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 2 8 8 2 e1 2 8 9 2

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Highly efficient Co/NC catalyst derived from ZIF-67

for hydrogen generation through ammonia
decomposition

Guoru Li a,b, Houfu Zhang b, Xiaoting Yu b, Zhiping Lei a,**,

Fengxiang Yin b,*, Xiaobo He b
a
School of Chemistry & Chemical Engineering, Anhui Province Key Laboratory of Coal Clean Conversion and High
Valued Utilization, Anhui University of Technology, Ma'anshan, 243002, Anhui Province, China
b
Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, School of Petrochemical Engineering,
Changzhou University, Changzhou, 213164, China

highlights graphical abstract

Small-size cobalt nanoparticles

distributed on nitrogen doped
carbon support.

The moderate CoeN bond strength
plays a key factor on catalytic
activity.

Co/NC-600 catalyst demonstrates
an ammonia conversion of 80% at
500  C.

The activity of catalysts is higher
than many reported Co-based
catalysts.

article info abstract

Article history: Small-size cobalt nanoparticles (NPs) distributed on nitrogen doped carbon support (Co/
Received 14 December 2021 NC-X) were prepared by pyrolysis of ZIF-67 at various temperatures (X ¼ 500, 600,700 and
Received in revised form 800  C) in nitrogen atmosphere and utilized as catalysts for hydrogen production through
25 January 2022 ammonia decomposition. Characterizations of the catalysts including XRD, HRTEM, XPS,
Accepted 4 February 2022 H2-TPR, CO2-TPD, etc., were conducted for structure analysis. The NeC plate obtained from
Available online 25 February 2022 pyrolysis was coated with Co NPs to hinder its aggregation, which made the Co NPs
dispersed evenly and increased their dispersion. The calcination temperature and the
Keywords: strong base of the support can adjust the strength of CoeN bond. The activity of the Co/NC-
Ammonia decomposition X catalysts is attributed to the high content of Co0 and the moderate CoeN bond strength.
Hydrogen production The ammonia decomposition activity of Co/NC-X catalysts in this paper is higher than
ZIF-67 many reported Co-based catalysts. Co/NC-600 catalyst demonstrates an ammonia con-
MOF version of 80% at 500  C with a space velocity of 30,000 ml g1 1
cat h , corresponding to a

* Corresponding author.
** Corresponding author.
E-mail addresses: zplei@ahut.edu.cn (Z. Lei), yinfx@cczu.edu.cn (F. Yin).
https://doi.org/10.1016/j.ijhydene.2022.02.046
0360-3199/© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 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 2 8 8 2 e1 2 8 9 2
hydrogen production rate of 26.8 mmol H2 g1
development of highly active cobalt-based catalysts for hydrogen production through
ammonia decomposition.
© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Introduction
Currently there is about 96% of the hydrogen production that
comes from fossil fuels to cause severe environmental pollu-
tion issues. Hydrogen energy is regarded as the optimal solu-
tion to provide high calorific value and pollution-free product.
There have been widespread researches to produce hydrogen
energy such as methane reforming [1], water splitting [2],
photocatalytic hydrogen production [3], ammonia decompo-
sition [4]. Among which, the decomposition of ammonia to
produce hydrogen is alternative to yield no carbon-containing
products with beneficials like its high volumetric energy den-
sity and high hydrogen content [5]. However, it is not surpris-
ing that ammonia decomposition has not been investigated as
widely as some other hydrogen production techniques due to
the lack of effective catalysts [6,7].
The most studied catalysts for ammonia decomposition
have been Ru based catalysts while the high price and scarcity
limit their large-scale application [8]. To develop inexpensive
and highly active non-noble metal-based catalysts such as Fe,
Ni and Co is essential for ammonia decomposition [9e12].
Besides, catalyst supports with high surface area to facilitate
the uniform load of metal NPs ranging from activated carbon
[13], MgO [14], Al2O3 [15], ZrO2 [16], carbon nanotubes [17],
MCM-41 [18], etc. Have a great influence on the ammonia
decomposition performance. The support can stabilize the
metal NPs with preserved size and morphology, increase the
exposure of more active sites, and alter the electronic struc-
ture of the active metal. Cha et al. [6] loaded Ru onto four
different zeolite support and found that the ammonia
decomposition activity increased as the acidity of zeolite
decreased, which was due to the interaction between Ru
particles and the support that increased the electron density
of Ru and promoted the desorption of N on the catalyst sur-
face. Specifically, Co is considered as the best substitute for
Ru-based catalyst due to its nitrogen binding energy that is
closest to the optimal range [3]. For example, Huang et al. [19]
prepared three Co catalysts supported on CeO2 support with
different morphologies and structures for ammonia decom-
position performance and concluded that CeO2 support had a
significant effect on specific surface area and surface oxygen
vacancy, which was conducive to the formation of more active
sites. Bell et al. [20] loaded Co onto alumina through different
methods including adsorption, impregnation and precipita-
tion to catalyze ammonia decomposition reaction. It was
found that the particle size of Co played the most important
role determining the catalytic activity: the smaller particle
size significantly promoted the catalytic activity.
12883
1
cat min . The work provides insight for the
Metal-organic framework materials (MOFs) have attracted
extensive attention in recent years due to their unique ad-
vantages of high specific surface area, ordered porosity and
topological structure diversity. ZIF-67 (Co(Hmim)2, Hmim ¼ 2-
methylimidazole) is representative containing Co2þ ions and
2-methylimidazole anions with cubic crystal symmetry of cell
parameters a ¼ b ¼ c ¼ 16.9589 A [21]. The high specific surface
area (SBET >1700 m2 g1) and abundant micropores (pore size:
~0.34 nm) enable ZIF-67 to provide rich active sites and strong
affinity for guest molecules. ZIF-67 can be pyrolyzed to pro-
duce metal oxides or metal/carbon complexes in different
atmospheres to bring additional characteristics that ZIF-67
alone does not have. These advantages expanded the use of
ZIF-67-based materials in many applications, such as
adsorption and separation, drug delivery, supercapacitors and
catalysis [22e24].
In principle, a good catalyst for ammonia decomposition
should have moderate metal-N bond strength and be able to
provide the active surface that can continuous break the NeH
bonds and associate the desorption of N2 and H2 [25,26]. Huo
et al. [27] reported highly dispersed molybdenum nitride NPs
on in-situ assembled two-dimensional mesoporous silica/
reduced graphene oxide hybrid nanosheets (MoN/SBA-15/
rGO, Mo2N/SBA-15/rGO) through experiments and theoretical
calculations for ammonia decomposition process. The intro-
duction of rGo effectively weakened the association and
desorption of adsorbed N atoms. The more favorable Mo2N
surface indicated that the medium adsorption capability of N
on the Mo2N/SBA-15/rGo catalyst surface was beneficial for
better performance of ammonia decomposition.
In this paper, ZIF-67 was used as precursor to prepare a
series of carbon and nitrogen coated Co catalysts at different
pyrolysis temperatures in nitrogen atmosphere for ammonia
decomposition to produce hydrogen. The relationship be-
tween the structure and the performance of the catalysts was
analyzed by different characterization methods including
XRD, BET, SEM, TEM, ICP, XPS, H2-TPR and CO2-TPD. The re-
sults show that the structure of the catalysts has a great in-
fluence on the decomposition performance of ammonia. The
formation of cobalt NPs on the hetero-nitrogen atoms doped
porous carbon structure provided abundant catalytic active
sites for the ammonia decomposition reaction. The synergis-
tic effect between the cobalt NPs, nitrogen heteroatoms and
carbon in the support promoted the catalytic activity. The
medium-strength CoeN bond is conducive to the high cata-
lytic activity and the alkalinity of the catalyst have a great
influence on the performance of the catalyst. Co/NC-600 rea-
ches the ammonia decomposition conversion rate of 80% at
500  C with the space speed of 30,000 ml g1 1
cat h . The H2
12884 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 2 8 8 2 e1 2 8 9 2
formation rate is 26.78 mmol H2 g1 1
cat min , which is higher
than the most reported Co-based catalyst.
Experimental section
Catalysts synthesis
The synthetic process of Co/NC-X catalysts is shown in Fig. 1.
3.0 mmol cobalt nitrate (Co(NO3)2$6H2O) was dissolved in
35 ml methanol to form solution A, and 50 mmol 2-
methylimidazole was dissolved in 35 ml methanol to form
solution B. Then solution B was slowly added into solution An
under stirring at room temperature. After stirring for 8 h, the
obtained product was washed with methanol for three times
and dried overnight at 60  C. And then the resulting sample
was calcined in tubular furnace with nitrogen atmosphere at
different temperatures (500, 600, 700 and 800  C). After cooling
naturally, the catalysts were labeled as Co/NC-500, Co/NC-600,
Co/NC-700, Co/NC-800, respectively.
Structural characterizations
The D8FOCUSX X-ray diffractometer of AXS (Brook, Germany)
operated at 40 kV, 100 mA with Cu Ka radiation (l ¼ 1.54056
A)
was used for X-ray diffraction (XRD) analysis. X-ray photo-
electron spectroscopy (XPS) was carried out on Escalab 250 X-
ray photoelectron spectrometer (Thermfisher Scientific, USA)
equipped with an Al-Ka source and 30 eV passing energy. The
binding energies (BE) of measured elements were corrected by
the standard C 1s (284.6 eV). High-resolution transmission
electron microscope (HRTEM) images were obtained on the
EM-2100 transmission electron microscope (JEOL, Japan). A
Micromeritics ASAP2020 equipment (Micromeritics, USA) was
used to measure the surface area and pore size distributions of
Co/NC catalysts. All the samples were degassed at 400  C for
2 h prior to measurement. The inductively coupled plasma
optical emission spectrometer (ICP-OES, 720 ES, Agilent, US)
was used to detect the contents of Co.
H2 temperature-programmed reduction (H2-TPR) analyses
were carried out using Temperature-programmed chemi-
sorption apparatus with a thermal conductivity detector
Fig. 1 e Schematic illustration of the synthesis of Co/NC-X (X ¼ 500, 600, 700, 800).
(TCD). 30 mg of the as-prepared catalysts were pre-treated in a
high-purity nitrogen atmosphere at 300  C for 30 min and then
cooled to room temperature. Then, the pre-processed cata-
lysts were reduced with a mixture of 10% H2/Ar from 50 to
800  C at a ramping rate of 10  C min1.
CO2 temperature programmed desorption (CO2-TPD) was
employed to evaluate basic site distribution of the catalysts.
Prior to CO2-TPD experiment, the catalyst was pretreated by
passing N2 at 450  C for 1 h and then cooled to 60  C in N2 flow.
CO2 gas was then adsorbed on pretreated catalyst at 60  C for
1 h. After the completion of the adsorption the reactor tem-
perature was brought up to 100  C and flushed with N2 for 1 h
to remove the physically-adsorbed CO2. The temperature was
then increased linearly from 100 to 800  C at a ramping rate of
10  C min1. Desorption patterns were recorded using
Temperature-programmed chemisorption apparatus equip-
ped with a thermal conductivity detector.
CO temperature programmed desorption (CO-TPD) was
performed to measure the exposed Co surface area. Prior to
CO-TPD experiment, the catalyst was reduced at 500  C for 2 h
in 10% H2 (balance with Ar) and then cooled to room tem-
perature in He flow. Then, the 10% CO/He flow was introduced
for a period of 0.5 h at room temperature. After the adsorption
of CO was performed under cryogenic conditions, pure He was
introduced for 1 h to remove the physically-adsorbed CO. The
temperature was then increased linearly from room temper-
ature to 800  C at a ramping rate of 10  C min1. Desorption
patterns were recorded using Temperature-programmed
chemisorption apparatus equipped with a thermal conduc-
tivity detector. Co metal surface area was calculated by
assuming a stoichiometry of 1:1 for CO:Co.
Catalytic activity measurements
The ammonia decomposition performances of catalysts were
evaluated in a fixed-bed reactor under atmospheric pressure.
Typically, 100 mg of catalyst were place in a quartz tube with
an inner diameter of 4 mm, when the reactor temperature was
raised to 300  C, ammonia gas was introduced and kept for
30 min (50 ml min1, space speed 30,000 ml h1 g1). Then the
temperature was increased to the measured temperature
(300e800  C, step length 50  C), and the tail gas was on-line
 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 2 8 8 2 e1 2 8 9 2 12885

analyzed using the gas chromatography (Beijing East west

Electronic Analysis, GC4000A) with a thermal conductivity Results and discussion
detector (TCD) to obtain the ammonia decomposition con-
version rates at different temperatures. The chromatographic Characterizations
carrier gas was high purity hydrogen, and the chromato-
graphic column was Porapark N (1.5 m). In order to achieve Fig. 2A shows the XRD pattern of synthesized precursor ZIF-67
steady-state conditions, the reaction was stabilized for 60 min with crystal planes of (011), (002), (112), (022), (013), (222), (114),
at each temperature before measurement. A blank quartz tube (223) and (134). The diffraction peaks perfectly matched the
was also tested as reference. Ammonia decomposition con- standard simulation XRD pattern of ZIF-67. There are no other
version rate is calculated as follows: miscellaneous peaks, indicating the high crystallinity of syn-
thesized ZIF-67 precursor [24]. Fig. 2B displays the XRD pat-
ANH3 ;in  ANH3 ;out terns of ZIF-67 calcined at 500e800  C in N2. There are
XNH3 ¼  100%
ANH3 ;in diffraction peaks of cubic crystal at 44.15 , 51.4 and 75.7 (PDF:
where XNH3 is the conversion rate of NH3, ANH3 ;in is the total 04-001-2681), corresponding to (111), (200) and (220) crystal
amount of ammonia in feed gas, and ANH3 ;out is the uncon- planes in Co/NC-500, Co/NC-600 and Co/NC-700. Meanwhile,
verted amount of ammonia. the diffraction peak of (111) crystal plane is obviously higher
Hydrogen generation rate is calculated as follows: than other peaks, indicating that the growth of Co NPs is
preferentially on the (111) crystal plane [28]. When the calci-
  5022:4  X nation temperature was raised to 800  C, the diffraction peaks
1 NH3  1:5
H2 formation rate mmol $ g1
cat $ min ¼
mcat of Co3O4 were obviously observed in Co/NC-800 (PDF: 97-002-
8158), while these peaks could not be observed in Co/NC-500,
where, XNH3 is NH3 conversion rate.
Co/NC-600 and Co/NC-700, which is probably due to the high

Fig. 2 e XRD patterns of precursor (A) ZIF-67 and (B) Co/NC-500, Co/NC-600, Co/NC-700, Co/NC-800 catalysts.

Fig. 3 e (A) N2 adsorption-desorption isotherms and (B) pore size distribution from BJH desorption of Co/NC-500, Co/NC-600
and Co/NC-700 catalysts.
12886 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 2 8 8 2 e1 2 8 9 2

the N2 adsorption-desorption isotherms of Co/NC belonged to

Table 1 e BET SSA and average pore diameter of Co/NC-
type IV and H1 hysteresis loop in Fig. 3A. This indicates that
500, Co/NC-600 and Co/NC-700 catalysts.
the catalysts were mainly composed of micro and meso pores.
Sample BET SSA (m2 g1) Average pore diameter (nm)
The pore size distributions obtained from the isotherms
Co/NC-500 222.84 7.58 further indicate the mesoporous feature (Fig. 3B). The specific
Co/NC-600 236.64 4.07 surface area (SSA) of the catalyst was calculated by BET
Co/NC-700 273.67 3.76
method. The BET SSA and average pore size of the catalysts
are shown in Table 1. As can be seen from Table 1, with the
increase of pyrolysis temperature, the SSA of the catalysts
calcination temperature that crystallized the amorphous gradually increases, but the average pore size decreases. This
Co3O4. At the same time, a series of wide diffraction peaks in can be attributed to the mesoporosity deterioration during the
the range of 20e30 are observed due to the amorphous car- pyrolysis process [30].
bon formed during pyrolysis [29]. The morphology of Co/NC-500, Co/NC-600 and Co/NC-600
The N2 adsorption-desorption isotherms and pore size were characterized by HRTEM in Fig. 4. The small Co NPs
distribution of Co/NC-500, Co/NC-600 and Co/NC-700 catalysts with the size around 5e15 nm were evenly dispersed and
were shown in Fig. 3. According to the IUPAC classification, embedded on the NeC plate to form an ideal integrated

Fig. 4 e TEM (AeC), HTTEM (DeF) and particle diameter distribution profile (GeI) of the catalysts.
 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 2 8 8 2 e1 2 8 9 2
structure which can been seen in Fig. 4AeF. The particle size
distribution histogram (Fig. 4G) shows that 90% of the particle
size of Co/NC-500 is in the range of 4e7 nm. Correspondingly,
the particle distribution histogram of Co/NC-600 (Fig. 4H) and
Co/NC-700 (Fig. 4I) shows that its particle diameter range is
4e10 and 5e10 nm, respectively. With the increase of pyrol-
ysis temperature, the catalyst particles were aggregated but
not significantly, indicating that the active component Co of
the catalyst was evenly dispersed, and the NeC plate obtained
by pyrolysis could effectively protect the aggregation of Co
nanoparticles. In Fig. 5A, the lattice fringes of Co with a
spacing of 0.194 nm can be clearly observed, corresponding to
the cobalt (111) plane, which is consistent with the XRD re-
sults. In addition, Co nanoparticles are almost completely
encased in carbon skeleton. The EDS Mappings (Fig. 5BeF) of
Co/NC-600 catalyst show that C, Co, O and N elements are
uniformly distributed in Co/NC-600.
XPS was employed to analyze the elemental chemical
environment of catalysts surface. There are three types of N
can be identified from N 1s spectrum, in Fig. 6A, corresponding
to pyridinic N (398.7eV), pyrrole N (400.3eV) and graphite N
(401.5eV). It can be found that the peak of Pyridinic N shifts to
higher binding energy as the calcination temperature rises.
The relative atomic ratio of Pyridinic N decreases with the
pyrolysis temperature of catalyst increasing, which is due to
the instability of Pyridinic N at high temperature (Table 2). The
spectrum of C 1s (Fig. 6B) is fitted into three peaks attributed to
CeC (284.6 eV), CeN (285.4 eV) and CeO (286.9 eV). Fig. 6C of O
Fig. 5 e HRTEM (A, B) and EDS Mapping (C-F) of element C, N, O and Co for Co/NC-600.
12887
1s spectrum is fitted into C]O (531.8 eV) and CeO (532.5 eV)
peaks. Fig. 6D depicts the Co 2p3/2 spectrum with the peaks at
778.2 eV, 780.6 eV and 782.6 eV corresponding to Co0, CoeO
and CoeN/C, respectively [31]. Since CoeN and CoeC bonds
have similar binding energies, it is difficult to distinguish
them from XPS spectra. Meanwhile, the CoeN/C bond shifts
obviously to the lower binding energy, which is consistent
with the XPS results of N. Table 2 presents the relative atomic
ratio of surface composition, which also included the mass
fraction of Co obtained by ICP. There is only a small amount
(11.6%) of Co0 in Co/NC-500. When the temperature continues
to rise to 600  C, Co0 ratio increases to 23.3%. However, when
the temperature increases to 700  C, the content of Co0 de-
creases (18.6%). The formation of Co0 is due to the thermal
reduction of Co2þ central cation in ZIF-67 during carboniza-
tion, which is consistent with the XRD results. Co2þ mainly
exists on the surface and forms chemical bond with N. It can
be found from the high resolution XPS spectrum of N that the
peak located at 398.7eV of Co2þ is attributed to NeCo bond [32].
The H2-TPR is used to analyze the interaction between
active component and support, and further to evaluate cata-
lytic activity (Fig. 7). According to previous reports [33], the TPR
spectrum of Co based catalysts usually includes two parts: (1)
the reduction peak at low temperature (150e375  C) corre-
sponds to the process of Co3O4 reduction to CoO. (2) The
reduction peak at high temperature (375e650  C) corresponds
to the process of CoO reduction to metal Co. The TPR diagram
of Co/NC-500 showed a weak shoulder peak at about 217  C
12888 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 2 8 8 2 e1 2 8 9 2
and a major reduction peak at about 483  C. The peak at 217  C
corresponds to the reduction of Co3þ to Co2þ, while the peak at
483  C corresponds to the reduction of Co2þ to Co0, where the
wide peak is caused by methanation overlap [34]. Similarly,
the TPR diagram of Co/NC-600 shows a major reduction peak
at 506  C, and the reduction temperature shifts to higher
temperature relative to Co/NC-500. Meanwhile, there is a
small peak at 205  C attributed to the reduction from Co3þ to
Co2þ. The TPR diagram of Co/NC-700 shows a major reduction
peak at about 533  C and a weak shoulder peak at about 180  C.
It can be seen that with the increase of the pyrolysis tem-
perature, the reduction peak of the sample at about 500  C
shifts to higher temperature, which is due to the existence of
CoeN bonds that make the reduction process more difficult.
The desorption behavior of CO from the catalysts to
explore the number of active sites was showed in Fig. 8A. The
desorption peaks of Co/NC-500, Co/NC-600 and Co/NC-700
catalysts were 196, 148 and 175  C, respectively. Based on
the peak area of CO-TPD diagrams and assumption of an
adsorption of one per metal atom, the Co metal dispersion
ratios of Co/NC-500, Co/NC-600 and Co/NC-700 catalysts were
17.1%, 28.4% and 21.9%, respectively. Fig. 8B shows the CO2-
TPD diagram of Co/NC-X samples. As an acidic probe
Fig. 6 e XPS diagrams of Co/NC-500, Co/NC-600 and Co/NC-700 catalysts: (A) N 1s, (B) C 1s, (C) O 1s, and (D) Co 2p.
molecule, CO2 was adsorbed and desorbed by temperature-
programmed desorption to determine the alkaline potential
of the catalyst. The desorption peak in the range of 100e200  C
is attributed to the interaction between CO2 and the weakly
alkaline site in the catalyst [35]. The desorption peak in the
range of 300e500  C is due to the interaction between CO2 and
the moderately alkaline site in the catalyst, while the
desorption peak in the range of 600e800  C is due to the
interaction between CO2 and the strongly alkaline site. The
desorption peaks of Co/NC-500 were observed at 230  C, 420  C
and 600  C, corresponding to weak alkaline sites, moderate
alkaline sites and strong alkaline sites. Compared with Co/NC-
500, the moderate alkaline sites and strong alkaline sites of
Co/NC-600 migrates to high temperature. The moderately
alkaline and strongly alkaline sites of Co/NC-700 also shift to
high temperature. However, there are significantly less strong
basic sites which is due to the high temperature reduction of
pyridinic N portion.
Catalytic activity
Fig. 9A shows the catalytic activities of the Co/NC-X catalysts
for ammonia decomposition. When the temperature is below
 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 2 8 8 2 e1 2 8 9 2 12889

corresponding to a hydrogen production rate of 26.8 mmol H2

Table 2 e Relatively atomic ratios of pyridinic N and
g1 1
cat min . It can be seen that the catalyst prepared in this
various Co species in the XPS spectra of Co/NC-X
(X ¼ 500,600,700). work has excellent activity for ammonia decomposition, even
comparable to some Ru catalysts such as Ru/Al2O3, Ru/MCM-
Samples Pyridinic N (%) Co0 (%) Co (%)a
41 (Table 3).
Co/NC-500 84.1 11.6 25.9 The activities of the catalysts were further analyzed by
Co/NC-600 75.1 23.5 34.4
Arrhenius equation (lnðrateÞ ¼ Constant  Ea 1
R T), in which the
Co/NC-700 61.7 18.6 33.1
a
rate means H2 generation rate, Ea is activation energy, R is gas
The mass fraction of Co obtained by ICP.
constant, T is reaction temperature, Constant is the pre-
exponential factor. The activation energy of the catalysts is
in the order of Co/NC-800 (112.07 kJ mol1) > Co/NC-500
(89.54 kJ mol1) > Co/NC-700 (84.80 kJ mol1) > Co/NC-600
(75.16 kJ mol1) (Fig. 10A). By comparing the ammonia
decomposition performance, it can be concluded that the
activation energy has more influence on ammonia decom-
position performance than the pre-exponential factor. The
activation energy of the catalyst also represents the minimum
energy barrier required for the catalytic reaction. Catalyst
stability is the key to industrial applications. Fig. 10B presents
the stability curve of the Co/NC-600 at 550  C. It is evident that
the ammonia conversion rate hardly decreased after 72 h
reaction.

Brief discussion

Co0 is generally regarded as the active site for ammonia

Fig. 7 e H2-TPR diagram of Co/NC-X (X ¼ 500, 600, 700)
catalysts.
300  C, none of the catalysts is active enough. With the in-
crease of temperature, the ammonia conversion rate of Co/
NC-600 is obviously higher than that of others. In the test
temperature range, the order of catalytic activity was Co/NC-
600 > Co/NC-700 > Co/NC-500 > Co/NC-800. In the pure
ammonia gas flow, the H2 generation rates of the catalysts
varies with the reaction temperatures shown in Fig. 9B. The
hydrogen generation rate of the catalysts follows the same
order. The Co/NC-600 catalyst provides an ammonia conver-
sion of 80% at 500  C with a space velocity of 30,000 ml g1
cat h ,
decomposition reaction [15,27]. According to the HRTEM
micrograph and particle diameter distribution profile in Figs. 4
and 5, Co NPs are uniformly distributed on the carbon support
and coated to prevent agglomeration. As can be seen from
Figs. 6D and 8A and Table 2, the mass fraction of Co (34.4),
dispersion of Co (28.4%) and quantity of Co0 (23.5%) of Co/NC-
600 catalyst are higher than those of the other two catalysts,
which is consistent with their measured activity.
The decomposition of ammonia occurs in a series of
dehydrogenation reactions [44], including: (1) Ammonia
adsorbed on the active site of the catalyst; (2) The NeH bond
on adsorbed ammonia continuously breaks to release nitro-
gen and hydrogen atoms; (3) Gaseous nitrogen and hydrogen
molecules are formed by recombination and desorption of N
1
and H atoms, as shown below:

Fig. 8 e (A) CO-TPD and (B) CO2-TPD diagrams of Co/NC-X (X ¼ 500, 600, 700) catalysts.
12890 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 2 8 8 2 e1 2 8 9 2

Fig. 9 e (A) Diagram of ammonia decomposition activity of the catalyst; (B) Hydrogen production rate diagram.

Table 3 e Comparison of Ammonia conversion over NH,ad* þ * / Nad* þ H* [4]

cobalt based catalysts at 500  C.
Active phase GHSV GHSV Ammonia ref Nad* þ Nad* / N2 þ 2* [5]
(ml g1 1
cat h ) (h1) conversion (%)
Co/CNTs 5200 8 [36] H* þ H* / H2 þ 2* [6]
Ru/AC 30,000 14 [37]
Co/Al2O3 36,000 21 [38] where * and NHx,ad (x ¼ 0e3) represent an empty active site
Ru/MCM-41 30,000 24 [36]
and intermediates adsorbed on the surface of the catalyst.
Co/MCM-41 36,000 28 [39]
According to previous reports, associative desorption of N
Co/AC 6000 34 [40]
Ru/Al2O3 30,000 42 [41] atoms or dehydrogenation of NHx (x ¼ 1e3) has been consid-
Co/MgeLa 6000 53 [42] ered as a rate-controlling step. Therefore, the bond strength
Co/MgOeLa2O3 6000 60 [35] (M  N) between the active metal and N is one of the key
Co/CeO2 6000 62 [43] factors affecting the decomposition of ammonia. If the M  N
Co/MWCNTs 6000 75 [33] bond strength is too weak, the adsorption of NH3 on the metal
Co/NC 30,000 80 This
is difficult and the NH2 intermediate is easy to desorption
work
before further dehydrogenation, resulting in low catalyst ac-
tivity. If the M  N bond strength is too strong, NH3 is easy to
be adsorbed on the metal and it is difficult to desorbed the
bonded N atoms from the catalyst. Therefore, the active sites
NH3 þ * / NH3,ad [1] of high active metals are difficult to be reused for many times,
resulting in reduced catalyst activity. Therefore, metals with
NH3,ad þ * / NH2,ad* þ H* [2] medium M  N bond strength show higher activity. From the
spectra of N 1s, Co 2p and H2-TPR, it can be concluded that the
NH2,ad* þ * / NH,ad* þ H* [3] CoeN bond energy of Co/NC-600 is in the middle range,

Fig. 10 e (A) Arrhenius plots for NH3 decomposition over catalysts; (B) Ammonia decomposition stability of Co/NC-600
catalyst.
 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 2 8 8 2 e1 2 8 9 2
neither weak nor strong, which is just conducive to the reac-
tion. Huo et al. [45] also obtained that Co0$89Fe2$11O4@mSiO2
showed the highest catalytic activity of ammonia decompo-
sition due to medium M  N bond energy. Wang et al. [25] used
N2-TPD and mass spectrometry to test the strength of M  N
bond (M is Fe, Co, Ni and Cu), among which CueN bond is the
weakest and FeeN bond is the strongest. Meanwhile, the re-
sults of ammonia decomposition activity showed that CoeN
bonds of moderate strength give high NH3 conversions.
As is known to all, the support strongly affects the elec-
tronic state of the active sites to alter the catalytic activity and
the decomposition performance of ammonia [46,47]. It has
been reported that the contribution of the alkaline electron-
donor to the active sites can reduce the binding energy of
the active center and the N, thus increasing the activity of the
catalyst [48,49]. From the order of the strong alkaline potential
of the catalyst in Fig. 6, Co/NC-700 > Co/NC-600 > Co/NC-500,
with the increase of the calcination temperature, the strong
alkaline potential of the catalyst shifts to high temperature,
indicating that the interaction between Co and support N
doped C is gradually enhanced and the alkaline potential of
Co/NC-600 is in the middle range. This is consistent with the
results of H2-TPR and XPS analyses, which further indicates
that the moderately strong CoeN bond promotes the
ammonia decomposition reaction.
Conclusion
Co/NC-X (X ¼ 500, 600, 700, 800) catalysts have been prepared
by directly pyrolyze ZIF-67 precursor at different tempera-
tures for ammonia decomposition. The Co/NC-600 catalyst
possesses 80% conversion of ammonia at 500  C with a space
velocity of 30,000 ml g1
cat h
1
and maintains even 72 h without
attenuation. The size-dependent effect of Co/NC catalyst with
nanoparticle size of 4e10 nm is not the main factor. The NeC
plate obtained from pyrolysis can effectively protect the ag-
gregation of Co nanoparticles, so that the active components
of the catalyst are evenly dispersed and the number of active
sites is increased. Tuning the calcination temperature of
catalyst can significantly adjust the CoeN bond strength and
subsequently optimize the catalytic performance. This
approach could be extended to fabricate more metal sup-
ported carbon doped nitrogen for promising energy storage
and conversion application.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
This work is supported by the National Natural Science
Foundation of China (21878001, 22078002 and 22078027). Spe-
cial thanks to the support from Advanced Catalysis and Green
12891
Manufacturing Collaborative Innovation Center, Changzhou
University (ACGM2016-06-02 and ACGM2016-06-03), A Project
Funded by the Priority Academic Program Development of
Jiangsu Higher Education Institutions.
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