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DOI: 10.1002/ijch.201900175

Green Synthesis of M0 Nanoparticles (M=Pd, Pt, and Ru) for

Electrocatalytic Hydrogen Evolution
Shanti G. Patra+,[a] Krishnamoorthy Sathiyan+,[a] Michael Meistelman,[b] and Tomer Zidki*[a]
Dedicated to Prof. Michael Zinigrad’s 75th anniversary

Abstract: In recent years the demand for green synthesis and resonance infra-red (ATRIR) spectroscopy. Moreover, acetic
green energy has increased immensely. Herein M0 nano- acid was detected as a byproduct of the hydrothermal
particles were synthesized using a metal precursor and reaction. NaHCO3 can be considered as the dissolution of
NaHCO3 under hydrothermal conditions without using any CO2 in a mildly alkaline solution. Thus, during the reaction,
reducing agent. The nanoparticles were characterized using CO2 was converted to carbonaceous material, which can be
powder X-ray diffraction (PXRD), scanning electron micro- considered as a fixation of CO2. The synthesized nano-
scopy (SEM), and energy dispersive X-ray analysis (EDX). particles are also efficient catalysts for the electrocatalytic
Surprisingly, it found that the Pt and Pd nanoparticles hydrogen evolution reaction (HER). It was found that Ru
contain a high concentration of carbon. The presence of nanoparticles exhibit the highest activity among the three
carbon is also evident from the attenuated transmission catalysts studied.
Keywords: Green synthesis · Metal nanoparticles · Hydrothermal · CO2 fixation

1. Introduction Ru, Pd, and Pt nanoparticles using an aqueous solution of

NaHCO3 under hydrothermal conditions. To the best of our
The development of new synthetic methods for preparing knowledge, there is no report on the preparation of metal NPs
metal nanoparticles (NPs) is indispensable, owing to their using such a cheap reagent. Interestingly, we found that this
implications in catalytic processes. From that perspective, over agent affords a very efficient and green synthesis of metal
the years, it has been found that the Pt-group metal NPs (Ru, NPs.
Os, Rh, Ir, Pd, and Pt) have exhibited elevated activity Surprisingly, it has been found that under hydrothermal
compared with other metals.[1,2] The properties of metal NPs conditions, the synthesized metal NPs catalytically convert
are considerably altered by their size and shape.[3] In the past NaHCO3 to acetic acid. Catalytic conversion/fixation of CO2
few decades, a wide range of synthetic approaches have been to formic and acetic acids under mild hydrothermal conditions
employed to synthesize metal NPs, for example, reducing using Fe nanoparticles and a Pd/C catalyst has been
metal precursors via wet-chemical,[4,5] hydrothermal,[6,7] reported.[16,17] A similar conversion by Mn employing solar
electrochemical,[8–10] radiolytic,[11] and sonochemical,[12] syn- energy has also been reported.[18] This conversion has two
theses. Some widely used reducing agents for the synthesis of outcomes: i) the catalysts are active towards CO2 capture; and
metal nanoparticles are polyethylene glycol (PEG),[4] poly- ii) the abiotic origin of the pure organic molecules, which have
vinylpyrrolidone (PVP),[5] and cetyltrimethylammonium direct implications regarding our understanding of the origin
bromide (CTAB).[13] One of the most significant drawbacks of of life on earth.
these reagents is their use of hazardous organic solvents and Another important aspect of metal NPs is their use as
chemicals, which act as pollutants in the environment. potential catalysts for the electrocatalytic hydrogen evolution
However, it is challenging to develop synthetic strategies for reaction (HER).[19–22] Among the precious metals, Pt is the
metal NPs free of organic solvents and hazardous reagents,
i. e., a green synthetic approach.
In the past years, an enormous effort has been directed [a] S. G. Patra,+ K. Sathiyan,+ T. Zidki
towards the green synthesis of NPs in aqueous medium using Department of Chemical Sciences and the Center for Radical
Reactions, Ariel University, Ariel, Israel
reagents that have dual functions: reducing and stabilizing E-mail: [email protected]
agents.[14] For example, the use of glucose and starch for the [b] M. Meistelman
synthesis of Ag, Au, and Ag Au alloy NPs as reducing and Department of Chemical Engineering, Ariel University, Ariel,
stabilizing agents has been reported by Raveendran et al.[15] So Israel
et al. have reported the synthesis of platinum group metal NPs [+] authors contributed equally.
using biocompatible 4-(2-hydroxyethyl)-1-piperazinethane- Supporting information for this article is available on the WWW
sulfonic acid (HEPES).[6] Herein, we present the synthesis of under https://doi.org/10.1002/ijch.201900175

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most efficient catalyst for this purpose.[23] A recent develop- obtained at 2θ (°) values of 43.90, 58.41, 69.34, and 78.25,
ment regarding the Ru-based catalyst via incorporation of which correspond to 101, 102, 110, and 103 planes,
carbon indicated that nitrogen has also shown promising respectively (JCPDS: 00-006-0663). For platinum, the peaks
activity.[19,20,24] Thus, we have performed electrocatalytic HER of 111, 002, and 022 planes appeared at 2θ (°) values of 39.89,
using the synthesized Pd, Ru, and Pt catalysts. The greenly 46.39, and 67.71, respectively (JCPDS: 98-002-1963). For
synthesized Ru catalyst exhibits the highest activity. palladium, the peaks at 2θ (°) values of 40.11, 46.65, and
68.10 are well matched to the 111, 002, and 022 planes,
respectively (JCPDS: 98–009-1155). The particle sizes were
2. Results and Discussion estimated by the Scherrer equation (1)[25] (crystallite phase
size) using the most intense peaks of metallic NPs (2θ (°)
2.1 Synthesis and Characterization values of 43.90, 39.89, and 40.11 for Ru, Pt, and Pd,
respectively). The calculated sizes were 22, 33, and 43 nm, for
The metal NPs were synthesized, starting from their respective Ru, Pt, and Pd, respectively.
precursors (K2[PdCl4], Ru2(OAC)4Cl, and K2[PtCl4]). The
precursors were taken in an aqueous solution containing KLl
t¼ (1)
NaHCO3, and then the hydrothermal reaction was carried out. bcosq
The product, obtained as a precipitate, was purified by
dispersion and centrifugation. The resulting NPs were ana- where τ is the mean size of the ordered (crystalline) domains;
lyzed using powder X-ray diffraction (PXRD), scanning K is the shape factor (a dimensionless parameter with a value
electron microscopy (SEM), energy dispersive X-ray analysis approaching unity, 0.94); λ, θ, and β are the X-ray wavelength,
(EDX), and attenuated transmitted resonance infra-red (AT- the Bragg diffraction angle, and the full width at half-
RIR). maximum (FWHM) of the diffraction peak, respectively. λ =
The hydrothermal products were metal NPs, as confirmed 0.1540 nm (the wavelength of the device emission).
from the PXRD pattern (Figure 1) and the SEM images The SEM images of the NPs are shown in Figure 2. The
(Figure 2). For ruthenium, the Bragg diffraction peaks were sizes of the Ru, Pt, and Pd NPs obtained from Figure S1 are
~ 24, 92, and 106 nm, respectively. Evidently, the ruthenium
NPs have the smallest size among the particles obtained.
Obviously, the size of the particles does not fit the crystallite
phase size[26] obtained using the Scherrer equation, although
the trend remains the same, i. e., Pd > Pt > Ru. Note that while
preparing samples for SEM, the Ru and Pd NPs have been
agglomerated, whereas the Pt NPs have not (they are shown as
single particles in Figure 2). The agglomeration could be due
to the presence of a charge on the particles. Furthermore, the
composition of the particles was examined by EDX analysis.
The EDX spectra of the Ru, Pt, and Pd NPs are shown in
Figure S2. The elemental compositions of the M0 NPs are
summed up in Table 1. In the case of Pt and Pd, some
elemental carbon was formed, which is more significant in Pt.
The percentage of oxygen in Ru is higher, which is attributed
to the presence of RuO2 and carbonate on the surface.
Figure 1. The powder X-ray diffraction patterns of the Ru, Pt, and Pd The elemental mapping was recorded to follow the
nanoparticles: the Bragg diffraction peaks at 2θ are assigned to the presence of carbon. The mapping of the Ru, Pt, and Pd NPs is
crystal-planes (Miller indices). shown in Figure 3. Probably, during or after the formation of
the M0 NP, the carbonate (i. e., CO2) was reduced to carbon.
Since in the XRD pattern, no shift in the peak position of the

Table 1. The elemental compositions (atomic %) of metal, carbon,

and oxygen in the Ru, Pt, and Pd NPs, obtained from the EDX
spectra.

Nanoparticle M C O
Ru 61.2 7.0 31.8
Figure 2. The SEM images of (a) Ru, (b) Pt, and (c) Pd nano- Pt 13.2 67.7 17.5
particles. Pd 62.1 27.2 10.7

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obtained through sonochemical synthesis.[28,29] In the sono-
chemical procedure, free radicals are formed by generating
cavitation under ultrasound irradiation at low frequency.
Cavitation is a process involving the formation, growth, and
collapse of small bubbles formed in the solution, which
produce extremely high pressure and temperature, leading to
the thermal dissociation of water molecules, consequently
* *
forming OH and H radicals. Similarly, under the hydro-
thermal conditions, high pressure is achieved when consider-
ing only the water molecules (~ 10 atm under the ideal gas
approximation). In such an environment, cavitation could be
* *
obtained along with OH and H radicals’ formation. The
formed hydrogen atoms and hydroxyl radicals react with
organic molecules, usually via H-abstraction, yielding a
reducing radical that reduces the metal ions to its M0 state.[30–32]
To verify this assumption, we also prepared the Pt NPs via the
sonochemical procedure in the presence of bicarbonate. The
product obtained showed morphology (Figure S4), and PXRD
patterns (Figure S5) identical to those of NPs obtained under
hydrothermal conditions. Unfortunately, we could not find any
report on hydrogen and hydroxyl radical formation under
hydrothermal conditions. Another possibility is that under
hydrothermal conditions, the metal ions (Pt2 +, Pd2 +, and Ru2 +
/3 +
) may oxidize water (2H2O!O2 + 4H + + 4e ) and reduced
Figure 3. The EDX elemental mapping of (a) Ru and C for Ru0
to the M0 state. However, the latter possibility seems less
nanoparticles (b) Pt and C for Pt0 nanoparticles and (c) Pd and C for
Pd0 nanoparticles. adequate. Further, to check the role of bicarbonate in the
synthesis of the metal NPs, blank reactions in the absence of
bicarbonate were carried out. Although Ru and Pd NPs were
metals was observed, we assume that an elemental carbon not formed in this process, Pt NPs were formed due to the
present rather than an alloy with the NPs. In this context, note thermal formation of PtO,[33] followed by the decomposition of
that siderite (FeCO3) undergoes decomposition under similar platinum oxide to platinum metal.[34] In this context, it should
conditions (high temperature of 300 °C and water-saturated be noted that chloride ligands are labile[35] in nature and
vapor pressure – Psat) to form carbonaceous material.[27] The substituted by H2O under the hydrothermal condition to form
carbonate’s reduction to carbon is presented in equation (2).[27] Pt(OH)2 which undergoes disproportionation[36] to form Pt and
In addition, the oxidation of the FeII in Siderite by water PtO2.
releases hydrogen. To answer the second question, one should look into the
previously reported mechanism by He et al.[16] They reported
6FeCO3 ! 2Fe3 O4 þ 5CO2 þ C (2) on the hydrothermal conversion of CO2 to formic and acetic
acid using iron powder. Similarly, Pd/C can catalyze the same
The Pt NP samples had the highest carbon content, as conversion.[17]
indicated in Table 1. The EDX mapping, shown in Figure 3,
confirms the coexistence of platinum, palladium, and carbon.
Therefore, the ATRIR spectrum (Figure S3) was recorded to 2.2 Catalytic Formation of Acetic Acid
study the peaks corresponding to the C H vibrations. Indeed,
1
the C H symmetric and antisymmetric stretching were H NMR spectroscopy was used to analyze the solutions
observed in the range of 3,000–2,800 cm 1. The peaks at the (filtrates) for byproducts after the hydrothermal reactions. The
region 1,304–1,383 cm 1 corresponded to the C H formation of acetate was confirmed from the peak at
deformation.[26] The peak of the C=O stretching was found at ~ 1.95 ppm (pH ~ 8.5, the intensity of the peak was higher for
1,727 cm 1, which implies the presence of carbonate, with its Pt than for Pd as expected Figure 4). Since the platinum NPs
corresponding carbon and oxygen atoms; which were detected show higher carbon content, it acts as a more efficient catalyst
in the EDX spectrum (Figure S2). compared to the other metals. Thus, it is expected to form a
From these results, two questions arise; i) how were the higher concentration of products/intermediates (acetic acid).
metal precursors reduced to the M0 state? and ii) how was As a result, a higher peak from the Pt NPs supernatant was
bicarbonate reduced to elemental carbon? To address the first observed. However, in the sonochemical procedure, lower
question, one has to think of other methods for metallic yields of acetate were obtained, which was also confirmed by
nanoparticle synthesis. It is well known that Pt0 NPs can be high-performance liquid chromatography (HPLC). In hydro-

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Figure 4. The 1H NMR spectra of the solution of Pt and Pd nanoparticles after synthesis in H2O (10 % D2O).

thermal synthesis, the yields of acetate in the solutions from Pt potential of 96 mV @ 10 mA cm 2, better than all the
and Pd NPs were 547 and 350 μg mL 1, respectively (the synthesized NPs. The as-prepared Pt NPs indicated an over-
HPLC procedure is presented in the supplementary material), potential of 135 mV @10 mA cm 2. The Pd NPs showed the
whereas sonochemical synthesis yielded only 139 μg mL 1 highest overpotential of 209 mV @10 mA cm 2. Hence, the
acetate. overpotentials follow the trend: Ru < Pt < Pd.
The electrochemical kinetics and the mechanism under-
lying the HER were assessed using the Tafel equation (η = a +
2.3 Electrocatalytic Hydrogen Evolution Reaction (HER) b log (j)), where η is the overpotential, b is the Tafel slope,
and j is the current density.[39] Figure 5 (b) presents the Tafel
The catalytic performance of the as-prepared NPs was slopes extracted from the linear fitting of the Tafel equation.[40]
evaluated electrochemically by the hydrogen evolution reac- The obtained Tafel slope of Pt, ~ 45 mV decade 1. The Tafel
tion. The electrochemical measurements were carried out in a slopes of Pd and Ru show values of 67 mV decade 1 and
three-electrode system. Figure 5 shows the linear sweep 78 mV decade 1, respectively, which are higher than the Pt
voltammograms (LSV) of the NPs. The overpotential required catalyst. The Tafel slopes lie between 40 and 120 mV
to deliver 10 mA cm 2 vs. the reversible hydrogen electrode decade 1, suggesting that the catalytic HER reaction undergoes
(RHE) is a standard method used to compare the HER between the Volmer-Heyrovsky pathway,[41,42] where the electrochem-
catalysts (denoted as a horizontal line in Figure 5 (a)).[37,38] As ical desorption of the hydrogen is the rate-limiting step.[43]
Figure 5(a) illustrates, the Ru NPs exhibit a very low over-

Figure 5. Electrochemical characterizations of the prepared catalysts. (a) HER (LSV) curves in N2 saturated 0.5 M H2SO4 solutions at a scan
rate of 5 mV s 1; (b) The corresponding Tafel plots.

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Figure 6 presents a summary of Tafel slopes and overpotentials directly related to the material). The values reported as Rct is
for the prepared electrocatalysts. from the second semicircle.[45] The EIS measurement and the
Electrochemical Impedance Spectroscopy (EIS) measure- fitted plot of the ruthenium catalyst are clearly shown in the
ments were performed to determine the charge transfer inset.
resistance (Rct) values[44] and the solution resistance of the To understand the origin of the enhanced HER perform-
catalysts. Figure 7 displays a Nyquist plot for the synthesized ance of the electrocatalysts prepared, the double-layer capaci-
catalysts, where Z’ and Z’’ represent the real and imaginary tance was evaluated, which is linearly proportional to the
components, respectively, of the impedance. The Rct values electrochemical active surface area (ECSA). The double-layer
were obtained by fitting the experimental data with Randle’s capacitance (Cdl) values were determined using cyclic voltam-
equivalent circuit, R(QR)(QR)(CW). The corresponding fitted metry (CV) at scan rates of 20, 40, 60, 80, and 100 mVs 1.
results were listed in Table S1. The CV measurements were performed in a non-Faradic
From these results, all three catalysts have almost similar potential window within the range of 0.40–0.50 V vs. RHE, as
values of solution resistance (Rs) but have different charge presented in Figure S9. It was observed that the current density
transfer resistance (Rct) values. The Rct value for Ru is very increases with the scan rates. The Cdl values were determined
low (4.76 Ω) when compared with Pt and Pd, which have from the linear slope obtained by plotting the difference in
higher Rct values of 117.8 Ω and 785.8 Ω, respectively. It current density ΔJ = (Ja–Jc) vs. RHE against the scan rate,
should be noted that two semicircles were obtained for all the where Ja and Jc are the anodic and cathodic current densities,
three cases where the first one represents the interface between respectively (Figure 8). The measured active surface area is
the glassy carbon electrode and electrolyte. The second one not an absolute value; however, it can serve as a guide for
represents electron transport resistance of the cell (a property comparing the surface roughness for a similar kind of material.
The double-layer capacitance (Cdl) value is obtained from the
equation (3),[38]

Cdl ¼ ic =n, (3)

where ic is the charging current (mA cm 2) and ν is the scan

rate (mV s 1).
The CV curves at various scan rates are shown in
Figure S9, and the corresponding capacitance (Cdl) values are
shown in Figure 8. The Ru NPs present the highest Cdl value
of 11.98 mF cm 2 compared with Pt (0.21 mF cm 2), and Pd
(0.03 mF cm 2). The gravimetric capacitance of the materials
2
is calculated to be 2.47 F g 1, 0.05 F g 1, 0.01 F g 1 for Ru, Pt
Figure 6. Summary of overpotentials at 10 mA cm vs. the RHE and
and Pd, respectively. These values represent the catalyst’s
Tafel slopes of the prepared electrocatalysts.
abundant active sites. Thus, it was found that the Cdl and Rct
follows opposite trend, which are in agreement with the fact
that Cdl is inversely related to Rct.

Figure 7. Nyquist plot of as-prepared NPs at an electrode potential

of 50 mV vs. RHE in 0.5 M H2SO4 (the symbols denote the Figure 8. Current density (ΔJ = Ja–Jc) as obtained from Figure S9 (at
Experimental data, and the solid lines represent the Fitted data) 0.45 V vs. RHE) against the scan rate. The slope values equal those
(Inset: a Nyquist plot of Ru NP). of Cdl.

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The chronoamperometry method was used to evaluate the Aldrich. All aqueous solutions of different concentrations
long-term HER stability of the Ru catalyst. Figure 9 shows the were prepared from deionized water purified by a Millipore
time-dependent chronoamperometric curve of the Ru catalyst Milli-Q setup with a final resistivity of > 15 MΩ cm.
at a constant overpotential of 50 mV in a 0.5 M H2SO4 solution
for 15 h. The catalytic current after 15 h remained steady,
indicating the excellent stability of the Ru catalyst. 4.2 Instrumentation and Methods

(SEM) studies were performed using a TESCAN MAIA3

3. Conclusions instrument. EDX analyses in SEM mode (SEM-EDX) were
performed using the Aztec materials characterization system.
In the 21st century, the use of alternative energy from materials pH values were measured using a SCHOTT 850 Benchtop pH
obtained via green synthesis is at its peak. Keeping that goal in meter using a pH electrode from SI Analytical, GmbH. The
mind, we demonstrated here the synthesis of Pt-group M0 ATR spectrum was recorded on a Bruker VERTEX 70 FTIR
nanoparticles (M=Ru, Pd, and Pt) from their corresponding Spectrometer. PXRD was performed by using an X’Pert Pro
ion precursors under hydrothermal conditions in the presence diffractometer using Cu-Kα radiation (λ = 0.154 nm). The
of NaHCO3. One of the significant achievements of this scanning for PXRD was made for a 2θ angle from 20 to 80°,
procedure is the lack of hazardous reducing agents. Unexpect- with a step time of 2 s. The acetic acid formation was
edly, it was found that the NPs contained a high concentration quantified using an HPLC system (Jasco) with a UV/Vis
of carbon (especially regarding Pt and Pd). Since NaHCO3 is detector (λ = 210 nm) along with an Agilent HPLC column
the only source for carbon, and CO2 is present in alkaline (Eclipse XDB-C18, 5 μm) with dimensions of 4.6 × 150 mm.
solutions as NaHCO3, it can be concluded that CO2 has been The eluent was H2O/CH3CN = 98 : 2 with 0.2 % H3PO4,
reduced to carbon. Furthermore, after the reaction, the filtrate pH 2.0, and a flow rate of 1.0 mL min 1. An ultrasonic
contained acetate, as detected from 1H NMR spectroscopy and sonicator from Vibra-cell (Model VCX 130) was used for the
quantified by HPLC measurements. Moreover, the electro- sonochemical synthesis.
chemistry results indicate that the synthesized NPs have
excellent electrocatalytic HER activity, where Ru exhibits the
best catalytic activity. Hence, we present here the fixation of 4.3 Electrochemical Measurements
CO2 by the green synthesis of metal NPs, along with their
exceptional electrocatalytic HER activity. Before the electrochemical measurements, the glassy carbon
working electrode was first polished with 1 μm Al2O3 to
remove any deposited material, followed by polishing with
4. Experimental 0.05 μm Al2O3 to make the surface smooth. Then, it was
sonicated in water for 30 s using an ultrasonic bath to remove
4.1 Materials any particles from the surface. Finally, 30 cycles of CV were
performed in 0.50 M H2SO4 to clean it electrochemically. The
NaHCO3, K2[PdCl4], K2[PtCl4], and RuCl3.3H2O were pur- electrochemical measurements were performed in a three-
chased from Alfa-Aesar. D2O was purchased from Sigma electrode cell on an EmStat3 PalmSens instrument. Impedance
measurements were measured using a PalmSens4 potentiostat.
A glassy carbon disk electrode (GCE) with a 3 mm diameter
was used as the support for the working electrode, with Ag/
AgCl (H2SO4, 0.5 M) as a reference electrode and platinum
wire as the counter electrode. The potentials mentioned in this
work were referenced to the reversible hydrogen electrode
(RHE).

E ðvs: RHEÞ ¼ E ðvs: Ag=AgClÞ þ 0:059 � pH þ 0:1976 V

Catalyst suspensions for the working electrodes were

prepared as follows: 2.0 mg of the catalyst were dispersed in a
1.0 mL solution containing 0.50 mL DI water, 0.45 mL
isopropyl alcohol, and 50 μL of 5 % Nafion solution. This
suspension was ultrasonicated for 20 min. Then, ca. 10 μL of
the catalyst was drop-casted onto the polished electrode
surface using a micropipette (giving a loading of 0.28 mg cm 2
Figure 9. Time-dependent current density curve at a static over- catalyst on the GCE), and then dried at ambient temperature.
potential of 50 mV. A continuous flow of N2 was maintained at the top of the

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electrolyte solution throughout the experiment to eliminate unreacted excess bicarbonate). The microcrystalline product
atmospheric oxygen. LSV experiments were performed in was dried in an oven at 60 0C for 24 hours.
0.5 M H2SO4 solution as an electrolyte at a scan rate of
5 mV s 1 to obtain the polarization curves. The Tafel slopes
were calculated from the logarithmic relationship between 4.4.3 Sonochemical Synthesis of Pt NPs
overpotential and current density, based on the LSV curves.
Chronoamperometry experiments were performed at a constant For the ultrasonic synthesis, the procedure reported by Chave
overpotential of 50 mV in a 0.5 M H2SO4 solution. EIS et al.[28] was followed, but with a slight modification. An
measurements were carried out at an overpotential of 50 mV ultrasonic generator and a titanium alloy Ti-6Al-4 V oscillator
from 10 kHz to 0.1 Hz (14 points per decade) with the of 3 mm diameter were used for the ultrasonic irradiation. The
amplitude of the sinusoidal perturbation fixed at 10 mV. The instrument was operated at 20 kHz, and an input power of
charging currents were measured from the double layer 200 W. K2[PtCl4] (207 mg, 0.5 mmol) was dissolved in 15 mL
charging curves using CVs at different scan rates of 20, 40, NaHCO3 solution (380 mg, 4.52 mmol). The solution was then
60, 80, and 100 m Vs 1 in a potential range from 0.40 to sonicated in an ice bath using the oscillator for three hours.
0.50 V vs. RHE for HER without redox processes. Then The product formed was purified and dried following the same
double-layer capacitance was calculated using equation 3. procedure as described for the hydrothermal synthesis.

4.4 Synthesis of the Metal Nanoparticles Conflicts of Interest

The Pd, Pt, and Ru NPs were synthesized from K2[PdCl4], K2 There are no conflicts to declare.
[PtCl4], and Ru2(OAC)4Cl, respectively. The synthesis of Ru
NPs is outlined in section 4.4.2; the same procedure was
utilized for the other metals. The precursor complex, Ru2 Acknowledgments
(OAC)4Cl, was synthesized following the literature method[46]
with a slight modification. We are indebted to the Pazy Foundation for a grant that
enabled this study (grant No. RA 1700000337). SGP thanks
Prof. Dan Meyerstein for a postdoctoral position. We thank Dr.
4.4.1 Synthesis of Ru2(μ-CH3COO)4Cl Vered Marks for her help with the NMR measurements. We
would like to acknowledge D.S. BioAnalytics for providing us
RuCl3 · 3H2O (1 g) was taken in a mixture of glacial acetic acid the PalmSens4 potentiostat for the electrochemical measure-
(35 mL) and acetic anhydride (7 mL) under an oxygen ments.
atmosphere and gently refluxed for one hour. During the
reaction, the initial brown color changed to dark green. The
black residue, which formed after ~ one hour, was removed by
filtration after cooling. Next, the solution was further refluxed References
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Isr. J. Chem. 2020, 60, 1 – 9 © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.ijc.wiley-vch.de 8
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S. G. Patra, K. Sathiyan, M. Meistel-
man, T. Zidki*
1–9
Green Synthesis of M0 Nanoparticles
(M=Pd, Pt, and Ru) for Electrocata-
lytic Hydrogen Evolution