Research Article

ISSN 1998-0124 CN 11-5974/O4

2019, 12(1): 000–000 https://doi.org/10.1007/s12274-019-2277-z

Novel highly active carbon supported ternary PdNiBi nanoparticles as

anode catalyst for the alkaline direct ethanol fuel cell
Bernd Cermenek1 (), Johanna Ranninger1, Birgit Feketeföldi2, Ilse Letofsky-Papst3, Norbert Kienzl4, Brigitte Bitschnau5,
and Viktor Hacker1 ()
1
Institute of Chemical Engineering and Environmental Technology, Graz University of Technology, NAWI Graz, Inffeldgasse 25/C, 8010 Graz, Austria
2
Institute for Surface Technologies and Photonics, JOANNEUM RESEARCH Forschungsgesellschaft mbH/Materials, Franz-Pichler-Straße 30, 8160
Weiz, Austria
3
Institute for Electron Microscopy and Nanoanalysis and Center for Electron Microscopy, Graz University of Technology, NAWI Graz, Steyrergasse
17, 8010 Graz, Austria
4
Bioenergy 2020+ GmbH, Inffeldgasse 21/B, 8010 Graz, Austria
5
Institute of Physical and Theoretical Chemistry, Graz University of Technology, Streymayrgasse 9, 8010 Graz, Austria

© The Author(s) 2019

Received: 14 October 2018 / Revised: 16 December 2018 / Accepted: 21 December 2018

ABSTRACT
The study focuses on the influence of Ni and Bi on alkaline ethanol oxidation reaction (EOR) activities, stabilities and structure characteristics
of carbon supported Pd-based nanocatalysts (Pd/C, Pd60Ni40/C, Pd60Bi40/C, Pd60Ni20Bi20/C) by cyclic voltammetry/chronoamperometry using
rotating disk electrode and various physico-chemical methods such as X-ray powder diffraction, X-ray photoelectron spectroscopy, transmission
electron microscopy coupled with energy dispersive X-ray spectroscopy and inductively coupled plasma optical emission spectrometry. Nickel
generates more adsorbed OH on the Pd catalyst surface than Bi and promotes the oxidation of adsorbed ethanol species. This results in a
low onset potential toward ethanol oxidation with high current density. The presence of Bi facilitates high tolerance toward various reaction
intermediates resulting from the incomplete ethanol oxidation, but might also initiate the agglomeration of Pd nanoparticles. The novel
Pd60Ni20Bi20/C nanocatalyst displays exceptional byproduct tolerance, but only satisfying catalytic activity toward ethanol oxidation in an
alkaline medium. Therefore, the EOR performance of the novel carbon supported ternary PdxNiyBiz anode catalyst with various atomic variations
(Pd70Ni25Bi5/C, Pd70Ni20Bi10/C, Pd80Ni10Bi10/C and Pd40Ni20Bi40/C) using the common instant reduction synthesis method was further optimized
for the alkaline direct ethanol fuel cell. The carbon supported Pd:Ni:Bi nanocatalyst with atomic ratio of 70:20:10 displays outstanding catalytic
activity for the alkaline EOR compared to the other PdxNiyBiz/C nanocatalysts as well as to the benchmarks Pd/C, Pd60Ni40/C and Pd60Bi40/C.
The synergy and the optimal content in consideration of the oxide species of Pd, Ni and Bi are crucial for the EOR kinetic enhancement in
alkaline medium.

KEYWORDS
alkaline direct ethanol fuel cell, catalytic activity, ethanol oxidation reaction, ternary PdNiBi nanocatalysts, structure characteristics

1 Introduction oxygen reduction reaction (ORR) are enhanced [1–6]. b) Non-noble

elements (e.g. Ni, Fe, Co, Bi or Mn) as admetals are used for the
The alkaline direct ethanol fuel cell (ADEFC) using non-Pt-based production of EOR and ORR catalysts to reduce the catalytic material
electrocatalysts, and cost-efficient materials to produce anion exchange costs and to enhance their catalytic performance [1–9]. c) The use of
membranes (AEMs), is a low-cost, environment-friendly and easy- the AEM instead of the cation exchange membrane (CEM) lowers
handling energy source as an alternative to batteries for small-scale the costs (AEM: 67.5 $·m−2 vs. CEM: 675 $·m−2) [1]. d) Due to the
portable applications [1]. reversed direction of ion conduction of AEMs (electro osmotic drag)
The ADEFC exhibits the following benefits compared to other low compared to CEMs, the ethanol-crossover is drastically reduced in
temperature fuel cells: the ADEFC [6, 10].
1) Ethanol is a sustainable, low-toxic, liquid fuel with high The main challenge of ADEFC, however, is to develop a highly
volumetric energy density (6.3 kWh·L−1) compared to methanol efficient anode catalyst for complete oxidation of ethanol to use
(4.8 kWh·L−1) and hydrogen (2.6 kWh·L−1) and thereby easy to handle, the total chemical energy stored in ethanol molecule in electricity.
store and transport [1–6]. Currently, there is no catalyst which cleaves the carbon–carbon bond
2) The production of ethanol from agricultural products or biomass of ethanol resulting in a CO2 efficiency of 100% according to C1
e.g. straw, corn, sugar cane or wheat compared to methanol and pathway (Scheme 1) at low temperatures due to mechanistic and/or
hydrogen avoids the use of limited availability fossil fuels as feedstocks sterical effects [11].
[3, 5]. The reaction mechanism of the ethanol oxidation on the
3) The usage of alkaline electrolytes leads to the following impro- currently used catalysts predominantly takes place on the C2 pathway
vements: a) The kinetics of ethanol oxidation reaction (EOR) and (Scheme 2), resulting in various reaction intermediate deposits on

Address correspondence to Bernd Cermenek, bernd.cermenek@tugraz.at; Viktor Hacker, viktor.hacker@tugraz.at

2 Nano Res.

CH3CH2OH → CH3CHOads → COads, CHx,ads → CO2 or CO32− The third element in carbon supported ternary anode catalysts
Scheme 1 Alkaline ethanol electrooxidation according to C1 pathway. for the ADEFC can additionally improve or strengthen the alkaline
EOR performances of the catalyst relating to catalytic activity
(onset potential and current density), long-term stability and byproduct
CH3CH2OH → CH3CHOads → CH3CHO/CH3COOH or CH3COO−
tolerance compared to carbon supported binary EOR catalysts
Scheme 2 Alkaline ethanol electrooxidation according to C2 pathway. [9, 19, 24–35].
For example, the addition of P and Zn to carbon supported PdNi
the active sites of the catalyst with a decrease of its performance. The catalyst (PdNi/C, C = Vulcan XC72R), forming ternary PdNiP/C
main products of alkaline EOR, generated by the reaction between and PdNiZn/C catalysts which exhibit higher EOR activity (lower
adsorbed ethanol and adsorbed OH on the present catalysts, are onset potential and higher peak current) than the binary PdNi/C
acetic acid (CH3COOH) and/or acetate (CH3COO−) [11]. catalyst [2, 9, 36].
The resulting reaction intermediates during the alkaline EOR Zhu et al. investigated the influence of elemental additives as Ni,
deactivate easily the carbon supported Pt-based catalysts and reduce Co and Ag on the electrocatalytic activities of binary PdSn-based
their efficiencies over time for the use in ADEFC [12–14]. Therefore, catalysts for alkaline EOR. This study demonstrated that the PdSn-
binary and ternary Pt-free catalysts are preferentially used for the based catalyst alloyed with Ag exhibited the best results related to
alkaline EOR. intrinsic activity and stability toward alkaline ethanol oxidation [19].
Carbon supported Pd (Pd/C) as monometallic catalyst exhibits In this study, the influence of Ni and Bi on the alkaline EOR
the best performance for the alkaline EOR compared to the other performance and the structure of carbon supported Pd-based
noble metals e.g. Pt and Au [14, 15] and is also more cost efficient nanocatalysts (Pd/C, Pd60Ni40/C, Pd60Bi40/C, PdxNiyBiz/C) were
than the others [1]. The addition of oxophilic elements such as Ni, Bi, investigated by electrochemical and various physico-chemical methods.
Ru, Sn, Zn or P improves the catalytic stability including tolerance to The optimization of the atomic composition of the novel carbon
poisonous species such as CO resulting from the ethanol oxidation supported ternary PdxNiyBiz catalyst was performed to improve
process (→ byproduct-tolerance) and activity (onset potential and its catalytic activity and stability for the alkaline EOR using the
peak current density or mass activity) of Pd catalysts with bi- and common instant reduction synthesis method with NaBH4 as reducing
polymetallic compositions due to bifunctional, electronic and agent for the ADEFC.
synergetic effects [2, 4, 7, 12, 16–20]. The poisoning of catalysts by
reaction intermediates of the incomplete ethanol oxidation thus
depends in particular on the nature of the catalyst used.
2 Experimental
The carbon supported bismuth (Bi/C) and nickel (Ni/C) electro-
2.1 Chemicals and materials
catalysts display no activities to alkaline EOR in the potential useful
range [2, 7, 21, 22]. A certain amount of Bi and Ni as elemental Palladium chloride (PdCl2, anhydrous, 59%–60% Pd basis, Aldrich),
additives (oxophilic elements) however, improve the alkaline EOR sodium chloride (NaCl; ≥ 99.5%, Aldrich), nickel nitrate hexahydrate
performance of Pd-based catalysts considerably [7, 22, 23]. (Ni(NO3)2·6H2O, Aldrich), bismuth(III) chloride (BiCl3, reagent
Nickel is often used as co-catalyst in Pd-based anode catalysts and grade, ≥ 98%, Aldrich), hydrochloric acid (HCl p.a. ≥ 32%, Fluka
promotes their alkaline EOR activities and stabilities for the ADEFC. Analytics), Vulcan XC72R carbon black (CABOT Corporation, USA),
One of many studies here, for example that of Shen and co-workers sodium borohydride (NaBH4, Sigma-Aldrich), 2-propanol (ASC ≥
confirms the performance improvement achieved by developing 99.8%, Sigma-Aldrich), sodium hydroxide (NaOH, Aldrich), 1.0 M
and testing of PdxNiy/C (C = Vulcan XC72R) catalysts with various potassium hydroxide standard solution (KOH, FIXANAL KA 180 mL,
atomic ratios. The enhancement of the alkaline EOR catalytic activities Sigma-Aldrich), Nafion ionomer solution (5 wt.%, Quintech), ethanol
was explained due to the affinity of Ni to form Ni–OHads species which abs. (99.999%, Aldrich), and ultra-pure water (≈ 18 MΩ·cm, Barnstead
facilitate the oxidation process to CH3COOH through a bifunctional NANOpure Water Purification system) were used for all in this study
mechanism and also by oxidative removal of poisonous ethanol performed experiments.
species from the catalyst surface. Furthermore, the alkaline EOR
performances of Pd-based electrocatalyst depend on the Ni content 2.2 Synthesis of ternary PdxNiyBiz/C nanocatalysts
which leads to a decrease in alkaline EOR activity when it is too high The carbon supported PdxNiyBiz nanocatalysts were synthesized by
due to the presence of Ni oxide species with low conductivity [4]. means of the instant reduction method using NaBH4 as a reducing
Shen et al. developed a carbon supported Pd-NiO catalyst with agent [37–40]. Firstly, PdCl2 and NaCl were completely dissolved in
lower onset potential and higher current density toward the alkaline 10 mL of ultra-pure water using an ultrasonic bath for several hours.
EOR compared to other Pd-oxide/C catalyst. The Pd-NiO/C anode The added NaCl causes a better solubility of PdCl2 in ultra-pure
catalyst shows higher byproduct tolerance of ethanol oxidation than water due to complex formation of sodium tetrachloropalladate
Pt-based catalysts [16]. (Na2[PdCl4]) (Eq. (1)).
Neto et al. show the influence of Bi on the alkaline EOR per-
formances of carbon supported binary PdxBiy catalysts (PdxBiy/C, PdCl2 + 2 NaCl → Na2[PdCl4] (1)
C = Vulcan XC72R) with various atomic ratios of (95:05), (90:10), Ni(NO3)2∙6H2O and BiCl3 were dissolved in 10 mL of ultra-pure
(80:20) and (70:30) using cyclic voltammetry for determination water. A few drops of HCl were added to the BiCl3 solution to dissolve
of their catalytic activities in comparison to a carbon supported the precipitated bismuth oxychloride (BiOCl). These dissolved pre-
monometallic Pd/C catalyst. The Bi content of 5 at.% and 10 at.% in cursor salts were added to the Na2[PdCl4] solution in a definite
Pd catalysts shifts the onset potentials toward the alkaline EOR to stoichiometry. Vulcan XC72R carbon black as support material was
lower potentials in contrast with Pd/C. The PdBi/C with the atomic suspended in 54 mL of 2-propanol and 6 mL of ultra-pure water for
ratio of (95:5) exhibits the best results relating to electrocatalytic 0.5 h using an ultrasonic bath. The metal salt solutions were added
activity and stability compared to the other catalysts. This study with additional 40 mL of ultra-pure water to suspended carbon
reveals that the kinetics of alkaline EOR and the byproduct tolerance support material (catalyst composition: 40 wt.% of metals and
on PdBi catalysts with low Bi content are improved by the oxidative 60 wt.% of carbon support material). The pH of the metal salts
removal of adsorbed ethoxy species (rate-determining step; Scheme 2) containing solution was adjusted to 10 using 5 M NaOH. After
from the catalytic sites of Pd [7]. drop-wise addition of the reducing agent solution (~ 3 eq. of NaBH4(s)

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Nano Res. 3

in 0.6 mL of 1 M NaOH and 6 mL of ultra-pure water) to the salt 2.4 Electrochemical characterization
suspension, the reaction mixture was vigorously stirred at 60 °C for
The EOR activities and stabilities of carbon supported Pd-based
4 h to reduce to respective metals on carbon support material Vulcan
electrocatalysts were determined by means of cyclic voltammetry
XC72R, giving the corresponding PdxNiyBiz/C. After cooling of the
(CV) and chronoamperometry (CA) using a rotating disk electrode
reaction mixture to room temperature (rt), multiple washing (three
(RDE; Model AFE5T050GC from PINE Research Instrumentation),
times) of the catalyst suspension was performed with ultra-pure
respectively [37, 40–42].
water including centrifugation at 3,500 rpm for 30 min. After each
The electrochemical measurements were performed in an elec-
washing process, the water was decanted from the product. Finally,
trochemical glass cell (Metrohm) with a three-electrode-arrangement
the obtained cleaned carbon supported PdxNiyBiz nanoparticles were
consisting of platinized titanium rod (Bank Elektronik – Intelligent
dried at 80 °C until constant weight was adjusted.
controls GmbH) as counter electrode, reversible hydrogen electrode
The syntheses of the other Pd-based nanocatalysts (Pd/C, Pd60Ni40/C
(RHE; HydroFlex®, gaskatel) as reference electrode and RDE as
and Pd60Bi40/C) were performed by the same procedure as for the
working electrode. A GAMRY (bi-)potentiostat (Reference 600TM
development of PdxNiyBiz/C nanocatalysts.
Potentiostat/Galvanostat/ZRA, GAMRY Instruments Inc., Pennsy-
2.3 Physico-chemical characterization lvania, USA) was used as control system. Before starting the
electrochemical measurement, the RDE with glassy carbon substrate
The actual elemental composition of each catalyst was analyzed by (geometric area: 0.196 cm2) was polished using 0.05 μm alumina
inductively coupled plasma optical emission spectrometry (ICP-OES). suspension (MasterPrep® Polishing Suspension; Buehler) and was
Metal concentrations of catalysts were determined by this method finally rinsed with ultra-pure water.
after microwave-assisted pressurized acid digestion. A Multiwave The synthesized catalysts were dissolved in a mixture of 1.75 mL
3000 microwave system (Anton Paar, Graz, Austria) was used for of 2-propanol, 0.737 mL of ultra-pure water and 13 μL of Nafion
digestion. Each material was analyzed in triplicate by digesting ionomer solution (5 wt.%, Quintech) as binder and were sonicated
5–10 mg of catalyst with 7 mL of concentrated nitric acid and for 15 min in an ice-bath until a homogeneous dispersion was formed.
0.2 mL of HClO4 (Carl Roth, Karlsruhe, Germany). Temperature An appropriate amount of catalyst ink was dropped onto the RDE
was ramped to 195 °C within 15 min with the application of 1,500 W in order to achieve the desired loading of 56 μgPd·cm−2. The RDE
of power, followed by a dwell time of 25 min at maximum tem- with the catalyst ink was dried by rotation to air at a rotation speed
perature. Samples were diluted to 25 mL with deionized water. The of 700 rpm for approximately 1.5 h. In the meantime, the alkaline
ICP-OES system was an Arcos SOP by Spectro (Kleve, Germany). electrolyte (1.0 M potassium hydroxide standard solution; FIXANAL
Following detection wavelengths were used for each element: Bi KA 180 mL, Sigma-Aldrich) was purged with nitrogen gas (N2, purity
223.061 nm, Ni 231.604 nm, Pd 340.458 nm. Sample blanks and spikes of 5.0, Air Liquide) for 30 min to remove the dissolved oxygen out
were included in all preparation procedures. of it, before the measurements were started. After that, the RDE with
The morphology, particle size distribution and the chemical the respective catalyst was immersed in the 1.0 M KOH, saturated
composition (atomic ratio) of each catalyst were determined by with nitrogen and CVs of each catalyst were recorded at a scan
means of the transmission electron microscopy coupled with energy rate of 50 mV·s−1 (cleaning cycles are fast oxidation and reduction
dispersive X-ray spectroscopy (TEM-EDX), respectively. The images processes to remove the impurities from the surface of the catalyst)
were acquired using a monochromated TF20 TEM (FEI) equipped and finally at a scan rate of 10 mV·s−1 in a stationary condition,
with a Schottky field emission gun and operated at 200 kV. The EDX respectively. After the addition of 1.0 M ethanol (purchased from
spectra were detected with an EDAX Si(Li) detector. For preparing ethanol absolute, 99.999%, Aldrich) to 1.0 M KOH, further CVs of
the TEM grids, we followed the standard preparation procedure for each catalyst was also recorded at a scan-rate of 10 mV·s−1 to determine
powder samples by depositing a drop of alcohol suspended sample the specific activity toward the ethanol oxidation in an alkaline
particles onto a copper TEM grid which was covered with a holey medium.
carbon support-film. Finally, all synthesized Pd-based catalysts were applied at a constant
The structural composition from each synthesized catalyst was potential of 0.83 V for 1 h under the same operating conditions as
investigated with X-ray powder diffraction (XRD), using a Bruker for CV-measurements to investigate their catalytic stabilities.
D8-Advance diffractometer with Lynxeye detector. XRD measurements
were performed from 20° to 100° 2θ, with a step size of 0.02° and a
scan time of 2 s per step. Cu-Kα radiation (λ = 0.15418 nm) was 3 Results and discussion
used for the XRD analysis. Lattice parameters and peak-widths were
calculated with Rietveld method, using PANalytical X’Pert Highscore 3.1 Physico-chemical characterization
Plus software. An estimation of mean crystallite size was performed An extensive physico-chemical characterization is very important
using Scherrer-method. for a better interpretation and understanding of performances of all
The X-ray photoelectron spectroscopy (XPS) is a qualitative and synthesized nanocatalysts for the alkaline EOR. Pd-based nanocatalysts
quantitative method to find more information about the chemical were analyzed by various methods, such as, ICP-OES, TEM-EDX,
composition from the binding energies of core-level-electrons of each XRD and XPS in this study.
contained element in synthesized catalysts. The X-ray photoelectron ICP-OES is an appropriate method for the quantitative deter-
spectrometer works under ultrahigh-vacuum (UHV) conditions mination of the elemental concentrations of the carbon supported Pd,
with a residual gas pressure below 10−10 mbar. Each catalyst sample PdxNiy, PdxBiy and various PdxNiyBiz catalysts with the calculated
was transferred into the analysis-chamber within several hours via atomic ratio of (100), (60:40), (60:40), and (60:20:20), (70:25:5),
load-lock. The system is also equipped with a UV-photoelectron (70:20:10), (80:10:10), (40:20:40). Analysis results by ICP-OES are
spectrometer. The following instrumentation is used for XPS-analysis: in good agreement with calculated values (= subscripts of catalysts)
“Multiprobe” UHV-surface-analysis system (Omicron Nanote- from the preparation of nanocatalysts (Table 1, detailed in Table S1
chnology); X-ray source: DAR400 aluminium-anode; quartz-crystal in the Electronic Supplementary Material (ESM)).
monochromator XM 500; X-ray excitation energy: 1,486.70 eV Metal nanoparticles (black) of the Pd/C catalyst are more evenly
(Al Kα1-line); monochromated X-ray line width (FWHM): 0.3 eV; distributed on the carbon support material Vulcan XC72R (grey)
energy analyzer: hemispherical analyzer, type EA 125 signal-detection than the bi- and ternary Pd-based catalysts. It can be observed that
with pulse-counting channeltron. the presence of Bi and Ni in carbon supported Pd-based catalysts

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4 Nano Res.

apparently causes an agglomeration of the metal nanoparticles Applying fast Fourier transformation (FFT) on high resolution
(Figs. 1(a)–1(d), and Figs. S1 and S2(a)–S2(d) in the ESM). It is very TEM (HRTEM) micrographs show that all carbon supported Pd-
difficult to determine the particle size of these catalysts, because based catalysts exhibit inter-planar spacing of ≈ 0.21 nm determined
insufficient spherical particles are presented for showing reproducible which complies with lattice spacing of Pd (111) (Figs. 1(e)–1(h) and
results due to the agglomeration. Figs. S2(e)–S2(h) in the ESM). Furthermore, scanning transmission
electron microscopy high-angle angular dark-field imaging (STEM-
Table 1 Elemental analysis of Pd-based nanocatalysts by ICP-OES HAADF) was used to determine semi-quantitatively the metal contents
Catalysts Pd (at.%) Ni (at.%) Bi (at.%) of the carbon supported Pd-based catalysts at specific chosen areas
Pd/C 100 — — by recording of EDX spectra (Figs. S3–S7 in the ESM). This analysis
Pd60Ni40/C 60 40 — confirms that the metal nanoparticles of bi- and ternary Pd-based
Pd60Bi40/C 61 — 39
catalysts are not homogeneously distributed on the carbon support
material (further details in the ESM).
Pd60Ni20Bi20/C 61 19 20
The instant reduction method using NaBH4 as reducing agent
Pd70Ni25Bi5/C 71 24 5
is therefore not the optimal catalyst synthesis method especially
Pd70Ni20Bi10/C 70 19 11
for controlling the homogeneous deposition of bi- and tri-metallic
Pd80Ni10Bi10/C 78 10 12 nanoparticles on carbon support material. Alternatively, nanocapsule,
Pd40Ni20Bi40/C 46 17 37 aqueous solution phase synthesis or the polyol method are other
synthesis procedures to minimize the agglomeration effect for
polymetallic catalysts [2, 9, 43].
The XRD patterns of all carbon supported Pd-based catalysts
exhibit the typical diffraction peaks approx. at the 2θ values of 40°,
47°, 68°, 82° and 86° which can be assigned to the Pd face-centered
cubic (fcc) crystalline structure (Pd_64922-ICSD) with miller indices
of (111), (200), (220), (311) and (222), respectively (Fig. 2 and Fig. S8
in the ESM) [2, 4]. The diffraction peak located approx. at the 2θ
value of 25° attributes to carbon black Vulcan XC72R as crystalline
structure of graphite (2H)_187640-ICSD with the miller indices of
(002) for all catalyst samples (Fig. 2 and Fig. S8 in the ESM) [2, 4].
The 2θ values of the binary and ternary catalysts (Pd60Ni40/C,
Pd60Bi40/C, Pd60Ni20Bi20/C, Pd70Ni20Bi10/C and Pd40Ni20Bi40/C) are slightly
lower (Tables S4–S6, S8 and S10 in the ESM) and their d-spacing
values and lattice parameters (Table 2) are slightly higher than for
the Pd/C catalyst (Table S3 in the ESM), which indicates that the
Pd lattice expands and is modified by alloying with Ni and Bi.
This statement is confirmed by various research groups [2, 7, 9, 12,
44, 45]. The determined inter-planar spacing for the catalysts in the
recorded HRTEM micrographs (Figs. 1(e)–1(h) and Figs. S2(e)–2(h)
in the ESM) conforms to the XRD results (Table 2).
Furthermore, the XRD pattern of the Pd60Ni40/C catalyst has
additional diffraction peaks approx. at 41°, 48°, 70°, 84° and 89°
close to the diffraction peaks of Pd fcc crystalline structure, which
is assigned to an alloying compound with a crystalline structure of
Pd09Ni08_106936-ICSD with the same miller indices (Fig. 2).
The XRD patterns of Pd60Bi40/C, Pd60Ni20Bi20/C, Pd80Ni10Bi10/C
and Pd40Ni20Bi40/C catalysts also reveal additional diffraction peaks
approx. at 24°, 30°, and 33° and were identified as crystalline structure
of Bi2O2(CO3)_252588-ICSD (Fig. 2 and Fig. S8 in the ESM).
The diffraction peak located at 27° is assigned to the crystalline
structure of Bi_53797-ICSD with the miller indices of (210) for the

 
Figure 1 TEM micrographs of the (a) Pd/C, (b) Pd60Ni40/C, (c) Pd60Bi40/C and
(d) Pd60Ni20Bi20/C catalyst. HRTEM micrographs including the determined inter-
planar spacing of the (e) Pd/C, (f) Pd60Ni40/C, (g) Pd60Bi40/C and (h) Pd60Ni20Bi20/C  
catalyst. Figure 2 XRD patterns of carbon supported Pd-based nanocatalysts.

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Nano Res. 5

Table 2 Structure analysis of carbon supported Pd-based catalysts by XRD (→ metallic Pd) and PdII species (→ PdO) on the surface of all catalysts
(Figs. 3(a)–3(d) and Figs. S9(a)–S9(d) in the ESM) according to Su
d-spacing Pd Lattice parameter Crystallite size
Catalysts
(111) (nm) (nm) (nm) et al., Wang et al. and Simões et al. [9, 12, 46]. It is observed that the
binding energy of the 3d5/2 peak of PdO for the Ni and Bi containing
Pd/C 0.2244 Pd: a = 0.3891 Pd: 9
Pd catalysts shifts negatively compared to Pd/C catalyst (Tables S11
Pd60Ni40/C 0.2245 Pd: a = 0.3904 Pd: 6–12 and S12 in the ESM and detailed in Tables S13–S20 in the ESM).
Pd09Ni08: a = 0.3816 Pd09Ni08: 9 Wang et al. explain this issue by a down-shift of the d-band center
Pd60Bi40/C 0.2259 Pd: a = 0.3904 Pd: 9 of Pd i.e. the down-shift of the core-level of Pd to the Fermi level of
PdBi_tetrag: a = 0.4567; PdBi_tetrag: 10 Pd due to alloying with oxophilic elements which enhance its ethanol
b = 0.726; c = 1.068 reaction intermediate tolerance resulting in a weak-interaction with
Pd60Ni20Bi20/C 0.2247 Pd: a = 0.3894 Pd: 5 the active sites of the catalyst (see electrochemical characterization
Bi2O2(CO3): a = 0.385; Bi2O2(CO3): > 10 results in Figs. 4(d), 4(h) and 4(l)) [9, 47].
b = 0.388; c = 1.3750 Furthermore, the decrease of PdII binding energies of 335.81,
Pd70Ni25Bi5/C 0.2230 Pd: a = 0.3863 Pd: 4 336.14, 335.95, 335.8, 335.86, 335.72 and 335.93 eV for Pd60Ni40/C,
Pd70Ni20Bi10/C 0.2247 Pd: a = 0.3892 Pd: 4 Pd60Bi40/C, Pd60Ni20Bi20/C, Pd75Ni20Bi5/C, Pd70Ni20Bi10/C, Pd80Ni10Bi10/C
Pd80Ni10Bi10/C 0.2229 Pd: a = 0.3894 Pd: 5 and Pd40Ni20Bi40/C catalysts compared to the PdII binding energy
of 336.27 eV for Pd/C catalyst suggests a suppression of the PdO
Pd40Ni20Bi40/C 0.2248 Pd: a = 0.3894 Pd: 5; Bi2O2(CO3): 8
formation due to alloying with Ni and Bi on the surface of bi- and
ternary Pd-based catalysts as reported by Su et al. (Tables S11 and
Pd60Bi40/C catalyst (Fig. 2). Also, tetragonal PdBi alloy (PdBi_tetrag_ S12 in the ESM and detailed in Tables S13–S20 in the ESM) [12].
56279-ICSD) is one of the main constituents of this catalyst (Table S5 Figures 3(e) and 3(f) show the doublets of Ni 2p1/2 and Ni 2p3/2
in the ESM). which assigned to NiII species such as NiO and Ni(OH)2 can be
The XRD patterns of Pd40Ni20Bi40/C and Pd60Bi40/C catalysts exhibit formed on the catalyst surfaces of Pd60Ni40/C and Pd60Ni20Bi20/C
a diffraction peak approx. at 28°, which is attributed to the crystalline according to Wang et al. [9]. The Ni 2p XPS spectra of the Pd75Ni20Bi5/C,
structure of Bi2O3_beta_189995-ICSD with the miller indices of (120) Pd70Ni20Bi10/C, Pd80Ni10Bi10/C and Pd40Ni20Bi40/C catalysts show that
(Fig. S8, Tables S5 and S10 in the ESM). More details about XRD data in the doublets of Ni 2p1/2 and Ni 2p3/2 only one NiII species is
with Rietveld-refinement for the carbon supported Pd-based catalysts observed which is attributable to NiO (Figs. S9(e)–S9(h) in the ESM)
are given in Tables S3–S10 in the ESM. compared to the XPS results of the Pd60Ni20Bi20/C and Pd60Ni40/C
The crystallite sizes of Pd and the alloyed compounds in the catalysts catalysts where Ni(OH)2 as the second NiII species was identified.
(Pd/C, Pd60Ni40/C, Pd60Bi40/C and PdxNiyBiz/C) were experimentally The measured values of the Ni 2p XPS spectra for all catalysts are
estimated in accordance with the Scherrer equation, assuming undefined (Figs. 3(e) and 3(f) and Figs. S9(e)–S9(h) in the ESM)—
spherical crystallites. The crystallites are in the order of 4 to 12 nm most likely due to the inhomogeneous distribution of the metal
(Table 2). nanoparticles on the carbon support material (see TEM-EDX results:
XPS was used to investigate the surface oxidation states, chemical Figs. S3–S7 in the ESM).
compositions and binding energies of Pd, Ni and Bi in all synthesized The surface of the Pd80Ni10Bi10/C catalyst contains the most oxide
catalysts. The recorded XPS spectra of Pd/C, Pd60Ni40/C, Pd60Bi40/C species of Pd, Ni and Bi (Tables S11, S12 and S19 in the ESM),
and the various PdxNiyBiz/C catalysts show different oxidation states but limits its catalytic activity for the alkaline EOR (Fig. 4(k)). The
for their elements (Fig. 3 and Fig. S9 in the ESM). presence of the lower Ni oxide content (lower electron and proton
As expected, the XPS results relating to the atomic content conductivity) of the Pd80Ni10Bi10/C catalyst is the main limiting factor
determinations in the bi- and ternary carbon supported Pd-based for its lower EOR activity compared to the other catalysts (Tables S11
catalysts have a discrepancy to ICP-OES analysis due to predominant and S12 in the ESM and detailed in Tables S13–S20 in the ESM). It
overlapping of Pd and Bi on Ni at the catalyst surface leading to has been shown literature that Ni oxide promotes significantly the
lower Ni content (Tables S11 and S12 in the ESM and detailed in EOR performance of the catalysts used [4, 16].
Tables S13–S20 in the ESM: deconvolution results of the elements). The doublets of Bi 4f5/2 and Bi 4f7/2 peaks (Fig. 3(g)) for the Pd60Bi40/C
The doublets of Pd 3d3/2 and Pd 3d5/2 peaks are attributed to Pd0 catalyst can be attributed to Bi0 and BiIII species such as metallic

 
Figure 3 Pd 3d XPS spectra of the (a) Pd/C, (b) Pd60Ni40/C, (c) Pd60Bi40/C and (d) Pd60Ni20Bi20/C catalyst. Ni 2p XPS spectra of the (e) Pd60Ni40/C and (f) Pd60Ni20Bi20/C
catalyst. Bi 4f XPS spectra of the (g) Pd60Bi40/C and (h) Pd60Ni20Bi20/C catalyst.

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6 Nano Res.

 
Figure 4 CVs of carbon supported Pd-based nanocatalysts (a), (e) and (i) in de-aerated 1.0 M KOH solution at 30 °C with a scan rate of 10 mV·s–1 and (b), (f) and (j) their
resulting determined EASA; (c), (g) and (k) in a mixture of 1 M KOH and 1 M EtOH at 30 °C with a scan rate of 10 mV·s–1. (d), (h) and (l) Determined tolerances of
Pd-based nanocatalysts toward ethanol reaction intermediates using the EOR measurements.

Bi, Bi2O3 and Bi(OH)3 located at 157, 158.21 and 159.19 eV [46]. homogeneous distribution on the glassy carbon substrate of RDE to
Metallic Bi and Bi2O3 species were also identified by XRD (Table S5 obtain reproducible results for electrochemical characterization.
in the ESM) in Pd60Bi40/C catalyst, which confirmed the XPS results. The addition of Nafion ionomer as binder shows according to
By contrast, the doublets of Bi 4f5/2 and Bi 4f7/2 peaks (Fig. 3(h)) Shinozaki et al. a better quality of catalyst dispersion than is the
for the Pd60Ni20Bi20/C catalyst are attributed to Bi2O3 and Bi(OH)3 case without Nafion ionomer in the context of the reproducibility
located at 157.78 and 159.35 eV [46]. It is assumed that no complete of the electrochemical active surface area (EASA), mass activity and
reduction of Bi oxide species to Bi has occurred for the synthesis the specific mass activity determinations of the catalyst in RDE
of the Pd60Ni20Bi20/C catalyst because the Bi peak (Bi0) in the XPS measurements [48]. The research group has found that the optimal
spectrum of Pd60Ni20Bi20/C catalyst is absent (Fig. 3(h)) compared to dispersion of catalyst particles was obtained if the Nafion ionomer
the XPS spectrum of Pd60Bi40/C catalyst, which conforms to the XRD with a concentration of 24 wt.% is used. Furthermore, it was stated
results (Table S5 in the ESM). that the temperature of the catalyst slurry increased while sonication
The resulting Bi 4f XPS spectra show that metallic Bi and Bi oxide whereby the EASA decreased due to thermally induced degradation
species are distributed on the surfaces of Pd70Ni25Bi5/C, Pd70Ni20Bi10/C of smaller catalyst particles. This temperature increase can be
and Pd40Ni20Bi40/C catalysts (Figs. S9(i), S9(j), and S9(l) in the ESM). counteracted by cooling of the catalyst slurry using an ice-water
It can be observed, however, that the doublets of Bi 4f5/2 and Bi 4f7/2 bath during the sonication process [48].
peaks from the Pd80Ni10Bi10/C catalyst shift by more than 1 eV Pollet and co-workers investigated the effect of the sonication
to higher binding energies, due to the increased measured oxygen parameters used in the distribution of catalyst inks based on Pt
content compared to the other catalysts (Figs. S9(i)–S9(k) and nanoparticles with Nafion ionomer as binder [49]. The frequency
Tables S11, S12, S17–S20 in the ESM) and the peak of metallic
and power of the sonication bath or probe significantly influence
Bi is absent. The explanation for the absence of Bi peak is already
the EASA, shown in a comparison of two samples with different
commented previously. An additional Bi oxide species on the
sonication times, the one sonicated for 120 min thus results in a
Pd80Ni10Bi10/C catalyst surface, such as Bi(OH)3, was identified
EASA decline of 45% compared to the other sonicated for 30 min.
(Fig. S9(k) in the ESM) as in Pd60Bi40/C and Pd60Ni20Bi20/C catalysts
(Figs. 3(g) and 3(h)) [46]. Furthermore, the XPS spectra obtained It was also reported that the Nafion ionomer separated from the Pt
for C and O are demonstrated in the ESM (Figs. S10 and S11 in the nanoparticles which then also agglomerated and dissolved by
ESM; additional information about XPS analysis). longer sonication time [49].
Subsequently, the results of the physico-chemical characterization The aforementioned studies concerning the effects of Nafion
will be used to interpret the electrochemical characterization results binder and the sonication parameters on the catalyst ink preparation
of all Pd-based electrocatalysts. and catalyst distribution on the RDE were also considered in our
experiments (see Experimental Section 2.4) and improvements were
3.2 Electrochemical characterization implemented. In this context we have thus developed an optimum
catalyst ink preparation procedure resulting in a homogeneous
3.2.1 Optimum catalyst ink preparation procedure
catalyst ink and homogeneous catalyst distribution on the RDE for
The catalyst ink preparation plays an important role for a reproducible results, respectively.

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Nano Res. 7

3.2.2 Ni and Bi effects on EOR performance of Pd/C catalysts The determination of the catalytic activity and stability toward
EOR of Pd/C, Pd60Ni40/C, Pd60Bi40/C and Pd60Ni20Bi20/C catalysts takes
CVs of Pd/C, Pd60Ni40/C, Pd60Bi40/C and Pd60Ni20Bi20/C catalysts place in a mixture of 1 M KOH and 1 M EtOH by means of CV using
were recorded stationary (without rotation) in a de-aerated 1.0 M RDE (without rotation) at 30 °C. The Pd60Ni40/C catalyst exhibits the
KOH electrolyte at 30 °C in a potential range of 0.05–1.2 V (Fig. 4(a)). best result relating to EOR activity compared to the other carbon
By the presence of Bi in carbon supported Pd electrocatalysts, the supported Pd-based catalysts (Fig. 4(c) and Table 3).
hydrogen adsorption/and absorption region (0.05–0.5 V) in the anodic Nickel as an additive is more oxophilic than Bi in the resulting
scan and cathodic scan of the CVs of Pd60Bi40/C and Pd60Ni20Bi20/C low onset potential of Pd60Ni40/C catalyst with a high produced
is drastically reduced (no distinct visible characteristic peaks) current density toward ethanol oxidation in alkaline medium
compared to the CVs of Pd/C and Pd60Ni40/C electrocatalysts compared to catalysts containing Bi (see small figure in Fig. 4(c)
(Fig. 4(a)). Neto et al. show the same effect of Bi in CVs of PdxBiy/C and Table 3) [51]. This means that Ni generates more adsorbed OH
catalysts in various atomic ratios [7]. Simões et al. confirm the on the Pd catalyst surface than Bi to oxidize the adsorbed ethanol
suppression of the hydrogen adsorption/absorption processes by Bi species quickly. Zhang et al. report that onset potentials of PdxNiy/C
on Pd and Pt containing Bi catalysts compared to monometallic Pd/C based catalysts toward ethanol oxidation depend significantly on
and Pt/C catalysts [46]. This suppression depends on the height of the surface concentration of Ni [2].
the amount of Bi atoms which are covered on the surface of the Pd Furthermore, in the synthesized Pd-based electrocatalysts Bi
catalyst and have strong interaction with Pd [46]. facilitates an essential improvement of the tolerance toward ethanol
Furthermore, another distinctive peak in the anodic scan for the intermediates from the EOR in the electrolyte mixture of 1 M KOH
Bi containing catalysts appears at approx. 0.9 V (Fig. 4(a)), which and 1 M EtOH (Fig. 4(d) and Table 3), but their onset potentials
attributed to Bi2O3 species from the reaction of Bi in the presence of shift to higher potentials (see small figure in Fig. 4(c) and Table 3)
an alkaline solution [50]. The Bi oxide species were also identified and their catalytic activities decrease (Fig. 4(c) and Table 3) compared
by XRD (Tables S5 and S6 in the ESM). The oxidation of Bi in KOH to Pd/C and Pd60Ni40/C catalysts, respectively. The higher onset
electrolyte starts at approx. 0.5 V to Bi(OH)3 as a non-soluble potential and the lower specific activity of the Pd60Bi40/C catalyst
compound, identified in the Bi2O3 phase according to Simões et al. toward the ethanol oxidation compared to the Pd60Ni20Bi20/C catalyst
(Fig. 4(a)) [46]. (Fig. 4(c) and Table 3) are due to its higher Bi content thus formed
The reduction current peak in the cathodic scan between the Bi oxide species block multiple active sites of Pd [7].
potential of 0.5 and 0.9 V can be attributed to the formation of Pd The tolerance toward EOR intermediates was determined by two
and/or Bi oxide species in the study synthesized catalysts (Figs. 4(a), different methods (Figs. 4(d), 4(h) and 4(l)): 1) using the ratio of
4(e) and 4(i)) [7, 13]. By integration of the reduction peak (PdO the peak current density of the forward (ip(EOR,f)) and backward scan
to Pd → catalyst charge QPd) with the Echem AnalystTM Software- (ip(EOR,b)) [12], and 2) using the ratio of the integrated oxidation peak
Gamry, the charge was determined to calculate the EASA of each current density area (total charge) of forward (Qpa(EOR,f)) and backward
catalyst according to Eq. (2). scan (Qpa(EOR,b)) from EOR measurements in alkaline medium
QPd æç 1 öæ ÷÷çç 1 ö÷÷
(Figs. 4(c), 4(g) and 4(k)), respectively [51]. Sekol et al. identified the
EASA =
Q * Pd çèç cL øè
÷ç AGC ø÷ (2) second method as being a more accurate method than the first one for
determining the catalyst tolerance toward reaction intermediates
The calculated EASAs (incl. standard deviation) of all catalysts resulting from the EOR [51]. The higher the value the better is the
using the parameters (Eq. (2)) such as Q*Pd (= reduction charge of tolerance of the catalyst toward the reaction intermediates of ethanol.
405 μC·cm−2 of PdO to Pd, assumed value according to Jongsomjit This means that the ethanol reaction intermediates or poisonous
et al. [29]), cL (= catalyst loading of 56 μgPd·cm−2 on the RDE) and the species which are not oxidized in the forward scan, are oxidatively
AGC (= surface area of 0.196 cm2 from the glassy carbon substrate removed in the backward scan [12, 51].
(GC) on RDE) are demonstrated in Figs. 4(b), 4(f) and 4(j) [13]. The Figure 4(d) shows that the Pd60Ni20Bi20/C catalyst exhibits the
charge of the reduction of Bi oxide to Bi could not be considered for best tolerance by far toward the reaction intermediates of ethanol
the EASA calculation of the Bi containing catalysts because the Bi compared to the other catalysts. The excellent results relating to the
oxide reduction arises in the same potential range as the Pd oxide byproduct tolerance of the Bi containing catalysts can be explained
reduction. Therefore, the excellent EASA result of the Pd60Ni20Bi20/C by the study of Paschos et al. [52]. In a CO stripping test was stated
catalyst compared to the other carbon supported Pd-based elec- that one Bi adatom blocked three Pd surface atoms for avoiding the
trocatalysts (Fig. 4(b) and Table 3) is only comparable with the poisoning of the Pd active sites in the BiPd-based catalyst [52].
Pd60Bi40/C catalysts. The Pd60Ni20Bi20/C catalyst with a 2.6-fold higher It should be noted, the if/ib or Qf/Qb ratio is not a sufficient but
EASA than the Pd60Bi40/C catalyst depends on the Bi content. Neto a necessary indicator for evaluation of anti-poisoning tolerance of a
et al. report that the increased addition of Bi to Pd catalysts causes catalyst as it has been discussed in Refs. [53, 54].
more agglomerations whereby the active sites of Pd are blocked After the Pd/C, Pd60Ni40/C, Pd60Bi40/C and Pd60Ni20Bi20/C nano-
resulting in decreasing of the EASA (Fig. 4(b)) and consequently catalysts were subjected to 1 h stress at an applied potential of 0.83 V,
the catalytic activity (Fig. 4(c)) [7]. the novel Pd60Ni20Bi20/C catalyst showed the best result in terms of
Additionally, Pd60Ni40/C and Pd60Ni20Bi20/C catalysts were inves- electrocatalytic stability toward alkaline EOR (Fig. 5(a) and Table 3).
tigated under the same measurement conditions in Fig. S12(a) in The order of the decrease of produced current density in percentage
the ESM, but using the potential range of 0.05–1.5 V to find out if of all catalysts from the start until to the end of CA measurement is
Ni is present in the catalysts. Figure S12(b) in the ESM shows that the given in Fig. 5(b). The decrease of current densities of all catalysts
peak in the anodic scan at the potential range of 1.3–1.5 V as the after 1 h stress is listed in following order: Pd60Bi40/C > Pd60Ni40/C >
oxidation of Ni(OH)2 to NiOOH whereas the peak in the cathodic Pd/C > Pd60Ni20Bi20/C.
scan at the potential range of 1.2–1.4 V as the reduction of NiOOH
to Ni(OH)2 are represented for both catalysts Pd60Ni40/C and 3.2.3 Varying atomic ratios of Pd, Ni and Bi in EOR catalysts
Pd60Ni20Bi20/C according to Zhang et al. [2]. It is evident and also as Furthermore, the electrocatalytic activities and stabilities of the
expected that the current density of the Ni oxidation and reduction synthesized carbon supported PdxNiyBiz catalysts (Pd70Ni25Bi5/C,
peaks of Pd60Ni40/C catalyst are higher than for the Pd60Ni20Bi20/C Pd70Ni20Bi10/C, Pd80Ni10Bi10/C, Pd40Ni20Bi40/C) were characterized
catalyst (Fig. S12 in the ESM). by CV and CA using the RDE in static mode with metal loading

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8 Nano Res.

of 56 μgPd·cm−2 under same operating conditions (Figs. 4(e)–4(l)) as low Pd content and the high Bi content leading to agglomerations.
for Pd/C, Pd60Ni40/C, Pd60Bi40/C and Pd60Ni20Bi20/C catalysts. The Pd70Ni20Bi10/C catalyst exceeded the alkaline EOR performance
The influence of varied Bi content on the EOR performances of Pd60Ni40/C in terms of peak current density and onset potential
of the synthesized catalysts Pd40Ni20Bi40/C and Pd70Ni20Bi10/C were (Fig. 4(g) and Table 3). The onset potential for the alkaline EOR was
investigated and compared to the benchmarks Pd60Ni40/C and decreased by 54 mV using the Pd70Ni20Bi10/C and the peak current
Pd60Ni20Bi20/C (Figs. 4(e)–4(h)) which possessed the best catalytic density could be increased by 10 mA·cm−2 compared to Pd60Ni40/C
performances in terms of alkaline EOR activity and stability (Fig. 4(g) and Table 3). This result proves that small amounts of Bi
(byproduct tolerance), respectively (Figs. 4(c)and 4(d)). in the carbon supported PdxNiyBiz catalyst enhance the activity and
The recorded CV of the Pd70Ni20Bi10/C catalyst in de-aerated kinetics toward the EOR in an alkaline medium.
1.0 M KOH shows a peak in the potential region between 0.1 Even though Pd70Ni20Bi10/C catalyst shows the best results in respect
and 0.2 V indicating an occurring hydrogen sorption reaction to the onset potential and peak current density toward alkaline EOR
(Fig. 4(e)). It was confirmed that PdxNiyBiz/C catalysts with more (Table 3), the byproduct tolerance is not as good as for Pd60Ni20Bi20/C
than 10 at.% of Bi (Pd60Ni20Bi20/C and Pd40Ni20Bi40/C) lead to a catalyst. However, Pd70Ni20Bi10/C is the second best catalyst among
suppression of the hydrogen adsorption and the absorption process all of those tested if the total current for the calculation of the
itself compared to the CVs of Pd60Ni40/C and Pd70Ni20Bi10/C catalysts byproduct tolerance is used (Fig. 4(h) and Table 3). An explanation
(Fig. 4(e)). This effect was observed by adding a specific quantity for this result could be that in the Pd60Ni20Bi20/C catalyst containing
of Bi to Pd as well as to Pt-based catalysts [7, 21, 46]. Neto et al. 20 at.% of Bi, more Pd active sites are protected by Bi atoms.
improved the alkaline EOR activities of carbon supported Pd catalysts However, the reactant is hindered from reaching the active sites
by adding of decreased Bi contents [7], whereupon the PtxBiy based leading to lower activity and higher stability than Pd70Ni20Bi10/C
catalysts were enhanced by increasing of Bi contents [21]. catalyst. By contrast, in the Pd70Ni20Bi10/C catalyst only 10 at.% of Bi
Further distinctive peaks in the potential regions of the anodic protects the active sites of Pd from poisoning resulting in a lower
scan between 0.8 and 1.0 V and of the cathodic scan between 0.5 and byproduct tolerance than for Pd60Ni20Bi20/C catalyst. However, the
0.9 V are attributed to the oxidized and reduced Bi and Pd species, active sites are better accessible for ethanol and a higher EOR
respectively (Fig. 4(e)). From the obtained XPS and XRD data we activity is observed in an alkaline medium (Fig. 4(h)).
suggest that the peak around 0.9 V in the anodic scan (Figs. 4(e) The CA results of Pd70Ni20Bi10/C catalyst (Fig. 5(c)) correlate with
and 4(i)) mainly originates from the oxidation of Bi and Bi oxide the results obtained from the byproduct tolerance determinations
species. Simões et al. observed that this characteristic peak became (Fig. 4(h)). The Pd60Ni20Bi20/C catalyst, which exhibits the highest
higher in the CVs of carbon supported binary PdxBiy catalysts by byproduct tolerance was also found to be the most stable one in the
increasing of Bi content [46]. CA measurement followed by Pd70Ni20Bi10/C, which still had almost
The former statement does not coincide with our RDE-CV 40% of the starting current density after 1 h at an applied potential
measurements because this peak of Pd40Ni20Bi40/C is lower than of 0.83 V (Fig. 5(d) and Table 3).
for Pd60Ni20Bi20/C catalyst (Fig. 4(e)). Here, many cleaning cycles (= Since the previous studies on the influence of Ni and Bi in carbon
recorded CVs at a scan rate of 50 mV·s–1) of the Pd40Ni20Bi40/C catalyst supported ternary PdxNiyBiz catalysts have shown that a low Bi content
had to be conducted until a stable CV was obtained, because the peak, enhances the alkaline EOR activity of the catalyst, the attempt was
which was assigned to Bi oxide species, decreased with increased
cycles. This decreased trend can be thus explained by the presence
of impurities which undergo an oxidative removal or other species
that are dissolved with increasing potential. As this phenomenon
was also observed in the RDE-CV measurements of the Pd60Bi40/C
catalyst. It is assumed that Bi0-agglomerates, mentioned by Simões
et al., are oxidized and dissolved into the electrolyte [46].
Our studies are supported by the observation that the current
densities in the EOR measurements of Pd60Bi40/C and Pd40Ni20Bi40/C
catalysts increased when more cycles were performed. The proven
Bi0-agglomerates in the Pd60Bi40/C which block the active sites of Pd
are gradually dissolved and lead to higher activities after multiple CV
cycles and it is assumed that this is also valid for the Pd40Ni20Bi40/C
catalyst.
The study of Simões et al. reported that Bi0 agglomerates in catalysts
with a Bi content as high as 20% or higher by EDX analysis. However,
the agglomerations were not identified in carbon supported PdxBiy
catalysts with Bi content lower than 20% [46]. The prior statement
cannot be confirmed by our TEM results (Figs. 1(c) and 1(d), and
Figs. S1(c)–S1(h) and S2(a)–S2(d) in the ESM).
The Pd60Ni20Bi20/C catalyst as benchmark exhibits the highest EASA
among all in this study synthesized carbon supported PdxNiyBiz
catalysts, followed by Pd70Ni20Bi10/C catalyst (Table 3 and Fig. 4(f)).
These results are conclusive in respect to the findings of Simões
et al., that the reduction peak approx. at 0.75 V not only originates
from Pd oxide species alone but also that other oxidized species
are reduced in this region [46]. As more Bi is incorporated in the  
Pd60Ni20Bi20/C catalyst and more Bi species can be oxidized, the Figure 5 Stability tests of carbon supported Pd-based electrocatalysts (a), (c) and
reduction peak approx. at 0.75 V in the cathodic sweep is also more (e) in a mixture of 1 M KOH and 1 M EtOH at an applied potential of 0.83 V for
distinct compared to Pd70Ni20Bi10/C catalyst (Fig. 4(e)). 3,600 s using the CA method and (b), (d) and (f) their resulting current density
The EASA of the Pd40Ni20Bi40/C is assumed to be lower due to the decrease, given in percentage.

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Nano Res. 9

Table 3 Electrochemical characterization results of all carbon supported Pd-based electrocatalysts

EASAa ifb ibb Eonset e iStartf iEndf iDg
Catalysts if/ibc Qpa,f /Qpa,bd
(cm2·mg−1) (mA·cm−2) (mA·cm−2) (V) (mA·cm−2) (mA·cm−2) (%)
Pd/C 463 ± 78 81.17 125.95 0.70 ± 0.04 1.90 ± 0.18 0.280 ± 0.015 94.97 37.37 61
Pd60Ni40/C 339 ± 49 95.11 90.05 1.04 ± 0.15 2.57 ± 0.42 0.290 ± 0.018 84.14 21.77 74
Pd60Bi40/C 276 ± 22 34.03 14.96 1.70 ± 0.60 2.89 ± 0.67 0.352 ± 0.015 32.16 6.02 81
Pd60Ni20Bi20/C 983 ± 35 73.93 27.60 2.60 ± 0.09 5.60 ± 0.27 0.348 ± 0.007 56.59 34.39 39
Pd70Ni25Bi5/C 436 ± 94 87.28 98.19 0.81 ± 0.07 2.19 ± 0.18 0.239 ± 0.009 90.01 37.88 58
Pd70Ni20Bi10/C 549 ± 72 105.77 83.39 1.28 ± 0.20 3.57 ± 0.53 0.236 ± 0.005 93.88 36.34 61
Pd80Ni10Bi10/C 462 ± 21 62.55 52.30 1.24 ± 0.06 2.93 ± 0.53 0.274 ± 0.008 60.87 23.67 61
Pd40Ni20Bi40/C 421 ± 52 42.79 25.37 2.07 ± 0.54 3.43 ± 0.52 0.323 ± 0.033 37.14 8.36 77
a
Electrochemical active surface area (EASA) determination; bif and ib: peak current density of forward and backward scan; cif/ib: byproduct tolerance using peak
current density of forward and backward scan; dQpa,f/Qpa,b : byproduct tolerance using the charge of the integrated peak current density area of the forward and
backward scan; eEonset: onset potential of the ethanol oxidation; fiStart and iEnd: resulting current densities at an applied potential of 0.83 V after 0 s and 3,600 s; giD: loss
of current density after stress test at an applied of 0.83 V for 3,600 s.

made to decrease the Bi content even further than 10 at.% to 5 at.%. ternary Pd70Ni20Bi10/C catalyst is, despite agglomerations, an outstanding
Additionally, the Pd content was increased to test whether the value for the alkaline EOR compared to Ref. [55] as well as to Table S21
alkaline EOR activity would rise further with a higher Pd content. The in the ESM. Considerably higher maximum current densities of
catalysts Pd70Ni25Bi5/C and Pd80Ni10Bi10/C were therefore synthesized, the ternary Pd70Ni20Bi10/C catalyst could be achieved under the CV
electrochemically characterized and the obtained results were com- measurement conditions (e.g. with a scan rate of 50 mV·s−1 instead
pared with Pd70Ni20Bi10/C catalyst (Figs. 4(i)–4(l), 5(e) and 5(f)). of 10 mV·s−1) applied in Ref. [55] and Table S21 in the ESM.
In the EOR measurements, the Pd70Ni25Bi5/C and Pd80Ni10Bi10/C The electrochemical characterization results of all carbon supported
catalysts could not exceed the peak current density of the Pd70Ni20Bi10/C Pd-based nanocatalysts are summarized in Table 3. Further details
catalyst (Fig. 4(k)). However, Pd70Ni25Bi5/C has a low onset potential about the effects of the Pd, Ni and Bi species/ions on the catalytic
(0.239 V), very close to that of Pd70Ni20Bi10/C (0.236 V) (see small properties and surface structures are discussed in the ESM.
figure in Fig. 4(k) and Table 3). This supports the study that low
amounts of Bi enhance the kinetics at the anode for the EOR in 4 Conclusions
alkaline medium but the increase in peak current density could not
be confirmed. The onset potential and the peak current density of the Carbon supported Pd-based nanocatalysts (Pd/C, Pd60Ni40/C,
Pd80Ni10Bi10/C catalyst were both reduced compared to Pd70Ni20Bi10/C Pd60Bi40/C and PdxNiyBiz/C) were successfully developed using the
(Fig. 4(k)). This result is also conclusive when taking into account instant reduction synthesis method with NaBH4 as reducing agent,
that the Ni content was reduced and the addition of higher amounts comprehensively characterized and the influence of the admetals Ni
of Ni are necessary for a catalyst with high activity [2]. and Bi in the carbon supported binary and ternary Pd-based EOR
catalysts was determined.
As expected, the byproduct tolerance of Pd70Ni25Bi5/C decreases
The alkaline EOR performance (catalytic activity, byproduct
when the Bi content is reduced from 10 at.% to 5 at.%. Also for the
tolerance, and stability) of the novel carbon supported ternary
Pd80Ni10Bi10/C catalyst the byproduct tolerance is lower compared
PdxNiyBiz catalyst was optimized by varying the atomic ratios of Pd,
to Pd70Ni20Bi10/C but still higher than for Pd70Ni25Bi5/C (Fig. 4(l) and
Ni and Bi for the application in alkaline direct ethanol fuel cells. The
Table 3).
carbon supported Pd:Ni:Bi catalyst with the atomic ratio of 70:20:10
The CVs of the Pd70Ni25Bi5/C, Pd80Ni10Bi10/C and Pd70Ni20Bi10/C
exhibits the highest catalytic activity compared to the other
catalysts exhibit similar curve progressions in 1.0 M KOH solution
synthesized PdxNiyBiz/C catalysts as well as to the benchmarks Pd/C,
(Fig. 4(i)). The EASAs of Pd70Ni25Bi5/C and Pd80Ni10Bi10/C catalysts
Pd60Ni40/C and Pd60Bi40/C. The maximum onset potential reduction
are lower than the EASA of Pd70Ni20Bi10/C (Fig. 4(j) and Table 3). The
of 116 mV and the peak current density enhancement of 71 mA·cm−2
Pd70Ni25Bi5/C and Pd80Ni10Bi10/C catalysts also show lower stability were achieved for the alkaline EOR on the Pd70Ni20Bi10/C catalyst.
than Pd70Ni20Bi10/C in the CA measurements (Figs. 5(e) and 5(f) The low Bi content (≤ 10 at.%) in the synthesized ternary PdxNiyBiz
and Table 3). However, the results are still better than for Pd60Ni40/C catalysts promotes the alkaline EOR kinetics leading to high current
(Table 3) showing the positive effect of Bi on the stability toward densities and low onset potentials, whereas the use of high amounts
alkaline EOR. of Bi (> 20 at.%) blocks the active sites of the used catalysts resulting
3.2.4 Pd70Ni20Bi10/C as promising EOR catalyst in a decrease of the EOR activities.
For further improvement of the EOR performance of the
It can be concluded that higher amounts of Ni in Pd-based anode Pd70Ni20Bi10/C catalyst, the substitution of the support material and
catalysts for the alkaline DEFC enhance the activity for the EOR. alternative deposition methods for spherical metal nanoparticles
In case of Bi, it is confirmed that lower amounts of Bi enhance with defined particle size and low tendency to agglomeration are
the activity and kinetics at the anode for the EOR in an alkaline investigated.
medium. This was observed as a low onset potential and high peak
current density for catalysts with low Bi concentration. It was also
found that a higher concentration of Bi (20 at.%) improves the Acknowledgements
byproduct tolerance and the stability of the catalyst. Financial support from the Austrian Climate Energy Fund, Austrian
The Pd70Ni20Bi10/C catalyst is the most active catalyst toward Federal Ministry of Transport, Innovation and Technology (BMVIT),
alkaline EOR among all tested catalysts (Figs. 4(g) and 4(k)) and The Austrian Research Promotion Agency (FFG) through the program
exhibits the second best results in terms of byproduct tolerance “Energy Mission Austria” and the IEA research cooperation are
(Table 3). The maximum current density of 106 mA·cm−2 (mass gratefully acknowledged. We thank Dr. Christian Palfinger for
activity: 1,889 mA·mg−1—relating to Pd loading) from the novel performing of the XPS analysis.

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10 Nano Res.

Funding: Open access funding provided by Graz University of B.; Hammer, P.; Spinacé, E. V.; Neto, A. O.; Linardi, M.; dos Santos, M. C.
Technology Ethanol electro-oxidation in an alkaline medium using Pd/C, Au/C and
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