i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 7 6 e2 9 1

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A dotted nanowire arrayed by 5 nm sized

palladium and nickel composite nanopaticles
showing significant electrocatalytic activity
towards ethanol oxidation reaction (EOR)

Keqiang Ding a,b,c,d,*, Dongyue Zhang a, Jun Li b, Jiasheng Chen a,

Fujuan Shi a, Boxia Li a, Xiangming He c, Li Wang c,**, Hui Wang d
a
Hebei Key Laboratory of Inorganic Nano-materials, Hebei Key Laboratory of Organic Functional Molecules, College
of Chemistry and Materials Science, Hebei Normal University, Shijiazhuang, 050024, China
b
Guangdong Zhuhai Supervision Testing Institute of Quality and Metrology, Zhuhai, 519000, China
c
Institute of Nuclear & New Energy Technology, Tsinghua University, Beijing, 100084, China
d
Hebei LingDian New Energy Technology Co., Ltd, Tangshan, 064200, China

highlights graphical abstract

Metallic Ni was prepared from

CTAB using an air calcination
method.

A dotted nanowire arrayed by
5 nm sized NPs was fabricated.

The diffraction peaks of metallic
Ni were presented in PdxNiy.

The ECSA value of c1 was as high
as 80.4 m2 gPd1.

The current density of EOR on c1 at
3600 s was 1.47 mA cm2.

article info abstract

Article history: To the best of our knowledge, this is the first time to report the preparation of a dotted
Received 6 August 2021 nanowire arrayed by 5 nm sized palladium and nickel composite nanoparticles (denoted as
Received in revised form PdxNiy NPs) via a hydrothermal method using NU and PdO$H2O as the starting materials.
13 September 2021 The samples prepared at the mass ratio of NU to PdO$H2O 1:1, 1:2 and 2:1 were, respec-
Accepted 5 October 2021 tively, nominated as catalyst c1, c2 and c3. The chemical compositions of all synthesized
Available online 27 October 2021 catalysts were mainly studied by using X-ray diffraction (XRD) and X-ray photoelectron
spectroscopy (XPS), revealing that metallic Ni was one main component of all prepared
Keywords: catalysts. Surprisingly, the main diffraction peaks appearing in the XRD patterns of all
Calcined products prepared catalysts were assigned to the metallic Ni rather than the metallic Pd. Very
PdxNiy composite nanoparticles interestingly, as indicated by the TEM images, a large number of dotted nanowires arrayed

* Corresponding author. Hebei Key Laboratory of Inorganic Nano-materials, Hebei Key Laboratory of Organic Functional Molecules,
College of Chemistry and Materials Science, Hebei Normal University, Shijiazhuang, 050024, China.
** Corresponding author.
E-mail addresses: dkeqiang@263.net (K. Ding), wang-l@tsinghua.edu.cn (L. Wang).
https://doi.org/10.1016/j.ijhydene.2021.10.036
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 7 6 e2 9 1 277

Dotted nanowire by numerous equidistant 5 nm sized nanoparticles were distinctly exhibited in catalyst c1.
Hydrothermal method More importantly, when being used as electrocatalysts for EOR, all prepared catalysts
Ethanol oxidation reaction exhibited an evident electrocatalytic activity towards EOR. In the cyclic voltammetry (CV)
test, the peak current density of the forward peak of EOR on catalyst c1 measured at
50 mV s1 was as high as 56.1 mA cm2, being almost 9 times higher than that of EOR on
catalyst c3 (6.3 mA cm2). Particularly, the polarized current density of EOR on catalyst c1 at
3600 s, as indicated by the chronoamperometry (CA) experiment, was still maintained to be
around 1.47 mA cm2, a value higher than the latest reported data of 1.3 mA cm2
(measured on the pure Pd/C electrode). Presenting a novel method to prepare dotted
nanowires arranged by 5 nm sized nanoparticles and showing the significant ele-
trocatalytic activities of the newly prepared dotted nanowires towards EOR were the major
contributions of this preliminary work.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

utilized as the reducing agent [15]. In 2020, catalysts of Pd3Ni

Introduction
Recently, ethanol based fuel cells, namely, direct ethanol fuel
cells (DEFCs) have attracted considerable research attention
mainly due to their advantageous battery performances [1e4].
For example, the battery properties of DEFCs are significantly
superior to that of methanol based fuel cells. For instance, the
theoretical energy density and the theoretical volume energy
capacity of ethanol based fuel cell are evidently higher than
that of methanol based fuel cells, namely, 8 kWh kg1 vs.
6.1 kWh kg1 [5], as well as, 6.3 kWh L1 vs. 4.8 kWh L1 [6].
Besides above merits, the large-scale production from
biomass through fermentation and the convenient storage
and transportation were all obvious advantages of using
DEFCs which enabled DEFCs to be a kind of attractive fuel cell
[7]. Hence, ethanol oxidation reaction (EOR), one electro-
chemical reaction that can release electrons on the anode part
of a fuel cell, becomes into the core issue of a commercial
DEFCs. Unfortunately, it was revealed several years ago that
EOR could only proceed on the platinum (Pt)-based electro-
catalysts, which greatly hindered the final commercialization
of both DEFCs and DEFCs-related commodities [8]. Of late, an
inspiring finding, that palladium (Pd) based catalyst can also
exhibit evident eletrocatalytic activity towards EOR in alkaline
solution, is issued which is very beneficial to the development
of EOR catalyst since the reserves of Pd is abundant on the
earth's crust relative to that of Pt [9]. To further reduce catalyst
preparation cost, Pd based binary or ternary metal catalysts
have been urgently developed towards EOR in recent years
[10e13]. Among all prepared Pd based EOR catalysts, palla-
dium and nickel (PdeNi) composite catalyst has received
special interest mainly due to its significant electrocatalytic
activity towards EOR [14].
Up to now, a variety of strategies have been proposed to
prepare PdeNi catalysts. Generally speaking, there are two
main methods developed for producing PdeNi catalysts,
namely, the conventional chemical method and the electro-
chemical approach. For example, PdeNi nanoparticles sup-
ported on carbon nanofibers (CNF) were prepared via a
chemical method employing PdCl2 and NiCl2$6H2O as the
starting materials in which the dilute NaBH4 solution was
and PdNi [16] were also prepared using a traditional chemical
method where the reactants were PdCl2, NiCl2$6H2O and
NaBH4. Innovatively, Cai and his co-workers [17] prepared
PdeNi catalysts through a dealloying process of PdeNieP film.
In their works, PdeNieP film was firstly electrodeposited onto
an Au substrate in an electrolyte solution, and then, a CV
method was used to complete the dealloying process where
the as-obtained PdeNieP film and 0.1 M H2SO4 were respec-
tively utilized as the working electrode and the electrolyte
solution. Also, bimetallic PdeNi nanoparticles [18] were pro-
duced using a potentiostatic two-step electrochemical
method in which the electrolyte solution contained Ni(NO3)2-
$6H2O and PdCl2. Although many approaches have been pro-
posed to prepare PdeNi composite catalyst, as far as we know,
no work reporting the fabrication of PdeNi composite nano-
particles through a hydrothermal method using PdO$H2O and
the calcined product of NU (the main component of NU was
metallic Ni) as the initial materials was reported so far.
Apart from the nature of a catalyst, i.e., the chemical
composition of a catalyst, the morphology and the particle size
are all important factors greatly influencing the electro-
catalytic performance of a catalyst. Thus, PdeNi catalysts with
various morphologies have been urgently prepared in the last
few years. For instance, a three-dimensional flower-like Pd
nano-electrocatalyst [5] supported on Ni nanowire array was
fabricated by using a borohydride hydrothermal reduction
method in which Ni nanowire array, PdCl2 and NaBH4 were
utilized as the initial materials. In 2018, a plate like layered
structure with a mesoporous skeleton that was constructed by
PdeNi bimetallic particles was prepared by Ghiaci's group in
which the particle size of PdeNi nanoparticles ranged from
3.5 nm to 7.7 nm [19]. Although many kinds of morphologies of
PdeNi composite particles have been created in recent years,
so far as we know, the novel morphology of dotted nanowires
arranged by numerous 5 nm sized PdeNi nanoparticles has not
been reported yet. In most cases, the carbon carrier was an
indispensable part for a Pd based catalyst. To our knowledge, a
variety of carbon materials have been employed as supporters
of Pd based catalysts since the physicochemical property of the
supporter was also a key factor affecting the electrocatalytic
activity of a catalyst employed. For example, carbon powders
278 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 7 6 e2 9 1
[20] and carbon nanofibers [15], mainly due to their lower cost,
have been widely employed as carriers for preparing carbon
supported PdeNi catalyst. Very recently, Ni(OH)2/C [21],
heteroatom-doped carbon [22], nitrogen-doped graphene [23]
as well as N-doped reduced graphene oxide [24], and etc., have
been investigated as Pd-based catalyst carriers with an inten-
tion to greatly promote the electrocatalytic performance of the
Pd-based catalysts used. While in the present work, no catalyst
supporter was deliberately introduced in fabricating the final
catalysts. That is, the calcined product of NU was employed as
the starting material and the carrier of the prepared catalysts
as well.
In this work, firstly, the mixture containing urea and nickel
acetylacetonate was calcined at 500  C in air atmosphere
producing a calcined product of NU. To one's surprise, as
indicated by the XRD and XPS analysis, the main component
of NU was metallic Ni rather than the nickel oxides. And then,
the final catalysts were prepared through a hydrothermal
method employing NU and PdO$H2O as the starting materials.
The catalysts prepared at the mass ratio of NU to PdO$H2O 1:1,
1:2 and 2:1 were called as catalyst c1, c2 and c3, respectively.
Interestingly, in all obtained XRD patterns, the diffraction
peaks assigned to the metallic Ni rather than metallic Pd were
mainly exhibited which was rather different from the previ-
ously reported XRD patterns of Pd-based composite catalyst.
Also, as revealed by the TEM images, a dotted nanowire
arrayed by many nearly equidistant 5 nm sized nanoparticles
was distinctly displayed in c1, which was a novel finding. More
importantly, all as-prepared catalysts delivered significant
electrocatalytic activities for EOR. Summarily, the preparation
of metallic Ni via the calcination of a mixture, a novel
morphology of dotted nanowire as well as the significant
electrocatalytic activity of catalyst c1 towards EOR were all the
main dedications of this preliminary work.
Experimental details
Reagents and materials
The chemical reagents of nickel acetylacetonate and palladium
oxide monohydrate were, respectively, bought from Shanghai
Yien Chemical Technology Co., Ltd (China) and Guangdong
WengJiang Chemical Reagent Co., Ltd (China). Other conven-
tional reagents such as urea, potassium hydroxide and anhy-
drous alcohol were all purchased from Tianjin Damao
Chemical Reagent factory (China). All chemical reagents were
used as received with no further purifications. All electrodes
used in the electrocatalytic activity measurements were pur-
chased from Tianjin Aida Co., Ltd (China). The solution that
contained 1 M KOH and 1 M C2H5OH was employed as the
electrolyte solution to examine the electrocatalytic activities of
all prepared catalysts towards EOR. All aqueous solutions were
prepared by using secondary distilled water.
Preparation of PdxNiy composite nanoparticles via a
hydrothermal method
Prior to the preparation of PdxNiy composite nanoparticles, a
calcined product was prepared first through an air
atmosphere calcination method employing urea and nickel
acetylacetonate as the starting materials. In brief, a mixture
containing 0.2 g of urea and 2.0 g of nickel acetylacetonate was
thoroughly ground in an agate mortar at least for 20 min to
form a well-mixed mixture, and then, the resultant mixture
was pressed into several pieces of cylinder-shaped pills (the
height and diameter of each cylinder-shaped pill were about
1.0 cm and 1.2 cm, respectively). And then, several light green
cylinder-shaped pills were placed in a crucible and calcined at
500  C in the air atmosphere for 2 h generating some black
powders, which was again ground in an agate mortar to har-
vest the final calcined products. For the sake of simplicity, the
final calcined product was labeled as NU.
Next, the target catalysts were prepared via a hydrother-
mal method using above prepared NU and PdO$H2O as the
starting materials. The brief steps were as follows, a mixture
having 0.03 g of NU and 0.03 g of PdO$H2O was carefully dis-
solved in 4 mL double distilled water forming a suspension
solution, which was treated by ultrasonication for 1 h to
obtain a well dispersed suspension solution. After that, the
resultant suspension solution was transferred into a well-
sealed home-made autoclave and heated at 180  C for 2 h to
complete the hydrothermal process. After cooling down to the
room temperature, the residues were rinsed by double
distilled water for three times and dried in a drying box at
50  C for 5 h to harvest the final catalysts. The catalysts pre-
pared with the mass ratio of NU and PdO$H2O 1:1, 1:2 and 2:1
were, respectively, named as catalyst c1, c2 and c3.
Preparation of PdxNiy composite nanoparticles coated glassy
carbon (GC) electrodes
Firstly, 3 mg of catalyst c1 and 0.5 mL Nafion ethanol solution
(The mass content of Nafion is 0.1 wt%) were placed together
in a 1.50 mL centrifuge tube generating a suspension solution
which was subjected to ultrasonic vibration for 90 min at
room temperature to acquire a well-dispersed catalyst ink.
Subsequently, 12 mL of above resultant catalyst ink was placed
on the cross-section of a well cleaned GC electrode with the
help of pipette gun (The cross-section of the GC electrode used
was 3 mm in diameter). After being well dried in air, a working
electrode, namely, a PdxNiy composite nanoparticle coated GC
electrode was prepared successfully. The electrodes prepared
using catalyst c1, c2 and c3 were respectively nominated as
electrode c1, c2 and c3.
Characterization
XRD (X-ray diffraction) analysis was conducted on an X-ray
diffractometer with an intention to identify the crystal
structure and chemical components of all studied samples in
which the X-ray diffractometer used was Bruker D8 ADVANCE
X-ray diffractometer equipped with a Cu Ka source
(l ¼ 0.154 nm). The surface morphology and the particle size of
all studied samples were, respectively, observed by using
scanning electron microscopy (SEM, HITACHI, S-570) and
transmission electron microscopy (TEM, HITACHI, H-7650).
Both element types and element contents of all studied sam-
ples were analyzed by using energy dispersive X-ray spec-
troscopy (EDS, PV-9900, USA). FTIR analysis was conducted on
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 7 6 e2 9 1
a Fourier transform infrared spectrometry (FTIR) (Hitachi
FTIR-8900 spectrometer, Japan) from which the kinds of
functional groups existing in all produced samples could be
ascertained distinctly. The element compositions and the
element valence states of the produced samples were
measured by using X-ray photoelectron spectroscopy (XPS,
Kratos Analytical spectrometer, Al Ka radiation).
The main electrochemical measurements such as CV, CA
and EIS (electrochemical impedance spectroscopy) were all
carried out on an electrochemical workstation (CHI 660E,
Shanghai Chenhua Apparatus, China) via a conventional
three-electrode cell. In the traditional three-electrode cell, the
newly prepared PdxNiy composite nanoparticle coated GC
electrode was employed as the working electrode, a platinum
(Pt) wire as the counter electrode and a saturated calomel
electrode (SCE) as the reference electrode. All potential values
appearing in this work were relative to the electrode potential
of the SCE. A solution containing 1 M KOH and 1 M ethanol
was used as the electrolyte solution to evaluate the electro-
catalytic performances of all synthesized catalysts towards
EOR. In the EIS measurement, the frequency range and the
amplitude of the alternating current (AC) employed were from
10 Hz to 105 Hz and 5 mV, respectively. As a note, all the ex-
periments were performed at room temperature, and no
special protection measurements were conducted during the
whole testing period.
Results and discussion
Characterizations of the prepared samples
The XRD pattern of NU are illustrated in figure an of Fig. 1 in
which three sharp diffraction peaks prominently located at
about 44.7 (111), 51.9 (200) and 76.5 (220) matched well with
the standard XRD pattern of metallic Ni (JCPDS, No.87-712) [25]
suggesting that the main crystalline substance of NU was
metallic Ni. Also, four small diffraction peaks were exhibited
at 2q of 37.4 , 43.4 , 63.0 and 75.3 , respectively, correspond-
ing to the (111), (200), (220) and (311) facet of NiO (JCPDS, No.73-
1523) [21]. Evidently, the diffraction peak intensity of metallic
Ni was significantly higher than that of NiO implying that the
crystallinity of metallic Ni was superior to that of NiO. In
addition, no diffraction peaks indexed as Ni2O3 were found.
Therefore, the metallic Ni and NiO were the main substances
of NU. That is, metallic Ni was prepared from the mixture
having urea and nickel acetylacetonate through a very simple
air calcination method.
The XRD patterns of catalyst c1 are presented in figure b of
Fig. 1. Apparently, three main diffraction peaks in figure b of
Fig. 1 could be well assigned to metallic Ni confirming that
most crystal substances of catalyst c1 were still the metallic
Ni. Also, a broad and weak diffraction peak ranging from 20 to
30 was explicitly displayed which was generally referred to
the graphite (002) facet evidencing the presence of amorphous
carbon in catalyst c1 [20,26]. Careful observation indicated that
five small diffraction peaks centered at 40.1 , 46.7 , 68.1 , 82.0
and 86.5 could be well indexed as the plane of (111), (200),
(220), (311) and (222) of metallic Pd (JCPDS, No.5-681) [15],
respectively. Therefore, metallic Ni, metallic Pd and
279
amorphous carbon were the main substances of catalyst c1.
For catalyst c2 (figure c of Fig. 1), besides the diffraction peaks
assigned to both metallic Ni and amorphous carbon, the
diffraction peaks corresponding to PdO (JCPDS, No.43-1024)
[27] were also visible implying that metallic Ni and amor-
phous carbon and PdO were the main substances of catalyst
c2. Similar to the case of catalyst c1, only the diffraction peaks
attributed to both metallic Ni and metallic Pd were observed in
the XRD pattern for catalyst c3 (figure d of Fig. 1). All the XRD
patterns for the as-prepared catalysts are summarized in
figure e of Fig. 1. Evidently, in all XRD patterns the main
diffraction peaks were assigned to the metallic Ni rather than
the metallic Pd, which was a novel finding for the Pd-based
catalysts. In a word, as revealed by above XRD patterns, the
main crystal substance of all prepared catalysts was the
metallic Ni instead of the metallic Pd.
EDS patterns for all studied samples are collected in figure
an of Fig. 2. For NU, the peaks ascribed to the elements of C, O,
N and Ni were displayed clearly, and the atomic contents of
Ni, O, C and N in NU were roughly measured to be 54.0%,
27.1%, 13.4% and 5.5%, respectively. Consequently, it was
confirmed again, along with the XRD result shown in figure an
of Fig. 1, that metallic Ni was the main substance of NU. While,
for other three catalysts, a huge peak centered at about
2.84 KeV was displayed distinctly strongly clarifying the
presence of Pd element in all prepared catalysts. The atomic
contents of Pd, Ni, O, N and C in catalyst c1 were estimated to
be 27.0%, 28.6%, 34.3%, 3.4% and 6.6%, respectively. That is, the
atomic ratio of Pd to Ni in catalyst c1 was roughly equal to 1:1
generating a Pd1Ni1 composite catalyst. While for catalyst c3,
the atomic contents of Pd, Ni, O, N and C in were recorded to
be about 25.6%, 12.6%, 53.3%, 7.7% and 0.8%, respectively. It
seemed that a Pd2Ni1 composite catalyst was produced in
catalyst c3. Interestingly, for catalyst c2, besides the element O
(53.7 at.%), N (5.6 at.%) and C (3.9 at.%), the atomic contents of
Pd and Ni were evaluated to be 36.8% and 0.1%, respectively.
Thus, also based on the XRD results shown in figure c of Fig. 1,
it could be deduced that Pd element mainly existed in the form
of PdO in catalyst c2. Therefore, it was confirmed that element
Pd existed in all resultant catalysts which enabled all prepared
catalysts to have an electrocatalytic activity towards EOR [28].
The EDS maps of all elements existing in catalyst c1 are pre-
sented in figure b of Fig. 2. Besides the EDS map for the
element of N, the spots in the EDS maps for the element of C,
O, Ni and Pd all delivered a uniform distribution in the whole
observation window, which effectively indicated that no huge
aggregation of the prepared substances was generated in the
final catalysts.
FTIR spectra of all studied samples are given in figure c of
Fig. 2. The broad and evident absorption band at around
3447 cm1 should be attributed to the OeH bending vibrations
confirming the existence of hydroxyl group in all as-
synthesized samples [29]. Also, for all studied samples, four
absorption bands were successively exhibited at around 1637,
1416, 1031 and 448 cm1, respectively, being assigned to the
stretching vibrations of C]O [30], the symmetric stretching
vibration of CeO [31], the stretching vibrations of CeN [32] and
the stretching vibrations of NieO bonds [33]. Interestingly, for
catalyst c1, c2 and c3, an evident absorption band belonging to
PdeO bond [27] was displayed at 650 cm1 demonstrating the
280 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 7 6 e2 9 1

Fig. 1 e (a) XRD patterns for NU including the standard XRD patterns for NiO, metallic Ni and Ni2O3. (b)XRD patterns of
catalyst c1 as well as the standard XRD patterns for both metallic Ni and metallic Pd. (c) XRD patterns of catalyst c2 as well as
the standard XRD patterns for both PdO and metallic Ni. (d) XRD patterns of catalyst c3 as well as the standard XRD patterns
for both metallic Pd and metallic Ni. (e) XRD patterns of catalyst c1, c2 and c3 as well as the standard XRD patterns of Pd, PdO
and metallic Ni.

presence of PdO in all prepared catalysts. Obviously, the band
peak intensity of at 650 cm1 for catalyst c2 was greatly higher
than that of catalyst c1 and c3 suggesting that more amounts
of PdO were prepared in catalyst c2, which was consistent with
the XRD (figure c of Fig. 1) and EDS results (figure an of Fig. 2).
Raman spectra for as-prepared catalysts are shown in
figure d of Fig. 2. For catalyst c2 and c3, the sharp peak at
about 634 cm1 was generally ascribed to the characteristic
band of PdeO bond [34]. Thus, combined with other three
typical peaks of PdeO (respectively situated at 275, 334 and
433 cm1) [34], it was confirmed that PdO as one component
existed in both catalyst c2 and c3. Except for a very small Pd
peak appearing in C1 (as red circled part), almost no evident
peaks assigned to metallic Pd were exhibited in all obtained
Raman spectra which was probably due to the insertion of
palladium atoms into the carbon materials [35]. The char-
acteristic peak attributed to the crystalline NieO lattice vi-
brations was not observed at about 530 cm1 [35], instead, a
broad peak at 1080 cm1 was presented clearly documenting
that metallic Ni also existed in catalyst c2 and c3 [35], being in
accordance with XRD results (figure c and d of Fig. 1,
respectively). While for catalyst c1, the typical peaks
assigned to PdO were hardly visible, indirectly signifying that
metallic Pd was the main Pd-based substance in catalyst c1,
agreeing well with the subsequent XPS results (figure f of
Fig. 3). The two obvious characteristic peaks belonging to
carbon (D-band at 1330 cm1 and G-band at 1580 cm1) were
not observed in figure d of Fig. 2 [29,35] manifesting that the
amount of carbon in the prepared catalysts was too lower to
be detected, which was well corroborated by the EDS results
(Fig. 2a).
The chemical valences of the elements existing in all
prepared catalysts were examined by using XPS (figures of
Fig. 3). In figure a, the peaks assigned to the elements of Ni, O,
Pd and C were clearly exhibited according well with the EDS
results (figure an of Fig. 2). Also, as indicated by the EDS
patterns (figure an of Fig. 2), the amount of N element in all
prepared catalysts was too small, thus, only a very small
peak was visible in the wide scan XPS spectra for catalyst c2.
As shown by the C1s XPS spectra (figure b), several peaks
attributed to C element were displayed confirming the
presence of carbon material in all prepared catalysts. For
catalyst c1, the binding energy (BE) peaks at 284.6, 285.9,
287.2, 288.6 and 289.9 eV were, respectively, attributable to
the carbon of sp2-C (C]C) [36], CeN or CeO [36], C]N or C]O
[36], NeC]O [36] and O]CeO [36]. For catalyst c2, only one
main peak assigned to the carbon of sp2-C (C]C) was dis-
played implying that C element existed in catalyst c2 mainly
by the means of C]C form. Interestingly, four peaks instead
of five peaks (situated respectively at 284.0, 285.5, 287.4 and
289.1eV) were presented in the C1s XPS spectra of catalyst c3.
Additionally, the BE peak intensity of sp2-C (C]C) of catalyst
c1 was obviously higher than that of catalyst c2 and c3, indi-
cating that more amounts of sp2 carbon atoms were fabri-
cated in catalyst c1. The O1s XPS spectra of all prepared
catalysts are illustrated in figure c of Fig. 3. For catalyst c1, the
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 7 6 e2 9 1 281

Fig. 2 e (a) EDS patterns of catalyst c1, c2, c3 and NU. (b) EDS mapping of element C, N, O, Ni and Pd in catalyst c1. (c) FTIR
spectra for catalyst c1, c2, c3 and NU. (d) Raman spectra for catalyst c1, c2 and c3.

Fig. 3 e XPS survey spectra for catalyst c1, c2 and c3. (a) Wide scan XPS survey spectra; (b) High resolution C1s spectrum of
XPS spectra; (c) High resolution O1s spectrum of XPS spectra; (d) High resolution N 1s spectrum of XPS spectra; (e) High
resolution Ni 2p spectrum of XPS spectra; (f) High resolution Pd 3d spectrum of XPS spectra.
282 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 7 6 e2 9 1
binding energy (BE) peaks positioned at 529.2, 531.2, 532.3,
533.6 and 535.2 eV were, respectively, assigned to the O1s of
NieO [37], PdeO [38], C]O [39], CeO [39] and NeO [40]. In
contrast to catalyst c1, four and three BE peaks were,
respectively, displayed in the of O1s spectra for catalyst c2
and c3, suggesting that the kinds of oxides existing in catalyst
c2 were different from that of catalyst c3. As shown by figure
d of Fig. 3, for catalyst c1, five BE peaks positioned at 398.2,
399.2, 400.3, 402.2 and 403.1 eV were respectively assigned to
the N atom of C^N [30], C]N [30], graphitic-N [41], NeH [20]
and oxidized-N [36], at least confirming the formation of C]
N bond in catalyst c1 agreeing well with the FTIR results
(figure c of Fig. 2). Evidently, the BE peaks at both 399.2 eV and
400.3 eV were the two largest peaks in each N1s XPS spectrun
indicating that element N mainly existed by the means of C]
N or graphitic-N in all prepared catalysts. As for the Ni 2p XPS
spectra (figure e of Fig. 3), almost no BE peaks were found in
the Ni 2p XPS spectrum of catalyst c2. It strongly indicated
that the content of Ni-based substance in catalyst c2 was too
lower to be detected, which was consistent with the EDS
result (figure an of Fig. 2). While for catalyst c1 and c3, four BE
peaks were successively located at 856.5 eV, 861.9 eV,
874.1 eV and 879.0 eV, effectively indicating the presence of
NiO in the prepared catalysts since the BE peak at 856.5 eV
and that at 874.1 eV were the characteristic Ni 2p peaks of
NiO [42]. In all resultant Ni 2p XPS spectra, the BE peaks
assigned to metallic Ni were not found, which was mostly
due to the fact that XPS was a surface analysis technique
through which only the surface substances like NiO could be
detected [43]. The Pd 3d XPS spectra of catalyst c1, c2 and c3
are illustrated in figure f of Fig. 3. Apparently, the intensity as
well as the area of the BE peaks appearing in catalyst c3 was
much lower than that of catalyst c1 and c2, indicating that the
content of Pd-based substances of catalyst c3 was lower
relative to that of catalyst c1 and c2. For catalyst c1, the BE
peaks centered at 334.9 eV and 340.3 eV were, respectively,
assigned to the orbit of Pd0 (3d5/2), and Pd0 (3d3/2) [20,44],
again convincing the presence of metallic Pd in catalyst c1.
And the BE peaks located at 336.3 eV and 341.7eV were,
respectively, originated from the core level of Pd2þ (3d5/2),
and Pd2þ (3d3/2) [20,45], demonstrating the presence of PdO in
catalyst c1. Evidently, for catalyst c1, the BE peak area of Pd0
was remarkably larger than that of Pd2þ, implying that
metallic Pd was the main Pd-containing material of catalyst
c1, being in line with the XRD result (figure d of Fig. 1). In the
case of catalyst c2, the intensity of the BE peaks assigned to
the metallic Pd greatly attenuated, and instead, the intensity
of BE peaks indexed as Pd2þ (one at 336.9 eV and the other at
342.3 eV) increased significantly, suggesting that PdO as the
main component existed in catalysts c2, being consistent
with the XRD result (figure c of Fig. 1). Interestingly, almost
no BE peaks assigned to Pd2þ were found in the XPS patterns
of catalyst c3, indicating that the amount of PdO in catalyst c3
was rather lower as compared to that of the metallic Pd.
Thus, combined with the aforementioned XRD analysis, it
could be inferred that PdO was the major Pd-based substance
in catalyst c2, and the main Pd-based substance in both
catalyst c1 and c3 was metallic Pd, which accorded well with
the XRD results.
SEM and TEM characterization
As shown by the photos of the mixture and the calcined
products (figure an of Fig. 4a), the light green powders were
converted into a black powder after the calcination process
indicating that novel substances were prepared in NU. As
presented by figure b of Fig. 4a, for the mixture, some irregular
particles with a size less than 500 nm were observed, and
some huge flaky particles appeared in NU after the calcination
process. Approximately, the thickness and side length of the
huge flaky particles in NU were, respectively, estimated to be
about 715 nm and 3.4 mm. As is known to all, the air calcination
product of an organometallic compound should be the metal
oxides since most elements such as C, H and O will be
chemically oxidized to be CO2 and H2O. Additionally, as shown
by the TG curve of the mixture containing urea and nickel
acetylacetonate (figure c of Fig. 4a), almost no mass loss
occurred when the temperature was up to 416  C. That is to
say, all the combustible substances in the mixture have been
totally consumed in the calcination process. Therefore, com-
bined with XRD, XPS, EDS and FTIR results, it was reasonable
to believe that those huge flaky particles appearing in NU
should be the metallic Ni rather than the nickel oxides. That
is, a novel method for preparing huge flaky metallic Ni parti-
cles was developed in this work which was a novel finding, to
our knowledge.
The SEM images with a scale of 500 nm for all synthesized
catalysts are illustrated in Fig. 4b. For catalyst c1 (image c1), a
cotton fiber shaped surface morphology constructed by
numerous very small particles was clearly presented in which
a three-dimensional space structure was generated. While in
the case of catalyst c2 (image c2), some evident agglomerates
accumulated by a large number of small particles were dis-
played clearly in which a great many of cavities with different
sizes were also produced. For catalyst c3 (image c3), no obvious
aggregates were found, instead, a loose and porous structure
assembled by a great deal of small and uniform particles was
explicitly exhibited. That is, rather different morphologies
were exhibited by the prepared catalysts which could only be
attributed to the various mass ratios of NU to PdO$H2O.
TEM images with a scale of 100 nm for all studied samples
are given Fig. 4c. To be clear, prior to the TEM measurement all
studied samples were subjected to a 30 min alcohol solution
ultrasonic treatment. Evidently, for all studied samples, a lot
of small solid spherical particles were distinctly presented,
which substantially indicated that the huge flaky particles
observed in NU and those particles exhibited in the prepared
catalysts were all assembled by smaller solid particles. The
particle sizes of NU (image NU), c2 (image c2) and c3 (image c3)
varied respectively from 5 to 20 nm, from 5 to 55 nm and from
5 to 15 nm. Noticeably, among all prepared samples, catalyst
c1 (image c1) delivered the smallest particle size (about 5 nm in
size) as well as the most uniform particle size distribution.
Incredibly, the nanoparticles of catalyst c1 were spontane-
ously arrayed in a line forming a lot of dotted nanowires, and
the distances between two nanoparticles in each dotted
nanowire were almost identical to each other, which was
probably due to one unknown magnetic force [46]. Very
recently, Zhang's group [47] prepared Pd nanoparticles with an
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 7 6 e2 9 1 283

Fig. 4a e (a) Photos for the mixture and the calcined product of NU; (b) SEM images with a scale of 500 nm for the mixture and
the calcined product of NU; (c) Thermogravimetric (TG) curve for the mixture containing urea and nickel acetylacetonate.

unconventional hexagonal close-packed phase in which the
size of the Pd nanoparticles was close to 7.2 nm. Actually, Pd-
based particles with a size less than 5 nm have been prepared
in the previous work [48], however, as far as we know, 5 nm
sized Pd-based nanoparticles with such a well-defined equi-
distance as well as the morphology of dotted nanowire have
never been reported so far. In addition, a noteworthy phe-
nomenon, that all prepared catalysts could be attracted by an
iron medicine spoon, was found in this experiment which was
not investigated in this works since it was beyond the scope of
this research. Summarily, catalyst c1 not only delivered a
cotton-fiber shaped surface morphology but also presented
284 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 7 6 e2 9 1
Fig. 4b e SEM images with a scale of 500 nm for all studied samples. Image c1, c2 and c3 corresponded to catalyst c1, c2 and c3.
Fig. 4c e TEM images with a scale of 100 nm for all studied
samples. Image c1, c2, c3, and NU corresponded to catalyst
c1, c2, c3 and NU.
the smallest particle size among all prepared catalysts, which,
due to the greatly increased contacting area of between the
electrocatalyst and the electroactive substance of ethanol,
was very beneficial to the electrocatalytic activity enhance-
ment of a catalyst employed.
Electrocatalytic performance of the prepared catalysts
towards EOR
All the CV curves recorded on the resultant catalysts coated
GC electrodes are displayed in the figures in Fig. 5a. It was
evident, as shown by the black curve in figure an of Fig. 5a,
that in the absence of ethanol, only one main electro-
reduction peak at about 0.4 V was presented which was
generally assigned to the electro-reduction of PdO [49]. In the
presence of ethanol (as shown by the red curve in Figure an of
Fig. 5a), two evident electro-oxidation peaks were displayed
clearly suggesting that the EOR could proceed very well on
catalyst c1. In general, the electro-oxidation peak located at
about 0.2 V was called as peak f which was commonly
originated from the direct electro-oxidation of ethanol mole-
cules in the positive potential scanning, and the electro-
oxidation peak appearing in the negative potential scanning
was nominated as peak b which was regarded to be mainly
from the electro-oxidation of the intermediates that appeared
in electro-oxidization of ethanol molecules in the positive
potential scanning [50]. In the case of catalyst c2 (figure b) and
c3 (figure c), a pair of two electro-oxidation peaks was also
exhibited showing an evident eletrocatalytic activity towards
EOR. All measured CV curves for EOR, as well as the CV curves
measured on NU coated GC electrode, were collected in figure
d of Fig. 5a. Evidently, no CV peaks were found in the CV curve
recorded on NU implying that NU had no electrocatalytic ac-
tivity towards EOR. The EOR peak current densities of both
peak f and peak b were, respectively, found to be 56.0 and
62.2 mA cm2, 45.9 and 59.7 mA cm2, 6.4 and 8.5 mA cm2 on
catalyst c1, c2 and c3, roughly corresponding to a peak current
density ratio of peak f to peak b 0.90, 0.77 and 0.75. It was
worth noting that the peak current density of peak f on cata-
lyst c1 was almost 8.8 times higher than that of peak f on
catalyst c3. That is, the maximum EOR peak current density
was delivered by catalyst c1, indicating that more amounts of
ethanol molecules, as compared to the case of catalyst c2 and
c3, were directly electro-oxidized on catalyst c1. It should be
emphasized that the peak current density value of peak f on
catalyst c1 was significantly larger than the previously re-
ported value of 4.0 [51] and 36.3 mA cm2 [52], indicating that a
significant electrocatalytic activity was delivered by catalyst
c1. Meanwhile, the onset potentials of peak f on catalyst c1, c2
and c3 were roughly measured to be 0.72 V, 0.62 V and
0.56 V, respectively. That is, the EOR over-potential value
was greatly reduced by using catalyst c1 as compared to the
cases of using catalyst c2 and c3.
Cycling stability of an electrocatalyst was an important
factor which was closely related to its potential commercial
application. The 25 cycle-CV curves of EOR on all prepared
catalysts are given in the figures of Fig. 5b. In the case of
catalyst c1 (figure an of Fig. 5b), the peak current density values
of both peak f and peak b gradually decreased with increasing
the cycling number. For example, after 25 cycles, the peak
current density of peak f for EOR on catalyst c1 decreased from
71 mA cm2 to 56 mA cm2. Notably, the value of 71 mA cm2
was significantly higher than the latest reported data of
62.54 mA cm2 [53]. Interestingly, when using catalyst c2
(figure b of Fig. 5b), the peak current density values of both
peak f and b almost remained unchanged with increasing the
cycling number. For instance, after 25 cycles, the peak current
density of peak f varied from 44.7 to 45.9 mA cm2. To one's
surprise, in the case of catalyst c3 (figure c of Fig. 5b), the peak
current density values for both peak f and b evidently
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 7 6 e2 9 1 285

Fig. 5a e (a) A comparison of CV curves measured on various samples coated GC electrode at the scan rate of 50 mV s¡1 in
which the black curve was recorded in 1 M KOH and the red curve was measured in the electrolyte solution containing 1 M
KOH and 1 M ethanol. Figure (a), (b) and (c) corresponded to the case of using catalyst c1, c2 and c3. Figure (d) is the collection
of all CV curves measured on various samples coated GC electrode in 1 M KOH containing 1 M ethanol at the scan rate of
50 mV s¡1.

increased with increasing the cycling number. That is, the
peak current density value recorded at the first cycle was only
4.2 mA cm2 which was altered to be about 6.4 mA cm2 after
25 cycles. It was clear, as shown by figure d of Fig. 5b, that in
the whole cycling testing period catalyst c1 showed the largest
peak current density among all resultant catalysts.
To further study the electrocatalytic tolerance of the pre-
pared catalysts towards EOR, Chronoamperometry (CA)
curves of EOR, which were recorded at 0.23 V on all resultant
catalysts, were carefully plotted in figure a and b of Fig. 6.
Apparently, each CA curve was composed by two parts,
namely, a sharp decline stage and a relatively stable stage.
And, the sharp descending stage of the current density
emerging at the initial stage of a CA curve was commonly
attributed to the remarkable capacitance current variation,
which was reported to be directly relevant to the double-layer
capacitance formed on the surface of a working electrode [54].
And the relatively stable current density, which was generally
ascribed to the direct electrochemical oxidation of organic
small molecules, was nominated as faradaic current density
or polarized current density [54]. Evidently, in the whole
testing time, the largest faradaic current density was deliv-
ered by catalyst c1 among all studied catalysts. For instance, at
the end of testing time of 600 s, the current densities were
measured to be 23.9, 7.0 and 2.1 mA cm2 on catalyst c1, c2 and
c3, respectively. Thus, the current density delivered by cata-
lyst c1 at 600 s was almost 11.4 times larger than that on
catalyst c3. To further examine the long-term durability of the
electrocatalytic abilities of all prepared catalysts towards EOR,
the testing time was specially extended to be 3600 s and the
results are shown in figure b of Fig. 6. Inspiringly, at 3600 s, the
polarized current densities of EOR measured on catalyst c1, c2
and c3 were recorded to be 1.48, 0.70 and 0.45 mA cm2,
respectively, strongly suggesting that all prepared catalysts
had an excellent durability of electrocatalytic activity towards
EOR. In the whole testing period, the EOR current densities
measured on all prepared catalysts were in the following
decreasing order, namely, c1> c2>c3, being in line with the
sequence shown in figure d of Fig. 5b. It was worth empha-
sizing that the value of 1.48 mA cm2 was still higher than the
latest reported data of 1.30 mA cm2 measured on pure Pd/C
catalyst [22], indicating that all as-synthesized catalysts in
this work were superior relative to most Pd-based catalysts in
terms of the electrocatalytic activity.
The CV curves measured in 1 M KOH solution at the scan
rate of 50 mV s1 of all prepared catalysts are illustrated in
Fig. 7. Apparently, an evident electrochemical reduction peak
was, respectively, displayed at 0.39 V for c1, at 0.33 V for c2
and at 0.35 V for c3, which was commonly attributed to the
PdO electrochemical reduction, i.e., PdO þ H2O þ 2e4Pd þ
2OH [49]. As shown by the red-circled part, there was an
abnormal small electro-oxidation peak at 0.42 V in the CV
curve of catalyst c1, suggesting that the CV performance of
catalyst c1 was some different from that of the pure Pd elec-
trode. Evidently, catalyst c1 delivered the largest CV peak area
among all prepared catalysts. On the basis of the previous
286 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 7 6 e2 9 1

Fig. 5b e CV curves measured at the 1, 5, 10, 15, 20 and 25 cycles on different catalysts coated GC electrodes in 1 M KOH
containing 1 M ethanol at the scan rate of 50 mV s¡1. Figure a, b and c corresponded to the case of using catalyst c1, c2 and c3.
The curves of figure d described the relationship between the peak current density of the peak f for EOR and the cycling
number, in which curve c1, c2 and c3 corresponded to the case of using catalyst c1, c2 and c3. (For interpretation of the
references to color in this figure legend, the reader is referred to the Web version of this article.)

work [55], the electrochemical surface areas (ECSA) of all
prepared catalysts were also roughly evaluated employing the
following equation (1), namely,
ECSA ¼ QPdO/(m  C)
In equation (1), QPdO referred to the electric charge
consumed in the electrochemical reduction of monolayer PdO
which was equivalent to the ratio value of the electro-
reduction peak area to the scanning rate. And, m and C were,
respectively, denoted as the loading amount of the metallic Pd
and the electric charge consumed in the electrochemical
reduction of monolayer PdO on per unit area (424 mC cm2).
Thus, the largest value of QPdO was delivered by catalyst c1 due
to its largest CV peak area among all prepared catalysts.
Furthermore, the ECSA values were calculated to be 80.4 m2
gPd1, 14.0 m2 gPd1 and 11.4 m2 gPd1 for catalyst c1, c2 and c3,
respectively. Significantly, all ECSA values estimated in this
work were higher than that of the reported value of 1.7 m2
gPd1 [55]. In particular, the ECSA value of 80.4 m2 gPd1
measured on catalyst c1 was almost 5 times higher than that of
the latest reported value of 16.02 m2 gPd1 [53]. Also, as dis-
played by figure d of Fig. 5a, the EOR onset potential value
measured on all resultant catalysts were close to 0.60 V.
Thus, combined with the results shown in Fig. 7, it was
concluded that prior to the EOR process, PdO molecules
existing in the catalysts should have been electrochemically
reduced to be metallic Pd. Furthermore, the CV peak area was
commonly proportional to the amounts of electric charge
transferred [56]. That is to say, as compared with other cata-
lysts, more amounts of metallic Pd atoms have been prepared
on catalyst c1 before the EOR process. Summarily, results of
Fig. 7 effectively indicated that the largest CV peak of PdO/Pd
(1) was exhibited by catalyst c1 which was well consistent with
the fact that the maximum EOR peak current density was
delivered by catalyst c1 among all prepared catalysts.
Nyqusit plot as one main type of curves in EIS measure-
ment has been utilized as a traditional technique to compare
the charge transfer process of various electrochemical re-
actions [57]. The Nyquist plots of EOR on all prepared catalysts
are given in figure an of Fig. 8. In general, for a conventional
electrochemical reaction, the Nyquist plot was arranged by
one semicircle appearing in the high frequency limit and a 45
line existing in the lower frequency region [58]. The semicircle
was generally attributed to a parallel circuit containing a
capacitance element parallel to a resistance element in which
the diameter of the semicircle was roughly equal to be the
value of charge transfer resistance (Rct) [59]. And, the sloped
line appearing in the lower frequency region was commonly
ascribed to the diffusion of electroactive substances (or called
as Warburg impedance) [60]. While, in this case, for all pre-
pared catalysts, a nearly flat line appeared in the higher fre-
quency region, indicating that the value of Rct was too small to
be detected. Different from the cases of both catalyst c2 and c3,
for the Nyquist plot of catalyst c1, a large semicircle, rather
than a sloped line, was clearly exhibited in the lower fre-
quency region. The difference in the Nyquist plot shape
effectively indicated that the electrode surface microstructure
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 7 6 e2 9 1
Fig. 6 e Chronoamperometry (CA) curves of EOR on various
catalysts coated GC electrode in 1 M KOH containing 1 M
ethanol, in which the electrode potentials of the working
electrode was fixed at ¡0.23 V. Curve c1, c2 and c3
corresponded to the case of using catalyst c1, c2 and c3.
Figure a and b were respectively recorded at the elapsed
time of 600 s and 3600 s.
of each catalyst coated electrode was different from each
other, as has been evidenced by the SEM (Fig. 4b) and TEM
images (Fig. 4c).
The Bode curves of all as-synthesized catalysts are plotted
in figure b of Fig. 8. For catalyst c1 and c3, an evident broad
symmetric peak was exhibited in the total testing frequency
region. The summit of the symmetric peaks assigned to
catalyst c1 and c3 were, respectively, located at the value of log
of 3.57 and 3.25, indicating that a more stable and regular
microstructure was possessed by catalyst c1. While for cata-
lyst c2, no symmetric peak was found in the whole testing
frequency range. Meanwhile, the phase angle at 100 Hz for
catalyst c1, c2 and c3 was estimated to 15.9 , 64.2 and
36.3 , implying that the electrode surface microstructure of
catalyst c2 was closer to a capacitor structure relative to other
catalysts [61,62]. The curves showing the relationship
287
Fig. 7 e Cyclic voltammetry curves measured on various
catalysts coated GC electrodes in 1 M KOH at the scan rate
of 50 mV s¡1. Curve c1, c2 and c3 corresponded to catalyst
c1, c2 and c3. As indicated by the red circled part, an
abnormal oxidation peak appeared in the CV curve of
catalyst c1. (For interpretation of the references to color in
this figure legend, the reader is referred to the Web version
of this article.)
between the total resistances of the catalyst coated electrode
and the frequency are plotted in figure c of Fig. 8. The curve
shapes of both catalyst c2 and c3 were similar to that of our
previous work regarding a catalyst coated electrode [63]. To
one's surprise, in the case of catalyst c1, a sloping straight line,
decreasing from 51.9 U to nearly 32 U, was observed in the
whole frequency region. Especially, at 10 Hz, the total resis-
tance value for catalyst c1, c2 and c3 were measured to be 51.9,
1054.5 and 287.5 U, respectively. That is, among all prepared
catalysts, the minimum total resistance value was exhibited
by catalyst c1, which was mostly attributed to its special
morphology of dotted nanowire.
How did we understand the chemical reactions occurring
in the hydrothermal process? Taking catalyst c1 as an
example, as shown in figure c of Fig. 4a, many huge flaky
particles of metallic Ni were prepared in the calcined product
of NU. While, after the hydrothermal process, many small
particles appeared in catalyst c1, strongly indicating that the
huge particles of metallic Ni have reacted with PdO$H2O dur-
ing the hydrothermal process. That is to say, metallic Ni was
employed as a reducing agent to chemically reduce PdO to
produce metallic Pd since the standard electrode potential of
Ni2þ/Ni (0.25 V) was rather lower than that of Pd2þ/Pb
(þ0.92 V) [64]. Evidently, as indicated by the former work [65],
amorphous carbon existing in NU might also be used as a
reducing agent to react with PdO to produce metallic Pd. Thus,
in the hydrothermal process, PdO was chemically reduced to
be metallic Pd by the metallic Ni and amorphous carbon,
leading to the formation of the final Pd based EOR catalysts.
To sum up, the appropriate atomic ratio of Pd to Ni (1:1), the
smallest particle size (Fig. 4b), the largest ECSA value (Fig. 7) as
well as the smallest resistance value (figure c of Fig. 8) and the
newly prepared special morphology of dotted nanowires
288 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 7 6 e2 9 1
Fig. 8 e EIS results of all studied electrodes measured in
1 M KOH containing 1 M ethanol in which curve c1, c2 and
c3 corresponded to catalyst c1, c2 and c3. (a) Nyquist plots;
(b) Bode plots; (c) Curves showing the relationship between
the total impedance (Z) and frequency (f).
(Fig. 4c) were investigated as the main reasons endowing
catalyst c1 the best electrocatalytic ability for EOR among all
as-synthesized catalysts. Developing a novel way to prepare
metallic Ni and presenting a novel morphology of a dotted
nanowire are the major dedications of this pioneering work, to
our knowledge, which is believed to be very favorable not only
to the development of nanoscience but also to the exploration
of Pd-based EOR electrocatalysts.
Conclusions
For the first time, dotted nanowires arrayed by 5 nm sized Pd
and Ni composite nanoparticles were prepared via a hydro-
thermal method in which NU (the calcined product of the
mixture containing urea and nickel acetylacetonate) and
PdO$H2O were employed as the starting materials. In this
work, the final samples prepared with a mass ratio of NU to
PdO$H2O 1:1, 1:2 and 2:1 were named as catalyst c1, c2 and c3.
Different from the previously published XRD patterns for the
Pd-based composite particles, the diffraction peaks ascribed to
the metallic Ni rather than the metallic Pd were mainly pre-
sented in all obtained XRD patterns. In the light of the XRD, EDS
and XPS analysis results, it was concluded that (1) In catalyst
c1, those nanoparticles used for forming the dotted nanowires
were mainly composed by metallic Ni and metallic Pd. (2)
Those huge aggregates appearing in catalyst c2 were mainly
constructed by PdO nanoparticles. (3) The main components of
catalyst c3 were the metallic Ni and metallic Pd. The results of
SEM and TEM images effectively demonstrated that the mass
ratio of NU to PdO$H2O was a key factor which could remark-
ably not only influence the particle size of the final samples but
also affect the surface morphologies of the prepared samples.
Catalyst c1, namely, the catalyst that was constructed by
numerous dotted nanowires, showed the best electrocatalytic
activity for EOR among all as-synthesized catalysts based on
the results of CV and CA. Specially, even after 3600 s, the
polarized current density of EOR on catalyst c1 was still
maintained to be as high as 1.48 mA cm2, a value evidently
higher than the latest reported data. Presenting a fact that
dotted nanowires arrayed by 5 nm sized nanoparticles could be
prepared via a hydrothermal method, as well as, showing the
significant electrocatalytic activity of the newly prepared
dotted nanowires towards EOR were the main contributions of
this work, which was very meaningful not only to the further
exploration of nanoparticles due to the novel morphology but
also to the development of Pd-based EOR electrocatalysts
owing to the significant electrocatalytic activity and relatively
lower preparation cost as well, we think.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 7 6 e2 9 1
Acknowledgements
The work was supported by the Ministry of Science and
Technology of the People's Republic of China (No.
2019YFE0100200 and 2019YFA0705703) and the National Nat-
ural Science Foundation of China (No. U1564205) and the
Technical Innovation Advanced Research Foundation of Hebei
Normal University (L2018K03).
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