SS symmetry

Article
Exploiting Asymmetric Co States in a Co-N-C Catalyst for an
Efficient Oxygen Reduction Reaction
Qing Liang 1,2,3 , Fanling Meng 1,2,3 , Kexin Song 1,2,3 , Dong Wang 1,2,3 and Wei Zhang 1,2,3,4, *

1 School of Materials Science & Engineering, Jilin University, Changchun 130012, China
2 Key Laboratory of Automobile Materials MOE, Jilin University, Changchun 130012, China
3 Jilin Provincial International Cooperation Key Laboratory of High-Efficiency Clean Energy Materials,
Jilin University, Changchun 130012, China
4 Electron Microscopy Center, Jilin University, Changchun 130012, China
* Correspondence: [email protected]

Abstract: Co-NC catalysts have attracted extensive concerns derived from their high oxygen reduction
reaction (ORR) activity, but the catalytic mechanism of Co species with different forms remains
controversial. Herein, we prepare Co-NC catalysts with a cobalt nanoparticle-supported and nitrogen-
doped carbon structure using the ZIF-67 precursor, in which the Co states in the catalyst present
an asymmetric state of an exposed carbon coating (Asy-Co) and a symmetric state of buried carbon
(Sy-Co). The acid etching process removed the exposed asymmetric cobalt nanoparticles on the
surface. The specific role of cobalt nanoparticles with different forms in the Co-NC catalysts was
comprehensively clarified through analyzing the chemical coordination environment by XPS and
XAFS. The half-wave potential (E1/2 = 0.83 V) and onset potential (Eon = 1.04 V) of the Co-NC
catalysts obtained after acid etching decreased significantly. Thus, the cobalt species removed by
the acid etching process offered confirmed contributions to the catalytic activity. This work puts
forward an important reference for the design and exploitation of non-noble metal catalysts using
symmetry-derived motifs.
Citation: Liang, Q.; Meng, F.; Song,
K.; Wang, D.; Zhang, W. Exploiting Keywords: Cobalt; Catalyst; ORR; Co-N-C
Asymmetric Co States in a Co-N-C
Catalyst for an Efficient Oxygen
Reduction Reaction. Symmetry 2022,
14, 2496. https://doi.org/10.3390/
1. Introduction
sym14122496
Owing to their highly efficient energy conversion and virtually no emissions, fuel cells
Academic Editor: Marcelo Preite and zinc batteries have received intensive research and development attention [1]. The
Received: 8 October 2022 cathodic occurrence of an oxygen reduction reaction (ORR) exhibits slow reaction kinetics,
Accepted: 19 November 2022 which limits the dynamic of the catalytic reaction. Noble metal catalysts including Pt-based
Published: 25 November 2022 metals hold excellent ORR activity, but their disadvantages such as a high cost, poor stability
and poisoning seriously hinder their large-scale application in practical production [2–5].
Publisher’s Note: MDPI stays neutral
In recent years, transition metals (i.e., Co) have developed a solid research foundation in
with regard to jurisdictional claims in
ORRs attributed to their low cost, high catalytic activity and high stability, being one of the
published maps and institutional affil-
promising substitutes to noble metal catalysts [6–8].
iations.
Cobalt (Co) is considered to be a promising transition metal in ORR due to its highly
delocalized d-band electron configuration (3d7 4s2 ). In the development from metal macro-
cyclic compounds to transition metal carbon-based catalysts, the catalytic activity and
Copyright: © 2022 by the authors. stability of Co-NC have been continuously improved through considerable modification of
Licensee MDPI, Basel, Switzerland. the preparation methods. For Co-NC catalysts, metallic cobalt species exist in two forms:
This article is an open access article exposed Co on the surface and encapsulated Co within the carbon layers. It has been
distributed under the terms and recognized that Co-NPs encased in carbon layers can effectively activate the inert electronic
conditions of the Creative Commons structure of carbon layers through the electron shuttle effect and act as the active sites of
Attribution (CC BY) license (https:// reaction. In most preparation methods for Co-NC, the Co-NPs exposed on the surface are
creativecommons.org/licenses/by/ usually removed by pickling [9,10]. It was found that bare Co-NPs may significantly reduce
4.0/).

Symmetry 2022, 14, 2496. https://doi.org/10.3390/sym14122496 https://www.mdpi.com/journal/symmetry

Symmetry 2022, 14, 2496 2 of 7

the utilization of a metal’s active components and are not conducive to the enhanced cat-
alytic activity [11]. In fact, whether exposed Co-NPs are profitable to the enhanced catalytic
activity still needs to be clarified. Metal–organic framework (MOF)-derived nitrogen-doped
carbon composites have recently been widely taken as ORR catalysts [8,12–16]. The unique
structural advantages are conducive to supporting metal sites with different forms on a
support, which can be used as model catalysts to pinpoint the mechanism of different metal
components in a catalytic system.
Herein, we use ZIF-67 as a precursor to synthesize ZIF800H-Anneal catalysts with a
nitrogen-doped carbon skeleton structure supported by metal cobalt nanoparticles. The
pickling and secondary pyrolysis processes remove cobalt species from the catalyst surface
and further repair the damaged carbon structure. The annealing temperature plays an
important effect on determining the existence form of cobalt species, and the optimal
carbonization temperature is 800 ◦ C. Various experimental characterization and electro-
chemical tests have verified the mechanism of asymmetric and symmetric cobalt states
in the catalyst on the catalytic activity. It provides new ideas for and insights into the
development and exploitation of catalysts with high activity and stability.

2. Results and Discussion

Typical ZIF-67 was prepared and annealed at different temperatures. The preparation
methods are exhibited in Supporting Information. As shown in Figure S1, ZIF-67 precursor
was annealed at 800 ◦ C in an Ar atmosphere (ZIF800), etched by acid and annealed again to
eliminate the surface functional groups introduced by the acid etching. As shown in Figure S2a,
the ZIF-67 precursor exhibited a rhombic dodecahedron structure. After high-temperature
annealing, the catalyst surface shrank, and a large number of nanoparticles was generated,
as shown in Figure S2b–e. With the increased annealing temperature, the grain size of the
nanoparticles on the surface gradually increased and agglomerated, and the degree of skeleton
collapse became obvious gradually. The cobalt nanoparticles seriously reunited at higher
temperature (1000 ◦ C), and the skeleton broke down (Figure S2e).
Transmission electron microscopy (TEM) was utilized to further analyze the mi-
crostructure and phase information of the catalysts. Figure 1a,d shows typical low-
magnification TEM images of the ZIF800 and ZIF800H-Anneal. The grain size of the
ZIF800H-Anneal was smaller than that of the ZIF800, which also confirmed the porous
structure of the ZIF800H-Anneal after annealing. Specifically, cobalt species can be divided
into larger-sized asymmetric (exposed and buried by carbon) Co (Asy-Co) species (~40 nm)
and smaller-sized symmetric (fully buried by carbon) Co (Sy-Co) species (~15 nm). These
graphitic layer-coated Sy-Co nanoparticles are inaccessible to hydrochloric acid because
they are still encapsulated completely in the graphitized carbon shell. In addition, high-
resolution TEM (HRTEM) images were used to characterize the phase structures for the
cobalt species (Figure 1b for the ZIF800 and Figure 1e for the ZIF800H-Anneal). Figure 1b
shows that the Sy-Co nanoparticles by carbon coating had lattice stripes corresponding to
the Co (111) plane and an interplanar spacing of 0.211 nm, which is well matched to the
(111) plane of Co (PDF #15-0806) in the Fm-3m space group [17]. As shown in Figure 1c,
the EDS spectrum demonstrated a uniform distribution of Co, N and C. After acid etching
and annealing, the crystal plane spacing of the ZIF800H-Anneal was reduced. For example,
the crystal plane spacing of Co (111) reduced from 0.211 to 0.204 nm. It might be due to
the oxidation of a small number of Asy-Co particles near the surface, which were exposed
to oxygen and partly oxidized into cobalt oxide during the first annealing. However, the
acid etched the exposed Asy-Co species and cobalt oxide species, but the acid could not
contact the carbon-coated Sy-Co species. Figure 1f shows the EDS elemental mapping of
the ZIF800H-Anneal, and Co, N and C were distributed uniformly.
Symmetry2022,
Symmetry 2022,14,
14,2496
x FOR PEER REVIEW 33 of
of 77

Figure
Figure 1. Morphology and
1. Morphology and structural
structural characterization
characterization ofof different
different treatments
treatments of
of ZIF800
ZIF800 and
and
ZIF800H − Anneal. TEM images of (a) ZIF800 and (d) ZIF800H − Anneal.
ZIF800H−Anneal. TEM images of (a) ZIF800 and (d) ZIF800H−Anneal. HRTEM images HRTEM images of
of (b)
ZIF800 and (e) ZIF800H−Anneal. The inset is the corresponding SAED pattern. EDS elemental
(b) ZIF800 and (e) ZIF800H−Anneal. The inset is the corresponding SAED pattern. EDS elemental maps
of (c) ZIF800
maps and (f)
of (c) ZIF800 andZIF800H−Anneal.
(f) ZIF800H−Anneal.

FigureS2f
Figure S2fshows
showsSEM SEMimage
imageofofthe the ZIF800H-Anneal.
ZIF800H-Anneal. AA large
large number
number of Asy-Co
of Asy-Co spe-
species
was
cies removed
was removed from from
the ZIF800, leaving
the ZIF800, only aonly
leaving small amount
a small of Sy-Co
amount species
of Sy-Co embedded
species embed- in
the
dedgraphitic layers after
in the graphitic layersacid treatment.
after The morphology
acid treatment. of the ZIF800H-Anneal
The morphology samples
of the ZIF800H-Anneal
obtained by a second
samples obtained by aannealing treatmenttreatment
second annealing remainedremained
the samethe as that
same before
as thatthebefore
pickling
the
treatment, which proved
pickling treatment, which that the second
proved that theannealing
second treatment
annealing was conducive
treatment was to the further
conducive to
repair of damaged carbon structures (Figure S2c). The phase structures
the further repair of damaged carbon structures (Figure S2c). The phase structures for the for the samples
was investigated
samples by the X-ray
was investigated by the diffraction (XRD) measurements.
X-ray diffraction (XRD) measurements. The XRD Thepatterns
XRD pat- of
the ZIF700, ZIF800, ZIF800H-Anneal, ZIF900 and ZIF1000 in Figure
terns of the ZIF700, ZIF800, ZIF800H-Anneal, ZIF900 and ZIF1000 in Figure S3 exhibited S3 exhibited obvious
diffraction peaks atpeaks
obvious diffraction 44.5◦ ,at51.8 ◦ and 76.1◦ , which could be ascribed to the 111, 200 and
44.5°, 51.8° and 76.1°, which could be ascribed to the 111, 200
220
andplanes of Co of
220 planes (PDF#15-0806),
Co (PDF#15-0806), respectively. In particular,
respectively. the diffraction
In particular, peak of graphite
the diffraction peak of
(PDF#75-1621) appeared in the ZIF800H-Anneal. This may be
graphite (PDF#75-1621) appeared in the ZIF800H-Anneal. This may be due to functionaldue to functional groups
produced
groups produced by etching carbon surface during the secondary annealing process,to
by etching carbon surface during the secondary annealing process, leading the
lead-
transition from amorphous carbon to graphite, which was consistent
ing to the transition from amorphous carbon to graphite, which was consistent with Fig- with Figure 1e. EDS
analysis
ure 1e. EDSin SEM (Figures
analysis S4 and
in SEM S5, Tables
(Figures S4 S1
andand
S5,S2) of theS1ZIF800
Tables and S2)andofZIF800H-Anneal
the ZIF800 and
showed that the content of Co species in the ZIF800 decreased
ZIF800H-Anneal showed that the content of Co species in the ZIF800 decreased from 22.71 wt.% tofrom6.96 22.71
wt.%
in the to
wt.% ZIF800H-Anneal.
6.96 wt.% in the EDS analysis in TEM
ZIF800H-Anneal. EDS(Figures
analysisS6inandTEM S7(Figures
and Tables S3 and
S6 and S4)
S7 and
showed that the content of Co species in the ZIF800 decreased from
Tables S3 and S4) showed that the content of Co species in the ZIF800 decreased from 34.934.9 wt.% to 5.5 wt.%
in the to
wt.% ZIF800H-Anneal.
5.5 wt.% in the ZIF800H-Anneal.
The coordination environment of the cobalt species of the ZIF800 and ZIF800H-Anneal
The coordination environment of the cobalt species of the ZIF800 and ZIF800H-An-
were further investigated using the X-ray absorption near edge structure (XANES) and
neal were further investigated using the X-ray absorption near edge structure (XANES)
extended X-ray absorption fine structure (EXAFS) techniques [18]. Figure 2a exhibited that
and extended X-ray absorption fine structure (EXAFS) techniques [18]. Figure 2a exhibited
Co species existed in the oxidation state. After pickling and the second annealing treatment,
that Co species existed in the oxidation state. After pickling and the second annealing
the near-edge absorption position shifted to the right, which proved that the valence of
treatment, the near-edge absorption position shifted to the right, which proved that the
the Co species had been improved. As shown in Figure 2b,c, the Co-Co spacing became
valence of the Co species had been improved. As shown in Figure 2b,c, the Co-Co spacing
smaller, which was consistent with the HRTEM results. It might be due to the removal of
became smaller, which was consistent with the HRTEM results. It might be due to the
cobalt species on the surface after acid etching. In the annealing process, the formation of
removal of cobalt species on the surface after acid etching. In the annealing process, the
CNTs produces compression stress, which results in a decrease in the Co-Co spacing [19].
formation of CNTs produces compression stress, which results in a decrease in the Co-Co
spacing [19].
Symmetry 2022, 14, 2496 4 of 7
Symmetry 2022, 14, x FOR PEER REVIEW 4 of 7

Figure2.2.Structural
Figure Structuraland
and compositional
compositional characterization
characterization of of ZIF800
ZIF800 andand ZIF800H−Anneal.
ZIF800H −Anneal. X−X−ray
ray
fine structure analysis of (a) XANES spectrum, (b) EXAFS spectrum and (c) WT−EXAFS spectrum
fine structure analysis of (a) XANES spectrum, (b) EXAFS spectrum and (c) WT−EXAFS spectrum
for Co K edge. High−resolution XPS spectra for (d) Co 2p, (e) N 1s and (f) C 1s for ZIF−800 and (g)
for Co K edge. High−resolution XPS spectra for (d) Co 2p, (e) N 1s and (f) C 1s for ZIF−800 and
Co 2p, (h) N 1s and (i) C 1s for ZIF800H−Anneal.
(g) Co 2p, (h) N 1s and (i) C 1s for ZIF800H−Anneal.
X-ray photoelectron spectroscopy (XPS) was used to characterize the surface chemi-
X-ray photoelectron spectroscopy (XPS) was used to characterize the surface chemical
cal state of C, N and Co. The Co 2p spectra in Figure 2d,g can be divided into Co 2p 1/2, Co
state of C, N and Co. The Co 2p spectra in Figure 2d,g can be divided into Co 2p1/2 , Co
2p2p andthethecorresponding
correspondingsatellite
satellite peaks. It provedthatthat a certain oxidation
statestate of me-
3/2
3/2 and peaks. It proved a certain oxidation of metallic
tallic cobalt existed in the catalyst. Compared with the ZIF800,
cobalt existed in the catalyst. Compared with the ZIF800, a chemical shift occurred in the a chemical shift occurred
in the ZIF800H-Anneal
ZIF800H-Anneal after treatment,
after treatment, indicatingindicating
that the Co that the Co
valence valence
state state After
increased. increased.
etching,Af-
ter etching, the content of Co was reduced from 1.1% to 0.5% (Figure
the content of Co was reduced from 1.1% to 0.5% (Figure S8, Tables S5 and S6). It meant that S8, Tables S5 and
S6). It removed
etching meant that theetching
exposedremoved
Co-NPs from the exposed Co-NPs
the surface. from thewere
The catalysts surface.
found The
to catalysts
contain
were found to contain the following species in the N 1s spectra:
the following species in the N 1s spectra: pyridine N (398.4 eV), Co-N (399.6 eV), pyrrolicpyridine N (398.4 eV), Co-
N (400.2 eV), graphitic N (401.2 eV) and oxide N (403.5 eV) [20], as shown in Figure[20],
N (399.6 eV), pyrrolic N (400.2 eV), graphitic N (401.2 eV) and oxide N (403.5 eV) 2e,h.as
shown in Figure 2e,h. After pickling and secondary pyrolysis,
After pickling and secondary pyrolysis, the content of the Co-N species increased, while the content of the Co-N
species
the contentincreased, while theNcontent
of the pyridine of the pyridine
was significantly N was significantly
decreased. It might be decreased.
because byItusingmight
be because by using XPS spectroscopy, one can detect the species
XPS spectroscopy, one can detect the species on the catalyst’s surface. The C 1s spectrum on the catalyst’s surface.
inThe
FigureC 1s2f,i
spectrum in Figure
also confirmed the2f,i also confirmed
existence the existence of four
of four carbon-containing carbon-containing
species such as C=C
species
(284.7 eV),such
C-C as C=CeV),
(285.2 (284.7
C-OeV),
(285.8C-CeV)(285.2
and C=OeV), (287.5
C-O (285.8
eV) ineV) the and C=O[9,21,22].
catalyst (287.5 eV) Theinspthe
2

Ccatalyst [9,21,22]. The spincreased

of the ZIF800H-Anneal 2 C of theafterZIF800H-Anneal
acid etching and increased
annealing,afterwhich
acid etching
may be and due toan-
nealing, which may be due to the fact that the second annealing
the fact that the second annealing increased the graphitization degree of the catalysts, thusincreased the graphitiza-
tion degree
promoting theofefficient
the catalysts,
electronthus promoting
transfer the efficient
in the catalytic electron transfer in the catalytic
process.
process.
To evaluate the ORR performance, linear sweep voltammetry (LSV) experiments were
conducted To evaluate
in a 0.1 the
M KOH ORR aqueous
performance,solutionlinear
at 25 ◦ C. The
sweep voltammetry
ORR activity (LSV)
of theexperiments
catalysts
were conducted
obtained at differentin aannealing
0.1 M KOH aqueous solution
temperatures at 25 ◦°C.
(700–1000 C) The
wasORR activity
analyzed of the cata-
in Figure 3a,
lysts obtained
which was completedat different
at 1600annealing
rpm. Ittemperatures
is obvious that (700–1000
the ZIF800 °C) was analyzed
samples in Figure
unveiled the
3a, which was completed at 1600 rpm. It is obvious that the ZIF800 samples unveiled the
Symmetry 2022, 14, x FOR PEER REVIEW 5 of 7
Symmetry 2022, 14, 2496 5 of 7

highest limiting current density of 4.28 mA cm−2, while the onset potential and half-wave
highest limiting current density −2 , while the onset potential and half-wave
potential were 1.04 V and 0.83 Vof(vs.
4.28 mA cm
RHE), respectively. With the annealing temperature
potential
increasingwerefrom1.04
600V°Candto 0.83 V (vs.
800 °C, theRHE), respectively.
ORR activity showed With the annealing
a gradual temperature
increasing trend. It
increasing
was due tofrom 600 ◦ C to 800 ◦ C,annealing
the high-temperature the ORR activity
formingshowed a gradual
more active cobaltincreasing
species. Whentrend.theIt
was due to the
temperature high-temperature
continued to increaseannealing
to 1000 °C,forming
the ORRmoreactivity
active cobalt
of the species.
catalyst When
showed thea
temperature continuedtrend.
significant downward to increase
Severeto 1000 ◦ C,
collapse of the ORR
carbonactivity
carrierofandthegreater
catalyst showed a
aggregation
significant downward trend. Severe collapse of the carbon carrier and greater
of the cobalt nanoparticles resulted in a decrease of active sites. The half-wave potential aggregation
of
of the
the cobalt nanoparticles
ZIF800H-Anneal resulted
catalyst in a decrease
obtained of active
after pickling andsites. The annealing
a second half-wavetreatment
potential
of the ZIF800H-Anneal
significantly decreased in catalyst
Figureobtained
3b, whichafter pickling
proved andsurface
that the a second annealing
cobalt speciestreatment
removed
significantly decreased
during the pickling in Figure
process 3b, which
contributed to proved that the
the catalytic surface
activity. Thecobalt
LSVspecies
curves removed
of differ-
during
ent speeds in Figure 3c proved that the catalytic reaction had first-order kineticsdifferent
the pickling process contributed to the catalytic activity. The LSV curves of related
speeds in Figureprocess.
to the diffusion 3c proved that the
Figure catalyticthe
3d showed reaction had first-order
corresponding kinetics related
Koutecky–Levich to
(K–L)
the diffusion process. Figure 3d showed the corresponding Koutecky–Levich
plots derived from the LSV curves. The results manifested that the reaction path of the (K–L) plots
derived
ZIF800 wasfrom the LSV
a direct curves. Thereaction
four-electron results manifested
path. Next, that the reaction
the durability and path of the ZIF800
resistance to poi-
was a direct four-electron reaction path. Next, the durability and resistance
soning of the catalyst were analyzed, as shown in Figure 3e,f. In the I-t stability test, it was to poisoning
of the that
found catalyst were analyzed,
the current density ofastheshown
ZIF800 inonly
Figure 3e,f. Inby
decreased the I-t stability
6.8% test,s of
after 35,000 it test-
was
found that the current density of the ZIF800 only decreased by 6.8%
ing. It proved that the catalyst exhibited good stability in an alkaline system. By TEM after 35,000 s of
testing. It proved that the catalyst exhibited good stability in an alkaline
(Figure S9), HRTEM (Figure S10) and XPS (Figure S8) analyses of the cycled catalysts, we system. By TEM
(Figure S9), HRTEM (Figure S10) and XPS (Figure S8) analyses of the cycled catalysts, we
found that the surface Asy-Co species were partially transformed into CoOOH species,
found that the surface Asy-Co species were partially transformed into CoOOH species,
which may continue to act as the reactive site to maintain catalytic activity and stability.
which may continue to act as the reactive site to maintain catalytic activity and stability.
The Sy-Co species coated with graphitic layers avoided direct contact with the external
The Sy-Co species coated with graphitic layers avoided direct contact with the external
electrolytes, thus maintaining high stability. In the I-t test, the current density did not
electrolytes, thus maintaining high stability. In the I-t test, the current density did not
change significantly after 10 mL of methanol was dropped in, indicating that the ZIF800
change significantly after 10 mL of methanol was dropped in, indicating that the ZIF800
had a good ability to resist methanol poisoning.
had a good ability to resist methanol poisoning.

Figure 3. Electrochemical oxygen reduction on ZIFs. (a) LSV curves of ZIF600, ZIF700, ZIF800,
Figure 3. Electrochemical oxygen reduction on ZIFs. (a) LSV curves of ZIF600, ZIF700, ZIF800,
ZIF900 and ZIF1000 (1600 rpm). (b) LSV curves of ZIF800 and ZIF800H−Anneal (1600 rpm). (c) LSV
ZIF900 and ZIF1000 (1600 rpm). (b) LSV curves of ZIF800 and ZIF800H−Anneal (1600 rpm). (c) LSV
curves of ZIF800 in O2−saturated 0.1 M KOH solution with different rotation rates (400-2500 rpm).
curves
(d) Koutecky–Levich −saturated
of ZIF800 in O2plots 0.1 M
of ZIF800 at KOH solution
different with different
potentials, where ωrotation rates (400-2500
is the rotation rpm).
speed. (e) I-t
(d) Koutecky–Levich plots of ZIF800 at different potentials, where ω is the rotation speed. (e) I-t
stability testing curve to evaluate the stability of ZIF−800. (f) Anti-methanol poisoning ability testing
stability testing curve to evaluate the stability of ZIF−800. (f) Anti-methanol poisoning ability testing
for ZIF−800.
for ZIF−800.
3. Conclusions
3. Conclusions
In summary, we utilized ZIF-67 as a precursor to prepare the ZIF800H-Anneal cata-
In summary, we utilized ZIF-67 as a precursor to prepare the ZIF800H-Anneal catalyst
lyst by high temperature annealing and acid etching. Electron microscopy combined with
by high temperature annealing and acid etching. Electron microscopy combined with
spectral analysis was used to analyze the catalytic effects of Co species with different
spectral analysis was used to analyze the catalytic effects of Co species with different forms
in the catalysts. As the temperature continued to rise, cobalt atoms were aggregated, and
Symmetry 2022, 14, 2496 6 of 7

the ZIF-67 structure was destroyed. Electrochemical tests proved that the Asy-Co species on
the surface removed by pickling also played a positive effect on the catalytic activity. The
ZIF structure-derived carbon support possessed a rich pore structure, which was conducive
to accommodating abundant active sites and promoting the catalytic mass transfer process.

Supplementary Materials: The following supporting information can be downloaded at

https://www.mdpi.com/article/10.3390/sym14122496/s1. Figure S1: Schematic illustration of
the typical preparation process; Figure S2: SEM images of different samples. (a) ZIF67 (b) ZIF700,
(c) ZIF800, (d) ZIF900 (e) ZIF1000 (f) ZIF800H-Anneal; Figure S3: XRD patterns of ZIF700, ZIF800,
ZIF800H-Anneal, ZIF900, and ZIF1000; Figure S4: SEM images and EDS analysis of different regions
in the ZIF800; Figure S5: SEM images and EDS analysis of different regions in the ZIF800H-Anneal;
Figure S6: EDS analysis of different regions in the ZIF800; Figure S7: EDS analysis of different regions
in the ZIF800H-Anneal; Figure S8: High-resolution XPS spectra for (a) Co 2p, (b) N 1s and (c) C 1s for
ZIF800 after the durability test; Figure S9: TEM image for ZIF800 after the durability test; Figure S10:
HRTEM image o for ZIF800 after the durability test; Table S1: Elemental contents of different regions
in the ZIF800 (the values are just for references, corresponding to Figure S4); Table S2: Elemental
contents of different regions in the ZIF800H-Anneal (the values are just for references, corresponding
to Figure S5); Table S3: Elemental contents of different regions in the ZIF800 (the values are just
for references, corresponding to Figure S6); Table S4: Elemental contents of different regions in the
ZIF800H-Anneal (the values are just for references, corresponding to Figure S7); Table S5: Element
contents of ZIF800 based on XPS results; Table S6: Element contents of ZIF800H-Anneal based on
XPS results.
Author Contributions: Conceptualization, Q.L., K.S. and W.Z.; methodology, Q.L.; formal analysis,
Q.L., K.S. and D.W.; investigation, Q.L.; resources, F.M.; writing—original draft preparation, Q.L. and
K.S.; writing—review and editing, W.Z.; supervision, W.Z. and F.M.; funding acquisition, W.Z. All
authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: We collected the X-ray absorption spectra (XAS) data at 1W2B diffraction experi-
mental station in the Beijing Synchrotron Radiation Facility (BSFR).
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Zhang, Z.H.; Liu, J.; Gu, J.J.; Su, L.; Cheng, L.F. An overview of metal oxide materials as electrocatalysts and supports for polymer
electrolyte fuel cells. Energy Environ. Sci. 2014, 7, 2535–2558. [CrossRef]
2. Lu, X.F.; Xia, B.Y.; Zang, S.Q.; Lou, X.W. Metal-Organic Frameworks Based Electrocatalysts for the Oxygen Reduction Reaction.
Angew. Chem. Int. Ed. 2020, 59, 4634–4650. [CrossRef]
3. Li, D.B.; Li, X.Y.; Chen, S.M.; Yang, H.; Wang, C.D.; Wu, C.Q.; Haleem, Y.A.; Duan, S.; Lu, J.L.; Ge, B.H.; et al. Atomically dispersed
platinum supported on curved carbon supports for efficient electrocatalytic hydrogen evolution. Nat. Energy 2019, 4, 512–518.
[CrossRef]
4. Yan, S.; Jiao, L.; He, C.; Jiang, H. Pyrolysis of ZIF-67/Graphene Composite to Co Nanoparticles Confined in N-Doped Carbon for
Efficient Electrocatalytic Oxygen Reduction. Acta Chim. Sin. 2022, 80, 1084–1090. [CrossRef]
5. Gao, J.J.; Hu, Y.X.; Wang, Y.; Lin, X.R.; Hu, K.L.; Lin, X.; Xie, G.Q.; Liu, X.J.; Reddy, K.M.; Yuan, Q.H.; et al. MOF Structure
Engineering to Synthesize Co-N-C Catalyst with Richer Accessible Active Sites for Enhanced Oxygen Reduction. Small 2021,
17, 2104684. [CrossRef] [PubMed]
6. Yang, Q.; Jia, Y.; Wei, F.F.; Zhuang, L.Z.; Yang, D.J.; Liu, J.Z.; Wang, X.; Lin, S.; Yuan, P.; Yao, X.D. Understanding the Activity of
Co-N4-xCx in Atomic Metal Catalysts for Oxygen Reduction Catalysis. Angew. Chem. Int. Ed. 2020, 59, 6122–6127. [CrossRef]
[PubMed]
7. Zhou, H.; Yang, T.; Kou, Z.K.; Shen, L.; Zhao, Y.F.; Wang, Z.Y.; Wang, X.Q.; Yang, Z.K.; Du, J.Y.; Xu, J.; et al. Negative Pressure
Pyrolysis Induced Highly Accessible Single Sites Dispersed on 3D Graphene Frameworks for Enhanced Oxygen Reduction.
Angew. Chem. Int. Ed. 2020, 59, 20465–20469. [CrossRef] [PubMed]
8. Xuan, J.-P.; Huang, N.-B.; Zhang, J.-J.; Dong, W.-J.; Yang, L.; Wang, B. Fabricating Co-N-C catalysts based on ZIF-67 for oxygen
reduction reaction in alkaline electrolyte. J. Solid State Chem. 2021, 294, 121788. [CrossRef]
9. Xia, B.Y.; Yan, Y.; Li, N.; Wu, H.B.; Lou, X.W.; Wang, X. A metal–organic framework-derived bifunctional oxygen electrocatalyst.
Nat. Energy 2016, 1, 15006. [CrossRef]
10. Liu, H.; Wang, M.Q.; Chen, Z.Y.; Chen, H.; Xu, M.W.; Bao, S.J. Design and synthesis of Co-N-C porous catalyst derived from
metal organic complexes for highly effective ORR. Dalton Trans. 2017, 46, 15646–15650. [CrossRef]
Symmetry 2022, 14, 2496 7 of 7

11. Wu, G.; More, K.L.; Johnston, C.M.; Zelenay, P. High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline,
Iron, and Cobalt. Science 2011, 332, 443–447. [CrossRef]
12. Tian, H.; Zhang, C.; Su, P.; Shen, Z.; Liu, H.; Wang, G.; Liu, S.; Liu, J. Metal-organic-framework-derived formation of Co-N-doped
carbon materials for efficient oxygen reduction reaction. J. Energy Chem. 2020, 40, 137–143. [CrossRef]
13. Suo, Y.; Zhang, Z.; Zhang, Z.; Hu, G. Cobalt and nitrogen-doped carbon with enlarged pore size derived from ZIF-67 by a
NaCl-assisted pyrolysis strategy towards oxygen reduction reaction. Ionics 2021, 27, 289–303. [CrossRef]
14. Xiong, J.; Chen, X.; Zhang, Y.; Lu, Y.; Liu, X.; Zheng, Y.; Zhang, Y.; Lin, J. Fe/Co/N-C/graphene derived from Fe/ZIF-67/graphene
oxide three dimensional frameworks as a remarkably efficient and stable catalyst for the oxygen reduction reaction. Rsc Adv.
2022, 12, 2425–2435. [CrossRef] [PubMed]
15. Giddaerappa; Manjunatha, N.; Shantharaja; Hojamberdiev, M.; Sannegowda, L.K. Tetraphenolphthalein Cobalt(II) Phthalocyanine
Polymer Modified with Multiwalled Carbon Nanotubes as an Efficient Catalyst for the Oxygen Reduction Reaction. Acs Omega
2022, 7, 14291–14304. [CrossRef]
16. Lokesh, K.S.; De Keersmaecker, M.; Adriaens, A. Self Assembled Films of Porphyrins with Amine Groups at Different Positions:
Influence of Their Orientation on the Corrosion Inhibition and the Electrocatalytic Activity. Molecules 2012, 17, 7824–7842.
[CrossRef] [PubMed]
17. He, B.; Wang, J.; Fan, Y.; Jiang, Y.; Zhai, Y.; Wang, Y.; Huang, Q.; Dang, F.; Zhang, Z.; Wang, N. Mesoporous CoO/Co-N-C
nanofibers as efficient cathode catalysts for Li-O-2 batteries. J. Mater. Chem. A 2018, 6, 19075–19084. [CrossRef]
18. Wang, X.; Li, L.; Zhang, T.; Lin, B.; Ni, J.; Au, C.T.; Jiang, L. Strong metal-support interactions of Co-based catalysts facilitated by
dopamine for highly efficient ammonia synthesis: In situ XPS and XAFS spectroscopy coupled with TPD studies. Chem. Commun.
2019, 55, 474–477. [CrossRef]
19. Zhu, Z.J.; Chen, C.M.; Cai, M.Q.; Cai, Y.; Ju, H.X.; Hu, S.W.; Zhang, M. Porous Co-N-C ORR catalysts of high performance
synthesized with ZIF-67 templates. Mater. Res. Bull. 2019, 114, 161–169. [CrossRef]
20. Li, Q.; Xu, P.; Gao, W.; Ma, S.; Zhang, G.; Cao, R.; Cho, J.; Wang, H.-L.; Wu, G. Graphene/Graphene-Tube Nanocomposites
Templated from Cage-Containing Metal-Organic Frameworks for Oxygen Reduction in Li-O-2 Batteries. Adv. Mater. 2014, 26,
1378–1386. [CrossRef]
21. Guo, X.; Qian, C.; Shi, R.; Zhang, W.; Xu, F.; Qian, S.; Zhang, J.; Yang, H.; Yuan, A.; Fan, T. Biomorphic Co Symbol of the Klingon
Empire N Symbol of the Klingon Empire C/CoOx Composite Derived from Natural Chloroplasts as Efficient Electrocatalyst for
Oxygen Reduction Reaction. Small 2019, 15, 4855. [CrossRef]
22. Liu, M.; Lin, H.; Mei, Z.; Yang, J.; Lin, J.; Liu, Y.; Pan, F. Tuning Cobalt and Nitrogen Co-Doped Carbon to Maximize Catalytic
Sites on a Superabsorbent Resin for Efficient Oxygen Reduction. Chemsuschem 2018, 11, 3631–3639. [CrossRef] [PubMed]