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Bifunctional OER/NRR Catalysts Based on a Thin-Layered Co3O4−x/

GO Sandwich Structure
Yu Sun,* Qiao Wang, and Zhongyuan Liu
Cite This: ACS Appl. Mater. Interfaces 2022, 14, 43508−43516 Read Online

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ABSTRACT: Due to ample low-coordinated surface atoms, a

distorted lattice endows thin-layered transition metal oxides with a
flexible electronic structure, making them the ideal candidates for
overall ammonia synthesis. This work proposes a novel and facile
method for the controllable synthesis of thin-layered Co3O4
catalysts with graphene as a conductive matrix to further enhance
the overall N2 fixation performance. X-ray photoelectron spectros-
copy (XPS) and synchrotron radiation X-ray absorption spectros-
copy (XAS) demonstrate that the sandwiched Co3O4−x/GO
catalysts enable exposure of more coordination unsaturated active
sites, resulting in numerous oxygen vacancies. With a higher
conductivity and distorted crystalline structure, excellent electro-
chemical NRR activity is realized with a NH3 production rate of 5.19 mmol g−1 h−1 and a Faradaic efficiency of 10.68% at −0.4 V vs
reversible hydrogen electrode (RHE). The density functional theory (DFT) calculation demonstrates that introducing oxygen
vacancies in thin-layered cobalt oxides could result in an increased density of states (DOS) near the Fermi level, which would
accelerate the NRR rate-determining step. Charge transfer could be accelerated through a weak Co 3d−N 2p σ hybrid bond with a
lower energy level. No obvious performance decay could be found after six cycles. Furthermore, the sandwiched Co3O4−x/GO
catalyst exhibits a low overpotential of 280 mV@10 mA cm−2 and an outstanding durability for the anode OER, even better than
those of the benchmark RuO2. Such an inexpensive sandwiched transition metal oxide catalyst shows great potential in the field of
overall N2 fixation.
KEYWORDS: bifunctional OER/NRR catalysts, transition metal oxides, oxygen vacancies, sandwich structure, 2D materials

1. INTRODUCTION overall electrocatalytic nitrogen fixation is strictly restricted by

Ammonia, one of the most important chemical substances,
shows great potential in many fields, such as fertilizers, dyes,
explosives, and resins. It could also be regarded as a carbon-
free energy carrier, which possesses a high gravimetric
hydrogen density and can be easily condensed to a liquid.
Owing to these advantages, a sharp increase in the demand for
ammonia has occurred in the past century. Due to the strong
nonpolar triple bond in the N2 molecule, industrial ammonia
synthesis requires a high temperature and pressure to
overcome the activation energy, which lead to nearly 2% of
global energy consumption. Therefore, the development of an
efficient nitrogen fixation method under mild conditions has
become one of the greatest challenges.1−3 Electrocatalytic
nitrogen fixation under ambient conditions has been proposed
recently, which is composed of the anodic oxygen evolution
reaction (OER, 2H2O → O2 + 4H+ + 4e−) and cathodic
nitrogen reduction reaction (NRR, N2 + 6H+ + 6e− → 2NH3).
Due to a similar electrode potential, the NRR is often
complicated by the side hydrogen evolution reaction.4−6 In
addition, the OER consists of four proton-coupled electron
transfer steps, leading to a high overpotential. Hence, the
both the NRR and OER. Compared with the separate
investigation on catalysts for the OER or NRR, the
bifunctional OER/NRR catalyst for practical application
remains scarce.
The flexible electronic and diverse crystalline structures
make 3d transition metal oxides the ideal candidate catalysts.
Numerous studies have already demonstrated that Co-based
catalysts are one of the best OER catalysts with an ultralow
overpotential.7,8 It could be attributed to the optimized eg
electron filling and proper d-band center. Based on the
similarity of molecular orbits for N2 and O2, cobalt oxides also
exhibit superior NRR catalytic performance. Further density
functional theory (DFT) calculations indicate that cobalt-
based materials possess a relatively strong interaction with N2
Received: July 1, 2022
Accepted: September 7, 2022
Published: September 15, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acsami.2c11674

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Figure 1. (a) Diagram of the gradient temperature elevation synthetic strategy for the precursor/GO sandwich structure, (b) ball-and-stick model
for thin-layered Co3O4−x/GO after annealing the precursor, (c) TEM image for their morphology, (d) cross-sectional image, (e) selected area
electron diffraction, (f) atomic force microscopy (AFM) image, and (g) Raman and (h) XRD spectrum of the thin-layered Co3O4−x/GO.

and weak binding to intermediate species.9,10 Unfortunately,
the primary Co3O4 spinel, as the most stable phase among all
Co-based materials, shows bad conductivity, which is a key
factor to their catalytic performance. It has been demonstrated
that lattice vacancies could enhance the conductivity of the
host materials and promote the redox reaction kinetics.11 In
addition, loading Co3O4 nanoparticles onto a conductive
matrix could accelerate the electrocatalytic reaction ki-
netics.12−14 However, excessive loadings will lead to the
agglomeration of nanoparticles. With a shorter charge transfer
distance and more exposed active sites, thin-layered cobalt
oxides will show great potential in the bifunctional OER/NRR
catalysts.15,16 Direct synthesis of thin-layered catalysts with a
conductive matrix will be an effective way to realize high-
efficiency nitrogen fixation. Because of the high-covalence
bonds, the preparation of thin-layered cobalt oxides is still a big
challenge.17,18
Through balancing the high surface energy, a template-
assisted method has been generally used to fabricate different
thin-layered oxides.19,20 With solution processability and an
ultrathin structure, graphene and derivatives (GO) show great
potential as substrates to fabricate layered materials. Herein,
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we report thin-layered Co3O4−x/GO with a sandwich structure
as bifunctional electrocatalysts for both the NRR and OER,
obtained through template-assisted methods. It has been
demonstrated that the morphology and size could be precisely
controlled through tailoring the hydrolysis process. Direct
growth of catalysts on a conductive matrix could effectively
enhance the interaction and accelerate the charge transfer
process. In addition, the ultrathin-layered structure could
balance the huge surface energy and introduce numerous
oxygen vacancies into the bifunctional electrocatalysts. For the
NRR, the novel thin-layered cobalt oxide exhibits 5.19 mmol
g−1 h−1 NH3 production rate and 10.68% faradaic efficiency at
−0.4 V. For the OER, the novel thin-layered cobalt oxide
shows an superior catalytic activity, even better than that of
commercial RuO2 at large current density, and good
electrochemical stability over 12 h. DFT calculations
demonstrate that the distorted structure with oxygen vacancies
could greatly reduce the potential barrier for rate-determining
steps in both the NRR and OER. Therefore, it is demonstrated
that two-dimensional 3d TMOs are a type of the most proper
candidates for overall electrocatalytic nitrogen fixation. This
work will boost the research of overall nitrogen fixation.
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2. EXPERIMENTAL SECTION
2.1. Synthesis of Thin-Layered Co3O4/GO. A 20 mg GO
template by modified Hummer’s method21 was dispersed in 50 mL of
mixed solutions of 0.01 M CoCl2 through ultrasonic treatment at
room temperature (RT) for 1 h. Due to the electrostatic interaction,
Co cations would be loaded on GO templates. Then, the hydrolysis
reaction was balanced using 50 mL of 0.1 M buffer solutions of Tris-
HCl. With increasing solution temperature using a water bath, a thin-
layered hydroxide precursor precipitate could be obtained. The
remnant salt was removed through ultrasonic cleaning and
centrifugation. After freeze drying, thin-layered Co3O4−x/GO could
be obtained by a 2 h annealing treatment at 450 °C at a rate of 2 °C
min−1 in Ar.20,22
2.2. Characterization Details. The crystalline phase of thin-
layered Co3O4/GO was confirmed by Rigaku D/MAX2550 X-ray
diffraction (XRD). Surface morphologies were analyzed by trans-
mission electron microscopy (TEM) with a Tecnai G2 S-Twin F20. A
Thermo ESCALAB250 XPS with the Al Kα (1486.6 eV) source was
used to analyze the binding energies of Co 3p and O 1s. The loading
weight of Co is obtained through the detection of the Co cation
concentration by inductively coupled plasma optical emission
spectrometry (ICP-OES) (Thermo iCAP 7600). The Raman
spectrum was collected using a Renishaw INVIA with a 532 nm
light source to analyze the crystal structure and chemical bonds. The
magnetization property at RT was characterized by vibrating sample
magnitude (VSM) in a ± 5T magnetic field, and we performed O K-
edge X-ray absorption spectroscopy (XAS) at National Synchrotron
Radiation Laboratory (Beamline BL12B-a), China.
2.3. Electrochemical Testing. NRR experiments were conducted
in a H-type cells connected with Nafion 211 membranes, which were
preprotonated through continuous treatment in boiling deionized
(DI) water for 1 h, 5% H2O2 for 1 h, and 0.5 M H2SO4 for 3 h at 80
°C. Before/after using, the Nafion membrane was soaked in DI water.
The TORAY carbon paper was soaked in concentrated sulfuric acid
for 1 h and cleaned with DI water to neutral. A total of 10 mg of
catalysts and 20 mL of Nafion solution (5 wt %) were added to 980
mL of mixed solution (380 mL of ethanol and 600 mL of H2O) by 2
h of sonication to generate a homogeneous ink. A total of 20 mL of
ink was dropped on carbon paper. A Ag/AgCl electrode (saturated
KCl electrolyte) and Pt plate electrodes with sizes of 2 × 2 cm2 were
used as the counter and reference electrodes, respectively. N2-
saturated 0.1 M K2SO4 solution was used as the electrolyte. To test
the durability, the UV−vis absorbance was measured every 2 h at 660
nm.23 The Faraday efficiency is calculated by the equation
3FnNH3
FE = . Here, F is the Faraday constant (C mol−1), nNH3 is the
Q
d
NH3 yield (mol), and Q is the total charge consumption (C), which is
obtained by the integral area in the j−t curve.
For the OER, acetylene black soaked in HNO3 was added to the
catalysts (5:1 wt %) to boost the conductivity. After adding
neutralized Nafion (5% weight), the catalyst ink was dropped on a
polished glassy carbon electrode. After being dried under ambient
conditions, the working electrode consisted of 250 μg cm−2 catalysts,
50 μg cm−2 acetylene black, and 50 μg cm−2 Nafion.4 The OER
activity was studied in 0.1 M KOH through linear sweep voltammetry
(LSV) with a scan rate of 5 mV s−1 at 1.0−1.8 V on a CHI 660E
electrochemical workstation. The test system consisted of a working
electrode (rotating disk electrode covered with catalysts), reference
electrode (Hg/HgO), and counter electrode (Pt).24
2.4. DFT Calculations. The first-principles calculations were
carried out through periodic density functional theory (DFT) using a
generalized gradient approximation within the Perdew−Burke−
Ernzerhof exchange correction functional. The plane waves were
expanded with a cutoff energy of 450 eV. A γ-centered k-point of 4 ×
4 × 4 or 2 × 2 × 1 has been used for the Co3O4 bulk or slab catalyst
surface. The geometry optimization was conducted with a
convergence accuracy of 1.0 × 10−5 eV atom−1 for total energy and
0.02 eV Å−1 for force. To prevent the periodic disturbance, a large
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vacuum of 15 Å has been used in slabs. PDOS and difference electron
density were used to study the electronic structures.25
3. RESULTS AND DISCUSSION
A template-assisted cation hydrolysis method has been used to
fabricate the sandwiched Co-hydroxide/GO precursors.22,26 It
mainly consists of three steps as shown in Figure 1a. Due to
the abundant surface functional groups, transition metal
cations in the solution will be attracted by the negatively
charged GO templates. Normally, electrostatic adsorption of
GO could not exhibit selectivity, which leads to the loading of
Co cations on both sides, and the presence of Co could be
confirmed by IPC-OES with a loading weight of 0.27 wt %.
Generally, heterogeneous nucleation on the GO surface is
much easier than homogeneous nucleation. The adsorbed Co
on both sides will serve as the nucleation site for hydroxide
precursors. Then, the hydrolysis reaction will occur because
the solubility product constant Ksp of the hydroxide precursor
is smaller than ion product constant Kip. With gradually
increasing temperature, more and more precipitation of
hydroxide will occur on the GO, just as the incrustation
scale in boiling H2O. Tris-HCl buffer solution (pH = 7.9) has
been used to balance the reaction rate. The low-temperature
step could result in heteronucleation on the GO template. As
shown in Figure S1, numerous small crystal nuclei and particles
formed on the GO template. The high-temperature step could
lead to hydroxide formation. The coverage of the hydroxide
precursor on GO increases with increasing solution temper-
ature. After the whole hydrolysis process, a flat and uniform
precursor with the Co-hydroxide/GO sandwich structure
could be obtained. Finally, a mild annealing treatment is
used to accelerate the dehydration and crystallization steps,
leading to the final Co3O4−x/GO sandwich structure (Figure
1b) with a total Co loading of 57.41 wt %. Here, a thin-layered
structure for these thin-layered Co3O4−x/GO could be easily
confirmed through transmission electron microscopy (TEM),
Figure 1c. This thin-layered Co3O4−x/GO shows a large size
(over 10 μm), which is generally dependent on GO templates.
Meanwhile, the wrinkled edges in the nanosheets could be
attributed to the large surface tension in the layer structure. It
will decrease the coordination number, which is helpful to
expose more metal cations in the catalytic reactions, and the
SEM image has been used to further confirm the uniform
surface morphology and large size of the thin-layered
Co3O4−x/GO (Figure S2).
The sandwich structure could be easily recognized through
high-resolution TEM (HRTEM) (Figure 1d) with a total
thickness of ∼16.97 nm, in which the GO thickness is ∼4.35
nm (six monolayers). Meanwhile, the gradually increase in the
precursor coverage on GO with increasing solution temper-
ature also demonstrates the sandwich structure (Figure S1).
Especially, the clear double-layer feature of the precursor could
be easily confirmed. Moreover, the Co3O4−x/GO sandwich
structure consisted of three layers. Because of the large
difference in the atomic number contrast of C and Co, only a
double-layer lattice fringe phase could be observed (Co3O4 on
both sides) with HRTEM from the top view. As shown in
Figure S3, the curly layered images of double-layer Co3O4
HRTEM, split by GO templates, could further demonstrate its
unique sandwich structure. In addition, element mapping was
used to confirm the sandwich structure. As shown in Figure S4,
the element Co (in Co3O4−x) exhibits a uniform distribution,
matching well with C (in the GO template). Furthermore,
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Figure 2. Electronic structures and vacancy characterization of the thin-layered Co3O4−x/GO sandwich structure. XPS spectra for Co 2p (a) and O
1s (b). Normalized XAS at the O K-edge (c) and top valance band (d). (e) Magnetization curve at room temperature.
HRTEM shows that the lattice spacing is 4.69 nm, which could
be indexed to the Co3O4(111). Clear diffraction spots of the
Co3O4(111) plane demonstrate that the thin-layered Co3O4−x/
GO catalyst consists of polycrystallinity, as shown in Figure 1e.
Furthermore, the atomic force microscopy (AFM) image has
been used to confirm the thin-layered morphology in Figure 1f.
The sandwiched sample was dispersed with ethanol onto the Si
substrate, and the thickness was obtained by the height
difference between the substrate and sample region along the
straight line in the AFM image. The thickness observed by
AFM is 20.17 nm, similar to that in TEM, which demonstrates
the uniformity of the catalysts. The slight difference may be
attributed to the dispersion of the samples. The existence of
the GO template in the final complex could be confirmed with
the D/G peaks in the Raman spectrum at 1590 or 1350 cm−1
(Figure 1g).21 The A1g peak at 672 cm−1 may be related with
the [CoO6] octahedron.27 X-ray diffraction (XRD) patterns for
the layered Co3O4−x/GO catalyst are shown in Figure 1h. The
pattern could be indexed to Co3O4 of PDF no. 80-1543 in the
Inorganic Crystal Structure Database.
The different morphologies will induce a great change in the
electronic structure and intrinsic catalytic activity. The
chemical valence state and surface state have been charac-
terized with X-ray photoelectron spectroscopy (XPS). For a
broad comparison, commercial Co3O4 powder (abbreviated as
c-Co3O4) is also discussed in this work. As shown in Figure 2a,
two peaks at 781 and 797 eV could be found in the Co 2p
spectrum, which correspond to Co 2p3/2 and Co 2p1/2,
respectively. Although the strong spin−orbit coupling will lead
to similar binding energies of Co3+ and Co2+, the non-
symmetric peak of Co 2p3/2 indicates the mixed valence states,
and fitting peaks at 780.3 and 781.7 eV could be assigned to
Co3+ and Co2+, respectively.28,29 Furthermore, the valance
states of Co cations could also be distinguished by shakeup
satellite peaks.30 The peak at 787 eV is attributed to Co2+,
while the peak at 797 eV could be attributed to Co3+. The
intensity of the Co2+ satellite peak is greater than that in the
layered Co3O4−x/GO catalyst (abbreviated as l-Co3O4). It
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mainly results from the distorted crystalline structure, which is
helpful to expose the coordination unsaturated Co cations.31
Consequently, the average valence state of the Co cation is
slightly smaller than that in c-Co3O4. In O 1s spectra, the peaks
at 530.5, 531.8, and 533.4 eV can be assigned to the lattice O
(in the metal−O−metal bond), adsorbed O, and adsorbed
OH, respectively. As shown in Figure 2b, the proportion of the
adsorbed O is enhanced in l-Co3O4. It may result from the
larger surface area and abundant active center.
Synchrotron radiation XAS for the oxygen K-edge was used
to investigate the valence/bond structure in catalysts (Figure
2c). Compared with c-Co3O4, a new peak appears at 537.1 eV
for l-Co3O4. According to the literature, it may be related to
oxygen vacancies.32 This is because the huge surface energy in
the ultrathin-layered structure could be balanced through the
formation of oxygen vacancies. The top valence band is closely
related to the catalytic performance. Synchrotron radiation
valence band spectra are collected in Figure 2d. For l-Co3O4,
the top of valence bands shifts (shown as the dotted line)
toward the Fermi Level, indicating that the electrical
conductivity increases gradually. A high conductivity for
transition metal oxide could accelerate charge transfer steps
in the catalytic reaction. It is believed that there is a certain
interaction between the GO layer and cobalt oxide layers. It
may be related with the hydrolysis growth mechanism. This
interaction will accelerate the charge transfer process during
electrocatalysis. Furthermore, oxygen vacancies will also induce
great change in the spin state of 3d electrons. Due to the high
sensitivity to spin electrons, the M−H magnetization curve at
room temperature was used to study the spin state of 3d
electrons, as shown in Figure 2e. The antiparallel spin state of
the adjacent Co cation makes c-Co3O4 a typical antiferro-
magnet. A clear hysteresis loop could be found in l-Co3O4,
which shows extraordinary ferromagnetism. It indicates that
net spin electrons appear in l-Co3O4. This is mainly because
energy level splitting in the crystal field will change from
octahedral to pyramid crystal field for Co3+ after the formation
of oxygen vacancies. The pyramidal crystal field will break the
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Figure 3. NRR performance of the thin-layered Co3O4−x/GO sandwich structure. (a) Difference in ammonia production rates between l-Co3O4
and c-Co3O4 at −0.4 and −1.1 V in 0.1 M K2SO4. (b) Faraday efficiency of l-Co3O4 at different potentials and (c) corresponding current density.
(d) Ammonia yields and FEs at −0.4 V during the cycling test.
degeneracy of both the t2g and eg orbitals. It will lead to great
change in spin states.33,34 Meanwhile, a clear ESR peak around
340 mT in l-Co3O4 indicates the existence of oxygen vacancies
(Figure S5).
The electrocatalytic NRR is conducted with a three-
electrode system (Pt plate, Ag/AgCl, catalyst-loaded carbon
paper as counter, reference, and working electrodes,
respectively). LSV is conducted in Ar/N2-saturated 0.1 M
K2SO4. As shown in Figure S6, the reaction current density in
N2 increases obviously in comparison with that in Ar at
potentials below −0.2 V (vs RHE), indicating an onset
potential of −0.2 V. NRR electrocatalytic activity is further
evaluated by indophenol blue spectrophotometry at different
controllable applied voltages (Figures S6 and S7).35 In Figure
3a, the ammonia production rates increase when the potential
is negatively shifted for both l-Co3O4 and c-Co3O4, which is
similar with the increase in net current density.36 l-Co3O4
shows an excellent NH3 production rate of 15.65 mmol g−1 h−1
at −1.0 V and 5.19 mmol g−1 h−1 at −0.4 V, which are much
higher than those of other reported Co oxides at the same
potential. It suggests that the NRR activity is synergistically
enhanced with oxygen vacancies and the conductive GO
template. The conversion efficiency has always been regarded
as the major challenge. We further analyze the average
ammonia production rates for l-Co3O4 with different potentials
(Figure 3b). Although the NH3 production rates and
formation partial current density increase as the potential is
negatively shifted, the current efficiency starts to decrease
when the potential is lower than −0.4 V (Figure S8). It may
result from the competition between nitrogen reduction and
hydrogen evolution reactions. In Figure 3c, current density
increases fast as an exponential function of potential. Because
the total current density ITotal = IHER + INRR, the formation rate
of NH3 increases slowly than that of the total current density.
It indicates that l-Co3O4 prefers to conduct the HER to the
NRR at a higher overpotential. Consequently, l-Co3O4 could
achieve a maximum Faraday efficiency of 10.68% for ammonia
synthesis, higher than that of recently reported nonprecious
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metal materials (0.1−8%) under similar conditions.3,37 Mean-
while, at this potential (−0.4 V), the ammonia production rate
(5.19 mmol g−1 h−1) is 2.6−40 times higher than that of other
Co-based materials (0.9−2.5 mmol g−1 h−1), even comparable
with that of the reported precious metal Ru-based materials
(7.05 mmol g−1 h−1).2 Detailed comparison with precious
metals and transition metal oxides is found in Table S1 in the
Supporting Information.
Figure 3c shows the chronoamperometric curves for l-Co3O4
at different potentials, which indicates the good stability. The
slight fluctuation in these I−t curves may be related with the
competitive HER through bubbling.38 The final ammonia
production rate could be obtained by UV−vis of these
electrolytes colored through indophenol blue every 2 h
(Figures S9 and S10). To eliminate N pollution, we have
performed electrolysis with l-Co3O4 in a N2-saturated electro-
lyte in the open-circuit system. In Figure S11, the production
rate of NH3 in all control experiments is quite lower than that
for l-Co3O4 at all potentials. For l-Co3O4 at the open circuit or
in Ar@−0.4 V, a weak signal in UV−vis may be related with
the lower visibility of the bubbled solutions and the small
amount of dissolved catalyst inks. It indicates that the N
contamination in DI water or high-purity N2 makes no
contribution to the ammonia production. In addition, we have
conducted the electrolysis with l-Co3O4 and bare GO
substrates in an Ar-saturated electrolyte under −0.4 V. No
peaks appear in the UV−vis absorption spectra. It demon-
strates that the as-obtained ammonia comes only from the
electrocatalytic NRR, rather than other contaminants.
Up to now, chemical stability is another challenge for the
design and architecture of NRR electrocatalysts. Here, the I−t
cycling test has been used to characterize the chemical stability
of l-Co3O4 under NRR conditions at −0.4 V (vs RHE). In
Figure S12, the current density for electrochemical N2
reduction to ammonia is stable. No obvious change could be
found in the corresponding UV−vis. Thus, it indicates an
excellent stability in the NH3 production rate and Faraday
efficiency of l-Co3O4 for the cycling test (Figure 3d).
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Figure 4. Density functional theory calculations for the NRR. (a) Gibbs free energy profiles during the N2 reduction reaction. Electron density
difference after N2 adsorption on the surface of (b) c-Co3O4 and (c) l-Co3O4. Density of states at the adsorbed site before (d) and after (e) N2
adsorption. The inset shows the empty hybrid orbit between Co 3d and N 2p.

Figure 5. OER performance of the thin-layered Co3O4−x/GO sandwich structure. (a) LSV curves and (b) corresponding current density curves at
10 mA cm−2. (c) DFT calculation for Gibbs free energy profiles during the O2 evolution reaction. (d) Reaction path for the OER and (e)
corresponding atomic structure configuration.

Furthermore, the stability of oxygen vacancies could be
confirmed by a clear ESR signal after the NRR test, similar
to that in the primer samples (Figure S5).
DFT calculations have been used to reveal the effect of
oxygen vacancies on the electrocatalytic NRR.39 In this work,
the Co3O4 (001) surface with/without oxygen vacancies has
been used for l-Co3O4 and c-Co3O4, respectively. A side-on
configuration for the adsorbed nitrogen molecule has been
demonstrated theoretically and experimentally.40−42 The
calculated Gibbs free energy profiles for the consecutive
pathways are shown in Figure 4a. It could be found that N2
43513
molecule adsorption is a spontaneous exothermic reaction for
both l-Co3O4 and c-Co3O4. A huge uphill of 0.74 and 0.93 eV
appears, representing rate-determining steps during the NRR,
e.g., transfer of the first proton−electron pair to the adsorbed
N2 molecule.43 It must be related to the strong nonpolar triple
bond in the N2 molecule. We further conducted a detailed
analysis on the adsorbed nitrogen molecule, as shown in Figure
4b,c. A shorter bond length of Co-N for l-Co3O4 (1.88 Å)
demonstrates an enhanced adsorption of N2, which will lead to
a larger adsorption energy on the l-Co3O4 (001) surface.
Consequently, the bond length stretches to 1.13 Å on l-Co3O4,
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which is slightly larger than that of c-Co3O4 (1.11 Å). It
indicates that the strong nonpolar triple bond is further
activated.37 Further investigations for the charge transfer
process between Co and N2 were conducted with electronic
density difference calculation based on the equation Δρ = ρAB
− ρA − ρB, where ρAB is the total charge density of the catalyst
with the absorbed N2 molecule and ρA and ρB represent the
charge density of the isolated catalyst and N2 molecule. The
cloud with blue/yellow represents gaining/losing electrons,
respectively.44 Alternating blue and yellow electronic clouds
along the N�N bonds mean that the catalysts could polarize
the nonpolar triple bond. Note that a larger scale charge
transfer (in black circle) could be found in l-Co3O4.
Consequently, the charge transfer of the first step is effectively
accelerated.
Here, PDOS is used to clarify the origin of catalytic activity.
It could be found that the top valance is occupied by Co eg
electrons in Figure 4d. According to the eg descriptor proposed
by Shao-Horn, filling of eg rather than t2g in transition metal
oxides could determine the energy accurately gained by
adsorption of O2.45 Considering the similarity of the molecular
orbit for N2 and O2, this rule also works here and the eg orbital
will direct toward a N2 molecule, overlapping the N 2pσ orbital
stronger than that between t2g and N 2pπ. To figure out reasons
why the first charge transfer step is accelerated after N2
adsorption, only the Co and N atoms at the active site are
selected in Figure 4e. Compared with c-Co3O4, a weak
unoccupied orbit (0.7−0.9 eV in the inset) between Co 3d and
N 2p above the Fermi level appears in l-Co3O4. The lower
energy of the unoccupied orbit makes the first hydrogenation
and reduction steps in the NRR more feasible.40 Consequently,
N�N bonds could be activated and the bond length is longer
for the absorbed N2 on c-Co3O4. Then, it will lead to the
alternating blue and yellow electronic clouds in Figure 4c. It is
reasonable that decreasing the thickness and increasing the
loadings could be used to further enhance the NRR activity. As
demonstrated in Figures 1 and S1, the precise control of
hydrolysis is the effective method to improve the morphology
and the corresponding activity.
As the anode reaction in the overall electrocatalytic
ammonia synthesis, the oxygen evolution reaction consists of
four-electron transfer steps, which generally exhibits a large
overpotential.24 The sluggish OER kinetics will lead to the
large efficiency loss for the overall ammonia synthesis. LSV has
been used to evaluate the catalytic performance for the oxygen
evolution reaction with l-Co3O4, c-Co3O4, and benchmark
RuO2 (Figure 5a). It can be found that great enhancement in
the OER performance has been realized in l-Co3O4, even
better than that of benchmark RuO2. The overpotential (10
mA·cm−2) for l-Co3O4 is 280 mV, smaller than that of c-Co3O4
(365 mV). In addition, a clear oxidation peak before oxygen
evolution in the inset of Figure 5a, belonging to the formation
of *CoOOH, could be found at 1.35−1.40 V (vs RHE) both in
l-Co3O4 and c-Co3O4. It is reported that *CoOOH could be
regarded as the precursor for oxygen evolution.46 A lower
potential indicates that l-Co3O4 is more efficient for the OER.
To emphasize its unique advantages, a OER performance
comprehensive comparison with the reported cobalt oxides can
be found in Table S2 in the Supporting Information. To assess
its durability for the OER, electrolysis has been conducted at
E@10 mA·cm−2 for 12 h (Figure 5b). In addition to the slight
fluctuation caused by O2 release from the catalyst surface, the
I−t curve remains stable during the whole test. Only 5%
43514
www.acsami.org Research Article
catalytic efficiency is lost after 12 h, indicating that thin-layered
Co3O4/GO is quite stable as OER catalysts. It mainly results
from the unique sandwich structure, which makes the oxygen
vacancies more stable.
To further evaluate the relation between the oxygen
vacancies and OER activity, the DFT calculation for the
proton-coupled four-electron transfer reaction is shown in
Figure 5c.47 It shows that the rate-determining step changes
from the formation of *OH (c-Co3O4) to the decomposition
of *OOH (l-Co3O4). The corresponding free energy barrier is
reduced from 0.51 to 0.34 eV. The diagram of the reaction
path is shown in Figure 5d,e. Since the adsorbed OH− will
occupy the origin oxygen vacancy, it can balance the large
surface energy of Co3O4 with the oxygen vacancy.46 Hence, the
formation of *OH in free energy is reduced in l-Co3O4. The
situation also changes for the decomposition of *OOH step. It
is demonstrated that oxygen vacancies are first filled with *OH
and facilitate preoxidation. Then, it could effectively promote
the reconstruction of intermediate Co-OOH, as shown in the
oxidation peak of the LSV curve. Due to the existence of
oxygen vacancies, both the O atoms in *OOH could bond
with the Co cation. A smaller bond length (1.79 Å) of Co-O in
Co-OOH will slightly increase the energy for the decom-
position of *OOH. Then, the above-mentioned two factors
synergistically change the rate-determining steps and corre-
sponding free energy.
4. CONCLUSIONS
In conclusion, a superior bifunctional OER/NRR catalyst has
been developed based on the thin-layered Co3O4−x/GO
sandwich structure via a template-assisted method. The
ultrathin-layered structure will lead to a distorted crystalline
structure. The formation of oxygen vacancies, demonstrated by
XAS, ESR, and the M−H curve, could balance the large surface
energy. The synchrotron radiation valance band spectrum
indicates that the introduction of the GO template inside the
cobalt oxide could optimize its conductivity. Then, the intrinsic
NRR/OER activity is synchronously enhanced. l-Co3O4 shows
an excellent catalytic NRR performance with a high production
rate of 5.19 mmol g−1 h−1 at −0.4 V (vs RHE) and an
enhanced current efficiency of 10.68%. It also shows an
excellent stability after six NRR cycles. The DFT calculation
demonstrates that the nonpolar triple bond could be activated
through the formation of a empty Co 3d−O 2p hybrid orbit.
Furthermore, l-Co3O4 exhibits an outstanding OER catalytic
activity and durability, even comparable with those of the
benchmark RuO2. Therefore, this work will make a novel leap
for the research of overall electrocatalytic NH3 synthesis.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.2c11674.
SEM images for sandwiched Co3O4−x/GO; cyclic
voltammetry curve for sandwiched Co3O4−x/GO in Ar
or N2; working curve for indophenol blue spectropho-
tometry; UV−vis absorption spectrum at different
applied voltages; UV−vis absorption spectra for the
cycling test; UV−vis absorption spectra in DI water, Ar
and open circuit; I−t curve for the cycling test; NRR
performance reported in the literature; and OER
performance for Co3O4 in the literature (PDF)
https://doi.org/10.1021/acsami.2c11674
ACS Appl. Mater. Interfaces 2022, 14, 43508−43516
ACS Applied Materials & Interfaces
■ AUTHOR INFORMATION
Corresponding Author
Yu Sun − School of Advanced Materials and Nanotechnology,
Xidian University, Xi’an 710126, P. R. China; orcid.org/
0000-0001-7318-2739; Email: sunyu@xidian.edu.cn
Authors
Qiao Wang − State Key Lab of Inorganic Synthesis and
Preparative Chemistry, College of Chemistry, Jilin University,
Changchun 130012, P. R. China
Zhongyuan Liu − State Key Lab of Inorganic Synthesis and
Preparative Chemistry, College of Chemistry, Jilin University,
Changchun 130012, P. R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.2c11674
Author Contributions
The article was written through contributions of all authors. All
authors have given approval to the final version of the article.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (21801089) and the Fundamental
Research Funds for the Central Universities (XJS211402).
The authors thank the NSRL beamline BL12B-a (National
Synchrotron Radiation Laboratory) for providing beam time.
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