AuNi en grafeno

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 5
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AueNi alloy nanoparticles supported on reduced

graphene oxide as highly efficient electrocatalysts
for hydrogen evolution and oxygen reduction
reactions
Gitashree Darabdhara a,b, Manash R. Das a,b,*, Mohammed A. Amin c,d,**,

Gaber A.M. Mersal c,e, Nasser Y. Mostafa c,f, Sayed S. Abd El-Rehim d,
Sabine Szunerits g, Rabah Boukherroub g,***
a
Advanced Materials Group, Materials Sciences and Technology Division, CSIR-North East Institute of Science and
Technology, Jorhat 785006, Assam, India
b
Academy of Scientific and Innovative Research, CSIR-NEIST Campus, India
c
Materials Science and Engineering Group, Department of Chemistry, Faculty of Science, Taif University, 888
Hawiya, Saudi Arabia
d
Department of Chemistry, Faculty of Science, Ain Shams University, Abbassia 11566, Cairo, Egypt
e
Department of Chemistry, Faculty of Science, South Valley University, Qena, Egypt
f
Chemistry Department, Faculty of Science, Suez Canal University, Ismailia, Egypt
g
Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 - IEMN, Lille F-59000, France
article info abstract
Article history: Bimetallic nanoparticles of Au and Ni in the form of alloy nanostructures with varying Ni
Received 11 September 2017 content are synthesized on reduced graphene oxide (rGO) sheets via a simple solution
Received in revised form chemistry route and tested as electrocatalysts towards the hydrogen evolution (HE) and
21 October 2017 oxygen reduction (OR) reactions using polarization and impedance studies. The AueNi
Accepted 6 November 2017 alloy NPs/rGO nanocomposites display excellent electrocatalytic activity which is found to
Available online xxx improve with increasing Ni content in the AueNi/rGO alloy nanocomposites. For HER, the
best AueNi alloy NPs/rGO electrocatalyst, the one with the highest Ni content, exhibits
Keywords: high activity with an onset overpotential approaching zero versus the reversible hydrogen
Electrocatalysis electrode and an overpotential of only 37 mV at 10 mA cm2. Additionally, a low Tafel slope
Aue Ni alloy nanoparticles of 33 mV dec1 and a high exchange current density of 0.6 mA cm2 are measured which
Reduced graphene oxide are very close to those of commercial Pt/C catalyst. Also, in the ORR tests, this electro-
Hydrogen evolution reaction catalyst displays comparable activity to Pt/C. The KouteckyeLevich plots referred to a 4-
Oxygen reduction reaction electron mechanism for the reduction of dissolved O2 on the AueNi alloy NPs/rGO cata-
High stability lyst. The electrocatalyst thus demonstrates excellent activity towards HER and ORR.
* Corresponding author. Advanced Materials Group, Materials Sciences and Technology Division, CSIR-North East Institute of Science
and Technology, Jorhat 785006, Assam, India.
** Corresponding author. Materials Science and Engineering Group, Department of Chemistry, Faculty of Science, Taif University, 888
Hawiya, Saudi Arabia.
*** Corresponding author.
E-mail addresses: mnshrdas@yahoo.com, mrdas@neist.res.in (M.R. Das), maaismail@yahoo.com (M.A. Amin), rabah.boukherroub@
iemn.univ-lille1.fr (R. Boukherroub).
https://doi.org/10.1016/j.ijhydene.2017.11.048
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article in press as: Darabdhara G, et al., AueNi alloy nanoparticles supported on reduced graphene oxide as highly
efficient electrocatalysts for hydrogen evolution and oxygen reduction reactions, International Journal of Hydrogen Energy (2017),
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 5
Additionally, it exhibits outstanding operational durability and activation after 10,000th

cycles assuring its practical applicability.
© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
metal in ORR have led to the use of Au NPs supported on

Introduction reduced graphene oxide [16], Pd NPs on different supports such
as Pd/Vulcan [17], Pd on multi-walled carbon nanotubes [18], Pd
Nourishing the ever increasing needs of the rapidly growing on nitrogen-doped graphene [19], alloyed Pd-Ag [20], polymer
and developing modern society has created enormous de- based hybrid catalyst with low Pt content [21], etc.
mand for clean, renewable, environmentally friendly and Efforts to circumvent the use of precious noble metals have
affordable energy sources. In this context, exploitation of led to an extensive research for alternate non-noble (Fe, Co,
hydrogen (H2) as a potential energy carrier, possessing the Ni, Mo) and metal-free (carbon based) electrocatalysts
capability of replacing fossil fuels, has been a very attractive [22e24]]. Other non-noble electrocatalysts include transition
approach, primarily due to its large combustion heat (287 kJ/ metal chalcogenides [25], carbides [26], metal alloys [27] and
mol) and liberation of green by-product water [1]. A large complexes [28]. Consisting of two elements, bimetallic NPs in
fraction of hydrogen is generated from fossil resources via a either alloys or core-shell nanostructures have gained
steam reforming process that results in the production of H2 immense interest as effective HER and ORR electrocatalysts as
along with CO2, the latter is considered as a potential candi- well as in different energy storage applications [29e32]. This is
date for environmental global warming [2]. Thus, sustainable mainly due to their enhanced and tuneable chemical and
hydrogen generation via water electrolysis has proved to be physical properties along with cooperative interactions which
one of the simplest, clean, renewable and large scale indus- contribute to their superior catalytic properties in comparison
trial methods [3]. Consisting of two half-cell reactions: to their monometallic counterparts [6]. Alloying two different
hydrogen evolution reaction occurring at the cathode (HER i.e. metals allows to increase the specific surface sites and also to
4Hþ þ 4e / 2H2) and oxygen evolution reaction occurring at decrease the amount of catalyst loading, leading to enhanced
the anode (OER i.e. 2H2O / O2 þ 4Hþ þ 4e), electrochemical HER and ORR [33]. Amongst bimetallic alloys, AuePd acts as an
water splitting demands advanced electrocatalysts that can ideal electrocatalyst towards HER [34,35]. Alloy nano-
reduce the overpotential and significantly improve the effi- structures based on Cu-Pt [36], Au-Pt [37] etc. exhibit excellent
cacy of the reaction [4]. Electrocatalysts for HER are classified HER activity. Core-shell nanostructures also possess the ca-
as homogeneous and heterogeneous on the basis of the phase pacity of replacing Pt in several HER reactions. For instance,
of reactants and the products. Widely used homogeneous HER Au@Pt [38], Cu@Pd/Ti [39], Au@Pd [40], Au@CdS coreeshell
catalysts include enzymes such as hydrogenases [5]. HER nanostructures [41] etc. have shown excellent performances.
electrocatalysts are generally solids and their performance Because of the high abundance, catalytic nature and low
mainly depends on their surface properties [6]. The ease of cost, Ni is chosen as a good candidate from the non-noble
separation makes the heterogeneous HER electrocatalysts elements for HER as well as ORR. However, the relatively
attractive candidates. high affinity of Ni for hydrogen attributes to the difficulty in
Because of its non-zero overpotential, Pt (Pt/C) is in depth hydrogen desorption. Additionally, Ni is prone to corrosion in
explored for both HER and ORR, even though Pt is restricted for acidic media upon continuous electrolysis [42]. Thus, far-
commercial applications because of its rare and expensive reaching efforts have been dedicated towards alloying Ni
nature [7]. The reaction rate at the cathode for HER using Pt with other elements for constructing active and durable
catalyst is extremely fast whereas the anodic reaction is slug- electrocatalysts. A large number of Ni-based alloys like Ni-Sn
gish and necessitates higher Pt loading. It is hence extremely [43], Ni-Mo [44], Ni-Fe [45], Ni-Se [46], etc. have been identified
important and challenging to design highly operative, cost in electrochemical conversion of H2O to H2. Alloyed Ni-Mo
effective and stable electrocatalysts for HER and ORR. [47], CoNi/ultrathin graphene layer [48] and core shell IrNi-
To tackle this problem, researchers have developed engi- nitride NPs [49], Pt@Ni3/C [50], Ni@Pd-polyethyleneimine-rGO
neered nanostructures of different Pt group metals (Ru, Rh, Ir, [51], etc. acted as active Ni containing bimetallics towards
Pd) possessing high surface to volume ratio for achieving high effective HER.
electrochemical performances [8]. Monolayer Pt supported on Another major influencing factor in electrocatalytic effi-
bulk tungsten carbide (WC) [9], Pt nanoparticles (NPs) supported ciency remains the conducting property of the electrocatalyst.
on TiO2, nitrogen-doped reduced graphene oxide (rGO) based A large number of carbon-based materials like carbon black,
PteTiO2 nanostructures [10], monolayer Pd and Au supported carbon nanotubes, or graphene supports for the synthesis of
on Mo2C [11] etc. were used as HER electrocatalysts exhibiting NPs as well as improving electrocatalytic activity have
excellent activity. Nanoscale Au-based nanocomposites such aroused [4]. Among them, the 2D wonder material “graphene”
as graphene quantum dots/Au hybrid NPs [12], Au/carbon has received widespread attention. Graphene oxide (GO) and
nanotubes, Au/graphene nanocomposites [13], Au NPs sup- rGO have emerged as excellent supports for NPs' synthesis,
ported on multi-walled carbon nanotubes [14], Au NPs sup- yielding nanocomposites with high potential for a myriad of
ported on rGO [15] etc. have also been explored as effective HER applications [52]. Theoretically, interaction between metal
electrocatalysts. Similarly, efforts to avoid the use of precious Pt and graphene leads to changes in the Fermi level of both
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 5 3
materials, leading to their enriched catalytic activity [53]. solid black catalyst. Basic medium (i.e. in presence of NaOH) is
Thus, designing GO- and rGO-based materials with excellent favorable for easy decomposition of the reducing species
catalytic applications is of great interest. N2H4: N2H4 þ 4OH ¼ N2 þ 4H2O þ 4e. These electrons
Taking into account the importance of graphene-based participate in the reduction of the metal salts to their corre-
bimetallic NPs as well as activity of both individual Au and sponding nanoparticles during the synthesis.
Ni for HER and ORR, we attempted to combine Au and Ni of Monometallic Au/rGO and Ni/rGO were prepared adopting
different Au/Ni ratios on rGO to form AueNi alloy NPs/rGO similar procedure by mixing GO suspension with either
nanocomposites using an easy and a simple solution chem- aqueous HAuCl4 or NiCl2 solution. All other reaction condi-
istry reduction method. The nanocomposites have been tions were kept similar to that required for the synthesis of
characterized by high resolution transmission electron mi- bimetallic AuNi/rGO nanocomposites.
croscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelec-
tron spectroscopy (XPS), thermal gravimetric analysis (TGA), Characterization
and diffuse reflectance infrared Fourier transform (DRIFT)
spectroscopy. The developed nanocomposite materials have The X-ray diffraction (XRD) patterns were obtained using a
been investigated for the first time as electrocatalysts towards Rigaku X-ray diffractometer (model: ULTIMA IV, Rigaku,
HER and ORR, employing various electrochemical techniques. Japan) at a scanning rate of 3 /min. The instrument uses Cu Ka
The best AueNi alloy NPs/rGO catalyst exhibited high HER (l ¼ 1.54056 A) as the X-ray source and operates at a generator
activity with an onset overpotential approaching zero versus voltage of 40 kV and a generator current of 40 mA. All the XRD
the reversible hydrogen electrode (RHE) and an overpotential patterns were recorded in the 2q value ranging from 5 to 80 .
of only 37 mV at 10 mA cm2. Additionally, a low Tafel slope of The shape, size, morphology and the crystal structure of the
33 mV dec1 and a high exchange current density of nanocomposites were determined using transmission electron
0.6 mA cm2 were recorded. These electrochemical HER pa- microscope (TEM) and high-resolution TEM (HRTEM), model-
rameters are very close to those of commercial Pt/C catalyst JEOL JEM 2100, Japan, operating at an accelerating voltage of
with outstanding operational durability and activation after 200 kV. For recording the TEM micrographs, standard carbon-
10,000th cycles. Also, in the ORR tests, this catalyst exhibited coated copper grids were used onto which dispersed colloidal
comparable activity to Pt/C with a 4-electron mechanism for solutions of the prepared nanocomposites in water were
the reduction of dissolved O2. dropped, followed by air drying at room temperature.
X-ray photoelectron spectroscopy (XPS) measurements
were carried out using an ESCALAB 220 XL spectrometer
Experimental having a monochromatic Al Ka X-ray source (1486.6 eV) and a
spherical energy analyzer that operates in the CAE (constant
Chemicals and reagents analyzer energy) mode using the electromagnetic lens mode.
The CAE for survey spectra is 100 eV and that for high-
Graphite powder (<20 mm, Sigma-Aldrich), sulfuric acid resolution spectra is 40 eV. The angle between the incident
(Qualigens), hydrochloric acid (Qualigens), hydrogen peroxide X-rays and the analyzer is 58 . The detection angle of the
(Qualigens), potassium permanganate (Merck), gold (III) chlo- photoelectrons is 30 .
ride trihydrate (>99.9%, Sigma Aldrich), nickel (II) chloride Thermal analysis (TGA) of the nanocomposite samples was
(>99.9%, Alfa Aesar), hydrazine hydrate (Sigma Aldrich), and carried out using a Thermal Analyzer (Model: Netzsch STA
sodium hydroxide (Qualigens) were used as received. 449F3). For TGA analyses, approximately 10 mg of each sample
were taken in the crucible and heated from 20 to 1000 C at a
Preparation of electrocatalysts heating rate of 10 C/min in a nitrogen environment.
Diffuse reflectance infrared Fourier transform (DRIFT)
GO was synthesized by the Hummers and Offeman method in spectra were recorded in transmittance mode at 4 cm1
which graphite powder (2 g) was oxidized in the presence of spectral resolution in the 400e4000 cm1 range using an IR
KMnO4 (6 g) and H2SO4 (46 mL) followed by exfoliation under Affinity-1 FTIR spectrophotometer (Shimadzu, Japan) fur-
high power ultrasonication (using SONICS Vibra cell ultra- nished with a DRS-8000 DRIFT accessory.
sonicator operating at a frequency of 20 KHz ± 50 Hz) for 1 h to Specific surface area of the samples was recorded at 77 K
obtain a homogeneous GO suspension [54]. A GO suspension via nitrogen gas adsorption by applying Brunauer
(10 mg/mL) was used to synthesize rGO modified with AueNi EmmettTeller (BET) calculations and using an Autosorb-
alloy NPs, yielding AueNi alloy NPs/rGO composites. The iQ Station 1 (Quantachrome, USA). The samples were previ-
nanocomposites were synthesized using different concen- ously degassed at 200 C for 3 h before performing the
trations of Ni. Typically, to an aqueous solution of 3, 5 or experiment.
10 mM NiCl2, HAuCl4 solution (3 mM) was added and allowed The metal content and the atomic ratio of Au:Ni was
to stir for 20 min followed by the addition of 15 mL of GO so- calculated using a flame Atomic Absorption Spectrophotom-
lution (10 mg/mL). To this solution, hydrazine hydrate (3.2 M) eter (Perkin Elmer, Analyst 200).
was added slowly and then heated to 75 C for 15 min. The
total volume of the entire reaction mixture was maintained at Electrochemical measurements
40 mL. Finally, 40 mg of NaOH was added and left to stir for
3 h at 80 C to obtain a black solution. The solution was filtered Electrochemical characterizations towards HER and ORR were
and dried in an air oven at a temperature of 65 C to obtain a carried out in a standard three-electrode electrochemical cell,
in which glassy carbon (GC, 3 mm) with various catalysts, internal diameter of 1/8 inch. The oven temperature was set to
saturated calomel, and graphite rod (Sigma-Aldrich, 99.999%) 45 C and the carrier gas was Ar at a flow rate of approximately
were used as the working, reference and auxiliary electrodes, 3 mL min1.
respectively. All electrochemical measurements were con- The durability and stability of the most active catalyst was
ducted without iR compensation, as the test solution is highly evaluated by 24 h of chronoamperometry measurements at a
conductive and the cell geometry is ideal, where the reference fixed cathodic overpotential and continuous potential cycling
electrode was inserted into a Luggin capillary filled with the up to 10,000 cycles. Each run was repeated at least 3 times to
test solution, too. The tip of the Luggin capillary was placed as confirm reproducibility of the results. The reported data are
close as possible to the working electrode to achieve found to be statistically significant; their arithmetic mean and
maximum reduction in iR drop in electrolytes. In addition, standard deviation were calculated and reported.
polarization curves without and with iR compensation were
found to be almost the same (see representative examples on
Fig. S1, Supporting Information). Results and discussion
All potentials were measured against saturated calomel
electrode (SCE) and calibrated here to the reversible hydrogen Characterization of AueNi/rGO, Au/rGO, and Ni/rGO
electrode (RHE) scale by adding a value of (0.241 þ 0.059 pH) V. nanocomposite materials
Various electrochemical techniques were applied to the GC-
loaded catalyst/H2SO4 interfaces by connecting the cell to an All the XRD patterns of AueNi/rGO nanocomposites with
Autolab, PGSTAT30/FRA system (Ecochemie, The Netherlands). various Ni contents prepared using different concentration of
Measurements were conducted in 200 mL deaerated and O2- Ni salt namely AueNi 1/rGO (Au ¼ 3 mM and Ni ¼ 3 mM), Aue
saturated aqueous solutions of H2SO4 (0.5 M). Temperature of Ni 2/rGO (Au ¼ 3 mM and Ni ¼ 5 mM), AueNi 3/rGO (Au ¼ 3 mM
the solution was maintained at (25 ± 0.2 C) using a temperature- and Ni ¼ 10 mM) and monometallic Au/rGO and Ni/rGO
controlled water bath. nanocomposites are presented in Fig. 1. The diffraction peaks
The GC working electrode was first polished with alumina of Au/rGO at 2q values of 38.06 , 44.28 , 64.58 and 77.58
powder of 0.3 mm followed by 0.05 mm till a mirror-like surface correspond to Au(111), Au(200), Au(220) and Au(222) planes,
was obtained. Then it was ultrasonically washed with doubly respectively (JCPDS: 01-071-3755). Also, the diffractions of Ni/
distilled-water for at least 20 min, and finally dried in air. The rGO occur at 2q values of 44.38 , 51.72 and 76.28 corre-
GC-loaded catalyst working electrode was prepared as fol- sponding to Ni(111), Ni(200) and Ni(220) planes, respectively
lows. The catalyst ink was first prepared via ultrasonic (JCPDS: 00-004-0850). Compared with the peaks of pure Au
dispersion of the catalyst powder in distilled water (Milli-Q) NPs, the diffraction peaks of AueNi/rGO nanocomposites shift
containing 0.5 wt % of Nafion. Then, an aqueous dispersion of slightly to higher 2q values thus confirming that Ni has
the catalyst (20 mL, 1.0 mg/mL) was dropped onto the freshly entered into the Au lattice forming AueNi alloy form. A
polished GC electrode. The amount of the catalysts was about similar observation has been reported by Chen et al. for NieAu
25 mg cm2. The working electrode was then inserted in a NPs [55,56]. Similarly, they also found that the characteristic
rotating disc system developed by U Metrohm Autolab B.V. peaks for the alloyed NieAu NPs were slightly broader than
(Serial no: RDE80526) for electrochemical measurements. those of individual Au as also obtained in our case, suggesting
Linear sweep voltammetry (LSV) was conducted at a scan lowered crystallinity of the alloy [57]. For the AueNi 1/rGO and
rate of 5 mV s1 in deaerated and O2saturated 0.5 M H2SO4 AueNi 2/rGO nanocomposites, the characteristic peaks of
aqueous solutions to assess the activity of our synthesized Ni(111) and Ni(220) at 44.38 and 76.28 overlapped with those
catalysts towards the HER and ORR. Electrochemical imped- of (200) and (311) planes of Au at 2q values of 44.28 and 77.58 .
ance spectroscopy (EIS) measurements were carried out using
working electrode biased at a cathodic overpotential of 0.35 V
vs. RHE, and superimposing a small sinusoidal voltage of 5 mV
in the frequency range of 100 kHz to 10 mHz. The experimental
data were fitted to an appropriate equivalent circuit
model using the complex nonlinear least-squares method.
HER Faradaic efficiencies for the studied catalysts were
determined by quantifying the amount of H2 generated during
controlled potential electrolysis by gas chromatography, and
dividing that by the amount of H2 expected based on the
charge passed (assuming 100% Faradaic efficiency) through
the working electrode (WE) during that electrolysis. Mea-
surements were conducted in a custom-made air-tight elec-
trolysis cell containing 0.5 M H2SO4 solution by holding the
electrode at 0.85 V vs RHE for 1 h. Gas chromatography was
conducted on an Agilent 7890A gas chromatograph with a
pneumatically operated automatic gas sampling valve to
monitor the evolved H2 gas. The electrolysis cell was con-
nected to the gas chromatography system via bespoke air- Fig. 1 e XRD patterns of monometallic Au/rGO, Ni/rGO and
tight glass-to-metal adapters and copper tubing with AueNi/rGO nanocomposites.
For AueNi 1/rGO, diffraction peaks were observed at 38.16 for bimetallic nature of the nanocomposite with clear lattice
Au(111), 44.34 for Au(200) and Ni(111), 64.74 for Au(220) and fringes of both Au (111) and Ni (111) plane with interplanar
77.62 for Au(222) and Ni(220). For AueNi 2/rGO, diffraction spacing of 0.230 and 0.203 nm, respectively. The HRTEM image
peaks appeared at 38.16 , 44.36 , 64.46 and 77.56 2q value. of AueNi 3/rGO nanocomposite also indicates a random
The (111) and (200) peaks of the synthesized AueNi/rGO mixture of both metals in one particle, confirming the alloy
nanocomposites lie between those of individual Au and Ni nature of the nanostructures. As the content of Ni in the Aue
NPs, suggesting the formation of fcc AueNi alloy. However, for Ni gradually increases in the AueNi/rGO nanocomposites, the
AueNi 3/rGO, although diffractions appeared at similar 2q NPs tend to be more polydisperse in nature and with further
values as those of AueNi 1/rGO and AueNi 2/rGO, an addi- increase in concentration the NPs tend to agglomerate.
tional weak diffraction at 2q value of 51.7 was observed, Nanoparticles' aggregation will decrease the surface active
corresponding to Ni(200). The intensity of the diffraction peak sites on the nanocomposites and consequently their catalytic
at 51.7 was distinct for AueNi 3/rGO. The presence of this efficiency decreases. Additionally, the TEM images show the
diffraction peak with increasing Ni concentration in AueNi 3/ presence of wrinkled and folded rGO sheets thus confirming
rGO indicated the presence of weak fcc Ni-phase [58]. In the formation of the bimetallic nanocomposites on their
accordance with Vegard's law which states that the diffraction surface.
peak of a metal alloy lies between the two set peaks of pure For comparison, TEM and HRTEM images along with
metals, the diffraction peaks for our synthesized AueNi size distribution histograms of monometallic Au/rGO and Ni/
nanoparticles lie between the diffraction peaks of pure Au and rGO are displayed and discussed in Fig. S2 (Supporting
Ni nanoparticles thus confirming the possible formation of Information).
metal alloy [56]. Thermal stability of the AueNi alloy/rGO nanocomposites
Furthermore, the peak of GO at 2q value of 11.7 was not was ascertained from the TGA analysis carried out under N2
observed in any of the synthesized nanocomposites and the atmosphere (Supporting Information, Fig. S3A). For compari-
presence of a broad peak ~24.5 confirmed the simultaneous son, the TGA plots of Au/rGO and Ni/rGO are shown in
reduction of GO to rGO during NP formation using hydrazine Supporting Information, Fig. S3B. They indicate major weight
hydrate. However, due to the strong diffraction peaks from the losses at 100 C and 200 C, and a slight loss above 500 C. Loss
bimetallic AueNi alloy as well as from the monometallic Au of water molecules that are present in between the layers of
and Ni, the diffraction, peaks from rGO might be shielded due graphene can be observed at 100 C. The weight loss above
to the high quantity of NPs in the AueNi/rGO nanocomposite. 200 C is due most likely to removal of residual oxygen-
We have reported similar observations in our previous publi- containing functional groups, like carboxyl, carbonyl, hy-
cations [59,60]. droxyl, and epoxy groups on the surface of rGO. The weight
The morphology, size, shape, crystallinity and distribution loss above 500 C is attributed to the loss of carbon skeleton of
of the AueNi alloy NPs on rGO sheets were investigated by the rGO sheets. For comparison, readers may refer to the TGA
TEM and HRTEM analysis. Typical TEM and HRTEM images of curves of GO and rGO in our previous publication [61].
different AueNi/rGO nanocomposites are displayed in Fig. 2. The presence of different functional groups on the nano-
The TEM images of AueNi 1/rGO show the formation of well composites was further demonstrated using DRIFT spectros-
dispersed and spherical shaped NPs distributed over the fol- copy (Supporting Information, Fig. S4). For all the
ded and wrinkled sheets of rGO with an average size diameter nanocomposites, the DRIFT stretching frequencies corre-
of around 14.5 ± 0.1 nm, calculated using Image J software sponding to the different functional groups on rGO surface are
(Fig. 2c). The selected area electron diffraction (SAED) pattern summarized in Table S1. It can be seen that compared to GO
(Fig. 2a (inset)) depicts several bright spots which reflect the (which is discussed elsewhere [62], the stretching of oxygen
polycrystalline nature of the AueNi 1/rGO nanocomposite. functionalities like OeH and C¼O groups are greatly reduced,
The HRTEM image validates the crystallinity as well as alloy indicating successful conversion of GO to rGO during nano-
nature of the AueNi 1/rGO nanocomposite. The HRTEM image composite formation.
in Fig. 2b exhibits clear lattice fringes that can be indexed to fcc The BET surface area of all the AueNi/rGO nanocomposites
Au (111) plane with an interplanar spacing of 0.230 nm and to and that of the monometallic Au/rGO and Ni/rGO are provided
fcc Ni (111) plane with an interplanar spacing of 0.203 nm. The in Table 1. As compared to support rGO, the surface area of all
presence of clear lattice fringes indicates a random mixture of rGO based monometallic/bimetallic nanocomposites is quite
both metals in one particle. Similar TEM and HRTEM images high. Monometallic Au/rGO has a surface area of 44.98 m2/g,
were recorded for AueNi 2/rGO with a size distribution of whereas Ni/rGO possesses the highest BET surface area of
17.2 ± 0.3 nm (Fig. 2def). The SAED pattern (Fig. 2d (inset)) and 268.29 m2/g probably due to its smallest size (~6 nm). All the
the HRTEM image confirm the crystalline nature of the bimetallic nanocomposites exhibit an average surface area
nanocomposite. Here also clear lattice fringes corresponding above 230 m2/g with highest value for AueNi 3/rGO nano-
to both Au (111) and Ni (111) with lattice fringes of 0.230 and composite (240.05 m2/g), which is in fact the most active
0.203 nm are clearly observed, confirming the presence of both catalyst among all synthesized nanocomposites.
metals in the form of bimetallic alloy structure. For AueNi 3/ The chemical composition of the different AueNi/rGO
rGO, the TEM image (Fig. 2g) shows the formation of poly- nanocomposites was examined using XPS (Fig. 3, Table 2). For
disperse NPs of AueNi with an average size diameter of comparison XPS results of the monometallic composites, Au/
16 ± 0.2 nm (Fig. 2i). The SAED pattern (Fig. 2g (inset)) along rGO and Ni/rGO, prepared under otherwise identical condi-
with the HRTEM (Fig. 2h) image reveal the crystalline nature of tions, are provided. The XPS survey spectrum of AueNi 3/rGO
the nanocomposite. The HRTEM image confirms the nanocomposite is displayed in Fig. 3A. It exhibits peaks
Fig. 2 e TEM images (a, d, g); HRTEM images (b, e, h), and size distribution histograms (c, f, i) of AueNi 1/rGO, AueNi 2/rGO
and AueNi 3/rGO nanocomposites, respectively. The insets in (a, d, g) correspond to the SAED patterns for AueNi 1/rGO, Aue
Ni 2/rGO and AueNi 3/rGO nanocomposites, respectively.
resolution XPS spectrum of AueNi 3/rGO displays two peaks

Table 1 e BET surface area of AueNi/rGO, Au/rGO and Ni/
corresponding to Au4f7/2 and Au4f5/2 at 84.0 and 87.6 eV,
rGO nanocomposites.
respectively (Fig. 3B), consistent with Au metal in zero valence
Material Surface area (m2/g) state. The Ni2p high resolution XPS spectrum displays two
AueNi 1/rGO 234.02 major peaks centered at 856.1 and 873.6 eV with a spin-energy
AueNi 2/rGO 233.47 separation of 17.5 eV due to Ni2p3/2 and Ni2p1/2, respectively
AueNi 3/rGO 240.05
(Fig. 3C). These bands are characteristic of Ni(OH)2 phase, in
AueNi 3/rGO after cathodic activationa 624.49
agreement with other literature reports [63e65]. The two extra
Au/rGO 44.98
Ni/rGO 268.29 peaks centered at 861.1 and 879.5 eV correspond to Ni2p3/2 and
rGO 37.02 Ni2p1/2 satellite peaks, respectively. Fig. 3D depicts the C1s high
rGO after cathodic activationa 108.07 resolution spectrum of AueNi 3/rGO. It can be deconvoluted
a
Repetitive cycling (10,000 cycles) between Ecorr and 0.2 V(RHE) at into four components with binding energies at about 283.8,
a scan rate of 100 mV s1 in 0.5 M H2SO4 solution at 25 C. 284.5, 287.3 and 289.2 eV assigned to C¼C (sp2 network), CC/
CH, C¼O and HOC¼O species, respectively. The C/O ratio
varies significantly depending on the initial Au/Ni ratio used
for the synthesis of AueNi/rGO (Table 2). Decreasing the Au3þ/
corresponding to C1s (284.4 eV), O1s (532.6 eV), Au4f (84.0 eV), Ni2þ ratio leads to a decrease in the atomic percentage of Au4f
and Ni2p (856.1eV). Representative Au4f, Ni2p and C1s high in the nanocomposite material. Surprisingly, the same trend
resolution XPS spectra are depicted in Fig. 3BeD. The Au4f high was observed for Ni.
Fig. 3 e XPS survey spectrum (A); High resolution XPS spectra of Au4f (B); Ni2p (C) and C1s (D) of AueNi 3/rGO nanocomposite.
catalytic activity. By contrast, bare rGO showed a larger EHER

Table 2 e Chemical composition (at.%) determined by
(344 mV vs. RHE) accompanied by much smaller reduction
XPS.
currents for the HER, thus exhibiting poor activity for the HER.
Material C1s O1s Ni2p Au4f C/O
The HER activity of the studied electrocatalysts, particularly
AueNi 3/rGO 43.8 34.2 19.1 2.9 1.28 the three synthesized AueNi alloy NPs/rGO catalysts (Fig. 4a:
AueNi 2/rGO 51.9 30.8 16.1 1.2 1.68 curves 4e6), come far beyond that of the bare rGO,
AueNi 1/rGO 81.7 12.7 4.8 0.8 6.44
approaching that of Pt/C. This is clear from their measured
Au NPs/rGO 91.3 7.9 e 0.8 11.5
EHER values (Table 3), where EHER value of Ni NPs/rGO catalyst
Ni NPs/rGO 84.9 13.5 1.6 e 6.2
(126 mV vs. RHE) is 59 mV more positive than that recorded
for Au NPs/rGO catalyst (185 mV vs. RHE), demonstrating the
high catalytic performance of the former. The relatively
The AAS technique also confirms the presence of both Au smaller size of the Ni NPs loaded on rGO, along with the high
and Ni in the AueNi/rGO nanocomposites and their contents specific surface area of the Ni NPs/rGO catalyst (6 nm and
are provided in Table S2 in the SI. 268.39 m2/g, respectively), are the main reasons behind the
higher HER activity of such catalyst as compared to Au NPs/
Electrochemical measurements rGO catalyst (13 nm and 44.98 m2/g, respectively). Au NPs/rGO
catalyst in turn is anodic to bare rGO by 159 mV vs. RHE. Table
Catalytic activity for the HER 3 also reveals that the values of EHER measured for any of the
Fig. 4a displays the HER performance of the AueNi NPs/rGO synthesized AueNi NPs/rGO catalysts are more positive than
(curves 4e6) in comparison with bare rGO (curve 1), Au NPs/ that of the Ni NPs/rGO catalyst. These findings mean that the
rGO (curve 2), Ni NPs/rGO (curve 3), and Pt/C (curve 7). All kinetics of the HER gets quicker when the NPs of both Au and
measurements were carried out in 0.5 M H2SO4 deaerated Ni are brought together on rGO as bimetallic (curves 4e6)
solution at a scan rate of 5.0 mV s1 at 25 C. The onset po- rather than loaded individually (curves 2 and 3). Similar re-
tential for the HER, EHER, needed for the Pt/C catalyst is close to sults were previously obtained for supported bimetallic NPs of
zero vs. RHE, demonstrating its well-known superior HER Au-Pd [34,66], Cu-Ti [67] as electrocatalysts for the HER. The
measured for our synthesized AueNi/rGO catalysts. As shown

in Table 3, the EHER values needed for AueNi 1/rGO, AueNi 2/
rGO, and AueNi 3/rGO catalysts are 50, 25, and 7 mV vs.
RHE, respectively. It is worth mentioning that for Ni NPs/rGO
(Fig. 4a, curve 3), the catalyst with the least average particle
size for the loaded NPs and the highest specific surface area
among the tested catalysts (Table 1), exhibited HER activity
much lower than any of the studied AueNi NPs/rGO catalysts
(Fig. 4a, curves 4e6). These findings suggest that the cooper-
ative catalytic influence between Au and Ni is the most
important parameter for the outstanding HER catalytic per-
formance of the AueNi alloy NPs/rGO catalysts.
The above findings reflect the high catalytic performance
of our catalysts, which originate from the synergetic chemical
coupling effects between the loaded metal NPs and the rGO
which allows the growth of highly dispersed metal NPs on the
rGO surface selectively. Such dispersed metal NPs could serve
as active catalytic sites for the HER. In addition, the substrate
used here provides a large surface area (37.02 m2/g), based on
the BrunauereEmmetteTeller (BET) analysis in Table 1, for
better dispersion of the supported NPs. This in turn results in
high contact area thus, facilitating Hþ reduction via the
exposure of more active sites.
Kinetics of the HER

The HER kinetics over such catalysts was investigated by the
corresponding Tafel plots, Fig. 4b. Tafel slope (bc) and ex-
change current densities (jo) were calculated by means of the
least-square analysis of the Tafel plots. The fitting parameters
are also shown in Table 3. The values of jo measured for these
catalysts were used to evaluate their HER inherent activity.
AueNi/rGO catalysts recorded the highest jo values (0.18, 0.35,
and 0.6 mA cm2 for AueNi (1, 2, and 3)/rGO, respectively)
Fig. 4 e (a) Polarization curves and (b) corresponding Tafel
among the studied materials (3.2 103, 1.3 102, and
plots of the synthesized electrocatalysts loaded onto a
4.1 102 mA cm2 for bare rGO, Au NPs/rGO and Ni NPs/rGO,
glassy carbon electrode (rotation speed 1600 rpm).
respectively). These results support the superior HER kinetics
Measurements were conducted in deaerated H2SO4
of AueNi/rGO catalysts. The jo of 0.6 mA cm2 for the most
aqueous solution (0.5 M) at a scan rate of 5 mV s¡1 at 25 C:
active catalyst, AueNi 3/rGO, is very close to that of Pt/C
(1) bare rGO; (2) Au NPs/rGO; (3) Ni NPs/rGO; (4) AueNi 1/
catalyst (0.8 mA cm2) and also outperforms that of most re-
rGO; (5) AueNi 2/rGO; (6) AueNi 3/rGO; (7) Pt/C.
ported HER catalysts (Supplementary Table S3).
In addition, in order to attain a high current density of
improved HER catalytic performance of the AueNi NPs/rGO 10 mA cm2, the AueNi (1, 2, and 3)/rGO catalysts only require
catalyst can be credited to the synergistic effect occurring overpotentials of about 70, 50, and 40 mV, respectively. How-
between Au and Ni [34,36,66,67]. Such cooperative influence ever, the overpotentials needed for their corresponding indi-
enhances with increasing the Ni concentration in the AueNi vidual catalysts, namely Au NPs/rGO and Ni NPs/rGO are
alloy/rGO catalyst. This is clear from the values of EHER about 222 and 158 mV, respectively. These results again
Table 3 e Mean value (standard deviation) of the electrochemical kinetic parameters for the HER on the surfaces of the
synthesized electrocatalysts in deaerated 0.5 M H2SO4 solution at 25 C, in comparison with those recorded for bare rGO
and Pt/C.
Tested cathode Onset potential Tafel slope (mV dec1) Exchange current density Overpotential at j ¼ 10 mA cm2
(EHER, mV vs. RHE) (jo, mA cm2) (h10, mV)
bare rGO 344(7) 211(3) 3.2(0.05) 103
Au NPs/rGO 185(4.8) 77(2.2) 1.3(0.02) 102 220(5)
Ni NPs/rGO 126(4.2) 66(2) 4.1(0.03) 102 158(2.4)
AueNi 1/rGO 50(3) 40(1.9) 0.18(0.01) 70(1.6)
AueNi 2/rGO 25(2.2) 35(1.5) 0.35(0.02) 50(1.4)
AueNi 3rGO 7(1.1) 33(1.2) 0.6(0.04) 40(1.2)
Pt/C ~0.0(0.04) 31(0.3) 0.8(0.01) 35(0.07)
confirm the high HER kinetics of the AueNi/rGO catalysts. The

catalyst AueNi 3/rGO with an overpotential of 40 mV, which is
very near to that of Pt/C (35 mV), to obtain a high current
density 10 mA cm2 also represents a more efficient catalyst
relative to other HER catalysts (Supplementary Table S3).
The HER inherent activity of our electrocatalysts was also
assessed by their measured Tafel slope. The values of bc
recorded in Table 3 showed a marked decrease from 211 mV
dec1 for bare rGO to 77, 66, 40, 35, and 33 mV dec1 for Au NPs/
rGO, Ni NPs/rGO, AueNi 1/rGO, AueNi 2/rGO, and AueNi 3/
rGO, respectively. This decrease in the bc values indicates
accelerated kinetics of the HER, as lower Tafel slopes refer to
the increase in the number of accessible active sites [68,69].
The low Tafel slopes (35 and 33 mV dec1) measured for the
two best catalysts are very close to that of Pt/C catalyst (31 mV
dec1) and comparable to or lower than other efficient cata-
lysts in the literature (Supplementary Table S3), thus signi-
fying the superior HER kinetics of these materials. Fig. 5 e Complex-plane impedance plots recorded for the
The low Tafel slopes measured for AueNi/rGO catalysts, studied electrocatalysts loaded onto a glassy carbon
which are close to that of Pt, suggest that the rate limiting step electrode (rotation speed 1600 rpm). Measurements were
is the recombination step [8,70,71]. These findings mean that conducted in deaerated H2SO4 aqueous solution (0.5 M) at a
the HER proceeds via a primary discharge step (Volmer reac- cathodic overpotential of ¡0.35 V vs. RHE at 25 C: (1) bare
tion, H3Oþ þ e ¼ Hads þ H2O, with bc ~ 120 mV), followed by a rGO; (2) Au NPs/rGO; (3) Ni NPs/rGO; (4) AueNi 1/rGO; (5)
recombination step (Tafel reaction, Hads þ Hads ¼ H2, with AueNi 2/rGO; (6) AueNi 3/rGO; (7) Pt/C.
bc ~ 30 mV) thus, the VolmereTafel mechanism is assumed to
control the HER on the AueNi/rGO catalysts.
(measured and calculated) of H2 recorded for the best catalyst
Turn over frequency (TOF), the number of hydrogen mol-
(AueNi 3/rGO) as well as for the other studied catalysts and Pt/
ecules that are formed per second per active site [72,73], was
C are compared in Fig. S5 (SI) as a function of time (10e60 min).
also used to assess the HER activity per site of a catalyst at a
The charge (C) e time (t) curves were also constructed for
given overpotential. Values of TOF were calculated, as
the studied catalysts in a comparison with Pt/C to gain more
described elsewhere [74], at 200 mV using the BET surface
insight into their electrochemical efficiency for H2 generation.
areas measured for the tested catalysts. It is seen that TOF of
Such plots, Fig. S6 (SI), were obtained during a controlled po-
the bare rGO increased significantly from 5.2 102 H2/s per
tential electrolysis process performed in 0.5 M H2SO4 solution,
active site to 1.02, 1.63, 2.2, 2.8, and 3.3H2/s per active site for
where the tested catalyst was held at 0.8 V vs RHE for 1 h. It
Au NPs/rGO, Ni NPs/rGO, AueNi 1/rGO, AueNi 2/rGO, and Aue
follows from Fig. S6 that the C-t plot of the best catalyst (curve
Ni 3/rGO, respectively. The obvious increase in TOF of the
5) is very close to that of Pt/C (curve 6). The measured volume
three AueNi/rGO catalysts with Ni content further confirms
of H2 produced by this catalyst (19.1 mmol h1, with a corre-
that the synergism in the AueNi nano-alloy is extremely
sponding FE of 99%) also approached that of Pt/C
helpful for the greatly enhanced HER electrocatalytic activity
(19.5 mmol h1, FE ~ 100%). These findings confirm the superior
of the AueNi/rGO catalysts. The enhanced TOF values of the
catalytic activity of AueNi 3/rGO catalyst. The catalytic impact
studied AueNi/rGO catalysts with Ni content are translated in
of AueNi alloy NPs' synergism, which enhances with Ni con-
increased Faradaic efficiency (FE), as shown in Table 4. Values
tent, is also evident here. This is clear from Table 4, where the
of FE were calculated from the ratio of the experimentally
values of FE were calculated to be 91.1, 93.9, 95.1, 96.6, and 99%
measured volume of H2 to its theoretical volume (more details
for Au/rGO, Ni/rGO, AueNi 1/rGO, AueNi 2/rGO, and AueNi 3/
are reported in the Supporting Information). Such volumes
rGO, respectively.
Table 4 e Mean value (standard deviation) of the measured and calculated volumes of H2 after 1 h of a controlled potential
electrolysis processa, together with the Faradaic Efficiency values, FE (%), for the studied catalysts.
Catalyst H2 measured by gas chromatography (H2/mmol h1) Calculated H2 based on the charge passed during
electrolysis
Charge passed/C H2/mmol h1 FE (%)
Au NPs/rGO 13.3(0.24) 2.82(0.026) 14.6(0.14) 91.1(0.77)
Ni NPs/rGO 14.8(0.28) 3.04(0.028) 15.76(0.15) 93.9(0.88)
AueNi 1/rGO 15.6(0.3) 3.16(0.03) 16.4(0.16) 95.1(0.9)
AueNi 2/rGO 17(0.33) 3.4(0.04) 17.6(0.19) 96.6(0.83)
AueNi 3/rGO 18.9(0.36) 3.69(0.05) 19.1(0.2) 99(0.85)
Pt/C 19.4(0.38) 3.75(0.05) 19.44(0.22) 99.8(0.83)
a
A potentiostatic experiment where the catalyst is held at 0.85 V vs RHE for 1 h in 0.5 M H2SO4 deaerated solution at 25 C.
EIS measurements were also carried out at a given over- which increase with Ni content, much higher than that of Ni
potential, 0.35 V vs. RHE, to further assess the HER kinetics NPs/rGO (252.44 mF cm2). These findings again highlight
over the studied catalysts. The Nyquist plots of the synthe- the highly important role of the synergism in the loaded AueNi
sized catalysts (Fig. 5, curves 2e6) are characterized by two alloy NPs in enhancing HER activity of AueNi/rGO catalysts.
well-defined depressed semicircles. The high frequency The high HER activity of such materials is likely due to
semicircle (with diameter R1) was assigned to adsorbed the abundance of active catalytic sites (the Au and Ni metallic
hydrogen, while that formed at medium- and low frequency, nanoparticles loaded on the rGO nanosheets), the in-
whose diameter is R2, was attributed to HER kinetics. The creased electrochemically accessible surface area, signi-
charge-transfer resistance (Rct) associated with the whole ficantly improved electrochemical conductivity, and the
process is given by the summation of R1 and R2 [34]. Bare rGO synergism that exists between Au and Ni NPs in the AueNi
and Pt/C displayed a single capacitive loop, which can be nano-alloy.
assigned to a resistance-capacitance (RC) network. This
network consists of a charge-transfer resistance due to the Catalytic activity for the ORR
reduction of Hþ and the corresponding capacitance (C) [34]. The promising HER kinetics (including a low onset potential of
The impedance data were fitted using the equivalent cir- 7 mV, a Tafel slope as low as 33 mV dec1, a large jo value of
cuits presented in Fig. 6, and fully described elsewhere [34]. 0.6 mA cm2, and a TOF value of 3.3H2/s per active site)
The obtained fitting parameters are listed in Table 5. It follows recorded for the best catalyst here, namely AueNi 3/rGO,
from Table 5 that our catalysts exhibited markedly reduced Rct highlight its outstanding HER activity. This catalyst also ach-
values (11e50 U cm2) than that measured for the bare rGO ieved higher catalytic activity towards ORR in comparison to
(Rct ¼ 6770 U cm2), demonstrating fast HER kinetics over their the other tested catalysts, where RDE measurements were
surfaces. The three synthesized AueNi alloy NPs/rGO cata- employed to study the kinetics of the ORR over all the syn-
lysts exhibited the least Rct values (23.6, 16.5, and 11.6 U cm2 thesized nanocomposite catalysts. Measurements were con-
for AueNi 1/rGO, AueNi 2/rGO and AueNi 3/rGO, respec- ducted in O2-saturated aqueous H2SO4 solution (0.5 M) at a
tively), which diminish with increasing Ni concentration in rotation speed of 1600 rpm and a scanning rate of 5 mV s1,
the AueNi alloy NPs, among the studied catalysts (49.9 and Fig. 7a.
30.4 U cm2 for Au NPs/rGO and Ni NPs/rGO, respectively). Like Pt/C, the value of EORR (the onset potential for O2
These results confirm the outstanding HER activity of such reduction) recorded for AueNi 3/rGO catalyst is ~1.0 V vs. RHE,
catalysts that arises from the synergism of Au and Ni in the which is about 20, 40, 55, 90, and 360 mV more positive than
loaded nano-alloy AueNi system. The low Rct values of these that measured for AueNi 2/rGO, AueNi 1/rGO, Ni NPs/rGO, Au
materials refer to their increased conductivity, which im- NPs/rGO, and bare rGO catalysts, respectively. The catalyst
proves the charge transfer characteristics of the loaded NPs. AueNi 3/rGO also exhibited the highest ORR limiting current
This in turn enhances electron transfer during the Hþ reduc- density (4.4 mA cm2 @ 0.5 V vs. RHE) among the tested cat-
tion process over their surfaces. Further inspection of Table 5 alysts, which is very close to that recorded for Pt/C
reveals that the Rct value (11.6 U cm2) of the best catalyst, (4.5 mA cm2) at the same potential. In addition, the AueNi 3/
namely AueNi 3/rGO, is very close to that of the Pt/C catalyst rGO achieved an ORR half-wave potential, E1/2, of 0.9 V vs. RHE,
(10.6 U cm2), thus confirming its superior HER activity. The which is very close to that of Pt/C, 0.91 V vs. RHE, and its cor-
capacitance (C) is proportional to the area of contact between responding ORR current density is the highest (~2.3 mA cm2;
the catalysts and the electrolyte; high contact area is favorable also very close to that measured for Pt/C, ~2.4 mA cm2),
for high activity. For instance, the total capacitance value, amongst the tested catalysts. This half-wave potential value is
Ctotal ¼ C1 þ C2, recorded for Ni NPs/rGO is 252.44 mF cm2, about 30, 70, 100, 140, and 410 mV more positive than that
which is ~2.2 times greater than that measured for Au NPs/ recorded for AueNi 2/rGO, AueNi 1/rGO, Ni NPs/rGO, Au NPs/
rGO (115.8 mF cm2) and 17 times larger in comparison to bare rGO, and bare rGO catalysts, respectively. Based on the above
rGO (14.8 mF cm2). These findings are consistent with the BET findings, the ORR activity of our synthesized catalysts follows
surface areas in Table 1. However, AueNi/rGO catalysts, the same sequence of increased HER activity, namely Pt/
whose BET surface areas are lower than that of Ni NPs/rGO C ~ AueNi 3/rGO > AueNi 2/rGO > AueNi 1/rGO > Ni NPs/
(Table 1), showed Ctotal values of 459.5, 822.7, and 965.1 mF cm2 rGO [ Au NPs/rGO.
for AueNi 1/rGO, AueNi 2/rGO, and AueNi 3/rGO, respectively
Mechanism of ORR
Fig. 7b shows the cathodic polarization curves that are
recorded for the most active catalyst in 0.5 M H2SO4 O2-satu-
rated aqueous solution as a function of the rotation speed
(100e3600 rpm). This figure is constructed to determine the
number of electrons that are transferred per O2 molecule
during ORR catalyzed by the best catalyst using the Koutecky-
Levich equation [75,76]. It is obvious that, at potentials anodic
to EORR, the ORR on the AueNi 3/rGO catalyst is under kinetic
control; ORR insensitive to the rotation speed. The ORR is
Fig. 6 e Equivalent circuits used to fit the experimental under mixed diffusion kinetic control at intermediate poten-
impedance data; (a) for Pt/C and bare rGO, (b) for the other tials. At less positive potentials, the reaction rate is controlled
tested catalysts. by mass transport, and a well-defined limiting current region
Table 5 e Mean value (standard deviation) of the impedance parameters recorded for the studied catalysts. Measurements
were conducted in 0.5 M H2SO4 deaerated solutions at a cathodic potential of ¡0.35 V vs RHE at 25 C.
Catalyst Q1 Sn (u1 cm2) R1 U cm2 n1 C1 mF cm2 Q2 Sn (u1 cm2) R2 U cm2 n2 C2 mF cm2 Rct U cm2
Au NPs/rGO 194.4(1.7) 14.9(0.22) 0.87 81.2(1.6) 72.4(0.48) 35(0.6) 0.89 34.6(0.4) 49.9(0.82)
Ni NPs/rGO 324.5(3.2) 9.4(0.14) 0.89 158.6(2.8) 175(1.4) 21(0.4) 0.9 93.84(1.2) 30.4(0.54)
AueNi 1/rGO 458(4.8) 7.8(0.12) 0.9 244.8(4.6) 358.2(3.1) 15.8(0.3) 0.91 214.7(2.9) 23.6(0.42)
AueNi 2/rGO 778.6(8.6) 6.8(0.1) 0.9 434.9(8.2) 606(5.43) 9.7(0.19) 0.92 387.8(5.2) 16.5(0.29)
AueNi 3/rGO 860.6(10.2) 4.1(0.07) 0.92 526.7(9.7) 653.6(6.14) 7.5(0.15) 0.93 438.4(5.9) 11.6(0.22)
ORR process catalyzed by this catalyst takes place via a four-

electron pathway.
Long term stability and catalyst activation

Understanding the stability of electrocatalysts is a critical
aspect in the development of this field [77]. For real working
devices, repetitive stability tests in excess of 10,000 potential
cycles are recommended [78]. For this reason, long-term po-
tential cycling was carried out for the best catalyst, namely
AueNi 3/rGO by recording continuous cyclic voltammograms
at an accelerated scanning rate of 50 mV s1 for 10,000 cycles,
Fig. 8a, to assess its durability properly.
It is seen that the HER activity of the catalyst is markedly
enhanced after 10,000 cycles, even at lower overpotentials,
thus the catalyst is activated during the reaction. Activation of
the catalyst during cathodic polarization of continuous po-
tential cycles was reproducible in this work, and was also
previously obtained [34,79]. At the end of the operation, the
HER activity of the activated catalyst is found to surpass that
of Pt/C (Tafel slope: 31 mV dec1 and exchange current den-
sity: 0.8 mA cm2). This is clear from the Tafel plot of the
10,000th cycle that is shown in the inset of Fig. 8a, where a
Tafel slope as low as 29.3 mV dec1 and an exchange current
density of 1.17 mA cm2 were obtained. During this long sta-
bility testing, where hydrogen evolves progressively, the
supported AueNi alloy NPs can adsorb hydrogen into their
structure [80,81] even the substrate itself, namely rGO adsorbs
hydrogen [82] and is found here to be activated during the run.
This adsorbed hydrogen breaks down AueNi alloy NPs and
rGO. This in turn increases the surface area of the catalyst and
also creates new defect sites required for HER [34,79]. BET
Fig. 7 e (a) Cathodic polarization curves recorded for the measurements also reveals that the specific surface area of
studied electrocatalysts loaded onto a glassy carbon the best catalyst has increased from 240.05 m2/g before acti-
electrode (rotation speed 1600 rpm). (b) Effect of rotation vation to 624.49 m2/g after activation (i.e., at the end of the
speed (100e3600 rpm) on the cathodic behavior of the best 10,000th cycle). Similar results were obtained for bare rGO,
catalyst, AueNi 3/rGO. Inset of Fig. 7 (b): K-L relation for the where its specific surface area has increased from 37.02 to
best catalyst demonstrating the 4e¡ mechanism of the 108.07 m2/g after 10,000 cycles of cathodic polarization (revisit
ORR. Measurements were conducted in deaerated H2SO4 Table 1). These findings reveal the catalytic impact of the
aqueous solution (0.5 M) at a scan rate of 5 mV s¡1 at 25 C. adsorbed hydrogen.
(1) bare rGO; (2) Au NPs/rGO; (3) Ni NPs/rGO; (4) AueNi 1/ The practical operation of the best catalyst was also
rGO; (5) AueNi 2/rGO; (6) AueNi 3/rGO; (7) Pt/C. examined by electrolysis at a fixed cathodic overpotential
(chronoamperometry measurements) up to 24 h, to further
confirm catalyst durability and activation during the long
appears. As expected, the density of current increases with term operation, Fig. 8b. Within the first 5 min of the run, the
the rotation speed due to the enhancement in the mass cathodic current density decreased quickly from 0.17 A cm2
transfer of O2 [76]. The number of electrons that are trans- to 0.06 A cm2. This decrease in current denotes catalyst
ferred during the ORR process on the AueNi 3/rGO cathode is deactivation due to catalyst poisoning and/or H2 bubble
estimated to be 4 electrons per one O2 molecule, see Koutecky- accumulation [83]. The catalytic current then declines over
Levich plot in the inset of Fig. 7b. This result suggests that the the 24 h of continuous operation due to H2 release [83], thus
Fig. 8 e Material stability: (a) effect of repetitive cycling (10,000 cycles) between Ecorr and ¡0.2 V vs. RHE at a scan rate of
50 mV s¡1 on the HER activity of AueNi 3/rGO (the best catalyst) - Inset: fitting to the Tafel equation after the 10,000th cycle.
(b) Chronoamperometry measurements (j vs. t) recorded on the best catalyst at a constant applied potential of ¡0.85 V vs.
RHE. Measurements were performed in deaerated H2SO4 aqueous solution (0.5 M) at 25 C.
showing an increased in the catalytic activity for the HER, to a simple solution chemistry approach. The nanocomposites were
reasonably steady value at ~ 0.12 A cm2. Such excellent characterized by high resolution transmission electron micro-
durability and activation is highly promising for practical ap- scopy, X-ray photoelectron spectroscopy, diffuse reflectance
plications of the catalyst over long term operation. infrared Fourier transform, X-ray diffraction, and thermal
gravimetric analysis. The nanocomposites exhibited high
electrocatalytic activity toward hydrogen evolution reaction
Conclusion (HER) and oxygen reduction reaction (ORR) in sulfuric acid
aqueous solutions. The catalytic activity of the Ni NPs/rGO
AueNi alloy nanoparticles have been synthesized on reduced catalyst exceeded that of Au NPs/rGO, due to the smaller
graphene oxide (rGO) sheets with three different ratios by a average particle size and the larger accessible electrochemical
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The authors are thankful to the Director, CSIRNEIST, Jorhat [15] Yang Q, Dong M, Song H, Cao L, Zhang Y, Wang L, et al.
for his interest to carry out the work. GD gratefully acknowl- Size dependence electrocatalytic activity of gold
edges DST, India for DST-INSPIRE Fellowship. The authors nanoparticles decorated reduced graphene oxide for
further acknowledge SAIF, NEHU, Shillong for the HRTEM fa- hydrogen evolution reaction. J Mater Sci Mater Electron
2017;28:10073e80.
cility. S.S. and R.B. acknowledge financial support from the
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Tammeveski K. Electrochemical reduction of oxygen on
Supplementary data related to this article can be found at
heat-treated Pd nanoparticle/multi-walled carbon nanotube
https://doi.org/10.1016/j.ijhydene.2017.11.048. composites in alkaline solution. Electrocatalysis
2013;4:42e8.
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i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 5

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/he

AueNi alloy nanoparticles supported on reduced

Gitashree Darabdhara a,b, Manash R. Das a,b,*, Mohammed A. Amin c,d,**,

article info abstract

Additionally, it exhibits outstanding operational durability and activation after 10,000th

metal in ORR have led to the use of Au NPs supported on

resolution XPS spectrum of AueNi 3/rGO displays two peaks

catalytic activity. By contrast, bare rGO showed a larger EHER

measured for our synthesized AueNi/rGO catalysts. As shown

Kinetics of the HER

confirm the high HER kinetics of the AueNi/rGO catalysts. The

ORR process catalyzed by this catalyst takes place via a four-

Long term stability and catalyst activation

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