Letter

http://pubs.acs.org/journal/aelccp

High-Valence-State NiO/Co3O4 Nanoparticles

on Nitrogen-Doped Carbon for Oxygen
Evolution at Low Overpotential
Muhammad Tahir,†,‡,§,∇ Lun Pan,†,‡,∥,∇ Rongrong Zhang,† Yi-Cheng Wang,∥ Guoqiang Shen,†,‡
Imran Aslam,⊥ M. A. Qadeer,†,‡ Nasir Mahmood,†,‡ Wei Xu,# Li Wang,†,‡ Xiangwen Zhang,†,‡
and Ji-Jun Zou*,†,‡
†
Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology,
Tianjin University, Tianjin 300072, China
‡
Collaborative Innovative Centre of Chemical Science and Engineering (Tianjin), Tianjin 300072, China
§
Department of Physics, The University of Lahore, Lahore, Pakistan
∥
School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0245, United States
⊥
National Centre for Nanoscience and Technology, Chinese Academy of Science, Beijing, China
#
Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, Beijing, China
*
S Supporting Information

ABSTRACT: The electrocatalytic oxygen evolution reaction (OER)

plays a critical role in sustainable energy conversion and storage, but
OER is severely hampered owing to the lack of highly efficient
catalysts. Here, we report an efficient electrocatalyst, with NiO/Co3O4
nanoparticles decorated on nitrogen-doped carbon (NiO/Co3O4@
NC). Abundant high-valence Ni3+ and Co3+ species were observed on
the surface of the hybrid due to the strong NC−metal oxide and
NiO−Co3O4 interactions. This unique structure leads to excellent
OER performance, delivering a very low overpotential of 240 mV@10
mA·cm−2 on glassy carbon and 200 mV@10 mA·cm−2 on Ni foam in
KOH and having a turnover frequency (@350 mV overpotential) 6
and 16 times higher than that of IrO2 and RuO2, respectively.

of Ni to Co plays critical role for OER.26 Furthermore,

O xygen evolution reaction (OER) is the most

imperative reaction for several energy conversion
and storage devices such as water-splitting, fuel cells,
and metal−air batteries.1−6 To date, RuO2 and IrO2 are
commonly used for OER,6−9 but these metals are rare and
expensive, and their activities are still unsatisfactory. Earth-
abundant first-row (3d) transition-metal-based electrocatalysts,
like Co and Ni-based oxides, are considered as good alternative
because they can produce O2 under mild conditions and
modest overpotentials.9−19 Moreover, the performance of
multimetal oxides usually outperforms that of single-metal
oxide.20−22 Co3+ has been confirmed as the active catalytic sites
for OER through inducing deprotonation of OOH species to
produce O2 for its lower coordination number and larger H2O
molecules adsorption energy.6,15,21,22 Similarly, surface Ni3+
species are regarded as the real active site for OER on nickel
oxide.22−25 Although there are some reports revealing higher
oxidation states of solely Ni or Co lead to good OER activity,
the fabrication of higher oxidation states of both Ni and Co to
get the combined benefit has not been reported. Also, the ratio
decorating these catalysts on highly conductive nitrogen-doped
carbon (NC) can improve the activity by enhancing the
conductivity and interaction between metal oxides and
carbon.12,13,27 In this work, we report coupled Co3O4 and
NiO nanocrystals on nitrogen-doped carbon backbone (NiO/
Co3O4@NC), which is rich in high-valence-state species (Ni3+
and Co3+) on the surface and shows excellent OER
performance (240 mV@10 mA·cm−2 on glassy electrode).
NiO/Co3O4@NC was synthesized through thermal anneal-
ing of the mixture of melamine (initially HNO3 treated), NiCl2,
and CoCl2 (Figure 1a). Upon annealing, g-C3N4, NiO, and
Co3O4 are obtained when individual melamine, nickel, and
cobalt salts are used (Figures S1 and S2), while the coexistence
of metal salts and melamine produces N-doped carbon (NC)
Received: August 1, 2017
Accepted: August 28, 2017
Published: August 28, 2017

© 2017 American Chemical Society 2177 DOI: 10.1021/acsenergylett.7b00691

ACS Energy Lett. 2017, 2, 2177−2182
ACS Energy Letters
Figure 1. (a) Synthesis process and schematic structure, (b) XRD pattern, (c) TEM image, (d) HR-TEM image, and (e−j) element mapping of
NiO/Co3O4@NC.
decorated with NiO/Co3O4 (NiO/Co3O4@NC, Figures S1
and S3), so the metal atoms enhance the carbonization of
melamine and the formed carbon may influence the status of
metal oxides. The X-ray diffraction (XRD) pattern reveals the
existence of both Co3O4 and NiO (Figure 1b). The broad but
weak peak at 2θ = 24° suggests the presence of graphitic
carbon, which is further confirmed by typical D and G bands in
Raman spectra (Figure S4).28−30 Thermogravimetric analysis
shows the hybrid contains 10−11%wt of NC (Figure S5a), and
inductively coupled plasma analysis shows the atomic ratio of
Ni/Co is ca. 1, almost identical to the ratio of metal precursors
used in the synthesis. The N2-adsorption isotherm measure-
ment shows the surface area of NiO/Co3O4@NC (25.5 cm2/g)
is between NiO@NC (21.1 cm2/g) and Co3O4@NC (38.5
cm2/g), but overall there is no big difference (Figure S5b).
The scanning electron microscopy (SEM) image of NiO/
Co3O4@NC delineates good distribution of oxides nanocrystals
on NC (Figure S3c). The transmission electron microscopy
(TEM) images show the surface of graphitic sheets is almost
fully decorated by nanocrystals (Figure 1c), consisting of
compactly connected Co3O4 and NiO nanoparticles with the
interplanar distances of d220(Co3O4) = 0.287 nm and d200(NiO)
=0.209 nm (Figure 1d). Importantly, the intimate interface
between well-defined Co3O4 and NiO is clearly observed
(Figure 1d). Element mapping spectra (Figure 1e−j) show the
distribution of Co and Ni in the hybrid, and importantly the
Co-rich places are Ni-deficient and vice versa, i.e., both are
present in the vicinity of each other. Moreover, the existence of
doped nitrogen in the carbon backbone is confirmed by
element mapping (Figure 1f,g); the ratio of N/C is 0.06% as
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determined by XPS analysis (Table S1). The size of pure
Co3O4, NiO, and Co3O4/NiO composite is 2−10 μm, while it
is decreased to 5−10 nm for NiO@NC, Co3O4@NC, and
NiO/Co3O4@NC (Figure S2, S3), indicating the function of
NC on inhibiting crystal growth.
The X-ray absorption near edge structure (XANES) and
extended X-ray absorption fine structure (EXAFS) studies were
carried out to characterize the oxidation state of metal atoms in
the bulk. The Co pre-edge peak of NiO/Co3O4@NC shifts
toward higher energy by ∼1.0 eV compared to standard Co3O4;
also, the main peak moves to higher energy (Figure 2a), and
the Co peak of NiO/Co3O4@NC is located between Co3O4
and Co2O3 (Figure S6), both suggesting Co atoms of the
hybrid are in higher oxidation state compared with pristine
Co3O4.31 In EXAFS, the Co−O bond of NiO/Co3O4@NC is
shortened because of less electron density of metal ions that
reduces the repulsion with O atom (Figures 2c and S6, Table
S2). Similarly, the pre-edge Ni peak and main Ni peak of NiO/
Co3O4@NC shift toward higher energy (Figure 2b), and the
Ni−O bond is also shortened compared to standard NiO
(Figure 2d, Table S2), supporting the higher valence state of Ni
in the hybrid. XPS characterization was further conducted to
detect the valence state of oxide on the surface. Peak fitting
shows NiO/Co3O4@NC possesses more Co3+ and Ni3+ than
Co3O4 and NiO (Figure 2e,f), respectively. XPS analysis also
indicates carbon in the hybrid is not in form of g-C3N4 (Figure
S7a),32−34 and fitting the C 1s spectrum shows four peaks
corresponding to the graphite-like sp2 C (39.6%), N-sp2-
C(39.5%), N-sp3-C (8.6%) along with some surface oxide
carbon (12.3%) (Figure S7b), which suggests the doping of N
DOI: 10.1021/acsenergylett.7b00691
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ACS Energy Letters
Figure 2. (a, b) Co and Ni K-edge XANES (inset is the magnified pre-edge adsorption), (c, d) Fourier transforms of k-space oscillations to R
space of Co and Ni K-edge EXAFS, and (e, f) XPS spectra of Co 2p and Ni 2p.
in the carbon matrix.27 The existence of pyrrolic (19.7%) and
pyridinic (41.9%) N 1s peaks furthermore confirms the N-
doping in carbon (Figure S7c), and importantly, the new peak
at 399.5 eV (38.4%) suggests an interaction between metal
oxides and NC through the N−M bonds.34
Accordingly, the XAFS and XPS results confirm NiO/
Co3O4@NC is rich in high-valence Co and Ni (i.e., Co3+ and
Ni3+). Meanwhile, the species of Co3+ and Ni3+ are also found
on the surface of Co3O4@NC and NiO@NC according to XPS
analysis (Figure S8), indicating melamine and/or the formed
NC has considerable influence on the electronic structure of
oxides, with the chemical bonding between nitrogen and metal
such as N−Co and N−Ni. In addition, the NiO/Co3O4@NC
possesses more Ni3+ than NiO@NC but slightly less Co3+ than
Co3O4@NC (Figure S8), suggesting the intimate interaction
between NiO and Co3O4 in the bond of Co−O−Ni, as verified
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by the intimate interparticle interface (Figure 1d), our density
function theory calculation (Figure S9), and previous research
that proved the electron transfer from Ni to Co.1,22 To
summarize, metal oxides transfer electrons to NC through
nitrogen−metal bonds, and that is why both Co and Ni have
high oxidation states in NiO@NC and Co3O4@NC. However,
in NiO/Co3O4@NC hybrid, Ni atoms transfer electrons to Co
through the intimate interface, so Ni3+ increases but Co3+
decreases, but overall both are increased compared with normal
NiO and Co3O4.
The NiO/Co3O4@NC hybrid was coated on glassy carbon
electrode and used for OER in 1 M KOH solution. As shown in
Figure 3a, a sharply increased anodic current response starts at
an onset potential of 1.4 V (the potential required to reach
current density of 2 mA·cm−2) is observed. It reaches current
density of 10 mA·cm−2 at 1.47 V vs RHE at a very low
DOI: 10.1021/acsenergylett.7b00691
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ACS Energy Letters
Figure 3. (a) LSV curves; (b) TOF and (c) Tafel plots of NiO@NC, Co3O4@NC, NiO/Co3O4@NC, IrO2, RuO2, and Pt/C for OER in 1 M
KOH; and (d) stability of NiO/Co3O4@NC @ 10 mA·cm−2.
overpotential of 240 mV. For comparison, IrO2 and RuO2 reach
10 mA·cm−2 at an overpotential of 340 mV and 350 mV,
respectively, agreeing with the reported data (Table S3). To
our best knowledge, this hybrid is one of the best catalysts with
the overpotential less than 250 mV@10 mA·cm−2 and is
superior to any other catalysts on glassy carbon electrode
(Table S3). Furthermore, it reaches a high current density of 30
mA·cm−2 and 161 mA·cm−2 at over potential of 300 and 500
mV, respectively (Figures 3a and S10a). The hybrid exhibits a
turnover frequency (TOF) of 0.49 (s−1) per total metal atoms
at 350 mV (Figure 3b), ca. 6 and 16 times higher than that of
IrO2 and RuO2, respectively. The Tafel slope is 73 mV/dec,
which suggests both water adsorption and O−O are rate-
determining;6,35 in addition, this value is comparable to that of
with IrO2 and RuO2 (Figure 3c). It also possesses excellent
stability without big change in the normalized current (with
efficiency of ∼95% after 48 h) and CV curve after 2000 cycles
(Figure 3d, S11). XPS characterization performed after OER
(Figure S12) shows Ni3+ is increased greatly while Co3+ is
decreased slightly, suggesting a synergy between these two
species in the electrocatalysis, although the accurate mechanism
is still unclear. The activity was further tested on Ni foam
(Figure S13), and it reaches 10 mA·cm−2 at an extremely low
overpotential of 200 mV, because the three-dimensional porous
structure of Ni foam contributes to better diffusion and transfer
and increased electrochemically active surface area (ESCA)
(Figure S14).
For pure NiO and Co3O4, the overpotentials @ 10 mA·cm−2
are 500 mV and 400 mV, respectively, while they are 310 and
270 mV for NiO@NC and Co3O4@NC, respectively (Figure
S10a and Table S4). The significant improvement by NC
support should result from the greatly reduced particle size
(from 2−10 μm to 5−10 nm), formation of high valence state
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(Co3+ and Ni3+), and the high conductivity of NC. Meanwhile,
when the two oxides are combined in the form of NiO/Co3O4
or NiO/Co3O4@NC, the overpotential can be significantly
decreased to 380 or 240 mV, respectively. Hybrids with
different Ni/Co ratios of 1:2, 1:1, and 2:1 all show improved
activity compared with individual oxides (Figure S10b),
although the 1:1 ratio is the best. It is worth noting that the
physical mixture of NiO+Co3O4 and NiO@NC+Co3O4@NC
does not show any synergetic improvement in OER perform-
ance (Table S4). Therefore, it is the intimate electronic
interaction, instead of physical mixture of metal oxides, that
plays an important role in the improvement of OER behavior.
Actually, the ECSA of NiO/Co3O4@NC (315 cm2) is much
higher than that of NiO@NC (50 cm2) and Co3O4@NC (55
cm2) (Figure S15), indicating more metallic sites are activated
when NiO and Co3O4 are coupled together by NC. Also,
smaller semicircle of EIS for NiO/Co3O4@NC (Figure S16)
indicate high ionic conductivity and low ionic residence as
compared to NiO@NC, Co3O4@NC, and mixture of NiO@
NC+Co3O4@NC. Therefore, the superior performance of
NiO/Co3O4@NC is mainly based on the unique surface
electronic structure of oxides, especially the high valence state
of metal atoms. The existence of Co and Ni in higher oxidation
state improves the electrophilicity of adsorbed oxygen (Co3+-O
or Ni3+-O) and therefore enables the formation of Co3+- or
Ni3+-OOH through nucleophilic attack with OH−. This is
thought to stimulate the OOH species deprotonation through
the inductive effect of electron-withdrawing to harvest O2.21−23
Moreover, the in situ formed N-doped carbon is also very
important to increase the conductivity of the hybrid,27−29
reduce the particle size of oxides, and anchor them to form
intimate interparticle interface.
DOI: 10.1021/acsenergylett.7b00691
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ACS Energy Letters
In summary, we have prepared a NiO/Co3O4@NC hybrid
with optimized electronic structure for OER. The in situ
formed nitrogen-doped carbon backbone decreases NiO and
Co3O4 particles to nanosize and anchors them to build intimate
interface. Importantly, the hybrid shows unique surface
electronic structure with high concentration of Co3+ and Ni3+
species. As a result, it exhibits superior activity for OER in
KOH, with an extremely low overpotential of 240 and 200 mV
(@10 mA cm−2) on glassy carbon electrode and Ni foam,
respectively, and has a turnover frequency (@350 mV
overpotential) that is 6 and 16 times higher than IrO2 and
RuO2, respectively. Furthermore, the hybrid shows excellent
stability and efficiency (∼95% after 48 h). Thus, the NiO/
Co3O4@NC is a very promising candidate for electrocatalytic
water splitting.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsenergy-
lett.7b00691.
Detailed experimental procedures, characterization, and
computation results; OER data (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: jj_zou@tju.edu.cn.
ORCID
Nasir Mahmood: 0000-0002-8340-1058
Wei Xu: 0000-0001-8006-2399
Ji-Jun Zou: 0000-0002-9126-1251
Author Contributions
∇
M.T. and L.P. contributed equally in this work.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors appreciate the support from the National Science
Foundation of China (51661145026, 21676193, 21506156),
Tianjin Municipal Natural Science Foundation
(15JCZDJC37300), and Pakistan Science Foundation PSF/
NSFC-Eng/P-UOL(02) . Authors also appreciate the help with
XAS characterization from Beijing Synchrotron Radiation,
Institute of High Energy Physics, Chinese Academy of Sciences,
Beijing, China.
■
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2182 DOI: 10.1021/acsenergylett.7b00691

ACS Energy Lett. 2017, 2, 2177−2182