Journal of Power Sources 412 (2019) 505–513

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Journal of Power Sources

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Microfluidic water splitting cell using 3D NiFe2O4 hollow spheres T

a a a a
A. Martínez-Lázaro , A. Rico-Zavala , F.I. Espinosa-Lagunes , Julieta Torres-González ,
L. Álvarez-Contrerasc, M.P. Gurrolab,d, L.G. Arriagaa,∗, J. Ledesma-Garcíab, E. Ortiz-Ortegaa,∗∗
a
Centro de Investigación y Desarrollo Tecnológico en Electroquímica, 76703, Santiago de Querétaro, Mexico
b
División de Investigación y Posgrado, Facultad de Ingeniería, Universidad Autónoma de Querétaro, 76010, Santiago de Querétaro, Mexico
c
Centro de Investigación en Materiales Avanzados, Complejo Industrial Chihuahua, 31109 CI, Mexico
d
CONACYT-TECNM/ Instituto Tecnológico de Chetumal, Av. Insurgentes 330, CP 77013, Chetumal, Quintana Roo, Mexico

HIGHLIGHTS

• AThesimple method to synthesize 3D NiFe O hollow spheres was reported.

• Microfluidic
2 4
Pt-Free material has large surface area and catalytic activity for OER.
• water splitting cell with Pt-Free material produced 2.5 mg s −1
of H2.

ARTICLE INFO ABSTRACT

Keywords: The present research work shows a simple method to synthesize 3D NiFe2O4 hollow spheres by a hydrothermal
Microfluidic electrolyser system route and its application as catalyst for water splitting in an alkaline microfluidic system. The NiFe2O4 was
Oxygen evolution reaction developed by a simple mechanism from the urea hydrolysis reaction and later subjected to a hydrothermal
PGM-Free catalyst process to carry out a single-step synthesis, obtaining novel 3D hollow nanospheres with doubles, triples and
Nickel ferrite hollow spheres
quadruples shells. 3D NiFe2O4 with large surface area and stability showed a catalytic activity for the oxygen
evolution reaction (OER) comparable with the commercial material commonly employed IrO2. The NiFe2O4-
based material was used as an anode and cathode in a microfluidic water splitting device, where the H2 pro-
duction was 2.5 and 2.7 × 10−5 mg s−1 for 3D NiFe2O4 hollow spheres and IrO2ePt/C, respectively.

1. Introduction
Water splitting is a simple and effective process to produce hy-
drogen and molecular oxygen. This is an acceptable alternative that
allows users to store clean and renewable energies in fuel cells or bat-
teries and reduce the consumption of polluting fuels. These devices can
even generate clean, environmentally friendly energy. The oxygen
evolution reaction (OER) is the basis for all these systems to carry out
this process [1–3]. It is necessary for the catalyst to reduce the potential
required for the reaction to occur with greater efficiency. Iridium oxides
(IrOx) and ruthenium oxides (RuOx) are the most used and effective
electrocatalysts in the OER, but their large-scale use is hampered by low
abundance and high cost, making this energy production system less
profitable [1]. The development of new technologies has shown that
elements of the iron group and their mixtures are characterized by high
electrical resistivity, low dielectric loss over a wide frequency range,
and high resistance to corrosion and thermodynamic stability [4, [3].
Recently, attention has focused on the controlled synthesis of hollow
nanosphere metal oxides [4–6] and the investigation of their size and
shape-dependent properties, as well as the corresponding applications.
Several methods have been developed for their manufacture. Nickel
ferrite is particularly interesting due to its unique magnetic structure
[2,7,8]. It is a cubic ferromagnetic oxide that has a reverse spinel
structure, which tends to form magnetic particles that have small pore
diameters and resistance to high temperatures. These particles are ideal
for oxidation reactions [3,9–11]. Accordingly, nickel ferrite is a suitable
material for the oxygen evolution reaction [712].
The main methods of nickel ferrite synthesis [13] include the sol-gel
method [14,15], coprecipitation [161718], hydrothermal [1920], and
solvothermal methods [21,22]. Hydrothermal methods have been de-
veloped for nickel ferrite preparation in simple syntheses that involve
minor complications in the metal oxide transition. They employ a

∗
Corresponding author.
∗∗
Corresponding author.
E-mail address: larriaga@cideteq.mx (L.G. Arriaga).

https://doi.org/10.1016/j.jpowsour.2018.11.073
Received 15 August 2018; Received in revised form 21 November 2018; Accepted 22 November 2018
Available online 03 December 2018
0378-7753/ © 2018 Elsevier B.V. All rights reserved.
A. Martínez-Lázaro et al.
reaction temperature similar to sol-gel methods, usually at approxi-
mately 100–200 °C. Teflon-lined autoclaves are used to contain the high
pressure generated by aqueous solutions at these temperatures. This
method allows a high yield of raw materials, the use of aqueous media
instead of organics, particle size control, and morphology, in addition
to allowing materials to be manufactured in considerably larger scales
in shorter times than other techniques. The hydrothermal method has
been developed to take advantage of the hydrophilic properties of the
material to adhere ferrite particles to their surfaces by developing 3D
morphologies, allowing them to reproduce at larger scales with high
performance [2324]. Furthermore, these methods allow elaborate
structures with 3D morphologies, which have larger surface areas with
respect to the 1D and 2D structures that gives them unique character-
istics and are an alternative in materials development that improves the
ferrite catalytic activity [2]. The nickel ferrite in 3D morphology has
not been fully studied in the OER [25].
This work shows that novel 3D NiFe2O4 hollow spheres based on
NiFe2O4 (as PGM-free catalyst, Platinum Group Metals) elaborated in a
single step by a simple mechanism taking advantage of the urea hy-
drolysis reaction present catalytic activity comparable with the cata-
lysts commonly used in water splitting as IrOx, in a microfluidic device.
2. Experimental
2.1. Chemical synthesis
The 3D NiFe2O4 hollow spheres-based catalyst was prepared by
dissolving inorganic salts of Ni(NO3)2·6H2O and Fe(NO3)3·9H2O, with a
ratio of 2:1 mM (Ni/Fe) [13] in 30 ml of deionized water and adding
4 mM glucose [26]; the solution was stirred for 60 min at 400 rpm.
Afterwards, 3 mM urea [11] was added, and the aqueous solution was
subjected to a hydrothermal method in an autoclave at 180 °C for 24 h.
The samples were washed several times with deionized water and
ethanol and dried at 80 °C for 24 h. The dry samples were calcined at
550 °C for 4 h to eliminate the organic matter remains.
The advantage of employing the urea hydrolysis process was the
incorporation of hydrated metal nitrate as a precursor salt instead of
ammoniacal salts or other inorganic compounds. For this reason, the
divalent and trivalent transition metals salts used for the synthesis of 3D
NiFe2O4 hollow spheres should be soluble in water and react with the
hydroxide and ammonium ions formed during urea hydrolysis:
CO(NH2)2 + H2 O 2NH 4+ + HCO3 + OH (1)
In this case, the hydroxide ions (OH ) react with metal ions (Fe+3
−
and Ni2+) in the aqueous solution at temperatures close to 100 °C and
with constant agitation [26]. The hydrothermal method allows the re-
actions below to occur consecutively in a single step; additionally, the
glucose promotes the formation of 3D hollow spheres during the
synthesis process and gives hydrophilic properties to the ferrite nano-
crystals [24].
Fe3 + + 3OH Fe(OH)3 (2)
Ni2 + + 3OH Ni(OH)2 (3)
Ni(OH)2 NiO + 2H2 O (4)
Fe(OH)3 FeO + 3H2 O (5)
NiO + Fe2 O3 NiFe2 O4 (6)
The 3D NiFe2O4 hollow spheres obtained by the hydrothermal
method in a single step have not been evaluated for the OER [4,11,25].
Considering the above-mentioned factors, the electrocatalyst synthe-
tized was evaluated as a PGM-free material towards the OER and
compared with commercial material commonly used (IrO2).
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Journal of Power Sources 412 (2019) 505–513
2.2. Physicochemical characterization
The size particles of the 3D NiFe2O4 hollow spheres were char-
acterized by a high-resolution transmission electron microscope (HR-
TEM) JEOL JEM2200 with spherical aberration correction. The crystal
structures were measured by X-ray diffractometry (XRD; XRD-6100
Shimadzu) equipped with a Cu K α (λ = 0.1541 nm, 40 kV, 30 mA,
1 K min−1). The morphology was observed by scanning electron mi-
croscopy (SEM, HITACHI SU3500) and elemental analysis by Energy-
dispersive X-ray spectroscopy (EDS). The specific surface area and the
pore size distribution were determined by isotherms of nitrogen sorp-
tion for mesopores and micropores by BET analysis (ASAP 2020). X-ray
photoelectron spectroscopy (XPS, Monocromatico Magics Thermo
Scientifics, and K-Alpha + Surface analysis) was used to perform the
surface composition and bonding configuration of 3D NiFe2O4 hollow
nanospheres.
2.3. Electrochemical measurements
2.3.1. Electrocatalytic activity in half-cell configuration
The electrochemical evaluation was performed in a Biologic VSP
Potentiostat/Galvanostat using a conventional three-electrode electro-
chemical cell in alkaline media (0.1 M KOH) at 10 mV s−1 of scan rate.
A glassy-carbon electrode (0.196 cm2) was the working electrode, Ag/
AgCl in KCl (saturated) was the reference and a graphite rod was the
counter electrode. The electrocatalyst ink was prepared using a mixture
of NiFe2O4 and Vulcan Carbon XC-72 a ratio of 1:1 (50 wt %), 20 μL of
deionized water, 8 μL of Nafion® (5%) and 4 μL of isopropanol per
milligram of catalyst. The ink was sonicated for 30 min, and then 9 μL
were deposited over the electrode surface.
The electrochemical profile of 3D NiFe2O4 hollow spheres was ac-
quired by cyclic voltammetry (CV) in a potential range between −1.5
and 0.6 V vs RHE, where the Faradaic processes were visible. The
electrolyte was bubbled with N2 for 30 min before the electrochemical
measurement.
The electrocatalytic activity of 3D NiFe2O4 hollow spheres towards
OER was tested by linear sweep voltammetry (LSV) using a rotating-
disk electrode (RDE) in electrolyte saturated with oxygen at a potential
range between 0 and 2 V vs RHE and 1600 rpm to disperse the oxygen
bubbles generated during the experimentation that could interfere with
the measurement on the electrode surface. The results were compared
with the electrocatalytic activity of commercial material, IrO2/C (Sigma
Aldrich) commonly used in OER.
EIS measurements were carried out before and after stability tests to
observe the charge transfer changes associated with the electrocatalyst
when was subjected to drastic conditions. The material was prepared
through a mechanical mix of 3D NiFe2O4 and Vulcan Carbon XC-72
(50 wt %), and at the same condition of the last ink. For comparison
purposes, the same procedure was performed with IrO2 and Vulcan
Carbon. Electrochemical impedance measurement for 3D NiFe2O4 and
IrO2 were performed in a three electrodes system applying 1.6 V vs RHE
of overpotential with 10 mV of amplitude. The measurements were
carried out in a frequency range from 100 KHz to 1 Hz. All electrolysis
measurement were carried out in N2-saturated 0.1 M KOH solution at
25 °C. To evaluate the electrochemical stability of the 3D NiFe2O4 as
electrocatalysts, 1000 cycles were carried out between 0 and 1.4 V vs.
RHE in alkaline media.
Finally, the water splitting performance was evaluated by chron-
oamperometry at 1.6 V for 60 min. The potentials obtained in the
electrochemical measurements were converted to the reversible hy-
drogen electrode (RHE) according to the Nerst equation:
ERHE = EAg/AgCl + 0.197 + 0.059 pH Eq. 1
A. Martínez-Lázaro et al.
Fig. 1. Microfluidic water splitting system.
2.3.2. Evaluation of the microfluidic water splitting system or microfluidic
electrolyser (ME)
The description of ME (Fig. 1) was previously reported [27]. In this
case for hydrogen production, both the anode and cathode were
NiFe2O4/XC-72 deposited on Toray carbon paper-060 (TCP)
(20 mm × 3 mm × 0.3 mm) until the electrocatalyst loading was
0.93 mg.
The hydrogen production was evaluated by injecting 1 M KOH at E
= 1.6, 1.8 and 2 V with a flow rate of 300 ml h−1 for 20 min. For
comparison purposes, IrO2/C as anode and Pt/C as cathode were de-
posited on TCP with the base metal loading of 0.93 mg and 0.75 mg,
respectively.
3. Results and discussion
3.1. Physicochemical characterization
The XRD pattern for the 3D NiFe2O4 hollow spheres formed by
nanoflakes is shown in Fig. 2. The characteristic peaks for Nickel Ferrite
were observed at 2θ = 18.31°, 30.4°, 37.21°, 43.3°, 54°, 57.5°, 63°,
74.8°, and 79° indexed to the (111), (220), (311), (222), (400), (422),
Fig. 2. XRD pattern for 3D NiFe2O4 hollow spheres.
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Journal of Power Sources 412 (2019) 505–513
(511), (440) and (533) crystalline planes, respectively. The most in-
tense peak at 2θ = 35.64° corresponds to the preferential plane (311),
confirming the typical Face Centred Cubic Spinel Structure (FCC)
(JCPDS 10-0325) [28–30]. In addition, the crystallite size of 8.17 nm
was calculated using the Debye-Scherrer equation; this value is within
the crystallite size range from 4.5 to 27 nm reported [23,28].
K
d=
cos Eq. 2
SEM images (Fig. 3a) showed that the NiFe2O4 presented a mor-
phology of 3D spheres, in the meantime, the glucose added during the
hydrothermal method allowed to obtain hollow spheres according with
those reported in the literature [24,31]. EDS element analysis (Fig. 3b)
confirmed the three elements present in the 3D NiFe2O4 hollow spheres
(Ni, Fe and O) and the mass ratio of Ni:Fe is approximately 1.5:1
[11,29,30]. On the other hand, there was no evidence of impurities that
could be acquired during the synthesis process.
The specific surface area and the pore size distribution of the 3D
NiFe2O4 hollow spheres were studied by BET analysis (Fig. 3c). The N2
adsorption-desorption isotherms exhibited a type IV hysteresis loop at
relative pressure (P/P0) between 0.65 and 1, representing a typical
mesoporous material [10,32,33]. In this sense, the pore size distribution
obtained confirms the presence of mesopores in a range between 10 and
50 nm, and the main pore size is centred at 29.35 nm. On the other
hand, the surface area and pore volume were 40.36 m2 g−1 and
0.2420 cm3 g−1, respectively; this surface area was comparable with
the hollow spheres already reported as Fe2O3 (38.1 m2 g−1), NiO
(35.6 m2 g−1) [24], NiFe2O4 (73.5 m2 g−1) [32] and different archi-
tectures of Ni0.5Fe0.5Ox (38.4 mg2 g−1) [30]. However, these results
were below the surface area and pore volume reported for CoFe2O4
hollow spheres, being 103.43 mg2 g−1 and 0.458 cm3 g−1, respectively
[31].
The formation of the mesoporous network and hollow spheres could
occur as follows: during hydrothermal treatment, the dehydration and
subsequent carbonization of the present glucose formed the carbon
spheres characterized by being hydrophilic and possessing C]O groups
where Ni2+ and Fe2+ ions can be anchored [34]. Therefore, an amor-
phous film of the material was formed around of the carbon spheres,
and afterwards, the crystal of nickel ferrite began to form by hetero-
geneous nucleation [4,34]. Further, in the calcination process, the im-
purities of the synthesis (organic compounds) and carbon spheres were
removed. Finally, the 3D NiFe2O4 hollow spheres were formed [24].
The morphologies of the 3D NiFe2O4 hollow spheres obtained at
550 °C are given in Fig. 4. The TEM images presented in Fig. 4a–c shows
A. Martínez-Lázaro et al.
Fig. 3. a) SEM images. b) EDS element analysis of 3D NiFe2O4 hollow spheres. c) BET analysis of 3D NiFe2O4 hollow spheres.
hollow spheres with double, triple and quadruple shells with shell
thickness about 41 nm. That the spheres have a pale center region in
contrast to a dark edge, suggesting the spheres are hollow. The dia-
meter, and therefore, hollow spheres size is not uniform, as can be seen
in the histogram presented as inset in Fig. 4d.
If no carbon precursors exist, the result is neither hollow spheres nor
solid spheres. Some irregular sized crystals as nanoflakes were formed
around 13–20 nm. This result suggest that the NiFe3O4 nanospheres are
disintegrated into smaller crystals in the reaction process and these
crystals could combine with each other to form hollow spheres by the
presence of carbon precursors. Fig. 4d) shows the crystallinity patterns
of the flakes that match the results obtained in the XRD analysis. The
Selected Area Electron Diffraction (SAED) pattern (Fig. 4d) coincides
with characteristic crystalline planes for nickel ferrite observed in the
XRD pattern (Fig. 2). The calculated interplanar distances from the HR-
TEM image (Fig. 4b) were 0.294 nm and 0.248 nm, which correspond to
the (220) and (311) crystalline planes, respectively [22,29]. These va-
lues agreed with the d220 (0.2948 nm) and d311 (0.25140 nm), corre-
sponding to standard bulk nickel ferrite reported [35].
In Fig. 4d) clearly can be seen more pronounced edges, which in-
dicates that the material is hollow and highly crystalline. The increased
viscosity reinforce and stabilize the gas bubbles generated and can be
used to form regular hollow cores. Additionally, the increased viscosity
decrease the movement rate of small crystals and the slow movement
rate allow small crystals to have enough time to aggregate into spheres.
In this case, the glucose concentration could supply appropriate
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Journal of Power Sources 412 (2019) 505–513
viscosity to stabilize the gas bubble and facilitate the formation of
hollow spheres [36]. In this work, urea is used as structure-directing
agent, since could be decomposed into NH3 at reaction temperature and
NH3 could serve as soft template to prepare the hollow spheres [37]. In
the absence of a structure-directing agent but in the presence of carbon
precursors, the result would be solid nanospheres of NiFe2O4. If there
were no gas bubbles produced in the solution, these crystal grains
would aggregate into solid spheres. The re-aggregated nanospheres
have different diameters from the original NiFe3O4 nanospheres. When
urea as structure directing agents is present, gas bubbles would be
formed in water solution to provide the aggregation centers for crystal
grains. Then these small crystals would aggregate around the gas–liquid
interface also driven by the minimization of interfacial energy. In this
stage, carbon precursors played an important role for the formation of
hollow spheres, based on the increased viscosity of the solution caused
by carbon precursors [38].
X-ray photoelectron spectroscopy (XPS) analysis was carried out to
obtain further information on the elements composition and oxidation
state of the as-prepare 3D NiFe2O4.
Fig. 5 a) Ni 2p XPS spectra are represented by two spine-orbit peaks
(2p3/2 and 2p1/2) at 853.9eV and 855.9 eV, which are characteristic of
Ni2+ and Ni3+, indicating that the Ni element exists as typical Ni2+ or
Ni3+ bound to oxygen. Is possible to observe that the area ratio of
Ni2+/Ni3+ after the OER is higher than before the OER, which suggests
that the amount of Ni3+ species has a large increase after the OER.
From this result, is possible to affirm that the oxygen evolution reaction
A. Martínez-Lázaro et al. Journal of Power Sources 412 (2019) 505–513

Fig. 4. a) to c) HR-TEM images of 3D NiFe2O4 hollow spheres, d) SAED crystal patterns of the NiFe2O4 nanoflakes and e) Diameter distribution of 3D NiFe2O4 hollow
spheres with double, triple and quadruple shells.

is being carried out when having the presence of oxygen in the species
Ni3+. Additionally, the electronic states change of the Fe element can
be clearly seen in Fig. 5 b), where it can be appreciated the Fe2+ to
Fe4+ oxidation, which confirms that the Fe species is highly oxidized
during OER measurements.
3.2. Electrochemical measurements
3.2.1. Electrocatalytic activity towards OER
The redox processes attributed to 3D NiFe2O4 hollow spheres were
tested by cyclic voltammetry (Fig. 6a). Two electrochemical process

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Fig. 5. High-resolution XPS spectrum (a) Fe 2p; (b) Ni 2p of 3D NiFe2O4 hollow nanospheres.

Fig. 6. a) Cyclic voltammetry of 3D NiFe2O4 hollow spheres in 0.1 M KOH at 10 mV s−1 b) Linear sweep voltammetry experiments c) Tafel plots and d)
Chronoamperometry at 1.6 V.

were identified. The first redox process (Fe2+|Fe3+) occurred at 0.62 V
(Eoxd) vs RHE (FeO⟶Fe2O3) and 0.25 V (Ered) vs RHE (Fe2O3⟶FeO).
The second redox process (Ni2+|Ni3+) occurred at 1.79 V (Eoxd) vs RHE
(NiO⟶Ni2O3) and 1.74 V (Ered) vs RHE (Ni2O3⟶NiO). Other authors
have reported transitions metals (Ni and Fe) have an important role for
water splitting, specifically in the Oxygen Evolution Reaction (OER),
possibly caused by the enhanced structural disorder and conductivity.
Both metals have been separated tested, but the OER-activity is better
when the transition metals are in single phase. Also, the molar ratio of
this metals is important, due to, if there is a high iron concentration
(above ∼20%) it could be formed two phases. One of this phase Fe-
rich, which significantly less OER-active [3,39].
The electrocatalytic activity of the 3D NiFe2O4 hollow spheres to-
wards the OER at 10 mA cm−2 of current density was comparable with
the commercial IrO2/C in alkaline medium (Fig. 6b). This means that
the overpotential for OER was similar between 3D NiFe2O4 hollow
spheres and IrO2/C around η = 370 mV vs RHE. According to the value
of overpotential obtained, the 3D NiFe2O4 hollow spheres are con-
sidered to be an excellent catalyst (between 300 and 400 mV at
10 mA cm−2) for OER [25]. From the lineal sweep voltammetry, the

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Table 1
Compilation of the current literature of abundant land materials.
Electrocatalyst Overpotential (mv) @ 10 mA cm-2 vs RHE Tafel slope (mV/dec) Ref.

IrO2/C 370 70 This work

3D hollow spheres 370 85 This work
Pt/C 690 225 This work
NiFe2O4 nanosheets 460 193 12
NiFe2O4 nanobipyramids 540 193 12
Fe0.5Ni0.5Ox 584 72 33
NiCo2O4 hollow Microcuboids 420 – 6
CoFe2O4 hollow nanospheres 450 – 39
Mesoporous NiFe2O4 412 – 36
Hollow Mo-doped CoP nanoarrays 305 56 3

Fig. 7. a) Cyclic Voltammetry of IrO2, b) Cyclic Voltammetry of 3D NiFe2O4, both in 0.1 M KOH 50 mv s−1 scan rate. c) Nyquist spectra for 3D NiFe2O4 and IrO2
before and after evaluation tests at E = 1.6 V vs RHE in N2-saturated 0.1 M KOH solution at 25 °C. Frequency range: 100 KHz to 1 Hz.

Tafel slopes were estimated for OER (Fig. 6c), resulting in 85 mV dec−1
and 70 mV dec−1 for 3D NiFe2O4 hollow spheres and IrO2/C, respec-
tively. This result indicates that 3D NiFe2O4 hollow spheres showed a
kinetic process of charge transfer for OER in alkaline medium very
closed to IrO2/C [25]. Considering that the hollow spheres morphology
for nickel ferrite material has not been reported for water splitting, the
performance was evaluated by chronoamperometry at 1.6 V vs RHE
(η = 370 mV) for 10 h. The current density remains constant, around
10 mA cm−2, during the entire test (Fig. 6d) and was the same value
obtained from LSV (Fig. 6b). This test evidences that the material had a
good stability over the time period.
3D hollow spheres, compared with other materials made from
transition metals, can be attractive for the production and development
of themselves for energy production systems based on the principle of
water splitting. Two factors are fundamental for this comparison, first
the overpotential generated by difference with 1.23 V over voltage

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Fig. 8. Hydrogen production in a microfluidic electrolyser employing 3D NiFe2O4 hollow spheres.

Table 2 NiFe2O4; 48.75 Ω and 44.24 Ω for IrO2 before and after OER, respec-
Comparison of hydrogen production between 3D NiFe2O4 hollow spheres and tively. A higher charge transfer resistance can be observed a low elec-
IrO2/C. tronic conductivity, which indicates a decrement in the electrocatalytic
Potential applied/V H2 production/μg s−1 activity. Therefore, from these values, it could means, that the re-
sistances are similar in the materials, so the electrocatalytic activity is
3D NiFe2O4 hollow spheres IrO2/C maintained before and after being subjected to a stability process under
drastic conditions. RCT values of 3D NiFe2O4 are 2819 Ω and 2578 Ω
1.6 25,76 27,10
1.8 27,76 28,21 before and after OER, meanwhile, for IrO2 are 296 Ω and 293 Ω re-
2.0 28,87 30,57 spectively. It is clear from the impedance data that the RCT value of
IrO2 are comparatively lower than the 3D NiFe2O4, however, also from
these data, it is possible to say that even when the RCT values of 3D
obtained at 10 mA @ cm−2, and in the second Tafel slope obtained NiFe2O4 are higher, these are maintained with a slight change before
value. A brief compilation of the current literature of abundant land and after the electrochemical stability process [40]. In this context, 3D
materials is showed in Table 1. NiFe2O4 synthesized has an electrocatalytic behaviour comparable with
respect to electrochemical stability to that observed in the traditional
electrocatalyst.
3.2.2. Electrochemical stability tests
Fig. 7 shows the voltammetric profiles in alkaline media for a) IrO2
and b) 3D NiFe2O4 at cycle 1, 200, 500, 800, and 1000 as stability test. 3.2.3. Hydrogen production by ME
In both cases, the typical electrochemical response of each material is A microfluidic water splitting system was used to produce hydrogen
demonstrated. When examining the behaviour of both as electro- in alkaline medium at different potential values: 1.6, 1.8 and 2 V vs
catalyst, no appreciable change in the shape of the voltammograms RHE (Fig. 8). The production of hydrogen was estimated through the
before and after the stability test (cycle 1 and cycle 1000) was found. current obtained from chronoamperometry and using the formula:
A comparative Nyquist spectra is shown in Fig. 7c) where electronic
MI
conductivity and charge/electron transfer process of these materials in m=
Eq. 3
nF
the OER can be observed. From the semicircles an adjustment was made
for each Nyquist plot. The observed data were fitted with an equivalent where M is the molecular weight, I is the current, n is the number of
circuit (Inset Fig. 7c) which is composed of three values RS (R1), usually transferred electrons and F the Faraday's Constant.
called as solution resistance, RCT (R2) as charge transfer resistance and The results for hydrogen production showed a characteristic trend
constant phase element (CPE1). RS values are 49.68 Ω and 48.7Ω for 3D in Table 2, when the applied potential increased the hydrogen

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production also increased from 25.76 to 28.87 μg s−1 and from 27.10 to
30.57 μg s−1 for 3D NiFe2O4 hollow spheres and IrO2/C, respectively
(Fig. 8c). Nevertheless, this increase was not significant, possibly since
at high applied potential (2 V), a greater amount of hydrogen is gen-
erated quickly, and consequently, an accumulation of oxygen bubbles
occurs over the surface anode that reduces the active sites.
Finally, comparing the two catalysts, there was no significant
change in the electrocatalytic activity towards hydrogen production, at
25.76 and 27.10 μg s−1 for 3D NiFe2O4 hollow spheres and IrO2/C,
respectively (Fig. 8d), indicating the 3D NiFe2O4 hollow spheres have a
good PGM-free catalyst performance [25,41].
4. Conclusions
In summary, the hydrothermal method coupling the urea hydrolysis
allowed obtaining unique 3D NiFe2O4 hollow spheres in a simple step.
The morphological characteristics, 0.2420 cm2 g−2 of pore volume and
41.79 m2 g−1 of surface area, were comparable with similar materials
previously reported. On the other hand, considering that there are no
reports of this morphology (3D hollow spheres) for the OER and hy-
drogen production, the results showed that the electrocatalytic activity
that resulted was considerably close to the commercial material as IrO2;
therefore, 3D NiFe2O4 hollow spheres are a promising PGM-free ma-
terial for OER or hydrogen production devices.
Acknowledgements
The authors thank the Mexican Council for Science and Technology
(CONACYT) for financial support through project LN-2018 293442 and
CB-2015 256749, SENER-246079. M.P. Gurrola thanks to PRODEP for
Postdoctoral fellowship.
References
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