Article

Cite This: ACS Nano 2018, 12, 1894−1901 www.acsnano.org

Carbon Nanosheets Containing Discrete

Co‑Nx‑By‑C Active Sites for Efficient Oxygen
Electrocatalysis and Rechargeable Zn−Air
Batteries
Yingying Guo,† Pengfei Yuan,§ Jianan Zhang,*,† Yongfeng Hu,∥ Ibrahim Saana Amiinu,‡ Xin Wang,†
Jigang Zhou,∥ Huicong Xia,† Zhibo Song,† Qun Xu,*,† and Shichun Mu*,‡
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†
College of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, People’s Republic of China
‡
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan
430070, People’s Republic of China
§
International Joint Research Laboratory for Quantum Functional Materials of Henan Province, and School of Physics and
Engineering, Zhengzhou University, Zhengzhou 450001, People’s Republic of China
∥
Canadian Light Source, 44 Innovation Boulevard, Saskatoon, SK S7N 2 V3, Canada
*
S Supporting Information

ABSTRACT: Structural and compositional engineering of atomic-

scaled metal−N−C catalysts is important yet challenging in boosting
their performance for the oxygen reduction reaction (ORR) and
oxygen evolution reaction (OER). Here, boron (B)-doped Co−N−C
active sites confined in hierarchical porous carbon sheets (denoted as
Co-N,B-CSs) were obtained by a soft template self-assembly pyrolysis
method. Significantly, the introduced B element gives an electron-
deficient site that can activate the electron transfer around the
Co−N−C sites, strengthen the interaction with oxygenated species,
and thus accelerate reaction kinetics in the 4e− processed ORR and OER. As a result, the catalyst showed Pt-like ORR
performance with a half-wave potential (E1/2) of 0.83 V versus (vs) RHE, a limiting current density of about 5.66 mA cm−2,
and higher durability (almost no decay after 5000 cycles) than Pt/C catalysts. Moreover, a rechargeable Zn−air battery
device comprising this Co-N,B-CSs catalyst shows superior performance with an open-circuit potential of ∼1.4 V, a peak
power density of ∼100.4 mW cm−2, as well as excellent durability (128 cycles for 14 h of operation). DFT calculations
further demonstrated that the coupling of Co-Nx active sites with B atoms prefers to adsorb an O2 molecule in side-on
mode and accelerates ORR kinetics.
KEYWORDS: atomic boron-doped Co−N−C species, oxygen evolution reaction, oxygen reduction reaction, Zn−air batteries,
electrocatalyst

carbon, and metal−nitrogen-doped carbons (M−N−C).14

M etal−air batteries with promising sustainable energy

conversion are highly dependent on the activity and
stability of the cathodic oxygen reduction reaction
(ORR) and anodic oxygen evolution reaction (OER).1−6
Platinum (Pt)-based materials have been identified as the
best performing ORR catalysts, whereas Ru- and Ir-based
catalysts are effective in the OER process.7−10 However, these
noble-metal-containing catalysts are plagued by scarcity, high
price, and limited stability, which inspire researchers to seek
effective, highly active, and durable bifunctional electrocatalysts
for ORR and OER.11−13
As reported, a wide range of nonprecious metal electro-
catalysts show promising activity in ORR/OER, including
earth-abundant transition metals, metal-free heteroatom-doped
Among them, the M−N−C active site containing materials
are considered to be the most promising alternatives to metal
catalysts for ORR. This is because density functional theory
(DFT) calculations suggest that the possible metal−N4 sites
could be as active as Pt for O2 adsorption and subsequent O
O bond breaking during the ORR.15,16 In particular, atomically
dispersed Co−Nx−C active sites with the critical structure of
nitrogen coordinated with a Co atom located in a 3D
nanoarchitecture (graphene aerogels,17 carbon nanotubes,18
Received: December 10, 2017
Accepted: January 23, 2018
Published: January 23, 2018

© 2018 American Chemical Society 1894 DOI: 10.1021/acsnano.7b08721

ACS Nano 2018, 12, 1894−1901
ACS Nano Article

Scheme 1. Synthetic procedure of the Co/N−B-doped carbon nanosheet (Co-N,B-CSs).

Figure 1. (a) SEM, (b) TEM, and (c, d) HAADF-STEM images; (e−h) EDS element mapping of C, Co, N, and B for Co-N,B-CSs (scale bar is
300 nm). (i) High-resolution XPS spectrum of N 1s for Co-N,B-CSs. (j) XANES spectra and (k) Fourier transformed EXAFS spectra of the
Co foil and Co-N,B-CSs and Co−N−Carbon. R (Å), distance in angstroms; k, wavenumber.

porous carbon,19,20 g-C3N4,21 etc.) have been considerably
attractive, since they can afford maximum atom utilization
efficiency and expose most active sites.22−24 However, to
achieve a breakthrough in promoting efficiency, intensively
studied atomically dispersed Co−Nx−C catalysts are frequently
hindered by a low content of active sites and a low surface area
of the carbon matrix. To this end, the key to promote the
catalytic activity of M−N−C catalysts is properly enhancing the
per unit area reactive efficiency of M−N−C active sites for
oxygen reactions.
It is widely accepted that the ORR activity is strongly
correlated with the adsorption of oxygen and formation of
superoxide through a one-electron reduction (O 2 + e −
[O2(ads)]−). This generally is viewed as initial ORR steps,
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with O2 adsorption proposed by Morcos and Yeager to be the
rate-determining step.25 Attractively, the electron-deficient B-
doped sites in carbon are favorable for O2 adsorption because
they can break the electroneutrality of the matrix to create
charged sites.26−29 Therefore, doping B within Co−N−C
catalysts is expected to be a promising strategy to enhance Co-
based catalysts in both ORR and OER. Here, we put forward
Co−N−C active sites confined in N,B-co-doped carbon
nanosheets (Co-N,B-CSs) via the self-assembly pyrolysis
method using a soft template. Thanks to the preferred O2
adsorption on electron-deficient B atom doped Co−N−C sites,
it lowers the oxygen reaction activation barriers on Co−N−C.
Therefore, although possessing a relatively low surface area, Co-
N,B-CSs exhibit superior electrocatalytic activity toward both
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ORR and OER under alkaline conditions. Furthermore, a
rechargeable Zn−air battery device fabricated with Co-N,B-CSs
shows a small charge−discharge voltage gap and long-term
stability. Undoubtedly, this work will promote development of
inexpensive non-noble metal hybrid materials for applications
in ORR/OER electrocatalysis.
RESULTS AND DISCUSSION
As illustrated in Scheme 1, the preparation of Co-N,B-CSs was
performed via a soft template self-assembled pyrolysis method.
A dry gel precursor was first made by mixing boric acid, urea,
polyethylene glycol (Mw = 2000, PEG-2000), Co(NO3)2·6H2O
(as Co source), and water and then drying at 120 °C for 10 h,
followed by carbonization at 900 °C (see details in the
Supporting Information). Figure S1 shows the transmission
electron microscope (TEM) images of the as-obtained sample.
Interestingly, the high-temperature pyrolysis can guarantee the
formation of two-dimensional (2D) carbon sheets with Co
nanoparticles (NPs) in the pores. The sample is denoted as
Co/Co-N,B-CSs. By contrast, the TEM image (Figure S2) of
the as-prepared sample without the addition of PEG-2000
shows an aggregated particle morphology with bulk Co,
demonstrating the structure-induced effect of the surfactant
PEG-2000 on forming a 2D sheet-like structure for Co/Co-
N,B-CSs during the carbonization. Urea, as is well known, is the
precursor of graphitic carbon nitride (g-C3N4) nanosheets,
which can be utilized as sacrificial template to generate the 2D
nanosheet morphology.30 To confirm this, we have shown the
TEM images of a sample obtained by pyrolysis at 550 °C in an
Ar atmosphere for 4 h at 2 °C min−1 followed by removing the
Co-containing species, giving a nanosheet structure (Figure
S3). Accordingly, after removing Co NPs by acid treatment,
Co-N,B-CSs (carbonized at 900 °C) reveals 2D sheets with
crumples, representing an internal porous structure (Figure 1a).
The corresponding highly magnified TEM images (Figures 1b
and S4) demonstrate that an individual sheet consists of
numerous macropores with diameter of 30−50 nm created by
the etching of Co NPs in Co/Co-N,B-CSs. Notably, the pore
size of Co-N,B-CSs is larger than that of the Co NPs in Co/Co-
N,B-CSs, probably caused by fusion and shrinkage of the
metallic cobalt. Coinciding with these results, the pore size
distribution calculated from the N2 sorption data is in the range
of 16−20 nm, confirming the coexistence of mesopores and
macropores (Figure S5a, Table S2). The hierarchical porous
structure and the sheet-like morphology deeply play an
important role in providing more exposure of active sites and
facilitating mass transport during the catalytic process.
Moreover, the structure of Co-N,B-CSs was further analyzed
by X-ray diffraction (XRD) and Raman spectroscopy. As shown
in Figure S5b, the XRD pattern shows very broad characteristic
2θ peaks at 26° and 44°, indicating the disordered structure of
the carbon sheet.31 Meanwhile, the Raman spectrum of Co-
N,B-CSs shows that the intensity ratio of two main bands
located at 1354 and 1591 cm−1 (ID/IG) is 1.03, further
confirming the defective structure of the carbon nanosheets
(Figure S5c). Based on our previous work, the disordered
structure is expected to play a vital role in increasing the
content of the atomically dispersed Co−Nx species.
The high-angle annular dark field scanning transmission
electron microscopy (HAADF-STEM), X-ray photoelectron
spectroscopy (XPS), and Co K-edge X-ray adsorption near-
edge structure (XANES) and extended X-ray adsorption fine
structure (EXAFS) spectroscopy Co k-space of Co-N,B-CSs
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show different oscillation curves were obtained to confirm the
atomically dipersed B-doped Co−Nx species in Co-N,B-CSs. As
shown in Figure 1c, a great number of atomic-scaled Co atoms
can be identified by the isolated bright dots and are marked
with arrows. As further evidence, the HAADF-STEM image
and STEM mapping display C, Co, N, and B elements in the
entire architecture (Figure 1e−h), which is in agreement with
the XPS analysis (Figure S5d). Significantly, Co-N,B-CSs give a
lower Co content of 0.52 at. % detected by XPS measurement
than most of the reported metal−Nx catalysts. As shown in
Figure 1i, the high-resolution N 1s XPS spectrum for Co-N,B-
CSs shows five features (pyridinic N, N-6; Co−Nx; pyrrolic N,
N-5; graphitic N, N-Q; oxidized N, N-O). The Co−Nx bond
with the binding energy of 398.32 eV, associated with the
cobalt−nitrogen functional moieties, indicates that there are
abundant Co−Nx active sites in Co-N,B-CSs.31 Additionally,
the high-resolution B 1s XPS spectrum (Figure S5e) shows
three valence states of boron element, including the B−C bond
(190.27 eV), B−N bond (191.37 eV), and B−O bond (193.2
eV), implying replacement of C atoms by B atoms as adjacent
atoms to N atoms.26,31 Because N atoms can induce positive
polarization of C atoms, while low-electronegativity B atoms
can be positively polarized, the positively polarized N−C and
C−B bonds favor attraction of O2 molecules during the O2
reaction process, further enhancing the ORR and OER
performance of Co-N,B-CSs. Therefore, both the HAADF-
STEM and XPS results suggested that the coupled hybrid
materials, atomic-scaled Co−N−C species uniformly disperse
on B,N-co-decorated carbon sheets, were successfully synthe-
sized.
Additionally, XANES and EXAFS spectra were performed to
further study the coordination environment of cobalt, as X-ray
absorption spectroscopy is sensitive to the electronic structure
and coordination properties of both crystalline and amorphous
forms of species. As the control experiments, a catalyst without
B doping (noted as Co−N−Carbon) was synthesized. As
shown in the SEM and TEM images in Figure S6, Co−N−
Carbon exhibits a similar porous nanosheet structure to Co-
N,B-CSs. As shown in Figure 1j, Co K-edge XANES spectra of
Co-N,B-CSs and Co−N−Carbon show different spectral
features (in terms of both edge postion and peak area), with
the formal Co oxidation state between that of the Co in Co foil
and CoO references.32,33 Co in Co-N,B-CSs is more reduced
since its edge jump is at a lower energy compared to Co−N−
Carbon. More importantly, the peak area (area after the edge
jump) in Co−N−C is much higher. The peak area (after
normalization, as shown) is directly proportional to the number
of vacancies in the Co np and nd orbitals.34 Because of the
electron donor property of boron, there is less density of
unoccupied state in Co-N,B-CSs, compared to Co−N−Carbon.
On the other hand, EXAFS analysis (R-space results shown in
Figure 1k) clearly indicates that there is no Co−Co interaction
observed in both Co-N,B-CSs and Co−N−Carbon, suggesting
that Co is atomically well dispersed in the carbon network. The
lack of Co−O peak in the R-space result of these two samples,
as observed at 1.64 Å in CoO, also confirmed these two
samples are not cobalt-oxide-like.34 The multiple peaks in the
low R region (0.95 and 1.5 Å) could be attributed to
interactions between Co and N and C in these samples,
including the Co−B for the Co-N,B-CSs sample. Taken
together, the data indicate that the Co is atomically dispersed
in the N- and B-doped carbon matrix, and it is in the ionic state
with nitrogen and boron atoms in the configuration. With the
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Figure 2. (a) LSV curves of Co-N,B-CSs, Co/Co-N,B-CSs, Co−N−Carbon, and Pt/C catalysts in O2-saturated 0.1 M KOH solution. (b) Tafel
slopes of Co-N,B-CSs and Pt/C. (c) LSV curves at different rotation rates in rpm. Inset is the corresponding K−L plot with a sweep rate of 5
mV s−1. (d) Chronoamperometric response for Co-N,B-CSs, Co−N−Carbon, and Pt/C electrode at 0.75 V (vs RHE) after the introduction of
9.7 mL of CH3OH into 230.3 mL of 0.1 M KOH solution. (e) ORR polarization LSV and CV curves of Co-N,B-CSs measurement before and
after 5000 potential cycles at the scan rate of 50 mV s−1 with a rotation speed of 1600 rpm. (f) LSV curves of different catalysts for both ORR
and OER in 0.1 M KOH at 1600 rpm and a sweep rate of 5 mV s−1.

advance of the configuration, the B doping coupled with the
atomic-scaled Co−N−C active sites could modify the
electronic properties, create more active sites, and improve
the electronic conductivity, thus allowing the enhancement of
the electrocatalytic activity for ORR and OER (Figure S7).34
The electrocatalytic performances toward ORR for the as-
prepared materials were first evaluated by rotating disk
electrode (RDE) techniques in O2 -saturated 0.1 M KOH
solution. Figures 2a and S8,9 show the comparison of linear
scan voltammogram (LSV) and cyclic voltammogram (CV)
curves, as well as the kinetic current densities for Co-N,B-CSs,
Co/Co−N,B-CSs, Co−N−Carbon, and Pt/C catalyst (details
are in Table S3). The Co-N,B-CSs exhibit a pronounced Pt/C-
like ORR activity with a half-wave potential (E1/2) of 0.83 V
and limiting current density (JL) of 5.66 mA cm−2, which
outperforms that of Co/Co-N,B-CSs (0.803 V, 4.7 mA cm−2)
and Co−N−C (0.640 V, 3.13 mA cm−2) catalysts. To further
gain information on the ORR mechanism, the Tafel slopes were
determined by mass transport correction from the mixed
kinetic−diffusion-controlled region. As shown in Figure 2b, the
fast ORR kinetics for Co-N,B-CSs is further confirmed by its
Tafel slope (64 mV dec−1), close to that of Pt/C catalyst (68
mV dec−1). To quantitatively investigate the ORR activity of
Co-N,B-CSs, a series of LSV curves are presented in Figure 2c
at different rotating speeds (400−2050 rpm). Likewise,
calculated from the Koutechy−Levich plots (K−L, J−1 vs
ω−1/2), the electron transfer number per oxygen molecule (n)
for Co-N,B-CSs is determined to be ∼4.0. In particular,
calculated from the rotating ring-disk electrode (RRDE) data,
the H2O2 yield measured for Co-N,B-CSs (highest yield is
2.2%) is much less than that for Pt/C (the highest yield is
5.9%) at all potentials, implying the value of n is between 3.98
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and 4.00 at 0.20−0.50 V, well consistent with the results
obtained from the K−L plots (Figure S10a). Taken together, it
suggests an efficient oxygen reduction activity via a dominant
four-electron pathway.
An excellent catalytic selectivity for cathode reactions against
fuel poisoning is important for an efficient ORR electrocatalyst,
especially displaying the superior tolerance to methanol
crossover of Co-N,B-CSs over Pt/C and Co−N−Carbon
catalysts. More significantly, Co-N,B-CSs exhibit a slight
current decrease retention over 2000 s during continuous
operation, whereas Pt/C exhibits a dramatic current loss with
only 64% retention. Moreover, the Co-N,B-CSs catalyst also
reveals excellent long-term stability after 5000 cycles at 0.1 to
−0.8 V with a scan rate of 500 mV s−1 in O2-saturated 0.1 M
KOH solution, more stable than the commercial Pt/C (Figures
2e and S11).
Figure 2f shows excellent ORR and OER bifunctional
electrocatalytic activities for Co-N,B-CSs, which can be judged
by the potential difference between OER and ORR (ΔE = EJ=10
− E1/2; the OER potential is taken at a current density of 10
mA cm−2, while the ORR potential is taken at half-wave). As a
reference, we also used a state-of-the-art OER electrode with
RuO2 nanoparticles and found that Co-N,B-CSs possess a
lower onset potential than RuO2 and Pt/C, and ΔE is minimal
at 0.83 V. This is probably because not only can the N atoms
(such as pyrrole-like, graphitic nitrogen atoms) positively
polarize the adjacent C atom but also the electronegative B
atom can activate the C atoms and Co−N−C active sites,
providing carbon chemistry between carbon-involving active
sites (Co−N−C, B−C, and N−C) and molecular oxygen.35
The superior ORR and OER bifunctional electrocatalytic
activities of Co-N,B-CSs inspired us to construct a rechargeable
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Figure 3. (a) Schematic representation of the rechargeable Zn−air battery. (b) Polarization and power density curves of the Zn−air batteries
of the Co-N,B-CSs and Pt/C catalysts. (c) Discharge curves of the Zn−air battery with Co-N,B-CSs as catalyst at 10 mA cm−2 current
densities. (d) Charge and discharge polarization curves. The catalyst loading on the air electrode was 0.5 mg cm−2. (e) Performance of the
battery cycling at the current density of 5 mA cm−2. (f) Photograph of a Co-N,B-CSs-based all-solid-state Zn−air microbattery with an open-
circuit voltage of 1.345 V and (g) a lighted green LED (8 mm, ∼3.4 V) powered by three all-solid-state Zn−air batteries interconnected in
series. (h) Galvanostatic cycling profiles of Co-N,B-CSs-based all-solid-state battery at the current density of 2 mA cm−2.

Figure 4. (a, b) Optimized geometry of the corresponding O2 adsorption configuration on the Co-N,B-CSs system. (c) Free-energy paths of
ORR on Co-N3B-CSs and Co-N4-CSs systems during the ORR in alkaline solution at the equilibrium potential of U = 0 and 0.24 V for Co-
N3B-CSs and U = 0 V, 0.48 V for Co-N4-CSs.

Zn−air battery with the same configuration as that of the
primary counterpart but using 6 M KOH with 0.2 M zinc
acetate as the electrolyte (Figure 3a).36,37 Figure 3b shows that
the maximum power density of the Zn−air battery using the
Co-N,B-CSs catalyst was determined to be 100.4 mW cm−2,
much higher than that of Pt/C catalysts (66.3 mW cm−2). The
battery with the Co-N,B-CSs air-cathode shows voltage
plateaus of ∼1.20 V at a current density of 10 mA cm−2
(Figure 3c). The as-formed Zn−air battery has an open-circuit
voltage of 1.43 V with Co-N,B-CSs as the air-cathode (Figure
S12). Figure 3d shows the discharge and charge polarization
curves for Zn−air batteries with Co-N,B-CSs as the ORR and
OER bifunctional catalyst.
Motivated by this initial performance, the robustness of the
Co-N,B-CSs cathode was further demonstrated by cycling at a
current density of 5 mA cm−2 (Figure 3e). The Zn−air battery
produces an initial charge potential of 2.25 V and discharge
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potential of 0.9 V, with a small voltage gap of 1.35 V and a high
round-trip efficiency of 58%. After a 128-cycle test (about 14
h), the Co-N,B-CSs air-cathode shows a slight performance loss
with a small increase in the voltage gap by 0.2 V. A lower
charge−discharge voltage gap is observed for the Zn−air
battery with the Co-N,B-CSs air-cathode, indicating the robust
rechargeability. The observed performance decay for Co-N,B-
CSs is most probably due to the inevitable exposure to positive
potential during OER that causes carbon oxidization and the
loss of active sites, porosity, which provided fast mass diffusion
pathways, and highly efficient single Co atom dispersion, while
the inner sheet can supply good electrical conductivity.
A potential challenge to rational design of electrochemical
energy devices is the realization of lab-scale performance. To
demonstrate this, we have further shown the applicability and
promise of Co-N,B-CSs as a Zn−air battery cathode electro-
catalyst for portable electronic devices. In this regard, a scalable
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all-solid-state Zn−air battery consisting of a free-standing Co-
N,B-CSs air-cathode, zinc foil anode, alkaline poly(vinyl
alcohol) (PVA) gel electrolyte, and pressed (for strengthening
conductivity) nickel foam current collector (the catalyst loading
on the air electrode was 0.5 mg cm−2) was fabricated via the
schematics shown in Figure S13. We also constructed a
discharge Zn−air battery with the same configuration as that of
the counterpart. Interestingly, a high open-circuit voltage of
1.345 V is obtained in Figure 3f, where it only needs three
batteries in series to power blue light-emitting diodes (LEDs, 8
mm, ∼3.4 V) with an open-circuit voltage of 4.058 V (Figure
3g). Galvanostatic cycling profiles of a Co-N,B-CSs-based all-
solid-state battery at the current density of 2 mA cm−2 are
shown in Figure 3h.
We propose that the outstanding activity and high stability of
the Co-N,B-CSs catalyst depend on the following two aspects:
(1) the high density of isolated atomic-scale Co−N−C boosts
electron transfer ability and provides highly active sites for
ORR; (2) the introduction of B atoms into the carbon matrix
can raise the unbalanced charge distribution and thus positively
polarize C atoms and Co−N−C sites, which favors the
adsorption of oxygen species.38 To demonstrate this, we
performed first-principles calculations using DFT methods to
determine how the addition of B reduces the H2O2 production
and favors the four-electron ORR pathway (Figure 4). As
shown in Table S5, Co-N3B and Co-N4 moieties at the edge of
an armchair graphene nanoribbon exhibit the lowest free
energies, indicating their highest structural stability. In this way,
we used the Co-N3B- and Co-N4-doped graphene nanoribbon
as a model reference to represent the difference of Co-N,B-CSs
and Co−N−Carbon catalysts. Considering the four-electron
paths of ORR and OER on Co-N4-CSs and Co-N3B-CSs in
alkaline solution, the free energy for each elementary step was
calculated by combining the enthalpy and the harmonic
entropy, which are listed in Tables S5−S7. Figure 4a,b show
the highest occupied molecular orbital plot of the correspond-
ing O2 adsorption configuration of Co-N,B-CSs. Due to the
higher electronegativity of oxygen, the adsorbed functional
groups attract electrons from surrounding carbon atoms,
resulting in charge redistribution on those carbon atoms. The
electron-deficient carbon B-doped sites in carbon can break the
electroneutrality of the matrix to create charged sites, favorable
for O2 adsorption. To this end, we suppose that most Co−N−
C active sites are located at the edge. As shown in Figure 4c, the
free energy changes of the Co-N3B-CSs catalyst during the
ORR process decrease slightly from 0 to 0.073 eV in the first
step, which is significantly lower than that for Co-N4-CSs
(−0.014 eV). Given an applied potential of 0.24 V, Co-N,B-CSs
in each step during the ORR process are energetically downhill,
significantly lower than that for Co-N4-CSs (0.48 V), which
supplies theoretical evidence for highly efficient ORR catalytic
activity of Co-N,B-CSs.
CONCLUSIONS
In summary, the M−N−C active site type of atomically
dispersed B-doped Co−N−C active sites, evidenced by
HAADF-STEM, XPS, XANES, and EXAFS characterization,
have been achieved and boosted bifunctional ORR and OER
activities, approaching that of Pt/C and RuO2, along with
significantly enhanced stability. Furthermore, the catalyst
exhibits good performances when equipped in liquid and all-
solid rechargeable Zn−air batteries compared with Pt/C.
Significantly, the control experiments and DFT calculations
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confirmed that the introduction of B atoms can strengthen the
positive polarization of the Co−N−C, N−C, and C−B
moieties, which favors the capture of oxygen species and thus
accelerates the 4e− process kinetics in ORR and OER. Besides,
the porous layered structure can supply a great number of
exposed edge sites. This work highlights that the atomic
reactive efficiency of M−N−C active sites can be enhanced by
decorating the sites with heteroatoms (B, P, S) for oxygen
electrocatalysis. The outstanding characteristics of our cost-
effective Co-N,B-CSs catalyst make it a promising candidate for
energy conversion and storage devices.
EXPERIMENTAL METHODS
Chemicals. Cobalt nitrate hexahydrate (Co(NO3)2·6H2O) was
obtained from Beijing Chemical Reagent Company (Beijing, China).
Boric acid (H3BO2) and urea were bought from Xilong Chemical
Technology Co., Ltd. Polyethylene glycol (PEG) (Mw = 2000) was
purchased from Beijing Tianjin Kermel Chemical Reagent Co., Ltd.
Sulfuric acid (H2SO4) was obtained from the Tianjin Chemical
Factory. Nafion (5.0 wt %) was purchased from Sigma-Aldrich. Pt
catalyst (20% Pt supported on Vulcan XC-72 carbon) was obtained
from Johnson Matthey. All chemicals were used as received without
any further purification Deionized water was used in all experiments.
Synthesis of Co-N,B-CSs. Co-N,B-CSs were synthesized via a
hydrothermal method. Typically, 5 g of urea (24 mmol), 0.051 g of
Co(NO3)2·6H2O (0.68 mmol), 0.15 g of boric acid, and 0.5 g of PEG-
2000 were dissolved in 50 mL of water under stirring and dried in an
oven at 120 °C for 10 h. Then, the temperature was further raised to
900 °C at a ramp rate of 10 °C min−1 and kept at 900 °C for 6 h under
an Ar atmosphere. For the removal of Co NPs, the as-obtained
material was immersed in 0.5 M H2SO4 for 24 h. After washing with
deionized water several times, Co-N,B-CSs were obtained. As the
control experiments, the synthesis of Co−N−Carbon and Co-N,B-
carbon bulk was similar to the above method but without boric acid
and PEG-2000, respectively.
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsnano.7b08721.
Additional experimental details, figures, and tables (PDF)
AUTHOR INFORMATION
Corresponding Authors
*E-mail: zjn@zzu.edu.cn.
*E-mail: qunxu@zzu.edu.cn.
*E-mail: msc@whut.edu.cn.
ORCID
Jianan Zhang: 0000-0002-7559-1090
Ibrahim Saana Amiinu: 0000-0003-4426-7893
Jigang Zhou: 0000-0001-6644-2862
Qun Xu: 0000-0002-2264-0266
Shichun Mu: 0000-0003-3902-0976
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work was financially supported by the National Natural
Science Foundation of China (21571157, U1604123, and
51173170), Outstanding Young Talent Research Fund of
Zhengzhou University (No. 1521320001), The Young Out-
standing Teachers of Univeristy in Henan Province (2016-
130), the Open Project Foundation of Key Laboratory of
DOI: 10.1021/acsnano.7b08721
ACS Nano 2018, 12, 1894−1901
ACS Nano
Advanced Energy Materials Chemistry (Ministry of Education)
(2017-29), Nankai University, and Open Project Foundation of
State Key Laboratory of Inorganic Synthesis and Preparation of
Jilin University. The XAS measurement was conducted at the
Canadian Light Source (CLS). CLS is supported by the
NSERC, NRC, CIHR of Canada, and the University of
Saskatchewan.
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1901 DOI: 10.1021/acsnano.7b08721

ACS Nano 2018, 12, 1894−1901