Rapid Controllable Synthesis of Atomically Dispersed Co on Carbon under High Voltage within One Minute

Article abstract of DOI:10.1002/smll.202007264

Developing a rapid and low cost approach to access atomically dispersed metal catalysts (ADMCs) supported by carbon is important but still challenging. Here, an electric flash strategy using high voltage for the rapid fabrication of carbon-supported ADMCs within 1?min is reported. Continuous plasma arc results in nitrogen-doped carbon ultrathin nanosheets, while an intermittent spark pulse constructs carbon hollow nanospheres via blasting effect, and both structures are decorated with atomically dispersed cobalt. The latter catalyst shows a half-wave potential of 0.887?V versus RHE (47?mV higher than commercial Pt/C) in an oxygen reduction reaction (ORR) in alkaline media. The authors’ work paves the way to rapid synthesis of carbon-supported ADMCs at both low cost and mass production.

Full text of DOI:10.1002/smll.202007264

ReseaRch aRticle
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Rapid Controllable Synthesis of Atomically Dispersed
Co on Carbon under High Voltage within One Minute
Junyi Du, Geng Wu, Kuang Liang, Jia Yang, Yida Zhang, Yue Lin, Xusheng Zheng,
Zhen-Qiang Yu,* Yuen Wu,* and Xun Hong*
features of the carbon support, such as
Developing a rapid and low cost approach to access atomically dispersed
metal catalysts (ADMCs) supported by carbon is important but still chal-
lenging. Here, an electric flash strategy using high voltage for the rapid
fabrication of carbon-supported ADMCs within 1 min is reported. Continuous
plasma arc results in nitrogen-doped carbon ultrathin nanosheets, while an
intermittent spark pulse constructs carbon hollow nanospheres via blasting
effect, and both structures are decorated with atomically dispersed cobalt.
The latter catalyst shows a half-wave potential of 0.887 V versus RHE (47 mV
higher than commercial Pt/C) in an oxygen reduction reaction (ORR) in
alkaline media. The authors' work paves the way to rapid synthesis of carbon-
supported ADMCs at both low cost and mass production.
high electronic conductivity, strong corro-
sion resistance, tunable morphology, and
ordered porosity, makes them efficient
[
10–14]
catalysts in numerous reactions.
In
particular, metal single sites embedded
in N-doped carbon (M/N-C) (M = Co, Fe,
Ni, etc.) are promising electrocatalysts
[
15–19]
for oxygen reduction,
ting,
water split-
[
20,21]
and carbon dioxide reduction.[22]
The typical bottom-up strategies to fab-
ricate carbon-supported ADMCs usually
involve an annealing process after the
[23]
wet-chemistry pre-treatment,
or the
direct pyrolysis of metal-containing pre-
[
24]
cursors, such as organometallics, poly-
mers,[25] and especially metal-organic frameworks (MOFs).
The top-down strategies featured with thermal atom trapping
by the substrate have also been adopted in the fabrication of
carbon-supported ADMCs, in which the metal nanoparticles or
bulk precursors can be directly transformed into atomically dis-
[26,27]
1
. Introduction
Atomically dispersed metal catalysts (ADMCs) supported by
carbon have attracted increasing attention.[
1–9]
The maximum
metal-atom efficiency of ADMCs combined with the specific
[
28–30]
persed metal sites under the calcination treatment.
Clearly, the calcination treatment is extensively used in the
fabrication of carbon-supported ADMCs, due to its multiple
effects for carbonization of the organics, introduction of
the defects, and diffusion of the metal atoms. However, the
furnace annealing process usually takes a long time, con-
sumes high energy, and requires large amounts of expensive
inert gas, which hampers its practical application. Therefore, a
rapid process favoring low cost and mass production of carbon-
supported ADMCs is highly desired, thereby meeting the
industrial demands.
Dr. J. Du, Prof. Z.-Q. Yu
College of Chemistry and Environmental Engineering
Shenzhen University
Shenzhen 518060, P. R. China
E-mail: zqyu@szu.edu.cn
Dr. J. Du, Dr. G. Wu, Dr. K. Liang, Dr. J. Yang, Dr. Y. Lin,
Prof. Y. Wu, Prof. X. Hong
Department of Applied Chemistry
Hefei National Laboratory for Physical Sciences at the Microscale
Collaborative Innovation Center of Chemistry for Energy Materials
(
iChEM)
University of Science and Technology of China
Hefei 230026, P. R. China
High voltage can rapidly elevate the reaction temperature
via electrical Joule heating, and quench the system at a high
cooling rate upon cut-off, leading to the graphitization of car-
E-mail: yuenwu@ustc.edu.cn; hongxun@ustc.edu.cn
Dr. J. Yang
Institutes of Physical Science and Information Technology
Key Laboratory of Structure and Functional Regulation
of Hybrid Materials
Ministry of Education
Anhui Graphene Engineering Laboratory
Anhui University
Hefei 230601, P. R. China
Y. Zhang, Prof. X. Zheng
National Synchrotron Radiation Laboratory (NSRL)
University of Science and Technology of China
Hefei 230029, P. R. China
[
31]
bonaceous materials in a short time. Although it may also
induce severe agglomeration of metal atoms due to the mobility
and metallization of metal ions in the electric field, the high
voltage still demonstrates great potential for the rapid produc-
tion of carbon-supported catalysts. Herein, we report the rapid
fabrication of carbon-supported ADMCs using high voltage for
the carbonization of metal-containing precursors.
We describe an electric flash strategy through rapidly carbon-
izing MOFs by either continuous plasma arc (PA method) or
intermittent spark pulse (SP method) under the high voltage.
Instead of excessive consumption of high-cost gas and elec-
tricity with expensive furnaces, the electric flash strategy is low
cost due to the rapid process and the cheap low-power facility.
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/smll.202007264.
DOI: 10.1002/smll.202007264
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Figure 1. Schematic illustration of the electric flash setups and their applications in synthesis of Co ADMCs. A) Plasma arc formed by a 20 kV DC supply
module. B) Spark pulse generated by a multistage Marx circuit. C) The plasma arc method to obtain Co/N-C(PA) nanosheets (top) and the spark pulse
method to construct Co/N-C(SP) hollow nanospheres (bottom), together with a photograph showing the gram-scale production of catalysts (right).
Besides, fixation of metal ions in the structure of MOFs as
nodes could inhibit their mobility and metallization upon high
voltage. The sample is loosely loaded into a quartz tube and
the system pressure is adjusted to mild vacuum (≈0.02 bar)
to facilitate outgassing. The continuous plasma arc (PA) can
be readily produced by a high-voltage direct-current (HVDC)
supply module (Figure 1A; Figure S1A, Supporting Informa-
tion), which could fabricate Co/N-C(PA) ultrathin nanosheets
in one minute (Figure 1C, top). By introducing a multistage
Marx generator into the circuit, the intermittent spark pulse
Co/N-C(PA) is readily accessible from ZnCo-ZIF (Figure S3,
Supporting Information) after a rapid carbonization process
under PA. The scanning electron microscopy (SEM) and trans-
mission electron microscopy (TEM) of Co/N-C(PA) clearly show
an ultrathin sheet-like morphology with lateral size extending up
to a few micrometers (Figure 2A; Figure S4, Supporting Informa-
tion). Atomic force microscopy (AFM) verifies the ultrathin char-
acteristic, showing a thickness of ≈8.3 nm (Figure S5, Supporting
Information). High-angle annular dark-field scanning transmis-
sion electron microscopy (HAADF-STEM) unambiguously dem-
onstrates the hole defects in the nanosheets (Figure 2B).
(SP) could be generated instead (Figure 1B; Figure S1B, Sup-
porting Information), which could construct Co/N-C(SP)
hollow nanospheres from the rhombic dodecahedral ZnCo-ZIF
crystals with a blasting effect (Figure 1C, bottom). Moreover,
Co/N-C(SP) exhibits high performance in the oxygen reduc-
tion reaction (ORR) and Zn-air battery test. Importantly, gram-
scale of catalysts could be easily harvested in 1 h, making the
electrical flash strategy suitable for commercial production of
carbon-supported ADMCs (Figure 1C, right).
As revealed by the corresponding energy-dispersive X-ray
(EDX) mapping analysis (Figure 2C), Co, C, and N atoms are
uniformly distributed throughout the ultrathin nanosheets of
Co/N-C(PA). Selected area electron diffraction (SAED) pattern
exhibits full halo rings without any diffraction spots (Figure 2D).
It implies the poor crystallinity of the N-doped carbon material
and excludes the existence of Co nanoparticles. This result is
in agreement with the X-ray powder diffraction (XRD) analysis
(
Figure 2G). In the Raman spectrum of Co/N-C(PA), the reflec-
−
1
tion at 1340 cm is ascribed to the D-band of the disordered
carbon, while the peak at 1585 cm is recognized as the G-band
of the ordered graphitic carbon (Figure 2H). The higher ratio
−
1
2
. Results and Discussion
[
32]
In the PA method, Co nanoparticles on nitrogen-doped carbon
denoted as np-Co/N-C, Figure S2, Supporting Information) can be
of D-to-G band intensity (I /I = 0.93) than that of np-Co/N-
D
G
(
C (I /I = 0.90) indicates that more structural defects are con-
D G
easily fabricated from precursor Co-ZIF-67. By partially replacing
Co with Zn in the precursor to extend the distance between Co
atoms, and using NaF as a salt template to prevent the agglom-
eration and control the morphology, the target ADMC material
structed in Co/N-C(PA), which is more favorable to stabilize
monodispersed metal sites.
The existing form of Co species in Co/N-C(PA) was
elucidated by aberration-corrected (AC) HAADF-STEM
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Figure 2. Morphological and structural characterizations of Co/N-C(PA) nanosheets. A) TEM and B) HAADF-STEM images. C) EDX elemental map-
ping shows the distribution of Co (violet), C (red), and N (green). D) SAED pattern. E,F) AC-HAADF-STEM and magnified images show the atomically
dispersed Co. G) XRD patterns, H) Raman spectra, and I) Co L-edge NEXAFS spectra of Co/N-C(PA) and np-Co/N-C.
characterization with sub-angstrom resolution (Figure 2E,F).
The isolated bright dots could be assigned to the heavier Co
atoms in comparison with C and N, suggesting the Co species
in Co/N-C(PA) are atomically dispersed, rather than aggregated
as observed in np-Co/N-C (Figure S2, Supporting Information).
To clarify the electronic structure of the isolated Co atoms, the
near-edge X-ray absorption fine structure (NEXAFS) analysis
was conducted (Figure 2I). The Co L-edge spectrum of Co/N-
C(PA) illustrates two peaks at 779.1 and 794.5 eV, corresponding
to the L and L edges of electronic excitation from 2p and
shells are clearly manifested by SEM (Figure S6, Supporting
Information). The driving force to induce the hollow-sphere
nanostructures is considered as the blasting effect of the vola-
tile components (like Zn atoms) triggered by the transient high
temperature upon SP. In addition, the pore sizes distribution
indicates that the mesopores in Co/N-C(SP) are not only cen-
tered at 3.9 nm, like those in Co/N-C(PA) and np-Co/N-C, but
also highly distributed from 5 to 50 nm (Figure S7, Supporting
Information). The hierarchical mesoporous structure, together
with the hollow cavities and porous shells, endows Co/N-C(SP)
with a high specific surface area (Figure S8, Supporting Infor-
mation) and numerous channels for convenient mass transfer
in electrocatalytic reactions. The elemental mapping of Co/N-
C(SP) reveals the homogeneous distributions of the Co and
N elements in the carbon matrix (Figure 3C; Figure S9, Sup-
porting Information). The defective nature of the carbon
support could be obtained and well maintained by limiting the
processing time of SP (Figure 3E), which is essential to avoid the
aggregation of Co species (Figure S10, Supporting Information).
AC-HAADF-STEM demonstrates a higher density of atomi-
cally dispersed Co element in Co/N-C(SP) as compared with
3
2
33]
3/2
[
2
p1/2 orbitals. A positive shift (≈1.1 eV) of Co L-edge peaks in
comparison with np-Co/N-C was found, implying the isolated
Co atoms in Co/N-C(PA) are positively charged, which is incon-
sistent with the Co 2p X-ray photoelectron spectroscopy (XPS)
result (Figure S14, Supporting Information).
Encouraged by the above results under continuous high
voltage, we further investigated the effect of an intermittent
discharge in the formation of atomically dispersed metal sites.
In the assistance of Marx generator (≈4 SP per second), the
resultant Co/N-C(SP) from ZnCo-ZIF unexpectedly exhibits a
hollow spherical morphology (Figure 3A,B). The porous thin
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Figure 3. Morphological and structural characterizations of Co/N-C(SP) hollow nanospheres. A) TEM and B) HAADF-STEM images. C) EDX mappings
showing the distribution of Co, N, and C. D) AC-HAADF-STEM image demonstrating the atomically dispersed Co. Inset: SAED pattern. E) Raman
spectra of Co/N-C(SP) (1 min) and samples subjected to spark pulse for 30 s and 10 min, respectively. F) High-resolution XPS for N 1s. G) Co K-edge
NEXAFS spectra and H) EXAFS spectra for Co/N-C(SP) and references. I) EXAFS fitting curve in the R space.
that in Co/N-C(PA) (Figure 3D). The corresponding Co content
of Co/N-C(SP) measured by inductively coupled plasma optical
emission spectroscopy (ICP-OES) is about 3.5 wt%, higher than
that of Co/N-C(PA) (≈0.7 wt%), and close to the results of EDX
and XPS analyses (Figures S11, S12, and Table S1, Supporting
Information). The high-resolution XPS N 1s spectrum of Co/N-
C(SP) can be well deconvoluted into three main regions asso-
ciated with pyridinic N (398.4 eV), pyrrolic N (400.3 eV), and
graphitic N (401.1 eV) (Figure 3F).[ The pyrrolic N species
could serve as the major anchors for the stabilization of the iso-
lated Co atoms, as evidenced by the relative lack of pyrrolic N
species in np-Co/N-C and Co/N-C(PA) (Figure S13, Supporting
Information).[ The Co 2p region of Co/N-C(SP) exhibits
the Co 2p3/2 region at a binding energy of 780.0 eV, which is
more positive than that of np-Co/N-C (Figure S14, Supporting
Information). It indicates the oxidation state of Co species in
Co/N-C(SP) is between those of metallic Co (778.2 eV) and
further clarified by the extended X-ray absorption fine structure
(EXAFS) measurement. In the Fourier transform of EXAFS for
Co/N-C(SP), only one remarkable peak (1.35 Å) corresponding
to the Co-N coordination is observed, and the absence of Co-Co
scattering paths unambiguously confirms the atomic disper-
sion of Co atoms (Figure 3H). The fitting result indicates that
each Co atom in Co/N-C(SP) is coordinated with nitrogen in
the configuration of Co-N (Figure 3I; Figure S15 and Table S2,
4
34]
Supporting Information).
The ORR performances of the synthesized Co catalysts were
investigated by linear sweep voltammetry (LSV) in an O -sat-
2
urated 0.1 ꢀ KOH aqueous solution. As shown in Figure 4A,
Co/N-C(SP) exhibits the highest ORR activity with a half-
35]
wave potential (E1/2) of 0.887 V and an onset potential (Eonset
)
of 0.998 V, surpassing those of Co/N-C(PA) (E1/2 = 0.845 V,
Eonset = 0.950 V), np-Co/N-C (E1/2 = 0.819 V, Eonset = 0.908 V),
and commercial Pt/C catalyst (E1/2 = 0.840 V, Eonset = 0.994 V)
(Figure 4B;Table S3, Supporting Information). Besides, Co/N-
C(SP) is comparable to the excellent nonprecious catalysts for
ORR in alkaline media (Table S4, Supporting Information). At
a potential of 0.88 V, the Co/N-C(SP) catalyst exhibits a much
3
+
[36,37]
Co (781.1 eV).
This result is consistent with the NEXAFS
analysis, in which the Co K-edge absorption energy for Co/N-
C(SP) is between Co foil and Co O (Figure 3G). The local
3
4
coordination environment of Co atoms in Co/N-C(SP) was
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−
2
higher kinetic current density (J ) (7.120 mA cm ) than Co/N-
was detected for Co/N-C(SP) upon the treatment with 1.0 ꢀ
methanol (Figure S18, Supporting Information). The stability of
Co/N-C(SP) could be ascribed to the robustness of the atomi-
cally dispersed Co sites, as demonstrated by the unchanged
XRD pattern of Co/N-C(SP) after the ORR test (Figure S19,
Supporting Information). To demonstrate the feasibility in real
energy devices, Co/N-C(SP) was utilized as the cathode mate-
K
−2
−2
C(PA) (1.687 mA cm ), np-Co/N-C (0.473 mA cm ), and Pt/C
1.893 mA cm ) (Figure 4B; Table S3, Supporting Informa-
tion). Additionally, the highest ORR kinetic process of Co/N-
−
2
(
−
1
C(SP) was confirmed by a smaller Tafel slope (63 mV dec )
−1
in comparison with Co/N-C(PA) (77 mV dec ), np-Co/N-C
−
1
−1
(
67 mV dec ), and Pt/C (89 mV dec ) (Figure S16, Supporting
Information). The high electrocatalytic performance of Co/N-
[
39,40]
rial for the Zn-air battery test.
As illustrated in Figure 4E,
C(SP) could be attributed to the active Co-N centers, the porous
structure, and the defective carbon support.
the assembled Zn-air battery shows maximum power density
4
[
38]
−2
of 208 mW cm at 0.65 V, which is superior to the Zn-air bat-
−
2
According to the Koutecký–Levich (K–L) analysis, the elec-
tron transfer number (n) during ORR over Co/N-C(SP) was
estimated to be 4 (Figure S17, Supporting Information), which
was verified by the rotating ring-disk electrode (RRDE) meas-
urement (Figure 4C). The stability of Co/N-C(SP) was evalu-
ated by the accelerated durability test. As shown in Figure 4D,
after 10 000 continuous cycles, only a 5 mV negative shift of E1/2
was observed. Besides, no apparent decay in current density
teries utilizing commercial Pt/C (185 mW cm ) and compa-
rable to the reported outstanding cathode catalysts (Table S5,
Supporting Information). At the discharge current density of
−
2
30 mA cm , the specific capacity of Co/N-C(SP)-based Zn-air
−
1
battery was calculated to be 716 mA h g (Figure 4F). In addi-
tion, two series-connected Zn-air batteries with Co/N-C(SP) as
cathode could power a light-emitting diode (2.2 V, Figure S20,
Supporting Information). Due to the rapid fabrication process,
Figure 4. Evaluation of ORR electrocatalysis and Zn-air battery performances. A) ORR polarization curves. B) Comparisons of J and E for different
K
1/2
catalysts at 1600 r.p.m. C) H O yield and electron transfer number obtained from RRDE measurements. D) Stability test. E) Discharge polarization
2
2
curves and corresponding power density plots of Zn-air batteries. F) Long-term galvanostatic discharge curves of Zn-air batteries. The specific capacities
−
1
−1
(
716 mA h g for Co/N-C(SP) and 648 mA h g for Pt/C) were normalized to the mass of consumed Zn anodes, respectively.
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it is anticipated that the industrial production of carbon-
supported ADMCs under high voltage could be realized in
a continuous streamlined process (Figure S21, Supporting
Information).
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2
In summary, we developed an electric flash strategy for the
rapid synthesis of carbon-supported ADMCs by employing
either continuous high voltage (PA method) or intermittent
high voltage (SP method) to carbonize the MOFs precursors.
Atomically dispersed Co on nitrogen-doped carbon with con-
trollable morphologies (i.e., 2D ultrathin nanosheets and 3D
hollow nanospheres) can be readily accessible. It is proposed
that the blasting effect of unstable components in the precursor
under the transient high temperature is the driving force to
construct the hollow spherical morphology. The resultant
Co/N-C(SP) catalyst can endow superior ORR activity and high
performance in the assembled Zn-air battery. Featured with
rapid synthesis, low cost, and morphological/structural control,
the electric flash strategy under high voltage opens up a new
way to prepare ADMCs and other carbon-based materials.
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Keywords
carbon, cobalt, electrocatalysis, high voltage, oxygen reduction,
supported catalysts
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Received: November 18, 2020
Revised: December 11, 2020
Published online: January 20, 2021
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