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https://doi.org/10.1007/s11581-017-2349-6

ORIGINAL PAPER

Multiwalled carbon nanotube supported Pt–Sn–M (M = Ru, Ni, and Ir)

catalysts for ethanol electrooxidation
S. Thilaga 1 & S. Durga 1 & V. Selvarani 1 & S. Kiruthika 2 & B. Muthukumaran 1

Received: 24 April 2017 / Revised: 1 November 2017 / Accepted: 10 November 2017

# Springer-Verlag GmbH Germany, part of Springer Nature 2017

Abstract
In the present study, Pt–Sn–M (M = Ru, Ni, and Ir) nanocatalysts were supported on multiwalled carbon nanotube and their
electrocatalytic activity for ethanol oxidation in membraneless fuel cells was investigated. The combination of monometallic Pt/
MWCNTs, bi-metallic Pt–Sn/MWCNTs, and tri-metallic Pt–Sn–Ru/MWCNT, Pt–Sn–Ni/MWCNT, and Pt–Sn–Ir/MWCNT
nanocatalysts were prepared by the ultrasonic assisted chemical reduction method. Transmission electron microscopy (TEM),
energy-dispersive X-ray spectroscopy (EDX), and X-ray diffraction (XRD) were used for the catalyst characterization. The
electrocatalytic activities of the catalysts were investigated in half-cell experiments using cyclic voltammetry (CV), CO stripping
voltammetry, and chronoamperometry (CA). During the experiments performed on a single membraneless ethanol fuel cell
(MLEFC), the Pt–Sn–Ir/MWCNTs exhibited a better catalytic activity from among all the catalysts prepared, with a power
density of 39.25 mW cm−2.

Keywords Multiwalled carbon nanotube . Membraneless fuel cell . Ethanol . Platinum . Tin . Iridium

Introduction fermentation of sugar containing raw materials. Thus, ethanol

is more attractive than methanol for direct alcohol fuel cell.
Membraneless ethanol fuel cell (MLEFC) is an electrochem- However, ethanol electrooxidation (EOR) on pure Pt does not
ical device which continuously converts chemical energy into display good catalytic activity due to poisoning of its active
electrical energy for as long as fuel and oxidant are supplied. sites by intermediates generated from the reactions occurring
The MLEFC uses ethanol as a fuel and sodium percarbonate in parallel with the oxidation of ethanol, which utilizes
as an oxidant. As a green fuel, ethanol is much safer and has overpotential for oxidation of the target fuel [1–4].
higher theoretical mass energy density than methanol (8 vs. Considerable efforts have been directed toward the develop-
6.1 kWh kg−1). Most of all, ethanol is a renewable energy ment of effective electrocatalysts that can oxidize ethanol at
source and can be easily produced in great quantities by lower potentials [5–7]. For example, alloys of Pt with other
elements such as Sn, Ru, Rh, Ir, Mo, W, and Ni have been
frequently studied as co-catalysts to minimize the effect of Pt
* B. Muthukumaran poisoning with CO and other byproducts, thereby improving
dr.muthukumaran@yahoo.com the catalytic activity [8–14]. Among these alloys, bimetallic
S. Thilaga Pt–Sn catalysts have been demonstrated a superior activity
thilagaasri@gmail.com toward electrooxidation of ethanol and these catalysts dimin-
ished the poisoning effect of CO because the OH groups that
S. Durga
durgasrika@gmail.com are generated on Sn promote the oxidation of CO on the Pt
catalyst.
S. Kiruthika
kiruthika.s@ktr.srmuniv.ac.in
In addition to the various types of alloy materials and com-
position ratios, the catalyst support material is also an impor-
1
Department of Chemistry, Presidency College, Chennai 600005, tant criterion for developing fuel cells [15]. Nanostructured
India carbon materials with graphene structures such as carbon
2
Department of Chemical Engineering, SRM University, nanotubes (CNTs) and carbon nanofibers (CNF) have been
Chennai 603203, India extensively studied as support material of electrocatalysts for

fuel cells, due to their unique electric and micro- and macro-
structural characteristics [16–18]. Especially, carbon nano-
tubes have drawn much more attention because of their un-
usual electronic properties and ability to improve catalytic
properties.
As a new form of carbon, multiwalled carbon nanotubes
(MWCNTs) have been regarded as a new support for metal
catalysts in MLEFC because of their small size, high chemi-
cal, thermal, mechanical stabilities, and their large surface area
to volume ratio [16, 19, 20].
In this work, MWCNT-supported Pt, Pt–Sn, and Pt–Sn–M
(M = Ru, Ni, and Ir) catalysts were prepared by ultrasonic
assisted chemical reduction method to explore the effect of
the nanostructure of Pt–Sn nanoparticles on the performance
of ethanol electrooxidation. The physical (X-ray diffraction
(XRD), TEM, energy-dispersive X-ray (EDX)) characteriza-
tion was carried out to clarify the microstructure, the compo-
sition, and the chemical environment of nanoparticles. The
electrochemical characterization, including cyclic voltamme-
try, and chronoamperometry of the prepared catalysts were
conducted to characterize the electrochemical activities to eth-
anol oxidation. Finally, the performance of MLEFC, with Pt/
MWCNT, Pt–Sn/MWCNT, and Pt–Sn–M/MWCNT (M = Ru,
Ni, and Ir) anode catalysts, was tested. The microstructure and
composition of prepared catalysts were correlated with their
performance for ethanol electrooxidation.
Experimental
Chemicals and materials
The metal precursors used for the preparation of
electrocatalysts were hexachloroplatinic acid (H 2PtCl 6·
6H 2 O) (from Aldrich), Tin(II) chloride dihydrate
(SnCl2.2H2O) (from Alfa Aesar), hexachloroiridic acid hexa-
hydrate (H2IrCl6·6H2O) (from Alfa Aesar), nickel(II) chloride
hexahydrate (NiCl 2 ·6H 2 O) (from Alfa Aesar), and
ruthenium(III) chloride hydrate (RuCl3·3H2O) (from Merck).
MWCNTs (from Sigma-Aldrich) were used as a support for
the catalysts. Ethylene glycol (EG) (from Merck) was used as
the solvent and reduction agent. Nafion® (DE 521, DuPont
USA) dispersion was used to make the catalyst ink. Ethanol
(from Merck), sodium percarbonate (from Riedel), and H2SO4
(from Merck) were used as the fuel, the oxidant, and the elec-
trolyte for electrochemical analysis, respectively. All the
chemicals were of analytical grade. For the experiment de-
scribed in this paper, the catalyst on the anode is MWCNT
supported bimetallic Pt–Sn 50:50 at.% and trimetallic Pt–Sn–
M (M = Ru, Ni, and Ir) (60:30:10) at.% with a metal loading
of 0.28 mgmetal cm−2. Pt/C (40 wt%, from E-TEK) was used as
the cathode catalyst.
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Catalyst preparation
Synthesis of nanocatalysts
The Pt–Sn/MWCNT, Pt–Sn–Ru/MWCNT, Pt–Sn–Ni/
MWCNT, and Pt–Sn–Ir/MWCNT nanocatalysts were synthe-
sized by the ultrasonic assisted chemical reduction method
(Fig. 1). For the synthesis of nanocatalyst, multiwalled
CNTs with purity higher than 95% were purchased from
Sigma-Aldrich. The main ranges of diameter, length, and sur-
face area of the MWCNTs were 6–13 nm, 20 μm, and
220 m2 g−1, respectively. Without surface modification,
CNT leads to poor dispersion and aggregation of metal nano-
particles, especially at high loading conditions. Therefore,
functionalization of CNT should be done in order to introduce
more binding sites and surface anchoring groups, before the
practical applications. An oxidative pretreatment of the
MWCNTs was performed by ultrasonic dispersion in a mix-
ture of concentrated sulfuric and nitric acids (1:1 v/v, 98 and
70%, respectively) at room temperature, for 2 h. This treat-
ment introduces surface-bound polar hydroxyl and carboxylic
acid groups for subsequent anchoring and reductive conver-
sion of precursor metal ions to metal nanoparticles. Then, the
MWCNTs were filtered and washed by deionized (DI) water
until the pH of the filtrate became 7 and subsequently dried in
a vacuum oven at 90 °C for 5 h. The Pt–Sn and Pt–Sn–M (M =
Ru, Ni, and Ir) content in each sample was 40 wt%, and Pt/Sn
and Pt/Sn/M (M = Ru, Ni, and Ir) atomic ratios were 1:1 and
6:3:1, respectively. Generally, 2.67 ml 0.038 M H2PtCl6 in
ethylene glycol and 2.78 ml 0.036 M SnCl2 in ethylene glycol
were mixed with 50 ml ethylene glycol in a two-necked flask.
About 70 mg of MWCNTs was added to the mixture, and the
pH value of the mixture was adjusted to 9 by adding 0.5 M
NaOH in ethylene glycol. The solution was ultrasonicated for
30 min and placed in a microwave oven and heated for 3 min.
The solution was then filtered and washed with ethanol and DI
water, and the filtration was repeated several times. Finally,
the Pt–Sn/MWCNT catalyst were dried in a vacuum oven at
80 °C for 5 h. The preparation of Pt–Sn–M/MWCNTs (M =
Ru, Ni, and Ir) catalysts was similar to that of the Pt–Sn/
MWCNT catalyst, except that an appropriate amount of
H2PtCl6, SnCl2, H2IrCl6, NiCl2, and RuCl3 in ethylene glycol
was mixed in the reaction solution.
Structural catalyst characterization
The morphology of the dispersed catalysts was examined
using TEM (Philips CM 12 Transmission Electron
Microscope). The particle size distribution and mean particle
size were also evaluated using TEM. The crystal structure of
the synthesized electrocatalysts was characterized by powder
XRD using a Rigaku multiflex diffractometer (model RU-200
B) with a Cu Kα1 radiation source (λ Kα1 = 1.5406 Å)
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Fig. 1 Schematic illustration showing synthesis of multiwalled carbon nanotube supported metal alloy catalyst by ultrasonic assisted chemical reduction

operating at room temperature. The tube current was 40 mA Results and discussion
with a tube voltage of 40 kV. The 2θ angular regions between
20° and 90° were recorded at a scan rate of 5° min−1. The Physical characterization
mean particle size analyzed from TEM was verified by deter-
mining the crystallite size from the XRD pattern using XRD
Scherrer formula [21]. The Pt (2 2 0) diffraction peak was
selected to calculate the crystallite size, and the Bragg’s equa- The XRD analyses were performed to obtain the structural
tion was used to obtain the lattice parameters of platinum alloy information of the catalysts. Figure 2 shows the XRD patterns
nanocatalysts. The atomic ratio of the catalysts was deter- of Pt/MWCNT, Pt–Sn/MWCNT, Pt–Sn–Ru/MWCNT, Pt–
mined by an EDX analyzer, which was integrated with a Sn–Ni/MWCNT, and Pt–Sn–Ir/MWCNT nanocatalysts,
TEM instrument. which clearly displayed the characteristic peaks (2θ = 25.6°)
of MWCNTs. The diffraction peaks at around 40°, 47°, 67°,
Electrochemical measurements and electrode and 82° were attributed to the Pt (1 1 1), (2 0 0), (2 2 0), and (3
preparation 1 1) crystalline planes, respectively, which represented the
typical character of the crystalline Pt, with a face-centered
All electrochemical measurements were carried out using an cubic (fcc) structure. In the case of Pt–Sn/MWCNT and Pt–
electrochemical workstation (CHI-6650; CH Instruments, Sn–M/MWCNT (M = Ru, Ni and Ir), the presence of Sn shifts
USA) in a conventional three electrode cell assembly the Pt peaks from 40° and 67° to lower diffraction angle 39°
consisting of a glassy carbon disk as a working electrode, a and 66° which confirms that the addition of Sn to Pt extends
Pt foil as a counter electrode, and Ag/AgCl as a reference the fcc lattice parameters. The slight shifts of the diffraction
electrode. The working glassy carbon electrode was prepared
using the following steps: First, 10 mg of Pt/MWCNT, Pt–Sn/
MWCNT, and Pt–Sn–M/MWCNT (M = Ru, Ni, and Ir) cat-
alysts was suspended separately in a mixed solvent (iso-pro-
pyl alcohol (500 μL), DI water (500 μL), and 5 wt% Nafion
solution (100 μL, Aldrich)), with ultrasonication for 20 min.
Ten microliters of ultrasonically homogenized ink were drop-
coated on to a freshly polished glassy carbon electrode (A =
0.125 cm2), and the solvent was then evaporated in open air at
room temperature. The loading of metal on the working elec-
trode was 0.28 mgmetal cm−2. The electrochemically active
surface areas (ECASA) of the Pt/MWCNT, Pt–Sn/MWCNT,
and Pt–Sn–M/MWCNT (M = Ru, Ni, and Ir) catalysts were
determined using CO stripping voltammetry in 0.5 M H2SO4
solution. CO adsorption was achieved at 0.1 V versus Ag/
AgCl in a CO saturated solution for 10 min, and the electrolyte
was purged with nitrogen for 10 min to remove the CO on the
surface. The electrochemical activity of the ethanol oxidation
reaction was measured by cyclic voltammetry in a half cell at a
scan rate of 50 mV s −1 at room temperature in 1 M
CH3CH2OH and 0.5 M H2SO4 solutions. All potentials in this Fig. 2 X-ray diffraction patterns of Pt/MWCNT, Pt–Sn/MWCNT, and
study were scaled versus Ag/AgCl. Pt–Sn–M/MWCNT (M = Ru, Ni, and Ir) nanocatalysts
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Table 1 Characterization parameters for the Pt/MWCNT, Pt–Sn/MWCNT, and Pt–Sn–M/MWCNT (M = Ru, Ni, and Ir) nanocatalysts

Nanocatalysts (2 2 0) Diffraction Lattice Average crystallite Average particle size

peak position parameter (A) size d from XRD (nm) from TEM (nm)
(2θ°)
Nominal Experimental

Pt100/MWCNTs – 67.8 3.906 3.8 3.6

Pt50–Sn50/MWCNTs Pt48–Sn52/MWCNTs 66.38 3.979 3.53 3.2
Pt60–Sn30–Ru10/MWCNTs Pt57–Sn32–Ru11/MWCNTs 66.42 3.978 3.35 3.0
Pt60–Sn30–Ni10/MWCNTs Pt58–Sn31–Ni11/MWCNTs 66.53 3.972 3.20 2.9
Pt60–Sn30–Ir10/MWCNTs Pt59–Sn29–Ir12/MWCNTs 66.75 3.960 3.10 2.6

peaks reveal the formation of an alloy involving the incorpo- observed in the XRD patterns. The average crystallite size d,
ration of Sn and M (M = Ru, Ni, and Ir) atoms into the fcc estimated from the Pt (2 2 0) diffraction peaks, according to
structure of Pt. No diffraction peaks related to pure Sn and M the Scherrer formula, were 3.8, 3.53, 3.35, 3.20, and 3.10 nm
(M = Ir, Ni, and Ru) atoms or their oxides/hydroxides were for Pt/MWCNT, Pt–Sn/MWCNT, Pt–Sn–Ru/MWCNT, Pt–

Fig. 3 TEM images and

histograms of a, d Pt–Sn–Ru/
MWCNTs, b, e Pt–Sn–Ni/
MWCNTs, and c, f Pt–Sn–Ir/
MWCNTs
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Sn–Ni/MWCNT, and Pt–Sn–Ir/MWCNT nanocatalysts, re-
spectively, which were very close to those obtained by TEM.
The lattice parameters and the average crystallite size of the
catalysts obtained from the XRD patterns are listed under
Table 1. When compared with Pt/MWCNT nanocatalysts,
Pt–Sn/MWCNT and Pt–Sn–M/MWCNT (M = Ru, Ni, and
Ir) nanocatalysts have smaller average particle sizes. In fact,
a decrease in the lattice parameters of the alloy catalysts re-
flects the progressive increase in the incorporation of Sn and
M (M = Ru, Ni, and Ir) atoms into the alloy state. Among the
four catalysts, Pt–Sn/MWCNT (3.979), Pt–Sn–Ru/MWCNT
(3.978), and Pt–Sn–Ni/MWCNT (3.972), the lattice parameter
of Pt–Sn–Ir/MWCNTs (3.960) is the smallest.
Transmission electron microscopy
The particle size, morphology, and size distribution have a
significant effect on the performance of electrocatalysts [22].
With this in mind, TEM was carried out to investigate the
particle size and distribution of Pt, Pt–Sn, and Pt–Sn–M (M
= Ru, Ni, and Ir) nanocatalysts on the surface of MWCNTs.
The TEM images of Pt/MWCNT, Pt–Sn/MWCNT, and Pt–
Sn–M/MWCNT (M = Ru, Ni, and Ir) nanocatalysts are shown
in Fig. 3a–f, together with the obtained averaged value of the
Fig. 4 The EDX spectra of a Pt/
MWCNTs, b Pt–Sn/MWCNTs, c
Pt–Sn–Ru/MWCNTs, and d Pt–
Sn–Ni/MWCNTs, e Pt–Sn–Ir/
MWCNTs
particle diameter distribution histograms. It can be seen from
Fig. 3a–f that the spherical Pt, Pt–Sn, and Pt–Sn–M (M = Ru,
Ni, and Ir) nanoparticles, with sizes of 2–4 nm, are uniformly
distributed on the surface of the MWCNTs. The small particle
size and the homogeneous size distribution of the catalysts are
ascribed to the rapid reduction of the metal salts, and the easy
granulation of the metal alloy nanoparticles on the MWCNTs
is facilitated by ultrasonic assisted chemical reduction [23,
24]. In comparison to the monometallic Pt/MWCNTs and
bimetallic Pt–Sn/MWCNTs, the mean particle size of the
trimetallic Pt–Sn–M/MWCNT (M = Ru, Ni, and Ir)
nanocatalysts was smaller. The variation in the mean particle
size of these catalysts was quite similar in both the cases (TEM
and XRD), indicating a good particle dispersion without for-
mation of large particle aggregates (Table 1).
Energy-dispersive X-ray analysis
Energy-dispersive X-ray (EDX) analysis was used to check the
presence of metal particles used to prepare catalysts by the
ultrasonic assisted chemical reduction method. The catalysts
prepared had the desired elements with some variations in com-
position. The EDX analyses of all the Pt/MWCNT, Pt–Sn/
MWCNT, Pt–Sn–M/MWCNT (M = Ru, Ni, and Ir) catalysts

are shown in Fig. 4a–e. Figure 4a–e indicates the presence of Pt,
Sn, Ir, Ni, Ru, and C, respectively. The EDX results are shown
in Table 1. The EDX results of the bimetallic Pt–Sn/MWCNT
and the trimetallic Pt–Sn–M/MWCNT (M = Ru, Ni, Ir) cata-
lysts were extremely close to the nominal values, indicating that
the metals were loaded onto the support without obvious loss.
Electrocatalytic activities of nanocatalysts
CO stripping To investigate the catalytic activity of synthe-
sized nanocatalysts supported on MWCNTs for EOR and
the performance of MLEFC, COads stripping voltammograms
were conducted in 0.5 M H 2SO4 at room temperature.
Figure 5 shows the COads stripping voltammograms of Pt–
Sn–Ir/MWCNT, Pt–Sn–Ni/MWCNT, Pt–Sn–Ru/MWCNT,
Pt–Sn/MWCNT, and Pt/MWCNT nanocatalysts at a CO ad-
sorption potential of 0.07 V and a sweep rate of 50 mV s−1
between 0.05 and 0.9 V versus Ag/AgCl. These conditions
allowed elimination of all adsorbed CO during the first cycle,
and the current in a second cycle coincided with the baseline
in the case of the pure supporting electrolyte. The COads oxi-
dation peaks of the MWCNT substrates were observed at 0.35,
Fig. 5 CO stripping voltammograms of Pt/MWCNT, Pt–Sn/MWCNT,
Pt–Sn–Ru/MWCNT, Pt–Sn–Ni/MWCNT, and Pt–Sn–Ir/MWCNT
nanocatalysts in 0.5 M H2SO4 at room temperature with a scan rate of
50 mV s−1
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0.25, and 0.2 V versus Ag/AgCl, for Pt, Pt–Sn, and Pt–Sn–M
(M = Ru, Ni, and Ir) nanocatalysts, respectively. For the Pt–
Sn–M/MWCNT (M = Ru, Ni, and Ir) nanocatalysts, there was
a cathodic shift of at least 150 mV because of CO oxidation,
compared to Pt/MWCNTs. The peak positions in the voltam-
mograms of the bimetallic Pt–Sn/MWCNTs and trimetallic
Pt–Sn–M/MWCNTs (M = Ru, Ni, and Ir) nanocatalysts were
similar, but the peaks of the bimetallic nanocatalysts were less
symmetric than those of trimetallic nanocatalysts. The higher
symmetry of the oxidation peak in the voltammograms of Pt–
Sn–M/MWCNTs suggested that effective, strong electronic
interactions took place between the Pt–Sn–M nanoparticles
and the MWCNTs.
Cyclic voltammetry
Electrocatalytic activities of the monometallic Pt/MWCNT, bi-
metallic Pt–Sn/MWCNT, and tri-metallic Pt–Sn–Ru/MWCNT,
Pt–Sn–Ni/MWCNT, and Pt–Sn–Ir/MWCNT nanocatalysts for
the oxidation of ethanol were investigated, using cyclic volt-
ammetry. Figure 6 shows the cyclic voltammetry of
nanocatalysts deposited on a glassy-carbon electrode in the
absence of ethanol. The voltammograms of the electrocatalysts
did not display a well-defined hydrogen adsorption–desorption
region (0–0.4 V) as observed for Pt alloys [25]. The current for
all the alloys in the double layer region (0.4–0.8 V vs. Ag/
AgCl) was larger compared to pure platinum. The behavior
of the voltammograms was characteristic of bi-metallic and
tri-metallic nanocatalysts containing transition metals [25].
The current values were normalized per gram of platinum,
considering that ethanol adsorption and dehydrogenation oc-
curred only on platinum sites at room temperature [10].
Fig. 6 Cyclic voltammetry of Pt/MWCNT, Pt–Sn/MWCNT, and Pt–Sn–
M/MWCNT (M = Ru, Ni, and Ir), nanocatalysts in 0.5 M H2SO4 at room
temperature with a scan rate of 50 mV s−1
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To investigate the electrocatalytic activity of the

nanocatalysts for ethanol oxidation, the electrochemically ac-
tive surface area (ECASA) was estimated using different pro-
cedures, namely, CO adsorption (ECASA/CO), hydrogen
adsorption/desorption charge (ECASA/H), and roughness of
electrodes. The ECASA values of the nanocatalysts were cal-
culated by using Eqs. (1) and (2).

QH ðμC=cm2 Þ
S ECASA=H m2 =g ¼ ð1Þ
210ðμC=cm2 Þ  0:77  ½Pt

QCO ðμC=cm2 Þ
S ECASA=CO m2 =g ¼ ð2Þ
420ðμC=cm2 Þ  ½Pt

where QH and QCO are the charges corresponding to desorption

of hydrogen and CO on the Pt surface, respectively; [Pt]
(mg cm−2) is the Pt loading on the electrode surface; 210 and
420 μC/real cm2 is the charge required to oxidize a monolayer
of hydrogen and CO, respectively, on the Pt surface; and 0.77 is
the hydrogen monolayer coverage [26]. The calculated
ECASA/H values are 98, 106, 118, and 128 m2 gPt−1 for Pt–
Sn/MWCNT, Pt–Sn–Ru/MWCNT, Pt–Sn–Ni/MWCNT, and
Pt–Sn–Ir/MWCNT, respectively. Obviously, the Pt–Sn–M/
MWCNTs (M = Ru, Ni, and Ir) have close ECASA, but they
are higher than that of Pt–Sn/MWCNTs, which is attributed to
the different active sites. The roughness of each electrode is
calculated by dividing the ECASA obtained with the apparent
surface area. Estimation of the electrode roughness and
ECASA values is shown in Table 2.
Figure 7 shows the cyclic voltammograms of ethanol oxi-
dation under acidic conditions (1.0 M CH3CH2OH and 0.5 M
H2SO4) catalyzed by Pt/MWCNT, Pt–Sn/MWCNT, Pt–Sn–
Ru/MWCNT, Pt–Sn–Ni/MWCNT, and Pt–Sn–Ir/MWCNT
nanocatalysts. The voltammograms consist of two oxidation
peaks: one in the forward scan and the other in the backward
scan. It was observed that the oxidation of platinum and its
alloy surfaces occurred during the forward scan, when the
switching potential exceeded 1.1 V versus Ag/AgCl, and dur-
ing the backward scan, the reduction peak was observed at
around 0.5–0.6 V versus Ag/AgCl. Hence, the CV was con-
ducted within the potential range of 1.1 and 0.2 V versus Ag/
AgCl. The forward scan was attributable to ethanol oxidation,
Fig. 7 Cyclic voltammetry of Pt/MWCNT, Pt–Sn/MWCNT, and Pt–Sn–
M/MWCNT (M = Ru, Ni, and Ir) nanocatalysts in 0.5 M H2SO4 and
1.0 M ethanol at room temperature with a scan rate of 50 mV s−1
forming Pt-adsorbed carbonaceous intermediates, including
carbon monoxide and CO2. This adsorbed carbon monoxide
(COads) caused the loss of activity of the electrocatalyst. The
backward oxidation peak was attributed to the additional ox-
idation of the adsorbed carbonaceous species to carbon
dioxide.
Therefore, the current ratio of the forward scan peak current
(IF) over the backward scan peak current (IB) shows the amount
of ethanol oxidized to carbon dioxide relative to carbon mon-
oxide [27, 28]. A higher IF/IB value suggests that the catalysts
are more efficient at lowering the adsorbed carbon monoxide.
The current ratio is a useful way of comparing the long-term
catalytic activity between the different catalysts. The MWCNT-
supported bimetallic and trimetallic nanocatalysts all exhibit at
least 60% higher IF/IB ratios relative to that of Pt monometallic
nanocatalysts (IF/IB), which is also prepared by the ultrasonic
assisted chemical reduction method. The calculated IF/IB ratios
are 1.05, 1.12, 1.19, and 1.25 for Pt–Sn and Pt–Sn–M (M = Ru,
Ni and Ir) respectively, which mean that the addition of M to
Pt–Sn improves the tolerance to carbonaceous species accumu-
lation. Table 3 summarizes the CV results of the prepared
nanocatalysts including the onset potentials, the forward peak
potentials, the forward peak current, and the current ratios (IF/
IB) of each nanocatalyst.

Table 2 Comparison of hydrogen

desorption charge and carbon Catalyst QH (μC) QCO (μC) Electrode real ECASA/H ECASA/CO Roughness
monoxide desorption charge and surface area (m2 gPt−1)a (m2 gPt−1)a
its electrochemical active surface (cm2)
area (ECASA) and electrode
roughness Pt/MWCNTs 889.3 2436 5.8 55 58 162
Pt–Sn/MWCNTs 792.3 2184 5.2 98 104 145
Pt–Sn–Ru/MWCNTs 979.4 2688 6.4 106 112 188
Pt–Sn–Ni/MWCNTs 1090 2880 6.8 118 121 201
Pt–Sn–Ir/MWCNTs 1182 3240 7.1 128 135 226

The electrochemical active surface area (ECASA/H and ECASA/CO) were calculated from Eqs. (1) and (2)
 Ionics

Table 3 CV results of Pt/

MWCNT, Pt–Sn/MWCNT, and Catalysts Onset potential Forward anodic peak Backward anodic peak IF/IB ratio
Pt–Sn–M/MWCNT (M = Ru, Ni, (IF) (mA cm−2) (IB) (mA cm−2)
and Ir) nanocatalysts at room
temperature Pt/MWCNTs 0.35 54 52 1.01
Pt–Sn/MWCNTs 0.25 81 77 1.05
Pt–Sn–Ru/MWCNTs 0.23 92 84 1.12
Pt–Sn–Ni/MWCNTs 0.21 103 86 1.19
Pt–Sn–Ir/MWCNTs 0.20 128 102 1.25

The CV results show that pure Pt/MWCNTs (Fig. 7) do not
behave as appropriate anodes for EOR because of their poi-
soning by strongly adsorbed intermediates such as CO [29].
However, the introduction of Sn and M (M = Ru, Ni, and Ir)
promotes the electrocatalytic activity of ethanol oxidation.
The EOR starts at approximately 0.35 V on the Pt/MWCNTs
electrode, while the onset potential on Pt–Sn/MWCNTs is
noted at 0.25 V versus Ag/AgCl. Furthermore, the introduc-
tion of a third metal M (M = Ru, Ni, and Ir) into the Pt–Sn/
MWCNTs, significantly reduces the onset potential to approx-
imately 0.2 V versus Ag/AgCl (i.e., it is shifted to the negative
potential by 0.15 V in comparison to Pt/MWCNTs) and raises
the current density at the Pt–Sn–M (M = Ru, Ni, and Ir)
nanocatalysts. Table 4 summarizes the CV results of the pre-
pared electrocatalysts positive peak potentials and the corre-
sponding peak current densities of EOR.
In fact, as observed in Fig. 7, the introduction of Sn and/or
M (M = Ru, Ni, and Ir) leads to an increase in the
electroactivity of the bimetallic and trimetallic electrocatalysts
compared to pure Pt. The synergistic effect obtained with
these elements can be explained by the activation of interfacial
water molecules at lower potentials than in the case of pure Pt
due to the presence of preferential sites for OH adsorption, as
proposed in the case of Pt–Ru for methanol electrooxidation
[30]. The presence of OH species in large amounts is neces-
sary for the complete oxidation of poisoning intermediates
such as CH x and CO. When compared with Pt–Sn/
MWCNTs, the superior activity of Pt–Sn–M/MWCNTs dur-
ing ethanol oxidation can be ascribed to the addition of the
third metal (i.e., Ru, Ni, and Ir), the effect of which can be
explained by the hydrogen-spillover phenomena [31] and
modification of Pt electronic states [32], resulting in a combi-
nation of electronic effect and bifunctional mechanism. The
third metal M (M = Ru, Ni, and Ir) promotes water activation,
which generates more species of –OHads to oxidize CO like
intermediates and release more active sites of Pt.
Chronoamperometry
Electrocatalytic activity toward ethanol electrooxidation of Pt/
MWCNT, Pt–Sn/MWCNT, Pt–Sn–Ru/MWCNT, Pt–Sn–Ni/
MWCNT, and Pt–Sn–Ir/MWCNT catalysts in 0.6 V potential
range is obtained from chronoamperometry (CA) measure-
ments. The potential was held at 0.6 V for 2 h. In all five CA
curves shown in Fig. 8, the current drops continually with time
and after some time it becomes relatively stable. The current
value may decay due to poisoning of surface active sites and
instability of catalyst particles. The trimetallic Pt–Sn–M/
MWCNT (M = Ru, Ni, and Ir) electrocatalysts gave higher
current than the bimetallic Pt–Sn/MWCNT electrocatalysts.
Higher current obtained for the trimetallic electrocatalysts
may be explained by the operation of a beneficial synergistic

Table 4 Positive peak potential and peak current density of Pt/

MWCNT, Pt–Sn/MWCNT, and Pt–Sn–M/MWCNT (M = Ru, Ni, and
Ir) nanocatalysts at room temperature

Catalyst Scan rate (50 mV s−1)

Positive peak potential Peak current density

(V vs. Ag/AgCl) (mA cm−2)

Pt/MWCNTs 0.77 54
Pt–Sn/MWCNTs 0.74 81
Pt–Sn–Ru/MWCNTs 0.72 92
Pt–Sn–Ni/MWCNTs 0.71 103
Pt–Sn–Ir/MWCNTs 0.70 128 Fig. 8 Chronoamperometry of Pt/MWCNT, Pt–Sn/MWCNT, and Pt–
Sn–M/MWCNT (M = Ru, Ni, and Ir) nanocatalysts at room temperature
Ionics
effect between Sn and M. This may indicate an increase in
structural defects or roughness, making the trimetallic
electrocatalysts better candidates for ethanol electrooxidation
[33]. Furthermore, the addition of small amount of M (M =
Ru, Ni, and Ir) to the Pt–Sn alloy electrocatalysts can lead to
an increase in the surface oxophilic character, thus increasing
the Sn–O bond strength and the acidity of the Sn–OH sites,
which can favor ethanol electrooxidation at lower potentials
[34]. On the other hand, introduction of M (M = Ru, Ni, and
Ir) may improve the activity of Pt–Sn catalyst, and the improve-
ment may be due to the ability of M (M = Ru, Ni, and Ir) to bind
to C [35]. This indicates that only a small amount of M in Pt–
Sn–M/MWCNT (M = Ru, Ni, and Ir) catalyst helps in
electrooxidation of ethanol. These results support the sugges-
tion that the trimetallic catalyst achieves good stability after
continuous run of 2 h.
Single cell performance
The effects of Pt–Sn–Ir/MWCNT, Pt–Sn–Ni/MWCNT, Pt–
Sn–Ru/MWCNT, Pt–Sn/MWCNT, and Pt/MWCNT
nanocatalysts were evaluated as anode catalysts in a single
membraneless ethanol fuel cell (MLEFC) for ethanol
electrooxidation. Figure 9 shows the polarization and power
density curves of the MLEFC with different catalysts at a
loading of 2 mg cm−2. The operating conditions were 1.0 M
ethanol and 0.1 M sodium percarbonate in 0.5 M H2SO4 as the
anodic and cathodic feed, respectively, at the flow rate of
0.3 mL min−1 in each stream, at room temperature. When
Pt/MWCNTs were used as the anode catalyst, the performance
of the single cell was poor. The open-circuit potential (OCP)
was 0.49 V, far less than the reversible OCP (1.145 V), which
was mainly attributed to poor catalytic activity and CO poi-
soning toward ethanol electrooxidation. The maximum output
power density for Pt/MWCNTs was 18.1 mW cm−2. The re-
sults of MLEFC adapting to different catalysts are summa-
rized in Table 5.
0.9 Pt/MWCNT
Pt-Sn/MWCNT
0.8
0.7
0.6
Potential (V)
0.5
0.4
0.3
0.2
0.1
0.0
0 20 40 60 80 100 120 140 160 180 200 220 240 260
Current density mA cm-2
Fig. 9 Polarization and power density curves of Pt/MWCNT, Pt–Sn/
MWCNT, and Pt–Sn–M/MWCNT (M = Ru, Ni, and Ir) nanocatalysts
Table 5 Summary of the performance of single fuel cell tests using Pt/
MWCNT, Pt–Sn/MWCNT, and Pt–Sn–M/MWCNT (M = Ru, Ni, and Ir)
nanocatalysts
Anode catalysts Open circuit Maximum Maximum current
voltage (V) power density density (mA cm−2)
(mW cm−2)
Pt/MWCNTs 0.66 18.1 125
Pt–Sn/MWCNTs 0.71 24.2 189
Pt–Sn–Ru/MWCNTs 0.76 37.1 215
Pt–Sn–Ni/MWCNTs 0.79 38.4 228
Pt–Sn–Ir/MWCNTs 0.85 39.25 247
When the current was normalized to the geometric area of a
single cell, it was observed that the cell performance of Pt–
Sn–Ir/MWCNTs was better than that of other catalysts. In the
low current discharging region, the power drawn from a single
cell was almost the same for all catalysts except Pt/MWCNTs.
However, as the voltage reached around 0.3 V, the Pt–Sn–Ir/
MWCNTs started drawing more current in comparison to
others. The open-circuit potential for bimetallic Pt–Sn/
MWCNTs was (0.71 V) lower than the Pt–Sn–M/MWCNTs
(M = Ru, Ni, and Ir) nanocatalysts. In addition, there was a
rapid initial fall in the cell voltage for all catalysts, which was
because of the slow initial ethanol electrooxidation reaction at
the electrode surface. After an initial drop of 30 mV, the
change in slope of the polarization curve for Pt–Sn–Ir/
MWCNTs decreased, and it started drawing more current.
This was attributed to the more effective catalytic ability of
Pt–Sn–Ir/MWCNTs, once the ethanol electrooxidation reac-
tion was initiated. On the basis of the peak power density
drawn from a single cell, Pt–Sn–Ir/MWCNT was the best
anode catalyst with a peak power density value of
39.25 mW cm−2. The results were similar to those of the cyclic
voltammetric and chronoamperometric measurements. The
enhanced performance could be attributed to the addition of
the third metal M (Ru, Ni, and Ir) to the Pt–Sn/MWCNT
Pt-Sn-Ru/MWCNT 40 catalyst for ethanol electrooxidation, and the promoting effect
Pt-Sn-Ni/MWCNT could be investigated in three aspects, the electronic effect, the
Pt-Sn-Ir/MWCNT 35
bifunctional mechanism, and the hydrogen spillover effect. As
30 evident from the results, the electron density of the third metal
Power density mW cm-2
25 M (M = Ru, Ni, and Ir) could be transferred to Pt. The catalytic
20
sites would increase because the coverage of COads on the Pt
surface was reduced on account of the decreased Pt–CO bind-
15
ing energy. On the other hand, the bifunctional mechanism has
10 been explored in previous studies as follows [36, 37].
5
MOx þ H2 O→MOx –OHads þ Hþ þ e− ð3Þ
0
þ −
Pt–COads þ MOx –OHads →Pt þ MOx þ CO2 þ H þ e ð4Þ
It is clear that MOx promotes the water activation to gener-
ate the species of OHads, which can oxidize CO, and thus,

enhance the activity of Pt–Sn–M/MWCNTs (M = Ru, Ni, and
Ir) nanocatalysts for ethanol oxidation.
Conclusion
In this study, Pt, Pt–Sn and Pt–Sn–M (M = Ru, Ni, and
Ir) nanocatalysts supported on MWCNTs were success-
fully synthesized by ultrasonic assisted chemical reduc-
tion. Well dispersion and size distribution were found
for the synthesized nanocatalysts. The trimetallic
nanocatalysts not only had a high electrochemically ac-
tive surface area and improved electrocatalytic activity
than that of bimetallic Pt–Sn/MWCNTs, for ethanol ox-
idation, but also indicated a simple way to prepare such
catalysts, while enhancing the electrochemical perfor-
mance. The effect of the operating conditions on the
performance of an MLEFC with Pt/MWCNTs, Pt–Sn/
MWCNTs, Pt–Sn–Ru/MWCNTs, Pt–Sn–Ni/MWCNTs,
and Pt–Sn–Ir/MWCNTs as anode catalysts was investi-
gated. The performance of an MLEFC using Pt–Sn–Ir/
MWCNTs as the anode catalyst was better than that of
the other catalysts synthesized by the same method,
which could be attributed to the electronic effect, the
bifunctional mechanism, and the hydrogen spillover.
These results indicated that MWCNTs could be good
candidates for use as supporting material in high-
loading metal catalysts in fuel cells. Durability of the
MLEFC was examined under acid media in a period of
about 2 h. The MLEFC maintained a relatively stable
performance with a little decay of cell voltage over the
test period. The fluctuation in the cell voltage was due
to addition of the new fuel solution, restarting the ex-
periments, or small variation in cell temperature. The
result of the durability test showed that the MLEFC in
our research has good stability at room temperature
which is able to satisfy the necessary conditions as por-
table power sources.
Funding information The financial support for this research from the
University Grants Commission (UGC), New Delhi, India, through a
Major Research Project 42-325/20134 (SR) is gratefully acknowledged.
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