Novel CoNi-metal-organic framework crystal-derived CoNi?C: Synthesis and effective cascade catalysis

Article abstract of DOI:10.1039/d0dt01558j

Evaluating the catalytic influence of metal sites on derivates obtained from the calcination of metal-organic frameworks (MOFs) is very important for the rational construction of novel MOFs. Based on this catalytic functional guidance, two new Co-MOF and CoNi-MOF crystals were designed and synthesized, and further pyrolyzed to obtain corresponding porous carbon-based catalysts. Interestingly, the derivates exhibited better catalytic performance toward the tandem reaction of dehydrogenation of NH3BH3 and subsequent hydrogenation reduction of nitro/olefin compounds than those of the CoNi-ZIF (a star MOF)-derived CoNi?carbon and most metal catalysts. Significantly, the CoNi?C maintained excellent activity, even after 30 cycles, demonstrating its great longevity and durability, which are especially important for the practical application of metal catalysts in industrial catalysis.

Full text of DOI:10.1039/d0dt01558j

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A Novel CoNi-Metal-Organic Framework Crystal Derived CoNi@C:
Synthesis and Effective Cascade Catalysis
Lin Wang,‡a Jian-Wei Zhang,‡b Chenchen Li,a Jia-Lu Sun,a Guo-Ming Wanga and Yu-Zhen Chen*a
Received 00th January 20xx,
Accepted 00th January 20xx
Evaluating the catalytic influence of metal sites on the derivates obtained from calcination of metal-organic frameworks
(MOFs) is very important for rational construction of novel MOFs. Based on this catalytic functional guidance, two new Co-
MOF and CoNi-MOF crystals have been designedly synthesized and further pyrolyzed to obtain corresponding porous
carbon-based catalysts. Interestingly, the derivates exhibit better catalytic performance toward the tandem reaction of
dehydrogenation of NH3BH3 and subsequent hydrogenation reduction of nitro/olefin compounds than those of the CoNi-
ZIF (a star MOF) derived CoNi@carbon and most metal catalysts. Significantly, the CoNi@C maintains excellent activity
even after 30 cycles, demonstrating its great longevity and durability. This is especially important for practical application
of metal catalysts in industry catalysis.
DOI: 10.1039/x0xx00000x
www.rsc.org/
MNPs have long been central in heterogeneous catalysis,
earth-abundant non-noble transition metal catalysts (TMCs)
have remained relatively unexplored.23-26 Recently, some
Introduction
Hydrogen, as a green and source-independent energy carrier,
is promising energy for various power devices, especially in
hydrogen fuel cells and hydrogen vehicles. Ammonia borane
(NH3BH3) has been recognized as an excellent hydrogen
storage material due to its good stability, high hydrogen
content (~19.6 wt%), and good water solubility.1-4 Recently,
development of effective metal catalysts to enhance the
reaction kinetics of hydrolysis of NH3BH3 has made an
important progress, especially as a moderate reducing agent.5-
transition MNPs stabilized by various supports have been
investigated, and exhibited great potential even beyond those
of precious metals.24 However, the preparation of
multifunctional TMCs with small size and long lifetime remains
to be great challenging due to their low electrode
potential.24,26 Therefore, most TMCs suffer from sintering
drawbacks during preparation process,6 largely impeding their
practical application.
The encapsulation of non-noble metal active species inside a
porous matrix could be an effective solution to address above
difficulty. Metal-organic frameworks (MOFs),27-31 featuring
specific crystalline structures, high surface areas, and synthetic
tailorability, have shown potential application in various
fields.32-39 In recent years, there have been intensive studies
on MOFs as templates/precursors for porous carbon-based
materials,40-47 which inherit the high porosity, specific
morphology and size from their parent MOFs. Moreover, the
derivates display much better performance than their parent
MOFs, such as ultrahigh stability, good conductivity, highly
dispersed active sites and excellent catalytic performance for
various reactions.48-55 Regardless of the recent progress in this
field, exploration of MOF-derived multifunctional catalysts is
still in its infancy. Firstly, although more than 20,000 MOFs
have been reported, only a few MOFs, such as Fe-MIL-88,40
ZIF(-8, -67),41-43 and PCN series44 have been investigated for
pyrolysis. Secondly, the single metal activity site (Fe or Co) due
to limited choice of MOFs largely hampers their catalytic
application.40 Thirdly, the MOF-derived materials with long-
term stability in catalytic reactions have been rarely reported.
Therefore, multifunction oriented-MOFs continue to be
8
Another important reaction, the hydrogenation of nitro
compounds, is a vital process in the production of dyes,
agrochemicals, polymers and pharmaceuticals.9-14 Traditionally,
aromatic amines are mainly acquired from the reduction of
nitro compounds over supported noble metal catalysts (Au, Pd,
etc.), and sometimes require stronger reductant (e.g.,
NaBH4).15,16 Fortunately, the H2 molecule in situ released from
dehydrogenation of NH3BH3 is highly dispersed in water
solution, therefore can effectively promoting the reduction of
unsaturated bond or nitro groups based on metal catalysts.17
During the cascade reaction process, choosing appropriate
metal catalysts is very crucial.
Metal nanoparticles (MNPs) have attracted increasing
attention in nano-catalysis field due to their unique electronic
structure and physicochemical properties.17-22 Whereas noble
aCollege of Chemistry and Chemical Engineering, Qingdao University, Qingdao,
Shandong 266071 (P. R. China).
bSchool of Chemistry and Chemical Engineering, Shangqiu Normal University,
Shangqiu, 476000, P. R. China.
*E-mail: chenzhen1738@163.com (Y.-Z. Chen)
†Electronic Supplementary Information (ESI) available: Experimental section, PXRD
patterns, SEM image and UV-vis absorption spectrum.
See DOI: 10.1039/x0xx00000x. CCDC 1919854 contains the supplementary
crystallographic data for this paper.
‡These authors contributed equally to this work.
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Preparation of Porous Carbon Materials.
explored to provide more novel metal catalysts, and this will
open a new chapter for MOFs application in many fields.
Preparation of Co@C and CoNi@C. The o
D
b
O
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a
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i
1
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e
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F or
C
9
o
/D
N
0
i
D
-MT0
O
15
5
8J
Co-MOF was put into a tube furnace with a flowing 20% H2/Ar
atmosphere, and heated directly to 500 oC, 600 oC, 700 oC, 800
o
o
oC, or 900 C at the rate of 5 C/min, and maintained for 2 h.
Then the final samples were cooled naturally to room
temperature.
Co
Ni
Pyrolysis
Preparation of Ni/AC, CoNi/AC, Ni@C-ZIF, Co@C-ZIF and
CoNi@C-ZIF. For Ni/AC or CoNi/AC, Ni(NO3)2∙6H2O (192 mg), or
Co(NO3)2∙6H2O (96 mg) and Ni(NO3)2∙6H2O (96 mg) were
dissolved in 5 mL of water respectively, and 20 mL of water
was put into a flask with 80 mg of active carbon (AC). The
NaBH4 solution with moderate concentration was added into
the flask to obtain Ni/AC or CoNi/AC; For Ni@C-ZIF, Co@C-ZIF
and CoNi@C-ZIF preparation, 500 mg of Ni@C-ZIF, Co@C-ZIF
or CoNi-ZIF was placed in a tube furnace with a flowing 20%
CoNi-MOF
Scheme 1. Schematic illustration showing the synthesis of new CoNi-MOF and
the derived CoNi@C catalyst.
CoNi@C
Bearing above points in mind,
a
novel cobalt-MOF
{[Co2(BPTC)(DMSO)2.5(MeOH)0.5]·2(MeOH)}, denoted as QDUC-1,
(BPTC = 3,3’,5,5’-biphenyltetracarboxylate) has been specifically
synthesized. In order to enrich the metal active sites, a nickel salt
was added into the synthetic system of QDUC-1, thus a bimetallic
CoNi-MOF (denoted as QDUC-2, the molar ratio of Co/Ni is 1:1) has
been successfully obtained. These MOFs were subsequently
calcinated under high temperature and 20% H2/Ar to finally
produce nanosized Co NPs or CoNi NPs stabilized with porous
carbon (denoted as Co@C or CoNi@C, Scheme 1). The
multifunctional CoNi@C catalyst not only displayed outstanding
performance toward the NH3BH3 hydrolysis and subsequent
hydrogenation of nitro or olefin compounds, but also exhibited
extraordinary recyclability and durability. Strikingly, the activity of
CoNi@C even surpasses those of ZIF-derived porous metal catalysts.
To the best of our knowledge, this is one of a few reports that
combines the synthesis of new MOF crystals and the performance
investigation of their derivates.
o
H2/Ar, and heated directly to 600 C and maintained for 2 h.
Then the samples were cooled naturally to room temperature.
Catalytic Activity Evaluation
Catalytic performance evaluation for CoNi@C toward the
hydrolysis reaction of ammonia borane. Typically, CoNi@C (20 mg)
catalyst and water (20 mL) were charged into a flask under
magnetic stirring. The flask was connected to a gas burette filled
with water to monitor the volume of hydrogen generated. The 15
mg of NH3BH3 was placed into above solution to induce the reaction.
The reaction was completed when there was no more produced
gas.
Catalytic performance evaluation for all samples toward the
cascade reactions. In general, the CoNi@C catalyst and
nitroarene or olefin were uniformly dispersed in a solvent
mixture of methanol and water in the flask. Then 15 mg of
NH3BH3 was placed into above solution to induce the reaction.
The catalytic hydrogenation reaction of nitroarene or olefin
was traced with gas chromatography. For cycling experiments,
the amount of nitroarene or olefin (0.1 mmol) and NH3BH3 (15
mg) were kept the same. For comparation, the Co@C catalyst
was used for the reaction while all other reaction conditions
remained the same.
Experimental Section
Preparation of samples.
MOF Synthesis.
Preparation of Co-MOF and CoNi-MOF. A mixture of ligand
(H4BPTC, 10 mg) and Co(NO3)2·6H2O (24 mg) was ultrasonically
dissolved in a mixed solution of DMSO (3 mL), MeOH (0.2 mL),
and HNO3 (0.04 mL, 1.4 M in DMF) in a 20 mL vial. The mixture
was tightly sealed and then put into an oven preheated at 110
oC for 96 h followed by cooling down to environment
temperature. Red cubic crystals were successively obtained by
filtration and washed with fresh DMF and CH2Cl2 several times,
Single-crystal X-ray crystallographic determination.
The crystal data collection for porous coordination compounds
was conducted on Agilent Gemini E/Eos equipped with a
graphite-monochromated Cu Kα radiation (λ = 1.54184 Å) at
134(3) K and the SADABS program. The structures were solved
using the direct method and refined with full-matrix least-
squares refinement using the SHELXL-2018/3 crystallographic
software package. CCDC-2008424 contains the supplementary
crystallographic data for this paper. Code for the individual
structure is listed in the Supporting Information. This
crystallographic data can be obtained free of charge from the
Cambridge Crystallographic Data Centre (CCDC) through
www.ccdc.cam.ac.uk/data_request/cif.
o
and dried at 60 C for 2 h (90% yield based on the ligand). For
the preparation of CoNi-MOF, Co(NO3)2·6H2O (12 mg) and
Ni(NO3)2∙6H2O (12 mg) was added and other synthetic
conditions were identify with the synthetic method of Co-MOF.
Preparation of Co-ZIF, Ni-ZIF and CoNi-ZIF. Generally, the
ligand of 2-methylimidazole (3.70 g) was mixed with certain
amount of methanol. The mixture was blended into 80 mL of
methanol with Co(NO3)2∙6H2O (0.87 g) and/or Ni(NO3)2∙6H2O
(0.87 g). The solution was reacted overnight to get the final
product.
Results and Discussion
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DOI: 10.1039/D0DT01558J
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batch was kept consistent, which demonstrated the uniform
dispersion of Ni and Co elements (Fig. S2a,b†). The powder X-
ray diffraction (PXRD) peaks of as-synthesized MOFs are
consistent with that of simulated Co-MOF (Fig. S3a†),
indicating the successful synthesis of QDUC-1 and QDUC-2.
CoNi-MOF exhibits considerable thermal stability up to 300 °C
from the thermogravimetric data (Fig. S3b†). The inductively
coupled plasma atomic emission spectrometry (ICP-AES)
analysis for CoNi-MOF shows the actual molar ratio of Co/Ni
is 1.05, which is very close to the theoretical value (1.0, Table
S2†). To gain a better understanding of the crystallinity and
morphology of QDUC-2, the microstructure was observed
using scanning electron microscopy (SEM). The result shows
CoNi-MOF microcrystals have uniform lamellar shape with a
length of ~500 nm (Fig. 2c). In order to obtain multifunctional
and more stable catalysts, porous carbon-based Co or CoNi
composites were prepared.
Fig. 1 The structure description for QDUC-1: (a) coordination environment of
Co(II), μ3-OH group and BPTC ligand in QDUC-1. (b) The coordination mode of
the BPTC4- ligand. (c) A 3D porous structure, viewed along the α-axis. and (d)
View of the crb-topology (Atom labeling scheme: C, gray; O, red; Co, green. All
the hydrogen atoms and the terminal DMSO molecules are omitted for clarity.
a
b
High-quality single crystal named as QDUC-1 was synthesized via a
solvothermal reaction of Co(NO3)2·6H2O and H4BPTC and in a
DMF/MeOH/DMSO/HNO3 mixed solvent system at 110 oC for 4
days (details in the Experimental Section). Single-crystal X-ray
diffraction analysis reveals that QDUC-1 crystallizes in the chiral
orthorhombic P21212 space group. The asymmetric unit contains
two crystallographically independent Co(II) centres, one BPTC4-
ligand, two and a half coordinated DMSO molecules, a half
coordinated MeOH molecule, and two MeOH solvent molecules
(Fig. S1†). As depicted in Fig. 1a, the adjacent Co(II) ions as
binuclear SBUs are bridged via one chelating μ2-O bridging
tridentate carboxylate and two bis-monodentate carboxylates
groups to give a 4-connected node. Each ligand binds to four
separated binuclear SBUs to form a 4-connected node (Fig. 1b).
Hence, each adjacent Co(II) subunit is interconnected through
BPTC4- ligand to form a three-Co-MOF (Fig. 1c). The analysis of
QDUC-1 shows the crystal is a (4,4)-connected crb-topology with
point symbol of {4.65} (Fig. 1d). Notably, the dihedral angles
between the two phenyl rings from the BPTC4- ligand is 33.772o
(Fig. S1b†), which is very different with other related Co-MOFs
based on the BPTC4- ligand.55-61 Crystallographic details are
summarized in Table S1†.
c
d
1 μm
500 nm
Fig. 2 Photos of as-synthesized MOF films on the glass substrate of (a) Co-MOF
and (b) CoNi-MOF. (c) SEM image of CoNi-MOF and (d) TEM image of CoNi@C.
Typically,
Co-MOF
or
CoNi-MOF
crystals
as
templates/precursors underwent pyrolysis at different
temperatures (500-900 oC) under H2/Ar atmosphere to produce
porous carbon encapsulated Co or CoNi NPs (abbreviated as Co@C
or CoNi@C-T, T = 500-900) (Fig. S2d,e†). The peaks located at
around 44.3o and 51.6o are assignable to the diffractions of
metallic CoNi alloy NPs (Fig. S4†, CoNi@C-600 as representative).
The transmission electron microscopy (TEM) image shows that the
particles are well dispersed and have retained their original
morphology, CoNi-MOFs (Fig. 2d). The Langmuir surface area of
as-synthesized CoNi@C-600 with high CoNi content (up to ~43
wt%) is 86.1 m2 g−1, and the porous texture can be revealed from
the N2 sorption isotherms at 77 K and pore size distribution (Fig.
S5†).
The bimetallic CoNi-MOF (named as QDUC-2) has also been
designly synthesized by putting moderate amount of Ni and
Co ions into the synthesis system. The results found that only
equimolar Ni and Co ions could be made into CoNi-MOF by
changing various Ni/Co molar proportion. The obvious
evolution of the crystal color from purple (Co-MOF) to pinkish
purple indicated the Ni element was successfully doped to
form CoNi-MOF (Fig. 2a,b). The powder colour from one
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Co 2p3/2
satellite
a
b
d
View A3/r2ticle Online
Ni 2p
DOI: 10.1039/D0DT01558J
a
Ni-Ox
Co-Ox
Co 2p1/2
d
Ni 2p1/2
sat.
sat.
sat.
100 nm
100 nm
6
8
10
12
14
16
Diameter (nm)
c
Co 2p3/2
CoOx
Co
Ni 2p3/2
Ni
b
Co 2p1/2
sat.
Ni 2p1/2
NiOx
sat.
100 nm
20
30
40
50
60
70
810
800
790
780
880
870
860
850
Diameter (nm)
Binding Energy (eV)
Bindind Energy (eV)
c
Fig. 4 Co 2p XPS spectra: (a) CoNi-MOF, (c) CoNi@C. Ni 2p XPS spectra: (b)
CoNi-MOF, (d) CoNi@C.
To gain better insight into the catalytic performance of CoNi@C,
the hydrolysis of NH3BH3 has been investigated. Fig. 5a shows the
dehydrogenation rate of NH3BH3 based on CoNi@C-T catalysts at
ambient reaction temperature (20 oC). The data shows that
CoNi@C-600 has the best performance and releases >99% H2 in ca.
4.7 min, indicating the optimum calcining temperature for CoNi-
100 nm
15
20
25
30
35
40
45
Diameter (nm)
Fig. 3 (a) TEM image of CoNi@C (inset: enlarged TEM), (b) CoNi/AC, (c)
CoNi@C-ZIF and their corresponding size distribution of CoNi NPs.
o
o
MOF is 600 C. The lower calcining temperature (500 C) possibly
lacks confinement effect from graphitized carbon, and the higher
calcining temperature (≥700 oC) might lead to aggregated CoNi
NPs. Both above situations can cause activity drop of metal
catalysts. Encouraged by the excellent catalytic performance of
CoNi@C-600, the hydrogenation of nitro compounds in presence
of NH3BH3 was further explored. The nitrobenzene was quickly
hydrogenated to give the corresponding aniline within 10 min as
expected (Fig. 5b, Table 1, entry 1), and the activity exceeded
most of the reported metal catalysts.24 For comparison, Co@C-600
derived from QDUC-1, performed lower catalytic activity than
CoNi@C-600, demonstrating the importance of the cooperative
catalysis between Co and Ni species (Fig. 5b, Table S4†).
To verify the heterogeneous catalytic property of CoNi@C, a hot
filtration experiment was carried out after 5 min of reaction, no
any aniline was produced even after 10 min of the reaction (Fig.
5b). Therefore, it is inferred that no leaching of the CoNi@C
catalyst occurred and the reaction process is truly heterogeneous.
For comparison, CoNi@C-ZIF, CoNi/AC and Ni/AC has been further
investigated for two-step reaction of NH3BH3 hydrolysis and
nitrobenzene hydrogenation (Fig. 5c). The catalytic results
demonstrated the higher activity of CoNi@C than those of
CoNi@C-ZIF, CoNi/AC and monometallic Co, Ni catalysts. For
industrial application, the catalytic scope of this cascade reaction
was proceeded to investigate. Different substituted aromatic
nitroarenes with electron-withdrawing (-Cl, -Br) and electron-
donating (-NH2, -CH3, -OH) substituent groups were completely
reacted with good yield (> 99%) within 10 min under moderate
conditions (Table 1).
TEM images of CoNi@C indicate that CoNi NPs are highly
dispersed inside carbon matrix and tightly encapsulated by carbon
layer (Fig. 3a, Fig. S6a†). The average size of CoNi NPs is ~9.7 nm,
which is less than 10 nm even for high CoNi content of 43 wt% (Fig.
3a, Table S2†). For comparison, the activate carbon (AC)
supported CoNi NPs with similar metal loading was synthesized
and the larger CoNi NPs (~35 nm) were obtained because of
lacking confinement effect of porous carbon (Fig. 3b). The CoNi-ZIF
(nCo/Ni = 1) has also been prepared and pyrolyzed at 600 oC to
generate the corresponding CoNi@C-ZIF (Fig. S7†). However, the
average size of CoNi NPs in CoNi@C-ZIF is larger than 28 nm
probably due to the massive collapse of skeleton during calcining
process (Fig. 3c). The total metal loading for CoNi NPs and the
Co/Ni molar ratio are summarized in Table S2†. The above results
reflect the good stabilizing effect of porous carbon derived from
QDUC-2.
In order to further understand the existing forms of Co and Ni in
samples, the X-ray photoelectron spectroscopy (XPS) was
investigated. As shown in Fig. 4, the XPS spectrum for QDUC-2
shows clear 2p peaks emerging at 781.4 and 855.9 eV, which are
assignable to two-valence Co and Ni, respectively (Fig. 4a,b). After
pyrolysis, the 2p peaks shift to lower binding energy at 778.4 and
852.8 eV, which were attributed to zero-valence Co and Ni in
CoNi@C, respectively (Fig. 4c,d, Table S3†), showing that most of
the metal salts were successfully reduced by hydrogen.62,63 These
results adequately demonstrate the successful preparation of
bimetallic CoNi-MOF and CoNi@C.
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35
a
View Article Online
DOI:>1909.10%39/D01D0T0m1i5n58J
H3C
NO2
H3C
NH2
6
30
25
20
15
10
5
HO
NH2
HO
NO2
7
>99 %
>99 %
-
10 min
10 min
10 min
900 oC
800 o
700 o
600 o
500 o
C
C
C
C
NO2
Cl
NH2
Cl
8
0
0
5
10
15
20
25
30
35
9c
NO2
-
Time (min)
100
80
60
40
20
0
b
aReaction conditions: 0.1 mmol nitroarenes, 15 mg NH3BH3, 20 mg CoNi@C, 10
mL MeOH, 10 mL H2O, 25 oC. bCatalytic yield was tracked by gas chromatography.
cWithout any catalysts.
Inspired by the remarkable catalytic performance of CoNi@C
catalyst for the cascade reaction, another important
transformation involved in industry field has been proposed.
Interestingly, the prominent catalytic activity of CoNi@C toward
the tandem reaction of hydrogenation of C=C in aromatic alkenes
paired with dehydrogenation of NH3BH3 was achieved (Table 2).
Co@C
CoNi@C
Filtration test
0
5
10
15
20 25
Time (min)
o
When the reaction temperature increases from 25 C to 50 oC by
c
100
80
60
40
20
0
heating, the reaction completes within 5-10 min (Table S5†).
Therefore, when coupling with NH3BH3 hydrolysis, the CoNi@C
exhibited good catalytic activity and chemo-selectivity for the
hydrogenation of various nitroarenes and alkene compounds to
produce their products.
Table 2. Tandem reaction of NH3BH3 hydrolysis and hydrogenation of unsaturated
double bond by CoNi@C catalyst.
F
C
F
C
C
A
F
I
C
@
I
I
A
Z
Z
Z
-
C
@
i
@
/
/
i
-
i
-
i
R
R
o
CoNi@C
C
@
N
C
N
o
N
C
o
@
i
C
C
o
N
N
C
NH3BH3, H2O, 25 o
C
o
C
Fig. 5 (a) Plots of reaction time versus the volume of hydrogen generated from
NH3BH3 dehydrogenation by different CoNi@C-T catalysts. (b) The conversion
of the reduction of nitrobenzene by CoNi@C and Co@C and the hot filtration
test. (c) The conversion of cascade reaction after 10 min of reaction over
various catalysts.
Entry
Substrate
Product
Yield b
>99 %
>98 %
>98 %
>98 %
>98 %
>98 %
-
Time
20 min
30 min
30 min
30 min
30 min
30 min
20 min
Table 1. Tandem reaction of NH3BH3 hydrolysis and subsequent nitroarene
hydrogenation over CoNi@C.
R
1
R
R
NH3BH3,CoNi@C
MeOH/H2O (v:v=1:1), 25 o
Br
2
3
4
5
6
7c
Br
Cl
NO2
NH2
C
Yield b
>99 %
>99 %
>99 %
>99 %
>99 %
Time
Cl
Entry
Substrate
Product
Cl
Cl
NH2
NO2
1
2
3
4
5
10 min
10 min
10 min
10 min
10 min
Cl
Cl
Br
NO2
Br
NH2
NH2
H3C
Cl
NO2
Cl
H3C
NH2
H3C
NO2
H2N
H3C
NH2
-
aReaction conditions: 0.1 mmol olefin, 15 mg NH3BH3, 20 mg CoNi@C, 20 mL H2O,
25 oC. bCatalytic yield was tracked by gas chromatography. cWithout any catalysts.
NO2
NH2
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1
2
3
4
5
6
P. Chen, Z. Xiong, J. Luo, J. Lin and K.L. Tan, Nature, 2002,
a
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80
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0
100 nm
6
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10 12 14
Diameter (nm)
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Cycles
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Fig. 6 Recyclability test for the hydrogenation of nitrobenzene through thirty
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removability of catalyst from solution via an external magnet. (b) TEM image of
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7
8
Furthermore, the recyclability and stability of CoNi@C for
the reduction of nitrobenzene with NH3BH3 has been
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6a, the catalytic activity of CoNi@C is well preserved and the
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This work is supported by the NSFC (21701093), Key Research and
Development Program of Shandong Province (2019GGX103043),
the NSF of Shandong Province (ZR201702200574) and China
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Science
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(2018T110664
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The authors declare no competing financial interest.
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For Table of Contents Use Only
A Novel CoNi-Metal-Organic Framework Crystal Derived CoNi@C: Synthesis and
Effective Cascade Catalysis
Lin Wang,‡a Jian-Wei Zhang,‡b Chenchen Li,a Jia-Lu Sun, a Guo-Ming Wanga and Yu-Zhen Chen*a
In this work, a new bimetallic CoNi-MOF has been designedly synthesized and utilized as precursor to prepare ultra-stable CoNi
alloy nanoparticles embedded in the porous carbon matrix. The final CoNi@C catalyst exhibits excellent catalytic activity and
great longevity toward the cascade reactions of NH3BH3 hydrolysis and subsequent hydrogenation of nitro compounds or
aromatic alkenes.
This journal is © The Royal Society of Chemistry 2016
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