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Phosphazene-Based Covalent Organic Polymer Decorated with

NiCo2O4 Nanocuboids as a Trifunctional Electrocatalyst: A Unique
Replacement for the Conventional Electrocatalysts
Pandiaraj Sekar, Nithya Murugesh, Ramasamy Shanmugam, Shanmugam Senthil Kumar, Stefano Agnoli,
Narendraraj Chandran, Seenuvasan Vedachalam, and Ramasamy Karvembu*
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sı Supporting Information

ABSTRACT: Developing nonprecious metal-based electrocatalysts to convert water

into green fuels (H2 and O2) is key to address urgent climate and energy challenges. We
Downloaded via UPPSALA UNIV on July 4, 2023 at 11:13:14 (UTC).

have prepared an electrocatalyst by the immobilization of NiCo2O4 on a phosphazene-

based covalent organic polymer (P-COP) through a facile hydrothermal method. The
elemental composition of the P-COP showed the presence of a greater amount of
heteroatoms N (6.62%) and P (5.62%) throughout the polymer support. Scanning
transmission electron microscopy (STEM) and electron energy loss spectroscopy
(EELS) were utilized to determine the atomic structure of the nanocuboids, which
depicted the formation of an inverse spinel structure. A NiCo2O4-P-COP-based
electrode was simultaneously used for the oxygen evolution reaction (OER) and
hydrogen evolution reaction (HER), and it displayed a minimum overpotential of 270
and 130 mV (V vs RHE), respectively, at a current density of 10 mA cm−2. In addition,
it acted as an oxygen reduction catalyst with a half-wave potential of 0.83 V (V vs RHE)
and a maximum current density of 4.5 mA cm−2. The electrocatalytic activity is
comparable with that of the commercially available Pt and RuO2 catalysts. The combined experimental and computational studies
confirm that the catalytic centers formed through the interaction between the heteroatoms (N and P) in the phosphazene matrix and
metal oxides (Co and Ni) play an important role in its improved durability and electrocatalytic activity.
KEYWORDS: phosphazene, covalent organic polymer, nonprecious metals, electrocatalyst, water splitting, oxygen reduction

■ INTRODUCTION
The generation of H2 and O2 from water is an important
process, for which the use of cost-effective, energy-efficient,
multifunctional, and sustainable electrocatalysts is really
challenging in the renewable energy area.1−3 The generated
H2 can be used as a feedstock to run fuel cells to produce
electricity and water, making the overall process green and
sustainable.4,5 Electrocatalytic hydrogen and oxygen evolution
reactions (HER and OER) and oxygen reduction reaction
(ORR) are the three critical processes that are at the heart and
drive ahead the energy conversion systems, which decide
nascent hydrogen economy. Owing to the sluggish kinetics
involved in the above reactions, particularly ORR and OER,
precious metal-based electrocatalysts such as Pt, Ru, and Ir
have been employed.6−8 However, regardless of their scarcity
and high cost, these catalysts cannot be used as multifunctional
electrocatalysts, wherein a single material can simultaneously
act as an electrocatalyst for more than two reactions,9 which
would be extremely helpful for the realization of reversible
multifunctional devices. Moreover, we cannot ignore the
possibility of deactivation of such materials during continuous
electrochemical cycling. Hence, it is highly challenging and
necessary to develop a multifunctional electrocatalyst with
readily available materials to realize commercial applica-
tions.10−12
Early transition metal (Fe, Co, and Ni)-based spinels, oxides,
phosphides, sulfides, and so forth have been found to be
emerging alternative electrocatalysts for water splitting and
ORR reactions.13−15 Further, the electrocatalytic performance
of transition metals can be improved by creating nano-
composites with heteroatoms (N, P, S, etc.) and doped and
undoped carbon materials (graphene, carbon nanotubes,
carbon fibers, etc.).16−18 However, several studies have
shown that most of the electrode materials are highly active
toward one particular reaction. For example, it can catalyze
either oxygen or hydrogen evolution or the ORR independ-
ently. Some literature reports reveal that considerable progress
Received: May 31, 2021
Accepted: August 13, 2021
Published: August 25, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acsaem.1c01550

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ACS Applied Energy Materials
has been made in the area of bifunctional electrocatalysts.19,20
However, until now, there are only a very few reports available
for a single material that can simultaneously catalyze the above
three reactions. In an early report, a trifunctional electro-
catalyst was obtained from pyrolyzing tannic acid-based metal
nanocomposites at high temperature and inert conditions. This
study predicts that Fe−P and Fe−N−P units form the main
reactive sites for these core reactions.21 Another interesting
study shows the formation of Co phosphide-based nanocrystals
with a preferentially exposed (211) crystal plane and maximum
number of phosphorus atoms on the surface. The prepared
materials were effectively used as multifunctional electro-
catalysts for water splitting and zinc−air battery applications.22
Similarly, FeCo/Co2P hybrid nanoparticle-incorporated and N
and P codoped carbon nanofibers were synthesized and
employed as the electrocatalyst for the zinc−air battery-
assisted water splitting reaction.23 A recent work by Good-
enough’s group in a similar direction highlights the synthesis of
a graphite-encapsulated Ni−Fe binary system that can
successfully catalyze the above-said reactions.24 Careful
evaluation of these studies proves that synergetic effects
operate between the heteroatoms such as N and P and metal
(Co, Fe, and Ni) nanoparticles or oxides or phosphides,
resulting in multifunctional electrocatalysts that can act as a
potential replacement for precious metal-based catalysts.
However, specific issues related to the synthetic strategy
need to be addressed to realize large-scale applications. Most of
the synthetic methods (i) include energy-consuming high-
temperature pyrolysis to achieve heteroatom doping, (ii) use
toxic gases such as phosphine and ammonia for the doping
process, and (iii) utilize high-surface-area materials that were
produced by template-assisted synthesis, followed by severe
acid (H2SO4, HF, etc.) washing to remove any metal
impurities. All these factors were the drawbacks for the
exploitation of these materials, despite their interesting
physicochemical properties and morphology.25,26 Hence, it is
most important to achieve a cost-effective, low-temperature
synthetic method for doping heteroatoms in order to replace
the conventional high-temperature pyrolysis method.
Poly(organo)phosphazenes are a new class of hybrid
polymers made up of a P−N backbone functionalized with
organic side chains.27 Synthesis of such polymers is quite facile
due to the presence of highly reactive chlorine atoms in
hexachlorophosphazenes [NPCl2]3, which are easily substi-
tuted by organic nucleophiles to form stable poly(organo)-
phosphazenes.28 Phosphazene-based polymers have found
various applications such as flame retardant, gel electrolyte in
batteries and fuel cells, in the extraction of heavy metals, and so
forth.29−31 In addition, the presence of heteroatoms (P and N)
in a close proximity motivated us to use phosphazene for
preparing catalyst support.
Recently, covalent organic frameworks (COFs) are being
widely used in various applications such as gas separation,
photo- and electro-catalysis, energy storage, sensors, and so
forth.32−34 This is mainly due to the facile synthesis, high
surface area, tunable pore size, possibility of heteroatom
incorporation in a controlled manner, presence of guests’
accessible voids and active centers for catalysis, and so forth.35
For example, a bipyridine-based COF was prepared and
employed as a solid support for the incorporation of cobalt
metal centers. Strong interaction between Co and N
(pyridinic) in the COF forms the major active centers to
trigger the OER in neutral electrolytes.36 In addition, many
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research works have been published in the same direction, that
is, preparation of single heteroatom (N)-doped COFs.37 To
the best of our knowledge, phosphazene-based dual heter-
oatom (N and P)-containing COFs have not been reported
yet. This is mainly due to the size mismatch between N and P,
which makes it quite challenging to incorporate both these
heteroatoms in a single matrix.38−40 By considering the facts
mentioned above, we have developed a novel phosphazene-
based covalent organic polymer (P-COP) and effectively
utilized it as a support for incorporating NiCo2O4 inverse
spinel cuboids through a facile hydrothermal method. Initially,
the prepared nanocomposite tested under half cell mode
displayed a better electrocatalytic activity for the OER, HER,
and ORR with maximum current density and minimum
overpotential. We have also fabricated full cell electrodes with
the home-made catalyst that displayed excellent trifunctional
performance for the overall water splitting. Interestingly, the
alkaline electrolyzer cell required just 1.5 V of output to reach a
current density of 10 mA cm−2, which was comparatively much
lower than that found in the literature.
■
EXPERIMENTAL SECTION
Chemicals. Catechol, hexachlorophosphazene, cobalt acetate,
nickel acetate, mesitylene, dioxane, and ethanol were procured from
commercial sources and used without any further purification.
Synthesis of Triphenylene-2,3,6,7,10,11-hexaol. A precleaned
500 mL round-bottom flask was charged with 8.25 g (0.075 mmol) of
catechol. A total of 25 mL of 70% aqueous sulfuric acid was added at
0 °C, followed by addition of 17.2 g of ammonium persulfate (0.075
mmol) portion-wise. Then, the reaction was carried out at room
temperature for 7 h under constant stirring. After that, deionized
water (300 mL) was added at 0 °C. Then, the resulting precipitate
was centrifuged, washed with deionized water, and dried under
vacuum for 12 h to yield crystalline triphenylene-2,3,6,7,10,11-hexaol.
Synthesis of the P-COP. A sealed tube was charged with
triphenylene-2,3,6,7,10,11-hexaol (490 mg, 1 equiv) and 5 mL of a
1:1 v/v solution of mesitylene-dioxane. After adding hexachlorophos-
phazene (500 mg, 1.1 equiv), the reaction was carried out at 120 °C
for 5 days to form a black-colored P-COP. After cooling, the P-COP
was washed with acetone thrice (3 × 10 mL) and dried under vacuum
(yield: 700 mg).
Synthesis of Co3O4-P-COP. Initially, 30 mg of the P-COP and 30
mg of cobalt acetate were mixed with 50 mL of an ethanol−water (3:2
v/v) mixture and further sonicated for an hour to get a uniform
dispersion. The resulting mixture was poured into a Teflon
hydrothermal vessel and heated at 120 °C for 12 h. After cooling
to room temperature, the end product (Co3O4-P-COP) was collected
by centrifugation, purified by washing many times with a copious
amount of ethanol, and dried at 60 °C.
Synthesis of NiCo2O4-P-COP. The doping of Ni onto Co3O4-P-
COP was carried out under a similar hydrothermal condition. The as-
synthesized Co3O4-P-COP (30 mg) and nickel acetate (30 mg) were
mixed well in 50 mL of an ethanol−water (3:2 v/v) solution and
subsequently sonicated for an hour. The resulting dispersion was
transferred to a Teflon-coated hydrothermal vessel to heat it at 120
°C for 12 h. The product formed was centrifuged, washed many times
with ethanol, and dried at 60 °C.
Synthesis of NiO-P-COP. NiO-P-COP was also prepared under
the hydrothermal condition. A total of 50 mL of an ethanol−water
(3:2 v/v) mixture was added to the P-COP (30 mg) and nickel
acetate (30 mg), sonicated for an hour, and transferred to a Teflon-
coated hydrothermal reactor to heat it at 120 °C for 12 h. The
product was centrifuged, washed with ethanol, and dried at 60 °C.
Physical Methods. Solid-state NMR analyses of the materials
were performed using 13C cross-polarization magic-angle spinning and
15
N and 31P NMR techniques (JEOL Resonance 400 MHz
spectrometer). Powder X-ray diffraction (PXRD) patterns of the
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Scheme 1. Schematic Illustration of the Steps Involved in the Synthesis of the P-COP and NiCo2O4-P-COP
materials were obtained using a PANalytical B.V. Empyrean
instrument furnished with Cu Kα radiation (40 kV, 40 mA). The
measurements were done over a 2θ range from 5 to 80° at a scan rate
of 0.5° per min. Scanning transmission electron microscopy (STEM)
studies were carried out using a Carl Zeiss Libra 200 FE microscope
operated at an accelerating voltage of 200 kV (Cs = 1.2 mm) and
equipped with an in-column omega-type electron spectrometer. The
“three-window method” was used for the energy-filtered elemental
mappings. The background contribution to the image intensity was
achieved from the two energy-filtered images in front of the ionization
edge of the element of interest. The measured background
contribution was subtracted from the third image which was acquired
at the ionization edge. The electron energy loss spectroscopy (EELS)
spectra were obtained in the STEM mode with less than a nanometer
size probe positioned on the region of interest using STEM images.
The EELS data were later processed using the HyperSpy package for
background subtraction. All the data were acquired in a Gatan Ultra
Scan 1000 detector. The samples for STEM analyses were prepared
by spreading the materials in isopropyl alcohol, followed by drop-
casting the solution onto a carbon film-coated copper grid. Scanning
electron microscopy (SEM) analyses of the electrocatalysts were done
using a Zeiss EVO-15 instrument with a LaB6 electron emitter at an
operating potential of 30 kV. The X-ray photoelectron spectra (XPS)
were recorded on a VG Microtech Multilab ESCA 3000 instrument
using a Mg Kα X-ray source (hν = 1253.6 eV). Nitrogen adsorption−
desorption experiments were performed using a Quantachrome
Quadrasorb automatic volumetric instrument using ultrapure N2
(99.9995%) at 77 K. Prior to the gas adsorption analysis, the polymer
was preactivated at 100 °C under ultrahigh vacuum (10−8 mbar)
overnight.
■
RESULTS AND DISCUSSION
Scheme 1 illustrates the schematic representation of the P-
COP synthesis, followed by the incorporation of NiCo2O4
nanocuboids. Initially, triphenylene-2,3,6,7,10,11-hexaol was
synthesized by following a procedure reported in the
literature.41 The addition of hexachlorophosphazene to the
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above-synthesized triphenylene hexaol under solvothermal
conditions yielded the P-COP as a black solid. By keeping
the P-COP as a solid support, we prepared nanocomposites of
Co and Ni oxides to get Co3O4-P-COP and NiO-P-COP
separately through hydrothermal reactions. Further, introduc-
tion of Ni into Co3O4-P-COP led to the formation of
NiCo2O4-P-COP.
The as-synthesized P-COP material was highly insoluble in
most solvents; hence, we utilized solid-state NMR for its
characterization. Figure 1a,b depicts 31P and 15N NMR spectra,
respectively, which illustrate the presence of a highly intense
single peak, proving the fact that both the N and P atoms were
in a single chemical environment. Also, the 13C NMR spectrum
of the P-COP had three peaks, which confirmed the existence
of three different carbon environments (Figure S1).42
Brunauer−Emmett−Teller measurements of the P-COP
(Figure 1c) showed a type-II isotherm with a surface area of
144 m2/g. Pore size distribution analysis (Figure 1d) displayed
that most of the pores were in the range of 10 Å with a narrow
distribution, suggesting a uniform microporous structure for
the P-COP.
The crystallinity and phase nature of the samples were
obtained from PXRD analyses. The P-COP showed a
characteristic broad peak between the 2θ values of 25 and
28° corresponding to the graphitic (200) plane and a sharp
peak at 35.0° due to the presence of the phosphazene matrix.43
Thus, from the above results, it can be suggested that the P-
COP was poorly crystalline and polymeric in nature. The
cobalt oxide-impregnated P-COP, that is, Co3O4-P-COP,
showed major peaks at 2θ values of 31.20, 36.65, and
44.89°, which corresponded to the (220), (311), and (400)
planes of spinel cobalt oxide, respectively (Figure S3).14 This
further confirmed the formation of the targeted metal oxide on
the P-COP. Interestingly, when we introduced Ni into the
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Figure 1. (a,b) Solid-state 31P and 15N NMR spectra and (c,d) BET isotherm and pore size distribution analyses of the P-COP.
above sample, that is, Co3O4-P-COP, Ni ions got doped into
the Co3O4 matrix and phase transformation from normal spinel
to inverse spinel occurred, and the sample is denoted as
NiCo2O4-P-COP. Careful analysis of the PXRD pattern of
NiCo2O4-P-COP showed that all the peaks could be well
indexed to the NiCo2O4 cubic phase (JCPDS card no. 20-
0781).44 Besides, no peak corresponding to the distinct nickel
oxide phase was observed, demonstrating the phase purity of
the prepared sample. The PXRD pattern of NiO-P-COP
(nickel oxide phase on the P-COP) was entirely different from
the spinel-based systems. Moreover, in the PXRD patterns of
all the metal oxide nanocomposites, the presence of a graphitic
peak at the 2θ values of 25−28° clearly suggested that the P-
COP support was intact even after the impregnation of metal
oxides.
The morphology and dimensions of the metal oxide
nanoparticles on the P-COP can be obtained from SEM,
transmission electron microscopy (TEM), and high-angle
annular dark-field scanning transmission electron microscopy
(HAADF−STEM) analyses. Figure S4 depicts the SEM
micrographs of the pristine P-COP, which clearly indicated
two-dimensional sheet-like morphology. The STEM analyses
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showed the Z contrast difference between the P-COP and
metal oxide nanoparticles, which easily allowed us to
distinguish one from the other (Figure S5). As it can be
realized from Figures S5a,d,g, Co3O4-P-COP displayed perfect
nanocubes of Co3O4 with sharp edges with a dimension range
from 25 to 30 nm. Similar analyses have been carried out for
other samples as well. The NiCo2O4-P-COP nanocomposite
showed a slight deviation from the perfect cube, that is, a
nanocuboid-like structure, which may be due to the doping of
Ni into spinel-based Co3O4-P-COP (Figures S5b,e,h). For
pure Ni-based sample (NiO-P-COP), a rod-like structure was
seen, which was entirely different from that of the above-
mentioned Co-based samples (Figures S5c,f,i).
Figure 2a shows the TEM image of the pure P-COP, a two-
dimensional layered material, which is in good agreement with
the SEM analysis. Figure 2b depicts the TEM image of
NiCo 2O 4-anchored P-COP sample. Figure 2c portrays
individual nanoparticles that were mostly cuboid in nature,
and their dimensions were in the range between 15 and 20 nm.
Figure 2d illustrates the magnified image of a nanoparticle, and
the inset shows fast-Fourier transformation of the HRSTEM
image. The high-magnification image revealed that the
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Figure 2. (a) TEM image of the P-COP, (b,c) TEM and HAADF images of NiCo2O4-P-COP, respectively (inset in image c displays the
occurrence of cuboid nanoparticles in NiCo2O4-P-COP), (d) HRTEM image (inset shows the lattice profile) of NiCo2O4-P-COP, and (f−k)
elemental mapping of NiCo2O4-P-COP.

Figure 3. EELS analysis of NiCo2O4-P-COP: (a) K line for O and (b,c) L3 and L2 lines for Co and Ni, respectively.

nanoparticle was oriented along the [110] zone axis. The
lattice planes (002) and (111) could be well witnessed with
the corresponding d-spacings of 0.4055 and 0.4682 nm,
respectively. These observations were well aligned with the
PXRD results. The energy-filtered transmission electron
microscopy (EFTEM) technique was employed on the
NiCo2O4-P-COP nanocomposite to record elemental mapping
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by forming images with inelastically scattered electrons.
Detailed analyses of Ni-Co2O4-P-COP showed a uniform
distribution of heteroatoms (N and P) and oxides of Co and
Ni throughout the sample (Figure 2e−k). Elemental mapping
at low magnification predicted that only Ni was present
wherever Co3O4 particles were seen. In order to attain detailed
information on doping of Ni on Co3O4, the formation of the
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Figure 4. (a) Survey spectra and (b) P 2p, (c) N 1s, (d) Ni 2p, (e) Co 2p, and (f) C 1s deconvoluted XPS spectra for NiCo2O4-P-COP.
NiCo2O4 inverse spinel phase, and the interaction of N and P
heteroatoms with the metal oxides in the nanometer regime,
we have used a high-resolution EELS technique. The EELS
spectra were acquired using a STEM electron probe by
positioning a nanometer beam on the NiCo2O4-P-COP
nanocomposite. Figure 3 shows the O−K edge (Figure 3a),
Co L3 and L2 edges (Figure 3b), and Ni L3 and L2 (Figure 3c)
edges. From the EFTEM and EELS data, the presence of Ni
was confirmed in the nanocomposite, attesting the doping of
Ni on Co3O4-P-COP. These results demonstrated highly
localized fingerprints of Ni in the specimen.
The elemental composition and the presence of different
metal oxide phases on the P-COP can be studied through X-
ray photoemission spectroscopy (XPS). Figure S6 shows the
XPS survey data of the P-COP, which mainly depicted the
presence of P, N, C, and O without any other impurities.
Elemental composition analysis of the P-COP revealed a
higher content of heteroatoms (N = 6.62% and P = 5.62%)
throughout the polymer matrix, which was much higher when
compared to the N- and P-doped carbon materials, which were
synthesized through the high-temperature pyrolysis meth-
od.39,40 The deconvolution of the C 1s spectrum showed two
prominent peaks at 284.6 and 286 eV due to CC and C−O
bonds, respectively. The N 1s spectrum showed a main peak at
401 eV that can be associated with P-bonded N atoms in the
phosphazene ring. Information regarding the nature of P
comes from the P 2p spectrum. A doublet (spin−orbit splitting
= 0.9 eV) at 133.5 eV was due to the P atoms bonded to both
N and O, and a smaller component at 130 eV was associated
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with chemical or structural defects. In the case of the
nanocomposite (NiCo2O4-P-COP), the Co 2p photoemission
line was the typical fingerprint of cobalt-based spinel oxide, and
the high-energy satellite peaks were relatively weak in intensity
(Figure 4).
The Co 2p3/2 peak has been deconvoluted into two major
peaks at 779.8 and 781.2 eV corresponding to Co3+ and Co2+
ions, respectively. Further, two satellite peaks at higher binding
energy were due to multiplet and final-state effects. Overall, the
line shape and binding energy values are in very good
agreement with those reported in the literature for the
NiCo2O4 phase.45 The Ni 2p spectrum confirmed the presence
of Ni2+ ions, which showed an intense peak corresponding to
Ni2+ ions in an octahedral environment at 854.6 eV, together
with a broad and intense satellite peak at 860 eV. There was
also a small component at 856.2 eV, which could be associated
with Ni3+ cations. It is well known that the exact composition
and distribution of the cations in mixed spinels are highly
variable and dependent on the synthesis procedure.46−49
Regarding the C 1s, N 1s, and P 2p spectra, there are no
significant changes compared to those of the bare P-COP
support. XPS studies were useful to determine the composition
of the samples, and the results are given in Figures S7 and S8
and Table S1 in Supporting Information.
The initial electrochemical screening of the prepared
catalysts was done by cyclic and linear sweep voltammetry
(CV and LSV) techniques. Recently, NiCo2O4 and metal
phosphide-based electrocatalysts showed remarkable oxygen
evolution activity. Therefore, we have employed the prepared
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Figure 5. Analyses of electrocatalytic OER and HER under 0.1 M KOH (a) LSVs for the OER measured at a scan rate of 10 mV s−1, (b) Tafel plots
for the OER, (c) chronopotentiometric analysis of NiCo2O4-P-COP for the OER (inset represents the LSV analysis before and after the
electrolysis), (d) LSVs for the HER, (e) Tafel plots for the HER, and (f) chronopotentiometric analysis of NiCo2O4-P-COP for the HER (inset
represents the LSV analysis before and after the electrolysis).
P-COP and metal oxide nanocomposites as electrocatalysts for
the OER.
Figure 5a shows the LSV curves of the custom-made
catalysts and commercial RuO2 (for comparison) measured
using the glassy carbon electrode in 0.1 M KOH with a scan
rate of 10 mV/s. The synthesized P-COP did not show much
activity toward water oxidation. However, introduction of a
metal oxide into the P-COP promoted the OER. Co3O4-P-
COP showed a higher current density (normalized with
respect to the geometrical area of the working electrode) of 45
mA/cm2 with a less overpotential (0.325 V @ 10 mA/cm2)
compared to the bare P-COP. The NiO-P-COP-modified
electrode showed an oxidation peak at 1.28 V (vs RHE)
corresponding to the oxidation of Ni2+ to Ni3+, while an
overpotential of 0.281 V for the OER was observed.
Interestingly, the bimetallic nanocomposite (NiCo2O4-P-
COP) showed a very sharp increment in the OER current at
1.45 V (vs RHE) and an overpotential of 0.248 V (@ 10 mA/
cm2), which was lower than that of the single-metal-oxide
systems. The enhanced OER activity mainly arose due to the
formation of more catalytically active centers due to the
interactions of Co/Ni ions with the heteroatoms (P and N).
Further, the superior activity of NiCo2O4-P-COP was
attributed to the synergetic effect that might operate between
the metal ions and P-COP. Tafel analysis of NiCo2O4-P-COP
displayed a slope of 0.035 Vdec−1 which was much lower than
that of Co3O4-P-COP, NiO-P-COP, and commercial RuO2
catalysts (Figure 5b and Table S2). To study the long-term
durability under electrochemical conditions, we have per-
formed chronopotentiometric analysis of NiCo2O4-P-COP at a
constant current density of 10 mA/cm2 for 10 h (Figure 5c).
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NiCo2O4-P-COP showed a highly stable performance without
much change in the current density of the OER. In addition,
LSV analyses were carried out before and after the durability
studies (inset in Figure 5c), which revealed less onset potential
difference (0.050 V) and meagre decrease in the current
density. This clearly confirmed the excellent stability of the
NiCo2O4-P-COP electrocatalyst under the operating con-
ditions.
The electrocatalytic activity of the nanocomposites towards
the HER was evaluated in a conventional three-electrode cell
with Ag/AgCl as a reference and a graphite rod as a counter
electrode. First, it was investigated through LSV analyses, and
the performance was compared with that of the commercial
Pt/C catalyst. Evaluation of the polarization plots (Figure 5d)
showed that NiCo2O4-P-COP exhibited a minimum over-
potential (0.144 V) with respect to the benchmark current
density of 10 mA/cm2 when compared to the single-
component catalysts (Co3O4-P-COP and NiO-P-COP showed
0.252 and 0.199 V, respectively). However, the overpotential
displayed by NiCo2O4-P-COP toward the HER was slightly
higher than that of the commercial 40 wt % Pt/C (0. 075 V).
However, still the overpotential is comparable with that
exhibited by nonprecious metal- and metal/COF-based
electrocatalysts (Table S3). The enhanced activity of
NiCo2O4-P-COP in the HER might be due its metal
phosphide-like structure, which is the main active site for the
HER. In addition, details of HER kinetics can be obtained
from Tafel analyses (Figure 5e). The calculated Tafel slope for
NiCo2O4-P-COP was 0.039 V/dec, which was comparatively
lower than that of Co3O4-P-COP and NiO-P-COP. The
obtained Tafel value for NiCo2O4-P-COP showed that the
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Figure 6. Analysis of the electrocatalytic ORR under 0.1 M KOH (a) LSVs measured at 1600 rpm rotating speed of the working electrode at a scan
rate of 10 mV s−1, (b) yield of H2O2 at different potentials, (c) KL plots, and (d) Tafel plots.
HER occurred via the Heyrovsky step-determined Volmer−
Heyrovsky-type mechanism. Further, durability of NiCo2O4-P-
COP was investigated using the chronopotentiometry method
at a constant current density of 10 mA/cm2; this catalyst
displayed a stable performance without any degradation for 10
h. The inset of Figure 5f shows the LSV plots for NiCo2O4-P-
COP before and after the durability analyses. The minimum
onset potential difference of 0.030 V proved very good stability
of the catalysts during continuous cycling.
Since NiCo2O4-P-COP showed remarkable OER and HER
activities, it was employed for overall water splitting. The
custom-made electrolyzer (two-electrode configuration) made
of Ni foam as a current collector was utilized for this purpose
(Figure S9). The NiCo2O4-P-COP-coated electrodes required
only 1.5 V to deliver a current density of 10 mA/cm2. The
electrolysis has been continued for more than 10 h under a
constant potential and showed a stable current density.
Meanwhile, bubbles continuously emerged from both the
electrode surfaces (ESI). In order to understand the stability of
the catalyst, we have performed post-XPS analysis. After
completing the electrolysis experiments, the electrodes were
removed from the cell carefully, and the used catalysts were
scratched from the surface of the electrodes (details are
provided in ESI). Figure S10 shows the XPS spectra of used
NiCo2O4-P-COP. The survey spectra indicated the presence of
P, N, C, Co, and Ni along with K which might have come from
the electrolyte. Further, the individual photoemission spectra
did not show any deviation from those of pure NiCo2O4-P-
COP. The ratio of the heteroatoms (P and N) and the inverse
spinel phase remained intact even after continuous electrolysis
for more than 10 h, which again proved that the prepared
catalyst was highly stable under the electrochemical conditions.
To test the versatility of NiCo2O4-P-COP, the ORR was
investigated using a rotating-ring disc electrode (RRDE) in a
typical three-electrode setup with oxygen-saturated KOH (0.1
M) as an electrolyte. Figure 6a shows the comparison of linear
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polarization curves of Co3O4-P-COP, NiO-P-COP, NiCo2O4-
P-COP, and commercial Pt/C (40 wt %) catalysts. Co3O4-P-
COP and NiO-P-COP catalysts displayed less ORR activity
with a half-wave potential of 0.74 and 0.67 V (vs RHE) for a
current density of 2.90 and 3.36 mA/cm2, respectively. The
less activity of Co 3 O 4 -P-COP might be due to the
pseudocapacitance nature of cobalt oxide, which was further
confirmed by the CV analysis (Figure S11). NiO-P-COP
showed a slightly better ORR performance than Co3O4-P-
COP. Interestingly, the nanocomposite (NiCo2O4-P-COP)
showed a half-wave potential of 0.84 V with a maximum
current density (4.5 mA/cm2), which surpassed those of its
single-component counterparts, and was comparable with
those of commercial Pt/C [0.83 V (vs RHE)].
To determine the number of electrons involved in the ORR,
LSV analyses at different rotation speeds were performed. The
RRDE analyses of the catalysts showed that the gradual
increase of the rotation speed (from 400 to 2500 rpm)
increased the current density, which resulted from the
enhanced convectional mass transfer of oxygen molecules.
The Koutecky−Levich (KL) plots derived from the LSV
analyses showed excellent linearity (Figure 6c), which proved
the first-order reaction kinetics for the ORR with respect to
dissolved oxygen. The slope values of the KL plots provided
electron transfer number (n = 3.9) in the potential range of
0.30−0.45 V, suggesting a four-electron pathway for the ORR.
RRDE analyses also confirmed that H2O2 formation was less
than 10% for the NiCo2O4-P-COP system, which was slightly
higher than that formed when commercial Pt/C was employed
as an electrocatalyst. However, the peroxide formation
observed for the Co3O4-P-COP (n = 3.6) and NiO-P-COP
(n = 3.8) systems was 24 and 12%, respectively.
Generally, COFs and polymers are insulating in nature.
Hence, it is quite challenging to use these materials in energy-
related applications. In order to study the electrical
conductivity of the P-COP, current−voltage (I−V) measure-
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ACS Applied Energy Materials www.acsaem.org Article

Figure 7. Top view of the energy-minimized structures of (a) P-COP, (b) NiCo2O4, and (c) NiCo2O4-P-COP and (d) electron density difference
plot for the stable NiCo2O4-P-COP. Red denotes the regions of charge density shrink, while green denotes the regions of assimilation with the
isosurface value of 0.05 eau−3. Pink, cyan, blue, wine, white, gray, and yellow denote Ni, Co, N, O, H, C, and P, respectively.

Figure 8. PDOS of (a) P-COP, (b) NiCo2O4, and (c) NiCo2O4-P-COP [Fermi energy (EF) is set at zero]. Calculated free energy profile for the
reaction steps in (d) HER, (e) OER, and (f) ORR with zero potential. The intermediaries that are adsorbed on the catalyst surface are indicated by
*.

ments were carried out by scanning the applied potential from
0 to +10 V and then to −10 V, followed by a reverse scan
(Figure S14). The P-COP displayed a maximum conductivity
of 9.5116 × 10−3 S/cm, which was higher than that reported
for COFs in the literature (Table S3). The high conductivity
obtained is mainly attributed to the extended conjugation of
the phosphazene matrix and aromatic units of the polymer. As
a result, the P-COP can be used as an effective catalyst support.
To obtain necessary information on the internal equivalent-
series resistance (ESR) and charge-transfer resistance for the
ionic and electrical mobility occurring in the material, we have
performed electrochemical impedance spectroscopy (EIS)
analyses. According to EIS analyses (Figure S12), the
NiCo2O4-P-COP electrode possessed a minimum ESR of 9.8
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Ω as compared to that of the NiO-P-COP (13.2 Ω), Co3O4-P-
COP (15.5 Ω) and P-COP (17.8 Ω) electrodes. The lower
ESR value observed for NiCo2O4-P-COP is mainly attributed
to the facile electron transfer between the electrode and
electrolyte. In addition, we have measured the electrochemical
double layer capacitance (Cdl) in the nonfaradaic region to
determine the electrochemically active surface area (ECSA) of
the prepared nanocomposites (Figure S13). This indicates that
NiCo2O4-P-COP features a twofold higher ECSA (25.2 cm2)
than Co3O4-P-COP (12.28 cm2) and NiO-P-COP (10.2 cm2)
nanocomposites. This may have originated from the
conversion of uniform cubical Co3O4 to defect-rich nano-
cuboids NiCo2O4 via Ni doping, thereby resulting in higher
electrocatalytic activity for NiCo2O4-P-COP.
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ACS Appl. Energy Mater. 2021, 4, 9341−9352
ACS Applied Energy Materials
The above results clearly highlight the electrocatalytic
activity of the prepared NiCo2O4-P-COP material toward the
OER, ORR, and HER simultaneously. Density functional
theory calculations revealed the crucial role of P and N
heteroatoms in regulating NiCo2O4 sites and catalytic
mechanisms of NiCo2O4-P-COP. Figure 7 displays the
energy-minimized structures of the P-COP, NiCo2O4, and
NiCo2O4-P-COP. From the charge density variations, it was
obvious that the charge density was localized onto NiCo2O4
clusters (Figure 7d).
The isosurface contour of the charge density difference
revealed a certain amount of charge redistribution between the
P-COP and NiCo2O4. This facilitates a significant amount of
electron transfer, thus improving the activity of the catalyst.
Through the electronic structure features, partial density of
states (PDOS) was calculated to explore the electrocatalytic
behavior of NiCo2O4-P-COP. From the PDOS (Figure 8), it
was observed that the valence band (VB) occupation in the P-
COP, NiCo2O4, and NiCo2O4-P-COP was mainly due to 2p
(C and N), 3d (Co and Ni), and 3d-2p hybrids (3dCo and
Ni; 2pC and O), respectively. The conduction band (CB),
on the other hand, had unoccupied orbitals of the P-COP,
NiCo2O4, and NiCo2O4-P-COP. Based on this, the P-COP
exhibited a band gap of 2.0 eV. In NiCo2O4, the total DOS
crosses the VB and CB, although the smaller cluster size
creates distinct energy levels in the PDOS. Interestingly, in
NiCo2O4-P-COP, PDOS revealed that the VB and CB were
merged, and that the VB was mixed with d-p states and
localized from −4.7 to 0 eV. The higher charge density at the
Fermi level was responsible for the higher charge transfer from
the P-COP to NiCo2O4, which is consistent with the electron
density difference analysis (Figure 8).
The presence of more electrons around the Fermi level
caused the active electrons to be rapidly involved in the
electron-transfer reactions. The d-band center value has a
significant influence on the overall electrocatalytic activity. The
d-band center values for NiCo2O4 and NiCo2O4-P-COP were
found to be −1.66 and −1.75 eV, respectively. The low d-band
center value for NiCo2O4-P-COP might be responsible for its
high electrocatalytic activity.
Furthermore, free energy profiles for the HER, OER, and
ORR were calculated to comprehend the improved electro-
catalytic activity of NiCo2O4-P-COP (Figure 8). The activity
toward HER depends on the descriptor free energy of H*, and
especially, the catalyst is more active when the value is zero. As
seen from Figure 8d, NiCo2O4-P-COP exhibited a lower free
energy for H* compared to NiCo2O4, which was closer to zero,
revealing its higher electrocatalytic activity toward the HER.
The OER involves four-electron transfer in alkaline media,
with the main intermediates being OH*, O*, and OOH*. The
free energy profile for the OER steps is shown in Figure 8e.
With no applied potential, the production of OH* in NiCo2O4,
and OOH* in NiCo2O4-P-COP has an energy barrier of 1.28
and 1.01 eV, respectively. The energy barrier values suggest
that the reaction will intrinsically occur with more efficiency in
NiCo2O4-P-COP. Under alkaline conditions, OH*, O*, and
OOH* intermediate species are present, according to ORR
thermodynamics. Figure 8f shows the ORR free energy profile.
Obviously, until the formation of OH− on the NiCo2O4 and
NiCo2O4-P-COP catalyst surface, the free energy has a
negative value, indicating that the reaction occurs in a more
straightforward manner without the use of an external
potential. As shown in the figure, NiCo2O4-P-COP (−0.95
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eV) adsorbs O2 more readily than NiCo2O4 (−0.73 eV), which
propagates the ORR. Also, the OH* to OH− downhill free
energy of NiCo2O4-P-COP is larger than that of NiCo2O4,
which facilitates the electrocatalytic activity of NiCo2O4-P-
COP.
■ CONCLUSIONS
We have developed a phosphazene-based covalent organic
polymer (P-COP) using a low-temperature hydrothermal
method. The prepared P-COP can be used as a solid support
for anchoring the metal oxide nanoparticles. Initially, cubical
nanoparticles of Co3O4 were immobilized on the P-COP, and
the subsequent doping of Ni on spinel Co3O4-P-COP led to
the formation of an inverse spinel NiCo2O4-P-COP. With the
combined advantages of the numerous active sites (Ni/Co)
and phosphazene-induced electronic stabilization, the prepared
NiCo2O4-P-COP catalyst exhibited an enhanced multifunc-
tional electrocatalytic performance. The NiCo2O4-P-COP can
achieve high activity and stability for the OER in 0.1 M KOH
solution. It required an overpotential of 0.075 V to deliver a
benchmark HER current density of 10 mA cm−2, which is
slightly higher than that of the Pt/C system in 0.1 M KOH
electrolyte. The half-wave potential was 0.86 V for the
NiCo2O4-P-COP electrode toward the ORR in 0.1 M KOH,
which was comparable with the state-of-the-art electrocatalyst,
Pt/C (40%). Moreover, the NiCo2O4-P-COP-based overall
water splitting cell and ORR exhibited high performances that
exceed those of the existing earth-abundant electrocatalysts
and are comparable with those of Pt/C and IrO2. Our study
would offer a new strategy for developing a low-cost and highly
efficient multifunctional electrocatalyst as an alternative for
noble-metal catalysts applied in electrochemical conversion
and energy storage devices.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsaem.1c01550.
Characterization data of the materials such as NMR,
STEM, and XPS (PDF)
Overall water splitting reaction (WEO) (MPG)
■
AUTHOR INFORMATION
Corresponding Author
Ramasamy Karvembu − Department of Chemistry, National
Institute of Technology, Tiruchirappalli 620015, India;
orcid.org/0000-0001-8966-8602; Email: kar@nitt.edu
Authors
Pandiaraj Sekar − Department of Chemistry, National
Institute of Technology, Tiruchirappalli 620015, India
Nithya Murugesh − Department of Chemistry, National
Institute of Technology, Tiruchirappalli 620015, India
Ramasamy Shanmugam − Department of Chemistry,
Thiagarajar College, Madurai 625009, India
Shanmugam Senthil Kumar − Electrodics & Electrocatalysis
Division, CSIR-Central Electrochemical Research Institute,
Karaikudi 630 003, India; orcid.org/0000-0002-7035-
2920
Stefano Agnoli − Department of Chemical Sciences, University
of Padova, Padova 35131, Italy; orcid.org/0000-0001-
5204-5460
https://doi.org/10.1021/acsaem.1c01550
ACS Appl. Energy Mater. 2021, 4, 9341−9352
ACS Applied Energy Materials
Narendraraj Chandran − Tescan Brno S.R.O., Brno 623 00,
Czech Republic
Seenuvasan Vedachalam − Department of Chemistry,
National Institute of Technology, Tiruchirappalli 620015,
India; orcid.org/0000-0003-2444-1903
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsaem.1c01550
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
S.V. thanks the Department of Science and Technology, New
Delhi, for the DST-INSPIRE faculty award (DST/INSPIRE/
04/2015/000328). P.S. acknowledges UGC, India, for the
Junior Research Fellowship. We thank Prof. M. Premalatha for
providing electrochemical facilities and Dr. R. M. Ramsundar
for the scientific discussions. We acknowledge H. J. Bharath
Kumar (CSIR-NCL, Pune) for helping in electrical con-
ductivity measurement of the polymer.
■
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