i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 1 0 7 0 1 e1 0 7 1 4

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Bimetallic zeolitic imidazole framework derived

Co@NC materials as oxygen reduction reaction
catalysts application for microbial fuel cells

Gongjia Lan a,c, Huayi Li b,**, Jianquan Shen a,*

a
Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Green Printing, Institute of
Chemistry, Chinese Academy of Sciences, Zhongguancun North First Street 2, Beijing 100190, PR China
b
Beijing National Laboratory of Molecular Sciences (BNLMS), Key Laboratory of Engineering Plastics, Institute of
Chemistry, Chinese Academy of Sciences, Zhongguancun North First Street 2, Beijing 100190, PR China
c
University of Chinese Academy of Sciences, Beijing 100049, PR China

highlights graphical abstract

A facile, cost-effective, Co@NC-

Co1Zn3 exhibits superior ORR per-
formance and long-term stability.

A zinc-assisted evaporated pro-
duces Co@CNTs structure, which
is the essential for the superior
ORR activity.

The maximum power density of
Co@NC-Co1Zn3-MFC is higher than
that of Pt/C-MFC.

article info abstract

Article history: Microbial fuel cells (MFCs), a promising future energy conversion technology, play a sig-
Received 6 November 2021 nificant role in the area of sustainable and renewable energy. In air-cathode MFCs, the
Received in revised form catalytic activity for oxygen reduction reaction (ORR) of cathode electrocatalyst is the key
8 December 2021 factor to the performance of MFCs. Development of efficient and economical ORR elec-
Accepted 12 December 2021 trocatalysts is an important step for the wide application of MFCs. Herein, Co wrapped
Available online 12 February 2022 carbon nanotubes (CNTs) N-doped nanoporous carbon materials (Co@NC-CoxZny) are
constructed via a facile zinc-assisted growth pyrolytic approach of bimetallic zeolitic
Keywords: imidazole frameworks (BMZIFs)-derived strategy. They are directly prepared via carbon-
Bimetallic ZIFs ization of the precursor CoxZny-BMZIFs. During the pyrolysis process, the evaporation of
Microbial fuel cells zinc plays critical role in the in-situ growth of CNTs. For instance, the optimal catalyst,
Oxygen reduction reaction Co@NC-Co1Zn3, exhibits excellent ORR performance activity and stability with on-set po-
Co wrapped carbon nanotubes tential (Eon-set) of 0.830 V (vs. RHE) and diffusion-limited current density (jL) of
Air-cathode 6.706 mA cm2, which is superior to the benchmark catalyst of commercial 20 wt% Pt/C.
Additionally, Co@NC-Co1Zn3 displays four-electron pathway, long-term stability and better

* Corresponding author.
** Corresponding author.
E-mail addresses: lihuayi@iccas.ac.cn (H. Li), jqshen@iccas.ac.cn (J. Shen).
https://doi.org/10.1016/j.ijhydene.2021.12.114
0360-3199/© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
10702 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 1 0 7 0 1 e1 0 7 1 4

resistance to methanol tolerance. The MFC with Co@NC-Co1Zn3 cathode shows a

maximum power density of 1039 mW m2, and outperforms the MFC with commercial
20 wt% Pt/C catalyst (678 mW m2). This work paved the way for exploring cost-effective,
superior performance non-precious metal-based catalysts for air-cathode MFCs.
© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

microstructure or uncontrolled agglomeration of transition

Introduction
The shortage of energy and the serious environmental pollu-
tion caused by the consumption of a large amount of fossil
energy have become a major problem facing the whole world
[1e3]. Numerous of researchers are working to find clean,
renewable energy sources, for example, solar energy [4], wind
energy [5], biomass energy [6], hydrogen energy [7], and so on.
However, lots of renewable and clean energy has disadvan-
tages, such as low utilization rate and resources waste.
Therefore, it is significant to exploit energy conversion tech-
nology that can efficiently utilize these renewable clean en-
ergy to solve the current energy shortage and environmental
pollution problems.
MFC, as an environmentlly benign and bioelectrochemical
technology, could treat the waste water as an energy substrate
and convert generate electricity simultaneously, which is
more effective than traditional batteries [8e11]. However,
there is still some distance to practical industrial application.
MFCs could be separated into single-chamber [12] and double-
chamber [13] according to their structure. Double-chamber
MFC has disadvantages of higher internal resistance and
causing secondary pollution. Single-chamber MFC has many
advantages, such as higher output power density, without
expensive proton exchange membrane and oxygen in air as
electron acceptor [14e18]. Air-cathode was the most common
used in single-chamber MFC because oxygen in the air is
attainable. The high reduction overpotential of air-cathodes
caused by ORR sluggish kinetic process is the key factor that
affects the overall performance of energy generation [19e22].
So far, Platinum (Pt) is a mostly efficient ORR catalyst [23e25].
However, the scarcity and high cost are critical obstacles for
its broad practical industrial application of Pt. Numerous of
researchers are working on developing non-precious metal
materials to substitute precious metal materials.
In recent years, transition-metal-nitrogen-carbon (TM-N-C)
material catalysts exhibit excellent performance and attract
widespread attention [26]. Dispersion of transition metal (e.g.
Mn, Fe, Co, Cu, Zr, Mo, etc.) on porous carbon material could
form higher density active sites that could promote mass
transportation, increase the electrons transmission rate, and
enhance the ORR catalytic performance. Additionally, doping
heteroatoms (e.g. B, N, P, S, etc.) is beneficial to the sorption of
oxygen molecules and O]O bond dissociation by changing the
charge density of carbon atom [27e30]. Nevertheless, the py-
rolysis of TM-N-C material catalysts could reduce the exposure
of the catalytic active sites and decrease the ORR catalytic
performance because the stacking effect generate collapse of
metal particles. To tackle these technical issues, the rational
strategy of TM-N-C catalyst materials with excellent electro-
chemical performance and well-designed system is of vital
importance.
Metal organic frameworks (MOFs) are constructed by metal
ions and organic ligands with tunable pore structure and a
relatively larger specific surface area. Therefore, MOFs are
promising as precursors and templates of high ORR catalytic
performance owing their unique nature of outstanding des-
ignability and structural diversity. Zeolitic imidazolate
frameworks (ZIFs), as a subclass of MOFs, are considered as
remarkable precursors of carbon-based ORR electrocatalysts.
ZIFs' abundant nonsaturable metal-ion active sites, uniform
open cavities and plentiful functional groups are conducive to
immobilize guest molecules and encapsulate metal center.
After the pyrolysis of ZIFs, the derived carbon-based ORR
catalyst materials possess high specific surface area, easier to
doping heteroatoms, high N content, and abundant accessible
active sites. For instance, Song et al. [28] develop a series of
bimetallic leaf structure Co-ZIF/Zn-67 template derived
Co3O4-based ORR catalysts using for air-cathode MFC. Jung
et al. [29] combined ZIF-67 with activated carbon through
ultrasonication and solution precipitation, which was used to
produce make ZIF-67U and ZIF-67H cathodes. Ren [30] started
with ZIF-67 derived electrocatalysts containing CoN co-doped
carbon materials used in air-cathode MFC. Li et al. [31] re-
ported two-dimensional structure precursor (ZIF-L@ZIF-67)
derived leaf-like CoeNeC materials used as air-cathode MFC
electrocatalysts. Ghangrekar et al. [32] used sol-gel auto
combustion method to synthesize Co0.5Zn0.5Fe2O4, which was
used as ORR catalysts for MFC cathode. Fu et al. [33] and Su
et al. [34] demonstrated CoeZn bimetallic ZIFs (BMZIFs) as
precursor to provide Co embedded carbon nanotubes
(Co@CNTs) structure materials was applied to ORR catalyst of
air-cathode Zn-air battery. The application of CoxZny-BMZIF
precursors derived ORR catalysts was application for MFC has
not been reported in the literature.
Based on the above consideration, we herein controlled the
ratio of cobalt and zinc to synthesize CoeZn bimetallic zeolitic
imidazolate frameworks (CoxZny-BMZIFs) as precursor. Cox-
Zny-BMZIFs were a highly thermally stable dodecahedral
porous materials with 2-methylimidazole as ligand coordi-
nating to metal (Co2þ or Zn2þ) ions center in a bridging mode.
Then, Co wrapped CNTs (Co@CNTs) N-doped nanoporous
carbon materials (Co@NC-CoxZny) were obtained via carbon-
ization of CoxZny-BMZIFs at 900  C. The as-prepared Co@NC-
CoxZny maintained a relative intact morphology and structure
during the pyrolysis process, which was Co@CNTs on the
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 1 0 7 0 1 e1 0 7 1 4
dodecahedral rhomb structure with a larger specific surface
area. Meanwhile, the composites associating advantages of
nanoporous carbons derived from both ZIF-67 and ZIF-8
independently, possessed of Co-Nx species, and high
graphitic carbon and highly dispersed N. These factors
contributed to remarkable ORR performance. The as-
synthesized catalysts were optimized for the air-cathode
ORR catalysts performance in MFC, which were exhibited
higher activity, better durability and better resistance to
methanol tolerance than 20 wt% Pt/C application in MFC.
Therefore, the Co@NC-Co1Zn3 exhibited prominent electro-
catalyst performance in air-cathode MFC.
Experimental
Materials synthesis
The synthesis process of electrocatalysts is illustrated in Fig. 1.
The detail procedure is depicted as follows:
(1) Preparation of CoxZny-BMZIFs
CoxZny-BMZIFs were synthesized based on previous refer-
ence with slight modification [35,36]. The molar ratio of Co:Zn
was changed by varying the initial concentration of Co2þ/Zn2þ
(Co/Zn ¼ 1:0, 3:1, 1:1, 1:3, 1:6, 0:1) for the preparation of CoxZny-
BMZIFs. Typically, 2.60 g 2-MeIM was dissolved in 40 mL
anhydrous methanol to form solution A; then a certain amount
of Co(NO3)2$6H2O or Zn(NO3)2$6H2O was dissolved in 40 mL
methanol to form solution B. Solution B added into solution A
drop by drop. The mixture was thoroughly stirred at ambient
temperature for 24 h. After the reaction was completed, the
solution was static at 35  C for 2 h. The obtained precipitates
were obtained by centrifugation (10,000 rpm, 5 min), washed
with methanol for at least 6 times, and then dried in vacuum at
60  C for about 12 h. The molar ratio of metal ion (Co2þ/Zn2þ):
2-MeIM was 1:4. The amount of Co(NO3)2$6H2O/Zn(NO3)2$6H2O
and 2-MeIM was shown in Table S1.
(2) Preparation of Co@NC-CoxZny
The CoxZny-BMZIFs were placed in porcelain boat and then
heated from 30  C to 900  C kept 2 h with a ramp heating rate
Fig. 1 e Schematic diagram for the preparation of Co@NC-CoxZny from CoxZny-BMZIFs.
10703
of 5  C min1 under flowing N2 atmosphere. After it cooled to
ambient temperature the porous materials Co@NC-CoxZny
were finally obtained.
Electrochemical measurements and methods
The electrochemical performance of as-prepared catalysts
including cyclic voltammetry (CV), linear sweep voltammetry
(LSV), and chronoamperometric response (i-t) were recorded
on a computer-controlled electrochemical workstation (CHI-
1000c, Shanghai Chenhua Instrument Co., Ltd.) combined
with a rotating disk electrode (RDE) (ATA-1B, Jiangsu Jiangfen
Electroanalytical Intrument Co., Ltd.) with a three-electrode
system in 50 mM PBS at room temperature. Using Ag/AgCl
(saturated in 3 M KCl solution) as a reference electrode, Pt wire
as a counter electrode, and glass carbon electrode (GCE, 3 mm
in diameter, geometric area: 0.07069 cm2) coated with cata-
lysts film as a working electrode to constitute a complete
three-electrode test system. AC impedance measurements
were tested in air-cathode MFCs with different catalysts to
evaluate the total resistance values. The scanning frequency
range from 0.1 to 1  106 Hz and the amplitude potential was
5 mV.
Before each experiment, the GCE was buffed by 0.05 mm
Al2O3 powder and rinsed ultrasonically by ethanol aqueous to
remove residues. The electrocatalyst dispersion ink onto the
GCE surface was obtained as follows: 4 mg of catalyst (Co@NC-
CoxZny or 20 wt% Pt/C) was dispersed in mixed solution con-
taining 125 mL ethanol, 375 mL DI water and 50 mL 5 wt% Nafion
aqueous solution via sonication (20e30 min) to generate a
homogeneous ink. Then, 4 mL of the ink was taken by the
pipette gun and uniformly dropped onto the GCE (catalyst
loading is about 411.55 mg cm2). After natural drying, a ho-
mogeneous film was formed.
All the electrochemical tests were carried out in N2- or O2-
saturated 50 mM PBS at room temperature. Before ORR tests,
the electrolyte was purged by bubbling O2 at least 30 min, and
oxygen stream flow was then kept a certain rate to avoid
disturbance from ambient atmosphere during the measure-
ment. CV tests were conducted in O2-saturated 50 mM PBS at
the potential window of 0.4 to 0.8 V (vs. Ag/AgCl) with a scan
rate of 50 mV s1, and then LSV tests were conducted in O2-
saturated 50 mM PBS at the potential window of 0.4 to 0.8 V
(vs. Ag/AgCl) with a scan rate of 5 mV s1 by different rotation
10704 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 1 0 7 0 1 e1 0 7 1 4
speeds (2500, 2000, 1600, 1200, 900, 500) rpm. After that, the
electrolyte was flowed with N2 for 15 min, and the same tests
of CV as the above steps. All potentials v.s. the Ag/AgCl
reference electrode in this study were converted to the
reversible hydrogen electrode (RHE) (Supporting Information).
To evaluate the performance of durability and resistance to
methanol tolerance for Co@NC-Co1Zn3 and 20 wt% Pt/C in O2-
saturated 50 mM PBS via i-t technique at 1600 rpm (initial
potential, 0.1 V).
Preparation of the air-cathode
The air-cathode was preparation according to our previous
report method [37,38], including a GDL, a carbon-based layer, a
current collector, and a catalytic layer (shown in Fig. 7(a)
enlarged section). One side of the carbon cloth (64 cm2) was
brushed acetylene black dispersion solution, which was sin-
tered at 340  C for 5 min with a mixed solution of 99.84 mg
acetylene black (1.56 mg cm2) and 2.396 mL 30 wt% PTFE
solution (24 mL mg 1). Additional a GDL was made by a PTFE
solution with an emulsion of 320 mL 30 wt% PTFE solution
(5 mL cm2), followed by drying ambient temperature and
sintered at 340  C for 5 min. The GDL was brushed 4 layers by
repeating the above step.
The other side of coating carbon cloth as a catalytic layer
was tailored to diameter of 3.57 cm circle (10 cm2) and loaded
with catalyst 4 mg cm2. Then, 40 mg of catalyst was
dispersed in a mixed solution system of 266.8 mL 5 wt% Nafion
(6.67 mL mg1), 133.2 mL isopropanol (3.33 mL mg1), and 33.2 mL
water (0.83 mL mg1) under ultrasonic dispersion at least
30 min. The dispersion solution of catalyst was brushed on
carbon cloth uniformly and dried at ambient atmosphere. The
air-cathode with commercial 20 wt% Pt/C was prepared under
the same operation method.
MFC configuration and operation
Before setup of single-chamber MFC, the carbon felt
(8 cm  8 cm, thickness: 5 mm) loaded with electrogenic
microorganism bacteria, which was incubated about one
month in double chamber MFC. The microorganisms bacteria
were originated from our laboratory [39e43]. The configura-
tion of single-chamber MFCs (Fig. 7) included anode (carbon
felt with loaded microorganism bacteria) and air-cathode, an
effective volume of 1000 mL. During the whole process of MFC
running, an external resistance of 1000 U was connected be-
tween air-cathode and anode to form a closed circuit. The
anodic medium was periodically refreshed with the neutral
electrolyte containing 50 mM PBS, trace mineral solution
(12.5 mL L1) when the output voltage fell below 100 mV.
All the MFCs were operated at 35  C in biochemical incu-
bator equipped with magnetic stirring apparatus in order to
ensure a uniform dispersion of anodic solution. To measure the
curves of output voltage vs. time, the data of the whole process
was monitored using the data acquisition system (BTS-
5V50MA, Neware Co. Ltd, Beijing, China) by 1 min intervals.
The power density and electrode polarization curves of
MFC were collected via changing the external resistance from
the open-circuit, followed by a range from 5 kU to 25 U. When
the resistance was steady for some time, the output voltage
value (Eext) and the potential were recorded using steady state
discharge method by changing external resistances.
The power density (PD) was obtained from the above
recorded average data based on the air-cathode area as fol-
lows in equation (1):
PD ¼ Eoutput2/(Rext Acathode) (1)
where PD is power density of MFC (mW cm2), Eoutput is the
output voltage (mV), Rext is external resistance (U), Acathode is
the effective area of the air-cathode.
The power density and current density results of MFC were
normalized to the effective area of air-cathode (7.07 cm2).
Results and discussion
Physical characterization of Co@NC-CoxZny
SEM, TEM, HR-TEM, EDS, Element Mapping technologies were
used to present the structure and morphology of the catalysts.
As shown in Fig. 2, Fig. S1, and Fig. S2, the as-synthesized
catalysts by the BMZIFs precursors with Co/Zn mole ratio
shifted from 1:0 to 0:1, respectively. The Co1Zn3-BMZIF
showed intact dodecahedral rhombic structure in Fig. 2(a).
The SEM of (Fig. 2(b)) indicated that CNTs microstructure was
uniformly dispersed into the host of Co@NC-Co1Zn3 dodeca-
hedral nanoparticles. SEM images of Fig. S1 and Fig. S2 showed
the size of CoxZny-BMZIFs and Co@NC-CoxZny decreasing with
the increase of the Zn species. The surface of Co@NC-CoxZny
became much rougher after the precursors CoxZny-BMZIFs
were carbonized at 900  C, which could attribute to the vola-
tilization of Zn element introducing microstructure collapsed.
These images of CoxZny-BMZIFs and Co@NC-CoxZny unveiled
that Co@NC-CoxZny particles were well inherited the
dodecahedral rhombic morphology and sizes from CoxZny-
BMZIFs. Notably, the structure Co@CNTs was generated after
the pyrolysis resulting in the hierarchically porous architec-
ture, which afforded a close-connected skeleton between
metal Co center and nitrogen atom [44]. The microstructure
was further characterized by TEM (Fig. 2(c and d)) and HR-TEM
(Fig. 2(e)). The TEM of the Co@NC-Co1Zn3 catalyst exhibited a
clear-cut nanoporous structure of Co@CNTs. The above re-
sults apparently proved that the higher contents of Zn
element in the precursor could constrain Co NPs aggregation
during the pyrolysis process [35].
HR-TEM image of Co@NC-Co1Zn3 demonstrated that
embedded Co NPs with clear-cut lattice fringes of 0.202 nm
and 0.36 nm consistent with the Co (111) planes of face
centered cubic (fcc) (PDF 15e0806) [45], and C (002) planes of
graphite [46], respectively. The Co NPs were wrapped by
graphitic carbon shell with crystal lattice (3.6 
A) of the inter-
planar distance of C (002) plane. It was manifested that the
evaporation of Zn element could simultaneously trigger some
Co NPs into dodecahedron skeleton, which was more benefi-
cial to the growth of CNTs. The EDS (Fig. 2(f)) and element
mapping (Fig. 2(gek)) of Co@NC-Co1Zn3 showed that Co, N,
and C elements were uniformly dispersed in the carbon ma-
trix. These feature structures of Co@CNTs were conducive to
enhance catalytic performance.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 1 0 7 0 1 e1 0 7 1 4
Fig. 2 e (a) SEM image of the precursor Co1Zn3-BMZIF; (b) SEM image of Co@NC-Co1Zn3; (ced) TEM image of Co@NC-Co1Zn3;
(e) HR-TEM image showing the Co@CNTs; (f) EDS analysis of Co@NC-Co1Zn3; (g) TEM image of Co@NC-Co1Zn3; (hek) the
corresponding EDS elemental mapping image showing the distribution of Co, N, C, O.
To analyze the crystalline structure and surface element
component of the synthetic catalysts, we determined the XRD
and XPS tests and the results were shown in Fig. 3. From
Fig. 3(a), the peak located around 26.3 , which was ascribed to
graphitic carbon C (002) (JCPDS NO.:01e0640). The resting
three diffraction peaks 44.2 , 51.5 , 75.9 were corresponding
to Co (111), Co (200), and Co (220) crystal planes of Co NPs in a
fcc structure (JCPDS NO.: 15e0806), respectively [45].The
metallic Co peaks showed more pronounced with the
increasing Co contents of the precursors CoxZny-BMZIFs.
These results were also consistent with HR-TEM measure-
ments (Fig. 2(e)) (see Table 1).
From Fig. 3(b), it was observed that all the XPS spectra of
Co@NC-Co1Zn0, Co@NC-Co1Zn3, NC-Co0Zn1 revealing four
obvious characteristic peaks were C1s, N1s, O1s, Co2p, indi-
cating the high purity of as-prepared catalysts. The contents
of them were listed in Table 2. The high resolution C1s spec-
trum (Fig. 3(c)) demonstrated the presence of three types
carbides, which could be ascribed to CeC (284.57 ± 0.13 eV),
CeO (285.62 ± 0.15 eV), CeN&C]O (286.43 ± 0.15 eV), respec-
tively [47]. It was observed that the fitting peak fields of CeC in
the whole catalysts were the largest, indicating the degree of
graphitization. As we all known, the structure of graphitic
carbon and CeN bonds could accelerate proton-electron
transfer in protonation. From Fig. 3(d), the N1s spectrum
could be fitting to Pyridinic-N, Pyrrolic-N, and Graphitic-N,
which situated around 398.30 ± 0.22 eV, 399.50 ± 0.41 eV,
401.41 ± 0.36 eV, respectively [48]. Commonly, Pyridinic-N and
Graphitic-N were considered to afford the ORR effective active
10705
site because they afforded lone pair electron and p electron
[49]. In order to get more convenient and comparative results,
Pyridinic-N and Graphitic-N were defined as N-ORR. Fig. 3(e)
showed the high resolution Co2p XPS of catalysts, exhibiting
several main characteristic peaks: Co0, Co2p3/2, Co-Nx, Co2p1/
2, and satellite peak, which were located around
777.63 ± 0.41 eV, 780.23 ± 0.30 eV, 783.67 ± 0.27 eV,
796.31 ± 0.43 eV, 803.25 ± 0.24 eV, respectively. The Co-ORR
including Co2p3/2, Co-Nx, Co2p1/2, were the critical active
sites responsible for the ORR. As shown in Fig. 3(f), the molar
ratio of N-ORR and Co-ORR for Co@NC-Co1Zn3 was higher
than other catalysts, illustrating the Co@NC-Co1Zn3 should
possess superior ORR activity. The prepared series of mate-
rials Co@NC-CoxZny were characterized by Raman spectra
(Fig. S5). The D band of Raman Shift represents defects
(1380 cm1), and the G band represents graphitization degree
(1590 cm1) [49]. As the evaporation of Zn could produce de-
fects, the increase of the proportion of Zn precursor corre-
sponds to the more defects of its derivative Co@NC-CoxZny
[50]. Then, the value of ID/IG increases from 0.935 to 1.120 as
the increasing proportion of precursor Zn. Therefore, we could
draw a conclusion that the superior ORR activity of Co@NC-
Co1Zn3 mainly attributed to the synergistic interactions of
Co@CNTs, Co-Nx active species, Pyridinic-N, Graphitic-N.
The specific surface area and pore size distribution of cat-
alysts determined the ORR catalytic active sites at three-phase
boundary. The N2 sorption isotherms at 77 K were measured
to investigate the specific surface area and the porous struc-
ture of Co@NC-CoxZny. As shown in Fig. 4 and Table 2, the BET
10706 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 1 0 7 0 1 e1 0 7 1 4

Fig. 3 e (a) XRD patterns, (b) XPS spectra, and the high resolution XPS spectrum (c) C1s, (d) N1s, (e) Co2p of different catalysts;
(f) The molar ratio content for different catalysts.

[36]. Additionally, the pore size distributions revealed their

Table 1 e C1s, N1s, O1s and Co2p XPS peak analysis of large pore volumes and co-existence of micropore and mes-
Co@NC-CoxZny
opore. The three-dimensional structure of micropore and
Sample (at.%, absolutely) C1s N1s O1s Co2p mesopore with large specific surface area would be beneficial
Co@NC-Co1Zn0 83.76 2.54 13.52 0.18 to efficient mass transfer of ORR relevant species and the
Co@NC-Co1Zn3 83.26 3.31 13.20 0.22 exposure of active sites at the three-phase boundary.
NC-Co0Zn1 83.06 3.31 13.63 0
Electrochemical performance of Co@NC-CoxZny

surface areas were 261.97, 309.37, 377.94, 570.15, 589.78, and
1155.58 m2 g1 for Co@NC-Co1Zn0, Co@NC-Co3Zn1, Co@NC-
Co1Zn1, Co@NC-Co1Zn3, Co@NC-Co1Zn6, Co@NC-Co0Zn1,
respectively. The values of the BET surface area increased
with the increasing Zn content of precursor CoxZny-BMZIFs
To evaluate ORR catalytic activity of catalysts Co@NC-CoxZny,
CVs and LSVs were conducted on RDE (Fig. 5(aec)). All the CV
curves demonstrated that there was no evident reduction
peak in N2-saturated PBS. Nevertheless, an obvious ORR peak
was appeared in O2-saturated PBS, which revealed good
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 1 0 7 0 1 e1 0 7 1 4 10707

Table 2 e Parameters and porous structure for Co@NC-CoxZny.

Catalysts SBETa* Smicrob* Smesoc* Pore volumed* Micropore volumed* Average pore diameter
(m2 g1) (m2 g1) (m2 g1) (cm3 g1) (cm3 g1) (nm)
Co@NC-Co1Zn0 261.97 164.32 97.64 0.2128 0.072 3.25
Co@NC-Co3Zn1 309.37 61.66 247.71 0.5237 0.028 6.77
Co@NC-Co1Zn1 377.94 248.90 129.04 0.3513 0.107 3.72
Co@NC-Co1Zn3 570.15 440.37 129.78 0.5432 0.180 3.81
Co@NC-Co1Zn6 589.78 485.67 104.12 0.5243 0.197 3.56
NC-Co0Zn1 1155.58 961.70 193.88 1.466 0.396 5.08

Fig. 4 e (a) N2 sorption isotherms and (b) pore size distribution of Co@NC-CoxZny.

electrochemical activity for ORR [50]. The ORR peak of
different catalysts (Table S2) was ordered as the following:
Co@NC-Co1Zn3 (0.705 V) > 20 wt% Pt/C (0.682 V)  Co@NC-
Co1Zn1 (0.682 V) > Co@NC-Co3Zn1 (0.673 V) > Co@NC-Co1Zn6
(0.651 V) > Co@NC-Co1Zn0 (0.650 V) > NC-Co0Zn1 (0.189 V). The
more positive ORR peak showed the better ORR catalytic
properties.
The LSV curves of various catalysts in O2-saturated PBS at
1600 rpm were determined to assess the ORR catalytic activity
as shown in Fig. 5(c). As we know that the Eon-set and the ab-
solute value of jL were more positive, the catalytic materials
would possess better catalytic activity [51]. The Eon-set and jL of
different catalysts were shown in Fig. 5(d) and Table S2. The
Tafel plot of Co@NC-Co1Zn3 (102.5 mV dec1) was much lower
than that of 20 wt% Pt/C (126.3 mV dec1), further confirming
the excellent ORR kinetics in Co@NC-Co1Zn3 catalyst (Table S3
and Fig. S6). The current density of Co@NC-Co1Zn3 increased
with the rotating speed 500~2500 rpm (Fig. 5(e)), and the
remaining catalysts of Co@NC-CoxZny also exhibited similar
rule (Fig. S3). From Table S2 and Fig. 5(d), Co@NC-Co1Zn3 dis-
played a more positive Eon-set (0.844 V vs. RHE), and higher jL
(6.176 mA cm2 at 0 V), indicating that it was a superior ORR
catalyst in the series.
In addition to the essential ORR activity, the electron
transfer number (n) was another critical essential for practical
applications. The mechanism of ORR process occurred four-
electron pathway to form H2O directly, and occurred two-
electron pathway to forming H2O2 as an intermediate [52].
Therefore, the Koutecky-Levich equation plots of Co@NC-
Co1Zn3 and other Co@NC-CoxZny were calculated by K-L
equation in Fig. 5(f) and Fig. S8, respectively. And the n of
Co@NC-Co1Zn3 at various potentials was 3.10~3.29, indicating
that ORR pathway of it mainly occurred via four-electron
process in PBS. Thus, these also demonstrated that Co@NC-
Co1Zn3 could possess better ORR performance in the serious
catalysts. The superior ORR catalytic activity of Co@NC-
Co1Zn3 was mainly due to its appropriate specific surface area,
hierarchically porous and Co@CNTs structure, which afforded
more occasion for O2 molecule absorb and reduce.
The long-term stability and methanol tolerance of the
catalysts were significant for practical industrial applications
of MFCs [53]. The long-term stability of Co@NC-Co1Zn3 and
20 wt% Pt/C were tested on chronoamperometric response (i-t)
at 0.1 V at 1600 rpm O2-saturated in 50 mM PBS. From
Fig. 6(a), after continuously working for 10,000 s, Co@NC-
Co1Zn3 displayed a slower normalized current decay with
initial current maintenance of about 90.1%, compared to 82.3%
of 20 wt% Pt/C. From SEM (Fig. S3) and XRD (Fig. S4) of Co@NC-
Co1Zn3 before and after the i-t test, the morphology and
crystal parameters of Co@NC-Co1Zn3 did not change evidently
after the i-t test, which manifested that the Co@NC-Co1Zn3
was outstandingly stable for ORR. As shown in Fig. 6(b), when
3 M methanol was added into PBS at 100 s, the normalized
current was dropped with initial 77.3%, compared to 57.1% of
20 wt% Pt/C. These results apparently proved that Co@NC-
Co1Zn3 catalyst possessed superior long-term stability and
stronger methanol tolerance than 20 wt% Pt/C. These superior
properties could be attributed to Co@NC-Co1Zn3 with open
three-dimensional porous structure and protection of the
OeH groups. Therefore, Co@NC-Co1Zn3 with outstanding
electrochemical performance and long-term stability is ex-
pected to be a great substitute for Pt/C in MFCs.
10708 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 1 0 7 0 1 e1 0 7 1 4

Fig. 5 e (aeb) CV curves of different catalysts in O2- and N2-saturated in 50 mM PBS at a scan rate of 50 mV s¡1; (c) LSV curves
of different catalysts in O2-saturated in 50 mM PBS at a scan rate of 5 mV s¡1; (d) the histogram of diffusion-limited current
density and on-set potential of different catalysts O2-saturated in 50 mM PBS at a scan rate of 5 mV s¡1 with a rotating speed
of 1600 rpm. (e) LSV curves of Co@NC-Co1Zn3 with rotating speeds of (500e2500) rpm in O2-saturated in 50 mM PBS; (f) the
fitting plots of K-L equation at different potentials of Co@NC-Co1Zn3.

Fig. 6 e (a) Long-term chronoamperometric response (iet) curves at ¡0.1 V for Co@NC-Co1Zn3 and 20 wt% Pt/C with a
rotating speed of 1600 rpm in O2-saturated in 50 mM PBS; (b) the resistance to methanol poisoning i-t curves at ¡0.1 V.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 1 0 7 0 1 e1 0 7 1 4
Fig. 7 e Schematic illustration (a) and photograph (b) of the configuration of MFCs: The set-up and work principle of the air-
cathode MFCs.
Power performance of MFCs
The schematic illustration and photograph diagram of the
working principles and the configuration in MFCs are shown
in Fig. 7. To evaluate the actual catalytic performance of the
catalysts, Co@NC-Co1Zn3 and Co@NC-Co1Zn1 were tested in
air-cathode MFCs. For comparison, 20 wt% Pt/C as catalyst of
the air-cathode of MFC was also running under the same
conditions. Accordingly, they were signed as Co@NC-Co1Zn3-
MFC, 20 wt% Pt/C-MFC and Co@NC-Co1Zn1-MFC. From Fig. 7, it
was obvious that the MFC consists of anode loaded with
electrogenic microorganism, air-cathode, and 28 mL chamber
filled with electrolyte. Fig. 7(a) showed the front of the air-
cathode, which includes collector (carbon cloth), carbon-
based layer, gas-diffusion layer (facing the air), catalytic
layer (facing the electrolyte). For the working principles of
MFC, electrogenic microorganism was tightly anchored to the
anode surface and consumed the substrate (1 mg mL1 su-
crose) to produce proton and electron. Then, the generated
proton and electron transfer to the air-cathode through elec-
trolyte or external circuit [38]. On the side of the air-cathode,
O2 in the air passes across the GDL to the catalytic layer.
Under the activation of the ORR catalysts, O2 eventually
accepted the proton and electron to accomplish the ORR.
Thus, the current circuit was generated by air-cathode MFCs.
Fig. 8 showed the power generation performance of MFC
using different cathode catalysts. The output voltage of all the
MFCs was collected for about 200 h. It could be seen that all the
10709
output voltage was increased rapidly until arriving at a stable
voltage platform as the PBS was updated. Then, they dropped
below 100 mV sharply when the substrate fuel was exhausted
after about 22e26 h. The output voltage of MFCs modified by
various catalysts was different due to the different ORR per-
formance of air-cathode catalysts. Theoretically, the catalyst
with better ORR performance will possess a higher output
voltage in air-cathode MFC. Specifically, the stable voltage
platform of Co@NC-Co1Zn3-MFC was obtained (541 ± 8) mV,
which was 10.0%, 20.2% higher than 20 wt% Pt/C-MFC (492 ± 17)
mV, and Co@NC-Co1Zn1-MFC (450 ± 29) mV. The output voltage
of MFC was consistent with the results of ORR catalytic activity.
Thus, it was demonstrated that Co@NC-Co1Zn3 possessed a
higher ORR catalytic property in practical industrial application
and even exceeded to commercial 20 wt% Pt/C.
The polarization curves of the Co@NC-Co1Zn3-MFC, 20 wt%
Pt/C-MFC, and Co@NC-Co1Zn1-MFC were shown in Fig. 8(b)
and (d). With the increasing of current density, the output
voltage and electrode potentials showed a similar tendency.
Co@NC-Co1Zn3-MFC held more positive output voltage and
cathodes potentials than that of 20 wt% Pt/C-MFC, Co@NC-
Co1Zn1-MFC, indicating the good electrochemical perfor-
mance in MFC. Moreover, Fig. 8(c) demonstrated the power
density curves of Co@NC-Co1Zn3-MFC, 20 wt% Pt/C-MFC, and
Co@NC-Co1Zn1-MFC. It was notable that the maximum power
density of Co@NC-Co1Zn3-MFC was raised to 1039 mW m2,
which was 53.2%, 100.6% superior than those of 20 wt% Pt/C-
MFC (678 mW m2) and Co@NC-Co1Zn1-MFC (518 mW m2).
10710 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 1 0 7 0 1 e1 0 7 1 4
Fig. 8 e Power generation performance of MFC using different cathode catalysts: (a) Output-voltage of MFCs after startup
period with external resistance of 1000 U; (b) Polarization curves; (c) Power density curves; (d) Anode/cathode potentials vs.
Ag/AgCl.
The resistance values of MFC with Co@NC-Co1Zn3 and 20 wt%
Pt/C were recorded by the Electrochemical Impedance Spec-
troscopy (EIS) measurements. The radius of Nyquist diagram
(Fig. S9) Co@NC-Co1Zn3-MFC is smaller than that of Pt/C-MFC,
indicating that the impedance of Co@NC-Co1Zn3-MFC is less
than that of Pt/C-MFC. From the above results, it demon-
strated that Co@NC-Co1Zn3 possessed better ORR perfor-
mance in air-cathode MFC, which was a promising ORR
catalyst candidate to practical industrial application of MFC.
Mechanism of catalytic process for Co@NC-CoxZny
The synergistic catalytic mechanism of ORR on Co@NC-Cox-
Zny electrocatalyst was presented in Fig. 9. From Fig. 9(a), the
metal center (Co2þ þ Zn2þ) with different concentration of
Co2þ was assembled to the ligand 2-MeIM to form the pre-
cursor CoxZny-BMZIFs. Then, the CoxZny-BMZIFs were
carbonization in the high temperature. When the temperature
exceeded 800  C [31], Zn element was volatilized away from
the precursors to form Co@NC-CoxZny electrocatalyst mate-
rials. Particularly, Co@NC-Co1Zn3 possessed the specific
structure of Co@CNTs [34]. However, the single element pre-
cursors derived Co@NC-CoxZny (Co@NC-Co1Zn0 and NC-
Co0Zn1) did not own CNTs structure, which was also proved by
Fig. 2 and Fig. S2. The synergistic effect with distinctive
structure of Co@CNTs determined Co@NC-Co1Zn3 superior
ORR catalytic properties. As shown in the right-most column
of Fig. 9(a), Co@NC-Co1Zn3 had the characteristic corre-
sponding to two people working together, while the Co@NC-
Co1Zn0 or Co@NC-Co0Zn1 was equivalent to one person
working lonely. Overall, the feature structures with Co@CNTs
leaded to exposed more catalytic active sites, thereby
cemented the synergistic interaction between Co@CNTs and
carbon matrix skeleton. Meanwhile, the synergistic interac-
tion and ORR active nitrogen components would be conducive
to the sorption and utilization of ORR active species.
Fig. 9(b) showed the ORR catalytic pathway process, which
was proposed according to the literatures [52,54,55]. ORR
pathway process included associative and dissociative mech-
anisms, respectively, depending on whether O2 dissociates (O]
O bond breaking) before or after the protonation. In air-cathode
MFCs, one should expect the ORR pathway was dominated via
the four-electron pathway to produce water. In associative
mechanism, O2 adsorption on active site bound one proton and
one electron to form *OOH, and then *OOH bound one proton
and one electron to form *O transition state and H2O. Next, the
*O combined one proton and one electron form *OH, and then
*OH bound a proton and an electron to generate water. The
associative pathway process was completed. For dissociative
pathway process, the O]O bond of O2 broke before the
chemisorbed O2 protonation, which *OOH transition state was
inexistence through this pathway process [56].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 1 0 7 0 1 e1 0 7 1 4 10711

Fig. 9 e Possible synergistic catalytic mechanism of Co@NC-CoxZny: (a) process of Co@NC-CoxZny; (b) pathway of ORR on the
active site.

Cost estimation considered one of the key factors for MFC industrial appli-
cation. As depicted in Table 3, the comparison of the
Better performance and lower cost ORR catalysts not only maximum power density, output voltage and price with
decreased the price of MFCs, but also provided significant cathode catalysts that reported in some literatures. It could
reference value for their large-scale application in the be seen that the cost of Co@NC-Co1Zn3 was only 0.03%
future. Therefore, the cost of cathode catalysts was (<0.01 $ m2) of that of the commercial Pt/C (33 $ m2).
Therefore, Co@NC-Co1Zn3 ORR catalyst could be beneficial
to implement MFC from a laboratory research to a com-
Table 3 e Costs of catalysts and maximum power mercial wide application.
densities of various cathodes.
Cathode Cost of Maximum Output Ref.
catalyst catalyst power density voltage Conclusion
($ m2) (mW m2) (mV)
Pt/C 33 512 237 [57]
In summary, we have successfully fabricated a facile, cost-
V2O5-NR/ 4.8 533 271 [57] effective, and scalable approach to prepare a series of
rGO Co@NC-CoxZny as ORR catalysts of air-cathode MFC by py-
MnO2-NTs/ 3.51 3359 400 [58] rolysis of the precursor CoxZny-BMZIFs. Among them, Co@NC-
GO Co1Zn3 with the higher content active Co-Nx moieties and
GO/MgO 2.2 755.6 568 [59]
ORR-Nx, exhibited an extraordinary ORR activity with Eon-
MnO/VC 1.6 606.1 e [60] 2
set ¼ 0.830 V (vs. RHE), jL ¼ 6.706 mA cm , excellent long-term
20 wt% Pt/ 33 678 492 This work
C durability superior to the 20 wt% Pt/C benchmark. The
Co@NC- <0.01 1039 541 This work maximum power density for Co@NC-Co1Zn3-MFC was
Co1Zn3 1039 mW m2, which was 53.2% superior to that of 20 wt% Pt/
10712 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 1 0 7 0 1 e1 0 7 1 4

C-MFC (678 mW m2). Moreover, the cost of Co@NC-Co1Zn3 references

was only 3333.3 times lower than that of the commercial 20 wt
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