2
12 0.0 Au-Ni(OH)2 1.64 rate of 0.01 V s− 1. The inset shows the enlarged CVs. (B)
j/mA cm -2

-0.2 Tafel plot of Ni(OH)2-NC/GCE (red line) and Au-Ni(OH)2-

10 1.585 V
1.62
j/mA cm -2

NC/GCE (blue line) for the OER. (C) RDE voltammograms

E/V vs. RHE

-0.4
8 1.60 (LSV) of Au-Ni(OH)2-NC/GCE in O2 saturated 0.1 M KOH at
6 -0.6 various rotation speeds at the scan rate of 0.005 V s− 1 (D)
0.5 0.6 0.7 0.8 0.9 1.0
1.58 K-L plots of Au-Ni(OH)2-NC/GCE at different potentials
E/V vs. RHE
4 derived from RDE measurements. (For interpretation of the
1.56
2 references to colour in this figure legend, the reader is re-
1.54 ferred to the web version of this article.)
0
1.52
-2
0.6 0.8 1.0 1.2 1.4 1.6 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6
E/V vs. RHE Log(j, mA cm-2)
C 0.0 D
1.25
0.55 V
0.50 V
-0.8 1.00 0.45 V
0.40 V
-1.6 0.35 V
1/(j, mA cm -2)
j/mA cm 2

0.75
-

-2.4

-3.2 100 rpm 0.50

400 rpm
-4.0 900 rpm
1600 rpm 0.25
-4.9 2500 rpm

0.00
0.0 0.2 0.4 0.6 0.8 1.0 0.02 0.04 0.06 0.08 0.10
E/V vs. RHE 1/(ω , rpm)1/2

Au-Ni(OH)2 which has an aggregated spongy nonporous structure with transfer mechanism is followed in the OER. Interestingly, during ne-
10 nm AuNPs, Fig. 2B’. It is worthy to observe that the particle size of gative direction of CV after the OER, the appreciable oxygen reduction
the AuNPs did not change even after electrochemical cycling in 0.1 M reaction (ORR) also occurred without purging the oxygen gas in an
KOH solution and it is distributed uniformly over the entire electrode alkaline electrolyte solution; especially on the Au-Ni(OH)2 (see inset
surface. Further, the presence of Au is confirmed by the high-resolution Fig. 3A). The onset potential for ORR on Au-Ni(OH)2 and Ni(OH)2 was
XPS spectra Fig. 2C with a peak corresponding to Au-4f (where Au in measured to be 0.907 V and 0.706 V, respectively. These results clearly
zero oxidation state) in Au-Ni(OH)2-NC film. In contrast to Ni(OH)2, confirms the presence of gold particles in the nanocomposite of Au-Ni
lower binding energy shift (~ 0.5 eV) was observed for the Ni in Au-Ni (OH)2 play a significant role in enhancing both the OER and ORR
(OH)2 corresponding to Ni(II)-2p (Fig. 2D). This shift in binding energy compared to Ni(OH)2 alone.
confirms the existence of an electronic interaction between Au and Ni Furthermore, as shown in fig. 3C, the ORR current response in-
and further proves formation the nanocomposite film. Also, a trace of creases with the increasing rate of rotation of the electrode. From the
Fe(II)-2p peaks is seen in both Ni(OH)2 and Au-Ni(OH)2-NC films which KL plot (Fig. 3D), the number of electrons involved during ORR was
confirms the presence of Fe(II) underneath the nickel oxyhydroxide film calculated to be ~4.00 indicating that Au-Ni(OH)2-NC could be a
(data not shown). In addition, the Energy Dispersive X-Ray (EDX) promising electrocatalyst for the ORR. As we discussed earlier the
analysis was carried out to find the composition of Au-Ni(OH)2/GCE AuNPs in Au-Ni(OH)2-NC may assist the formation of more active β-Ni
From EDX analysis the atomic ratio of Au and Ni was estimated to be (OH)2 and could enhance the electrocatalytic activity towards ORR and
1:3 (Au: Ni) in the electrochemically fabricated Au-Ni(OH)2-NC/GCE. OER compared to Au-free Ni(OH)2.
In order to study the bifunctional electrocatalytic activity of Ni
(OH)2/GCE and Au-Ni(OH)2-NC/GCE for OER and ORR, the cyclic
voltammetry (CV) experiments were performed in 0.1 M KOH solution 4. Conclusions
in the potential range between 0.477 and 1.677 V at the scan rate of
0.01 Vs− 1. Fig. 3 depicted the comparative cyclic voltammograms of Ni In this work, the fundamental insights in electrodeposition of Au-
(OH)2/GCE and Au-Ni(OH)2-NC/GCE. During the anodic sweep, OER NiHCF-NC/GCE and its corresponding Au-Ni(OH)2-NC/GCE is in-
starts at the potential of 1.589 V on Ni(OH)2/GCE and 1.527 V on Au-Ni vestigated in detail. The observed redox behaviors of the Au-NiHCF-
(OH)2-NC/GCE electrodes respectively. In addition, Au incorporated Ni NC/GCE revealed that the AuNPs and NiHCF films are grown simulta-
(OH)2 achieved benchmark OER current density of 10 mA cm− 2 at neously on GCE and the presence of AuNPs controls the film growth.
1.585 V (overpotential = 0.355 V). The obtained results clearly in- The morphological studies using FESEM confirm the spongy porous
dicate that the Au-Ni(OH)2-NC/GCE showed high electrocatalytic ac- nature of the nanocomposites. In contrast to classical Ni(OH)2/GCE
tivity for OER compared to Au free Ni(OH)2/GCE. It is known from the formation from NiHCF where no active OER phase is present, the
literature that the incorporation of Fe species in Ni oxyhydroxide films AuNPs in Au-NiHCF-NC/GCE helps formation of more active OER phase
promotes more OER activity. In the present case both the Ni(OH)2 and [β-Ni(OH)2] during the electrochemical cycling in alkaline solutions.
Au-Ni(OH)2-NC contains a trace amount of Fe(II) as evident from XPS The formed Au-Ni(OH)2-NC/GCE exhibited lower overpotential and
analysis, however, it is not influencing the electrocatalytic activity to- higher current density for both the OER and ORR when compared with
wards OER. The detailed kinetic analysis of OER was investigated by Ni(OH)2/GCE. The current simple two steps electrochemical metho-
Tafel plot (E vs log (j)) method. Based on the Tafel plots (Fig. 3B), the dology can be extended to prepare other noble metals mixed transition
slopes were calculated to be 0.76 and 0.56 V dec− 1 for Ni(OH)2/GCE metal oxyhydroxides nanocomposite films which may be useful for
and Au-Ni(OH)2, respectively. The lower Tafel slope of 0.56 V dec− 1 energy efficient electrochemical reactions.
suggests a fast electron transfer kinetics and a reversible one-electron

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P. Kanagavalli et al.
Acknowledgements
S.S·K thanks to the CSIR-MULTIFUN (CSC-0101) and Department of
Science and Technology (SB/EMEQ-212/2013) for their financial sup-
port.
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