Ni-based catalysts derived from a metal-organic framework for selective oxidation of alkanes

Article abstract of DOI:10.1016/S1872-2067(15)61067-1

Ni nanoparticles embedded in nitrogen-doped carbon (Ni@C-N) materials were prepared by thermolysis of a Ni-containing metal-organic framework (Ni-MOF) under inert atmosphere. The as-synthesized Ni@C-N materials were characterized by powder X-ray diffraction, N₂ adsorption-desorption analysis, scanning electron microscopy, transmission electron microscopy, atomic absorption spectroscopy, and X-ray photoelectron spectroscopy. The MOF-derived Ni-based materials were then examined as heterogeneous catalysts for the oxidation of alkanes under mild reaction conditions. The Ni@C-N composites displayed high activity and selectivity toward the oxidation of a variety of saturated C-H bonds, affording the corresponding oxidation products in good-to-excellent yields. Furthermore, the catalysts could be recycled and reused for at least four times without any significant loss in activity and selectivity under the investigated conditions.

Full text of DOI:10.1016/S1872-2067(15)61067-1

Chinese Journal of Catalysis 37 (2016) 955–962
a v a i l a b l e a t w w w . s c i e n c e d i r e c t . c o m
j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c h n j c
Article (Special Issue on Environmental Catalysis and Materials)
Ni‐based catalysts derived from a metal‐organic framework for
selective oxidation of alkanes
Ying Zhou, Jilan Long*, Yingwei Li#
State Key Laboratory of Pulp and Paper Engineering, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou
510640, Guangdong, China
A R T I C L E I N F O
A B S T R A C T
Article history:
Ni nanoparticles embedded in nitrogen‐doped carbon (Ni@C‐N) materials were prepared by ther‐
molysis of a Ni‐containing metal‐organic framework (Ni‐MOF) under inert atmosphere. The
as‐synthesized Ni@C‐N materials were characterized by powder X‐ray diffraction, N2 adsorp‐
tion‐desorption analysis, scanning electron microscopy, transmission electron microscopy, atomic
absorption spectroscopy, and X‐ray photoelectron spectroscopy. The MOF‐derived Ni‐based mate‐
rials were then examined as heterogeneous catalysts for the oxidation of alkanes under mild reac‐
tion conditions. The Ni@C‐N composites displayed high activity and selectivity toward the oxidation
of a variety of saturated C–H bonds, affording the corresponding oxidation products in
good‐to‐excellent yields. Furthermore, the catalysts could be recycled and reused for at least four
times without any significant loss in activity and selectivity under the investigated conditions.
© 2016, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
Received 27 January 2016
Accepted 25 February 2016
Published 5 June 2016
Keywords:
Nickel
Nanoparticle
Metal‐organic framework
Alkane
Oxidation
Heterogeneous catalysis
Published by Elsevier B.V. All rights reserved.
1. Introduction
hexane oxidation needs careful control (at conversions of <5%
with 75%–80% selectivity to KA‐oil) to prevent the production
The selective partial oxidation of alkanes is an important
transformation in the production of valuable chemicals and
intermediates such as ketones and alcohols [1]. For example,
cyclohexanone and cyclohexanol (also known as KA‐oil), the
two main products of the partial oxidation of cyclohexane, are
the key intermediates in the fabrication of polyamide and plas‐
tics such as Nylon 6 and Nylon 66 [2]. However, control over
the selective oxidation of saturated hydrocarbons is challeng‐
ing because of the inertness of the saturated C–H bonds and
subsequent oxidation issues resulting from the higher reactivi‐
ty of the products when compared with that of the reactants.
Accordingly, the industrial manufacture of KA‐oil from cyclo‐
of excessive amounts of byproducts owing to over‐oxidation
[3–5].
Over the past few decades, considerable research efforts
have been devoted to exploring efficient and environmentally
sound methodologies for the selective oxidation of alkanes. In
this regard, heterogeneous catalysis has received the most at‐
tention, and various efficient metal catalysts have been devel‐
oped [6–23]. These catalysts include metal‐incorporated mo‐
lecular sieves [12], metal‐substituted molecular sieves [13,15],
supported Au nanoparticles [6,7,10,23], metal‐organic frame‐
works (MOFs) [22], and carbon‐based materials [24,25]. How‐
ever, the development of cost‐effective, and highly active and
* Corresponding author. Tel: +86‐15182908656; E‐mail: xlong612@126.com
# Corresponding author. Tel: +86‐20‐87113656; E‐mail: liyw@scut.edu.cn
This work was supported by the National Natural Science Foundation of China (21322606, 21436005, 21576095), the State Key Laboratory of Pulp
and Paper Engineering (2015TS03), the Doctoral Fund of Ministry of Education of China (20120172110012), Fundamental Research Funds for the
Central Universities (2015ZP002, 2015PT004), and Guangdong Natural Science Foundation (2013B090500027).
DOI: 10.1016/S1872‐2067(15)61067‐1 | http://www.sciencedirect.com/science/journal/18722067 | Chin. J. Catal., Vol. 37, No. 6, June 2016

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Ying Zhou et al. / Chinese Journal of Catalysis 37 (2016) 955–962
selective heterogeneous catalysts for the oxidation of alkanes
remains a great challenge to date.
2.2. Characterization
Of particular interest, MOFs are a well‐known, new class of
porous functional materials constituting metal ions and organic
ligands. Owing to their ordered structures and relatively low
thermal stability, MOFs have been used for the preparation of
new metal oxides or carbon nanomaterials by thermal decom‐
position. As reported, MOF‐derived materials exhibit excellent
performance in various applications including heterogeneous
catalysis [26–36], electrochemistry [37,38], and gas adsorption
[39–41]. To our knowledge, reports on the use of MOF‐derived
materials as catalysts for liquid‐phase organic synthesis are
rare.
Herein, we report a novel, non‐noble Ni‐based heterogene‐
ous catalytic system for the selective oxidation alkanes. Various
alkanes, such as cyclohexane and ethylbenzene, could be selec‐
tively transformed into the desired aldehydes or ketones in
high yields under mild conditions. The catalysts were prepared
by simple thermolysis of a Ni‐containing MOF under inert at‐
mosphere.
Powder X‐ray diffraction (PXRD) patterns of the prepared
materials were recorded on
a
Rigaku diffractometer
(D/MAX‐IIIA; 3 kW) using Cu Kα radiation (40 kV, 30 mA, λ =
0.1543 nm). N2 adsorption‐desorption isotherms were meas‐
ured on a Micromeritics ASAP 2020M instrument at –196 °C .
The Ni content of the samples was determined quantitatively
by atomic absorption spectroscopy (AAS) on a HITACHI
Z‐2300. The surface topography of Ni‐MOF and the Ni@C‐N
materials was investigated by scanning electron microscopy
(SEM; MERLIN of ZEISS). Transmission electron microscopy
(TEM) images of the samples were recorded on a JEM‐2010HR
(JEOL) microscope. X‐ray photoelectron spectroscopy (XPS)
measurements were performed on a Kratos Axis Ultra DLD
system with a base pressure of 1.33  10–7 Pa.
2.3. Oxidation of alkanes over Ni@C‐N
The oxidation of alkanes (e.g., ethylbenzene) was conducted
in a 25‐mL Schlenk tube. Typically, ethylbenzene (0.5 mmol),
catalyst (10 mol% based on Ni), tert‐butyl hydroperoxide
(TBHP; 1.5 mmol), and DMF (2 mL) were added to the tube and
heated at 80 °C. After reaction, the catalyst was isolated from
the mixture solution by centrifugation, then washed with DMF
and methanol. The liquid mixtures were then analyzed by gas
chromatography mass spectrometry (Agilent Technologies
7890B‐5977A) on a chromatograph equipped with a 0.25 mm
× 30 m HP‐5MS capillary column.
2. Experimental
2.1. Synthesis of Ni@C‐N catalysis
All chemicals were purchased from commercial corpora‐
tions and used without further treatment.
Typically,
a
mixture of Ni(NO)3∙6H2O (0.9 mmol),
1,4‐benzenedicarboxylic acid (H2bdc; 0.72 mmol), triethylene‐
diamine (dabco; 0.58 mmol), and dimethylformamide (DMF; 15
mL) were added to a Teflon‐lined autoclave. The reactor was
heated in an oven at 120 °C for 2 d. The obtained green powder
was then washed with DMF and methanol, and finally dried
under vacuum at 150 °C for 2 h.
For the recyclability tests, the catalyst was separated from
the reaction mixture and washed with DMF and methanol for
several times. The solid was then dried at 80 °C in an oven and
reduced by H2 at 200 °C for 2 h before use for the next run.
The Ni@C‐N catalysts were prepared by pyrolysis of Ni‐MOF
in an inert atmosphere. Ni‐MOF was heated at a heating rate of
1 °C/min from room temperature to 200 °C and maintained at
this temperature for 2 h in Ar. Then, the temperature was in‐
creased to the target temperature (i.e., 500, 600, 700, 800, or
900 °C) at the same heating rate and subsequently maintained
for 8 or 15 h. The resulting samples were denoted as
Ni@C‐N‐x‐8h or Ni@C‐N‐x‐15h, where x indicates the target
thermolysis temperature (°C).
3. Results and discussion
3.1. Characterization of the materials
Ni‐MOF was prepared according to the procedures de‐
scribed in previous reports [42,43]. The PXRD pattern of the
as‐synthesized Ni‐MOF (Fig. 1(a)) matched well with the pub‐
lished XRD patterns [42,43]. The N2 adsorption‐desorption
isotherm measured at –196 °C indicated that Ni‐MOF was
500
(b)
(a)
400
300
200
100
0
5
10
15
20
0.0
0.2
0.4
p/p0
0.6
0.8
1.0
2/(o )
Fig. 1. (a) PXRD pattern and (b) N2 adsorption‐desorption isotherm of as‐synthesized Ni‐MOF.

Ying Zhou et al. / Chinese Journal of Catalysis 37 (2016) 955–962
957
mostly microporous (Fig. 1(b)). The Brunauer‐Emmett‐Teller
(BET) surface area was calculated to be ~1700 m2/g.
Ni@C‐N materials were calculated to be ~100–200 m2/g.
The surface morphology of the Ni@C‐N materials was ex‐
amined by SEM. The SEM images in Fig. 4(a)–(d) depict the
initial shape of the Ni‐MOF crystals when MOF was calcined
below 700 °C for 8 h. The surface of the materials became dis‐
torted and considerably rougher upon decomposition and car‐
bonization of the MOF. When the pyrolysis temperature in‐
creased to 800 °C, numerous nanotubes were obtained (Fig.
4(e)), which might be catalyzed by the generated Ni nanoparti‐
cles.
The TEM images in Fig. 5 revealed that the metallic Ni na‐
noparticles were highly dispersed in the carbon matrix derived
from carbonization of the organic linker in Ni‐MOF. At the
higher MOF pyrolysis temperatures, aggregation of the Ni na‐
noparticles into larger particles was observed. When the ther‐
molysis temperature increased to 900 °C, most of the particles
agglomerated into large particles with an average size of ~18
nm (Fig. 6). High‐resolution TEM analysis of an individual large
particle indicated that each Ni nanoparticle was tightly em‐
bedded in the graphitic carbon (Fig. 6(c)).
The Ni@C‐N materials were prepared by pyrolysis of
Ni‐MOF under a continuous flow of Ar for 8 or 15 h at varying
temperatures. The Ni contents in the samples were ~35–40
wt%. Fig. 2 shows the PXRD patterns of the Ni@C‐N materials.
All the prepared materials displayed five diffraction peaks at
~44.4°, 51.8°, 76.4°, 92.9°, and 98.5°, which are characteristics
of metallic Ni (JCPDS No. 04‐0850) [44]. The intensity of the Ni
diffraction peaks increased with increasing pyrolysis tempera‐
tures employed, indicating the formation of Ni phase with a
higher crystallization degree. The crystallite sizes of Ni Parti‐
cles in the materials were in the range of 7–10 nm, as calculated
by the Scherrer formula.
Fig. 3 shows the N2 adsorption‐desorption isotherms of the
Ni@C‐N materials measured at –196 °C . All isotherms featured
typical adsorption curves of types I and IV, with an apparent
hysteresis loop in the relative pressure (P/P0) range of 0.5–1.0,
suggesting the presence of a micro‐/meso‐/macroporous
structure in the Ni@C‐N materials. The BET surface areas of the
(a)
(b)
Ni@C-N-900-8h
Ni@C-N-900-15h
Ni@C-N-800-8h
Ni@C-N-700-8h
Ni@C-N-600-8h
Ni@C-N-500-8h
Ni@C-N-800-15h
Ni@C-N-700-15h
Ni@C-N-600-15h
Ni@C-N-500-15h
20
30
40
50
60
2/( o )
70
80
90
100
20
30
40
50
60
2/(o )
70
80
90
100
Fig. 2. PXRD patterns of (a) Ni@C‐N‐x‐8h and (b) Ni@C‐N‐x‐15h.
120
(b)
(a)
180
ads-500
ads-600
ads-700
ads-800
ads-900
des-500
ads-500
ads-600
ads-700
ads-800
ads-900
des-500
des-600
des-700
des-800
des-900
des-600
des-700
des-800
des-900
90
60
30
0
135
90
45
0
0.0
0.2
0.4
p/p0
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
p/p0
Fig. 3. N2 adsorption (ads)‐desorption (des) isotherms of (a) Ni@C‐N‐x‐8h and (b) Ni@C‐N‐x‐15h.

958
Ying Zhou et al. / Chinese Journal of Catalysis 37 (2016) 955–962
(a)
(b)
Mean size: 17.44 nm
SD: 1.16 nm
(c)
(d)
25
20
15
10
5
Graphitic structure
d=0.34 nm
0
5
10 15 20 25 30 35 40 45
D/nm
Fig. 6. (a, b) TEM images of Ni@C‐N‐900‐8h. (c) High‐resolution TEM
image of a Ni particle and (d) corresponding size distribution of the Ni
nanoparticles.
Fig. 4. SEM images of (a) Ni‐MOF, (b) Ni@C‐N‐500‐8h, (c)
Ni@C‐N‐600‐8h, (d) Ni@C‐N‐700‐8h, (e) Ni@C‐N‐800‐8h, and (f)
Ni@C‐N‐900‐8h.
their metallic states upon calcination in an inert atmosphere
[46–48]. The N 1s peak of Ni‐MOF appeared at 399.8 eV and
could be assigned to the N of triethylenediamine coordinated
with a metal ion [49]. Interestingly, this bonding energy was
slightly higher than that of amino nitrogen (399.6 eV) owing to
the influence of the magnetic metal center (i.e., Ni) [50,51].
After thermolysis, the N 1s spectra of Ni@C‐N‐900‐8h showed
two new peaks at 398.9 and 401.0 eV, which could be assigned
to pyridinic N and graphitic N, respectively [52]. This phenom‐
enon was consistent with the TEM result (Fig. 6(c)) with re‐
spect to the formation of a graphitic structure.
3.2. Catalytic oxidation of ethylbenzene over Ni@C‐N
First, ethylbenzene oxidation was employed as a model re‐
action to evaluate the catalytic activities of the as‐synthesized
Ni@C‐N materials. The catalytic reaction was conducted at 80
°C using TBHP as oxidant, and the results are summarized in
Table 1. The blank reaction, without any catalyst, achieved
minimal conversion performance only (Table 1, entry 1). In
contrast, in the presence of the Ni@C‐N materials, the oxidation
transformation was efficiently promoted. The activity of the
catalysts was strongly dependent on the pyrolysis temperature
and time. Generally, the Ni@C‐N materials prepared under
higher MOF thermolysis temperatures showed higher activities
(Table 1, entries 2–11), possibly because of the higher carbon‐
ization degree of the organic linkers in the MOF. In contrast, a
longer pyrolysis time reduced the catalytic activity of the ob‐
tained Ni@C‐N materials. Among the examined catalysts,
Ni@C‐N‐900‐8h displayed the best ethylbenzene oxidation
performance (Table 1, entry 6), achieving an ethylben‐
zene‐to‐acetophenone conversion of 77% within 48 h of reac‐
tion at 80 °C. Moreover, a higher yield of acetophenone could
be achieved by simply increasing the amount of TBHP, while
Fig. 5. TEM images of (a) Ni@C‐N‐500‐8h, (b) Ni@C‐N‐600‐8h, (c)
Ni@C‐N‐700‐8h, and (d) Ni@C‐N‐800‐8h.
The XPS spectra of Ni‐MOF and Ni@C‐N‐900‐8h are shown
in Fig. 7. The Ni 2p peaks at 856.0 and 873.6 eV could be as‐
signed to Ni2+ in Ni‐MOF (Fig. 7(a)). After thermolysis, the two
Ni 2p peaks of Ni@C‐N‐900‐8h respectively shifted to lower
binding energies by ~3.2 and ~3.3 eV relative to those of
Ni‐MOF, indicating that most of the Ni(II) ions in MOF were
reduced to Ni(0) [45]. This result agreed with common exper‐
imental observations, whereby central metal ions of MOF with
reduction potentials higher than 0.27 V are typically reduced to

Ying Zhou et al. / Chinese Journal of Catalysis 37 (2016) 955–962
959
(b)
(a)
0.9 eV
1.2 eV
3.2 eV
Ni@C-N-900-8h
3.3 eV
Ni@C-N-900-8h
Ni-MOF
405
Ni-MOF
880
850
860
870
B.E. (eV)
890
395
400
B.E. (eV)
410
Fig. 7. (a) Ni 2p and (b) N 1s XPS spectra of Ni‐MOF and Ni@C‐N‐900‐8h.
maintaining other conditions constant (Table 1, entry 12).
Subsequently, the recyclability of Ni@C‐N‐900‐8h catalyst
toward ethylbenzene oxidation was examined. The results are
presented in Table 1 (entries 6, 13–15); no significant decline
in the conversion and selectivity performance was observed
during repeated catalytic runs (up to four runs). These results
demonstrate the high stability of the Ni@C‐N catalyst under the
investigated conditions.
of various saturated alkanes under similar reaction conditions.
The results are summarized in Table 2. As observed, the vari‐
ous secondary C–H bonds were oxidized smoothly with excel‐
Table 2
Oxidation of various alkanes catalyzed by Ni@C‐N‐900‐8h.
Conversion
(%)
Selectivity
(%)
O
Entry Substrate
1
T/°C t/h
80 18
>99
>99
100
3.3. Oxidation of different alkanes over Ni@C‐N
O
O
O
2
3
80 22
80 18
To demonstrate the general applicability of the Ni@C‐N cat‐
alysts, we extended the use of the present catalytic system
(specifically, Ni@C‐N‐900‐8h) to the oxidation transformations
40
60
62
O
O
O
>99
>99
Table 1
38
Results of the oxidation of ethylbenzene catalyzed by different Ni@C‐N
catalysts.
O
4
5
100 20
100 48
80 50
O
100
Ni@C-N
O
TBHP 80 oC
58
Entry
Catalyst
Conversion (%)
Yielda (%)
100
O
1
Blank
7
47
47
48
65
77
37
45
50
47
40
>99
78
75
76
7
47
47
48
65
77
37
45
50
47
40
>99
78
75
76
2
Ni@C‐N‐500‐8h
Ni@C‐N‐600‐8h
Ni@C‐N‐700‐8h
Ni@C‐N‐800‐8h
Ni@C‐N‐900‐8h
Ni@C‐N‐500‐15h
Ni@C‐N‐600‐15h
Ni@C‐N‐700‐15h
Ni@C‐N‐800‐15h
Ni@C‐N‐900‐15h
Ni@C‐N‐900‐8h
Ni@C‐N‐900‐8h
Ni@C‐N‐900‐8h
Ni@C‐N‐900‐8h
3
6
>99
4
Br
Br
95
5
O
6
7
7
80 50
>99
Br
8
Br
96
9
O
10
11
12b
13c
14d
15e
8
9
80 20
80 36
>99
>99
99
O
a Reaction conditions: ethylbenzene (0.5 mmol), catalyst (Ni 10 mol%
relative to ethylbenzene), DMF (2 mL), TBHP (1.5 mmol), 80 °C, 48 h.
b TBHP 2.5 mmol. c Second run. d Third run. e Fourth run.
O
95
Reaction conditions: substrate (0.5 mmol), catalyst (Ni 10 mol%), DMF
(2 mL), TBHP (2.5 mmol).

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Ying Zhou et al. / Chinese Journal of Catalysis 37 (2016) 955–962
lent selectivities to their corresponding partial oxidation prod‐
ucts (Table 2, entries 1–5). For the oxidation of cyclohexane, a
moderate conversion with 100% selectivity to cyclohexanone
was achieved at 100 °C (Table 2, entry 5). Substituted
ethylbenzene containing either electron‐withdrawing or elec‐
tron‐donating functional groups also displayed excellent con‐
versions and selectivities to the corresponding ketones (Table
2, entries 6–8). It was interesting to note that Ni@C‐N was also
highly active and selective toward the oxidation of
1,4‐diethylbenzene, achieving >95% selectivity to the diketone
product (Table 3, entry 9). These results demonstrate the high
versatility of the MOF‐derived Ni@C‐N catalysts prepared
herein for the selective oxidation of alkanes.
References
[1] R. A. Sheldon, J. K. Kochi, Metal‐Catalyzed Oxidations of Organic
Compounds; Academic Press, New York, 1981, 26–33.
[2] U. Schuchardt, W. A. Calvarlho, E. V. Spinace, Synlett, 1993, 10,
713–718.
[3] K. Kamata, K. Yonehara, Y. Nakagawa, K. Uehara, N. Mizuno, Nat.
Chem., 2010, 2, 478–483.
[4] R. G. Bergman, Nature, 2007, 446, 391–393.
[5] K. Weissermel, H. J. Arpe, Industrial Organic Chemistry, 2nd ed,
VCH Press, Weinheim, 1993.
[6] B. P. C. Hereijgers, B. M. Weckhuysen, J. Catal., 2010, 270, 16–25.
[7] R. Zhao, J. Dong, G. M. Lu, G. Qian, L. Yan, X. L. Wang, J. S. Suo, Chem.
Commun., 2004, 904–905.
[8] L. X. Xu, C. H. He, M. Q. Zhu, K. J. Wu, Y. L. Lai, Catal. Commun.,
2008, 9, 816–820.
[9] P. P. Wu, P. Bai, K. P. Loh, X. S. Zhao, Catal. Today, 2010, 158,
220–227.
4. Conclusions
We have developed novel, efficient, and cost‐effective
Ni‐based catalysts for application in the selective oxidation of
alkanes. The Ni@C‐N materials were prepared by direct ther‐
molysis of a Ni‐containing MOF under inert atmosphere. The
as‐prepared Ni nanoparticles embedded in the C–N composites
displayed high activity and selectivity in the oxidation of al‐
kanes to their corresponding partial oxidation products under
mild reaction conditions, thus showing a broad substrate scope
for diverse saturated C–H bonds. Moreover, the catalysts are
highly stable and maintain high activity and selectivity during
numerous repeated catalytic cycles under the investigated con‐
ditions. The present strategy may be extended to the develop‐
ment of other novel metal–carbon composite catalysts for se‐
lective catalytic oxidation applications.
[10] L. Li, C. Jin, X. C. Wang, W. J. Ji, Y. Pan, T. van der Knaap, R. van der
Stoel, C. T. Au, Catal. Lett., 2009, 129, 303–311.
[11] Z. G. Sun, G. Li, L. P. Liu, H. O. Liu, Catal. Commun., 2012, 27,
200–205.
[12] J. Li, Y. Shi, L. Xu, G. Z. Lu, Ind. Eng. Chem. Res., 2010, 49,
5392–5399.
[13] R. Raja, G. Sankar, J. M. Thomas, J. Am. Chem. Soc., 1999, 121,
11926–11927.
[14] C. Chen, J. Xu, Q. H. Zhang, Y. F. Ma, L. P. Zhou, M. Wang, Chem.
Commun., 2011, 47, 1336–1338.
[15] H. X. Yuan, Q. H. Xia, H. J. Zhan, X. H. Lu, K. X. Su, Appl. Catal. A,
2006, 304, 178–184.
[16] X. Guo, D. H. Shen, Y. Y. Li, M. Tian, Q. Liu, C. C. Guo, Z. G. Liu, J. Mol.
Catal. A, 2011, 351, 174–178.
[17] G. Qian, D. Ji, G. M. Lu, R. Zhao, Y. X. Qi, J. G. Suo, J. Catal., 2005, 232,
Graphical Abstract
Chin. J. Catal., 2016, 37: 955–962 doi: 10.1016/S1872‐2067(15)61067‐1
Ni‐based catalysts derived from a metal‐organic framework for selective oxidation of alkanes
Ying Zhou, Jilan Long*, Yingwei Li *
South China University of Technology
Ni2+
+
+
120 oC
48 h
DMF
Ar
Calcining
DMF
TBHP
80 oC
Ni‐MOF
Ni@C‐N
We developed a series of novel Ni‐based catalysts by pyrolysis a Ni‐containing metal‐organic frameworks in an inert atmosphere at dif‐
ferent temperatures. These Ni‐based catalysts are highly active and selective in the oxidation of a variety of alkanes.

Ying Zhou et al. / Chinese Journal of Catalysis 37 (2016) 955–962
961
378–386.
[37] A. J. Amali, J‐K. Sun, Q. Xu, Chem. Commun., 2014, 50, 1519–1522.
[18] X. X. Yang, H. Yu, F. Peng, H. J. Wang, ChemSusChem, 2012, 7,
1213–1217.
[19] J. L. Gu, Y. Huang, S. P. Elangovan, Y. S. Li, W. R. Zhao, I. Toshio, Y.
Yamazaki, J. L. Shi, J. Phys. Chem. C, 2011, 115, 21211–21217.
[20] H. Zhao, J. C. Zhou, H. Luo, C. Y. Zeng, D. H. Li, Y. J. Liu, Catal. Lett.,
2006, 108, 49–54.
[21] R. Zhao, Y. Q. Wang, Y. L. Guo, X. H. Liu, Z. G. Zhang, Y. S. Wang, W.
C. Zhan, G. Z. Lu, Green Chem., 2006, 8, 459–466.
[22] J. L. Long, L. M. Wang, X. F. Gao, C. H. Bai, H. F. Jiang, Y. W. Li, Chem.
Commun., 2012, 48, 12109–12111.
[38] W. Chaikittisilp, N. L. Torad, C. L. Li, M. Imura, N. Suzuki, S. Ishi‐
hara, K. Ariga, Y. Yamauchi, Chem. Eur. J., 2014, 20, 4217–4221.
[39] T. K. Kim, K. J. Lee, J. Y. Cheon, J. H. Lee, S. H. Joo, H. R. Moon, J. Am.
Chem. Soc., 2013, 135, 8940–8946.
[40] H. L. Jiang, B. Liu, Y. Q. Lan, K. Kuratani, T. Akita, H. Shioyama, F. Q.
Zong, Q. Xu, J. Am. Chem. Soc., 2011, 133, 11854–11857.
[41] G. Srinivas, V. Krungleviciute, Z. X. Guo, T. Yildirim, Energy Environ.
Sci., 2014, 7, 335–342.
[42] J. Y. Lee, D. H. Olson, L. Pan, T. J. Emge, J. Li, Adv. Funct. Mater.,
2007, 17,1255–1262.
[43] J. L. Long, B. Yin, Y. W. Li, B. L. Zhang, AIChE J., 2014, 60,
3565–3576.
[23] J. L. Long, H. L. Liu, S. J. Wu, S. J. Liao, Y. W. Li, ACS Catal., 2013, 3,
647–654.
[44] Y. X. Yang, C. Ochoa‐Hernández, P. Pizarro, V. A. de la P O’Shea, J. M.
Coronado, D P. Serrano, Fuel, 2015, 144, 60–70.
[24] H. Yu, F. Peng, J. Tan, X. W. Hu, H. J. Wang, J. Yang, W. X. Zheng,
Angew. Chem. Int. Ed., 2011, 50, 3978–3982.
[45] M. C. Biesingera, B. P. Payne, A. P. Grosvenor, L. W. M. Lau, A. R.
Gerson, R. S. C. Smart, Appl. Surf. Sci., 2011, 257, 2717–2730.
[46] F. Severino, J. L. Brito, J. Laine, J. L. G Fierro, A. L. Agudo, J. Catal.,
1998, 177, 82–95.
[25] X. H. Li, J. S. Chen, X. C. Wang, J. Sun, M. Antonietti, J. Am. Chem. Soc.,
2011, 133, 8074–8077.
[26] H. H. Zhao, H. L. Song, L. L. Xu, L. J. Chou, Appl. Catal. A, 2013, 456,
188–196.
[47] P. Liu, E. J. M. Hensen, J. Am. Chem. Soc., 2013, 135, 14032–14035.
[48] J. M. L. Martínez, E. Rodríguez‐Castellón, R. M. T. Sánchez, L. R.
Denaday, G. Y. Buldain, V. C. Dall’ Orto, J. Mol. Catal. A, 2011, 339,
43–51.
[27] F. Zhang, C. Chen, W. M. Xiao, L. Xu, N. Zhang, Catal. Commun.,
2012, 26, 25–29.
[28] Y. F. Yang, L. T. Jia, B. Hou, D. B. Li, J. G. Wang, Y. H. Sun, J. Phys.
Chem. C, 2014, 118, 268–277.
[49] F. G. Souza, P. Richa, A. de Siervo, G. E. Oliveira, C. H. M. Rodrigues,
M. Nele, J. C. Pinto, Macromol. Mater. Eng., 2008, 293, 675–683.
[50] J. S. Stevens, S. J. Byard, C. A. Muryn, S. L. M. Schroeder, J. Phys.
Chem. B, 2010, 114, 13961–13969.
[29] W. X. Wang, Y. W. Li, R. J. Zhang, D. H. He, H. L. Liu, S. J. Liao, Catal.
Commun., 2011, 12, 875–879.
[30] R. Q. Fang, H. L. Liu, R. Luque, Y. W. Li, Green Chem., 2015, 17,
4183–4188.
[51] M. Shibata, Y. Kimura, D. Yaginuma, Polymer, 2004, 45,
7571–7577.
[31] K. Shen, L. Chen, J. L. Long, W. Zhong, Y. W. Li, ACS Catal., 2015, 5,
5264–5271.
[52] X. L. Li, H. L. Wang, J. T. Robinson, H. Sanchez, G. Diankov, H. J. Dai,
J. Am. Chem. Soc., 2009, 131, 15939–15944.
[32] X. Qiu, X. Wang, Y.W. Li, Chem. Commun., 2015, 51, 3874–3877.
[33] W. Zhong, H. L. Liu, C. H. Bai, S. J. Liao, Y. W. Li. ACS Catal., 2015, 5,
1850–1858.
Page numbers refer to the contents in the print version, which include
both the English version and extended Chinese abstract of the paper. The
online version only has the English version. The pages with the extended
Chinese abstract are only available in the print version.
[34] X. Wang, W. Zhong, Y. W. Li, Catal. Sci. Technol., 2015, 5,
1014–1017.
[35] J. L. Long, Y. Zhou, Y. W. Li, Chem. Commun., 2015, 51, 2331–2134.
[36] C. Bai, X. Yao, Y. W. Li, ACS Catal., 2015, 5, 884–891.