One-pot solvothermal synthesized CoS2@MoS2 nanocomposites for selective reduction coupling reaction to synthesize imines

Article abstract of DOI:10.1016/j.catcom.2019.03.007

Selective reduction coupling of nitroaromatics and aldehydes for imines synthesis has been investigated by using a series of bifunctional CoS₂@MoS₂ catalysts prepared by one-pot solvothermal method. Under optimal Co/Mo ratio of 0.75 and preparation temperature (180 °C), CoS₂@MoS₂–180-0.75 catalyst shows 96.5% nitrobenzene conversion, 93.0% imine selectivity and good versatility for substituted nitrobenzene and different aldehydes under mild conditions (60 °C, 1.5 MPa H₂). The characterizations reveal that high nitroaromatics hydrogenation activity and good selectivity are mainly due to the formation of CoMoS phase, the coupling reaction between aniline derivatives and aldehydes is achieved by the appropriate acidity of CoS₂@MoS₂ nanocomposites.

Full text of DOI:10.1016/j.catcom.2019.03.007

Accepted Manuscript
One-pot solvothermal synthesized CoS2@MoS2 nanocomposites
for selective reduction coupling reaction to synthesize imines
Wenpeng Han, Junwei Wang, Xuekuan Li, Ligong Zhou, Ying
Yang, Mingxing Tang, Hui Ge
PII:
S1566-7367(19)30074-3
DOI:
https://doi.org/10.1016/j.catcom.2019.03.007
CATCOM 5645
Reference:
To appear in:
Catalysis Communications
Received date:
Revised date:
Accepted date:
3 January 2019
2 March 2019
5 March 2019
Please cite this article as: W. Han, J. Wang, X. Li, et al., One-pot solvothermal synthesized
CoS2@MoS2 nanocomposites for selective reduction coupling reaction to synthesize
imines, Catalysis Communications, https://doi.org/10.1016/j.catcom.2019.03.007
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ACCEPTED MANUSCRIPT
One-pot solvothermal synthesized
CoS @MoS nanocomposites for selective
2
2
reduction coupling reaction to synthesize
imines
a, b
a
a
a
a
Wenpeng Han, Junwei Wang, Xuekuan Li, Ligong Zhou, Ying Yang, Mingxing
a*
a*
Tang, Hui Ge
a
Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
b
University of Chinese Academy of Science, Beijing 100049, China
*
Corresponding author. Mingxing Tang, Hui Ge
E-mail address: mxtang@sxicc.ac.cn; gehui@sxicc.ac.cn
ABSTRACT: Selective reduction coupling of nitroaromatics and aldehydes for
imines synthesis has been investigated by using a series of bifunctional CoS @MoS
2
2
catalysts prepared by one-pot solvothermal method. Under optimal Co/Mo ratio of
o
0
9
.75 and preparation temperature (180 C), CoS @MoS -180-0.75 catalyst shows
2
2
6.5% nitrobenzene conversion, 93.0% imine selectivity and good versatility for
o
substituted nitrobenzene and different aldehydes under mild conditions (60 C, 1.5
MPa H ). The characterizations reveal that high nitroaromatics hydrogenation activity
2
and good selectivity are mainly due to the formation of CoMoS phase, the coupling

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reaction between aniline derivatives and aldehydes is achieved by the appropriate
acidity of CoS @MoS nanocomposites.
2
2
Keywords: CoS @MoS ; solvothermal synthesis; selective reduction coupling;
2
2
imines
1
. Introduction
Imines, also known as “Schiff base”, are important organic intermediates, which
are widely applied for various biologically active compounds synthesis, such as
pharmaceuticals, agricultural chemicals and other fine chemicals [1]. The traditional
methods for imines synthesis include condensation of aldehydes/ketones with amines,
oxidative dehydrogenation (ODH) of amines and oxidative coupling of alcohols and
amines, and so on [2, 3]. Among them, the condensation of aldehydes/ketones with
amines is the most commonly used method. It has high atomic utilization and can
obtain various asymmetric imines, but this process requires Lewis acid catalysts,
dehydrating agents, suitable pH value and activated aldehydes/ ketones, which affects
efficiency and economics [4, 5]. Owing to the selective hydrogenation of
nitroaromatics to corresponding anilines can be carried out under mild conditions
[
6-8], the direct one-pot synthesis of imines via reduction coupling of nitroaromatics
and aldehydes becomes an attractive process.
In recent years, researchers have explored the catalytic performance of various
catalysts for imines synthesis using nitroaromatics and aldehydes [9]. For example,

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Corma’s group reported Au/TiO catalyst for imines synthesis. The high conversion
2
and selectivity (>90%) were obtained and the hydrogenation of the carbonyl, C=C and
C=N groups were avoided [10]. Qin et al. synthesized Pt-Fe O catalyst with
2
3
core-shell structure and showed high catalytic efficiency and selectivity of imines by
tailoring Pt-Fe O interfaces [11]. Ma et al. found that Ni/SiO and Ni/Al-SBA-15
2
3
2
catalysts exhibited high activity for imines synthesis [12, 13]. Besides, Au-Pd/Al O
2
3
and Au/TiO catalysts also have been applied to synthesize imines using CH OH/H O
2
3
2
or CO/H O as reducing agents [14, 15]. Although these catalysts have good catalytic
2
efficiency, there are still some limitations. For noble metal (Au, Pt, Pd) based
catalysts, the viability and cost would be a major barrier for applications [16]. For
non-noble metal (Co, Ni) based catalysts, the reaction process usually requires high
temperature. And high temperature usually has negative influence on the selectivity
[
17]. Therefore, developing non-noble catalysts for the direct one-pot synthesis of
imines at mild condition is imperative.
Transition metal disulfides (TMDs) have been widely studied as promising
candidates for replacing noble metal in the field of catalytic hydrogenation. For
example, MoS -based catalysts have been applied to hydrodesulphurization (HDS).
2
FeS , CoS or MoS materials have been used to selective hydrogenation of
2
2
2
nitroaromatics [18-20]. Although TMDs have been investigated in hydrogenation and
hydrodesulphurization fields, their selective reduction coupling for imines synthesis
has not been reported as far as we know. Herein we report that CoS @MoS
2
2

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nanocomposites prepared by one-pot solvothermal method can selective reduction
o
coupling of nitroaromatics and aldehydes to imines under mild conditions (60 C and
1
.5 MPa H ) with good efficiency.
2
2
. Experimental
The CoS @MoS nanocomposites were prepared by one-pot solvothermal
2
2
method [21-23] (see S1.2 of Supplementary Information). The obtained catalysts
were denoted as CoS @MoS -T-X, where T and X represent the preparation
2
2
temperature and the Co/Mo mole ratio, respectively.
3
3
. Results and discussion
.1 Reduction coupling of nitrobenzene and benzaldehyde over various catalysts
The resultant catalysts were tested for the reduction coupling of nitrobenzene and
o
benzaldehyde. The results were listed in Table 1. At 60 C for 2 h under 1.5 MPa H ,
2
the conversion of nitrobenzene and the selectivity of N-Benzylideneaniline (NB) were
only 42.1% and 85.9%, respectively with CoS as comparison catalyst (Table 1, entry
2
1
). As for MoS catalyst, the conversion was only 19.5%, but the selectivity for NB
2
was increased to 97.2% (Table 1, entry 2). With CoS and MoS mechanically mixed,
2
2
the yield did not improve, illustrating that mechanically mixture have no synergy
effect (Table 1, entry 3). In contrast, when using one-pot solvothermal synthesized
CoS @MoS catalysts, the catalytic performances were greatly improved (Table 1,
2
2
entry 4-7), suggesting the synergy effect between CoS and MoS . Among catalysts
2
2

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with different Co/Mo mole ratio, CoS @MoS -180-0.75 gave rise to the best result
2
2
with 96.5% conversion and 93.0% selectivity. The effect of preparation temperature
on catalytic activity are presented in entry 8 and 9 of Table 1 and Figure S1. When
o
o
preparation temperature was raised from 160 C to 180 C, the conversion and
selectivity were significantly enhanced. However, when the temperature further
o
increased to 200 C, both conversion and selectivity were decreased. In addition, the
effects of solvents on the NB yield of catalysts were investigated and results are listed
in Table S1. Among ethanol, isopropanol, tetrahydrofuran and acetonitrile, ethanol
solvent gave rise to the highest yield of NB (89.7%). Thus ethanol is used as the
solvent to prepare the catalysts.
Table 1. Comparison of catalytic performance with various catalysts to synthesize
a
N-Benzylideneaniline
Select. [%]
2
Target
product
yield [%]
b
Entry
Catalysts
Conv. [%]
1
3
1
2
CoS2
42.1
19.5
39.2
27.8
51.3
85.9
97.2
90.7
96.0
95.7
8.8
0.8
5.1
4.0
4.0
6.3
2.0
4.2
0
36.1
18.9
35.6
26.7
49.0
MoS2
c
3
CoS +MoS
2
2
4
5
CoS @MoS -180-0.25
2 2
CoS @MoS -180-0.5
0.3
2
2

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6
7
8
9
CoS @MoS -180-0.75
96.5
72.2
73.9
77.8
93.0
95.5
88.9
91.1
3.8
4.5
8.2
6.2
3.2
0
89.7
69.0
65.7
70.9
2
2
CoS @MoS -180-1
2
2
CoS @MoS -160-0.75
2.9
2.1
2
2
CoS @MoS -200-0.75
2
2
a
o
Reaction conditions: 60 C, 1.5 MPa H , 2 h, catalyst (40 mg), nitrobenzene (0.5
2
b
mmol), benzaldehyde (0.65 mmol), ethanol (3 mL). Determined by GC using
toluene as an internal standard and the conversion is represented by amount of
c
nitrobenzene. Co/Mo mole ratio is 0.75.
3
.2 Reductive coupling reaction using various substrates and other related
experiments
Encouraged by the excellent reduction coupling performance of nitrobenzene
o
and benzaldehyde at the mild temperature (60 C) with CoS @MoS -180-0.75
2
2
catalyst, its versatility was investigated by using different nitrobenzene derivatives
and benzaldehyde derivatives. As shown in Table 2, no matter substituted
nitrobenzene reacted with benzaldehyde or nitrobenzene reacted with substituted
benzaldehyde, the catalyst showed good activity for both electron-withdrawing and
electron-donating substituted groups (Table 2 Entry 1-7). When both substrates have
the electron-donating groups, the catalyst has good reactivity (Table 2 Entry 8).
However, when both substrates have the electron-withdrawing groups, the reaction
activity decreased, indicating that strong electron-withdrawing effect inhibits this
reaction to some extent (Table 2 Entry 9-10).
When
different
nitroaromatics
react
with
furfural
compounds,
CoS @MoS -180-0.75 catalyst also shows good catalytic performance (Table 3). The
2
2

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above results showed that CoS @MoS -180-0.75 catalyst is a promising catalyst in
2
2
producing various imines. In order to verify the reliability of the experimental data,
we used nitrobenzene and benzaldehyde as reactants, repeated three times and
obtained similar experimental results, which showed that the results of the reaction
were repeatable (Table S2). In addition, the reusability of the catalyst was tested with
o
a model reaction of nitrobenzene and benzaldehyde in ethanol at 60 C, 1.5 MPa of H
2
for
2
h
to synthesize N-Benzylideneaniline. Figure S2 exhibited that
CoS @MoS -180-0.75 catalyst was stable after four consecutive runs. Therefore, our
2
2
experiments prove that the CoS @MoS -180-0.75 catalyst does exhibit good activity,
2
2
adaptability and stability in producing imines by selective reduction coupling
reaction.
Table 2. Synthesis of imines using benzaldehyde compounds as substrates with the
a
CoS @MoS -180-0.75 catalyst
2
2
Reactants
Select. [%]
5
Target
product
yield [%]
b
Entry
R1
R2
Conv.[%]
4
6
1
2
3
Cl
CH3
OH
SH
H
H
H
H
87.7
90.3
98.6
95.5
87.8
92.5
97.6
94.7
6.7
4.6
1.0
3.2
5.5
2.9
1.4
2.1
77.1
83.5
96.2
90.4
c
4

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5
6
7
8
9
H
H
Cl
CH3
OH
CH3
Cl
91.4
90.8
96.9
92.5
73.2
80.1
91.3
92.7
81.8
94.0
90.2
89.1
3.0
3.5
2.1
2.6
7.2
8.7
5.7
3.8
16.1
3.4
2.6
2.2
83.5
84.2
79.3
87.0
66.0
71.4
H
CH3
Cl
1
0
OH
OH
a
o
Reaction conditions: 60 C, 1.5 MPa H , 2 h, catalyst (40 mg), nitro compounds
2
b
(0.5 mmol), aldehydes (0.65 mmol), ethanol (3 mL). Determined by GC using
c
toluene as an internal standard. In 4 h.
Table 3. Synthesis of imines using furfural compounds as substrates with the
a
CoS @MoS -180-0.75 catalyst
2
2
Reactants
Select. [%]
8
Target
product
yield [%]
b
Entry
R1
R3
Conv.[%]
7
9
1
2
3
4
5
6
H
H
H
92.5
96.7
60.7
96.6
93.5
89.7
89.5
92.5
80.5
86.1
90.8
94.4
5.8
4.7
3.8
6.1
6.1
3.4
6
82.8
89.5
48.9
83.2
84.9
84.7
CH3
2.8
15.7
7.8
3.1
2.2
H
CH OH
2
Cl
H
H
CH3
OH
H
a
o
Reaction conditions: 60 C, 1.5 MPa H , 4 h, catalyst (40 mg), nitro compounds
2
b
(0.5 mmol), furfural compounds (1 mmol), ethanol (3 mL). Determined by GC
using toluene as an internal standard.

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In order to study the mechanism of reductive coupling reaction. Different
reactants were used over CoS @MoS -180-0.75 catalyst and the results are shown in
2
2
Table S3. When the aniline as reactants under N atmosphere, the conversion is close
2
to 100%, indicating the process is an acid-catalyzed and a rapid reaction [24] (Table
S3 entry1). When the nitrobenzene reacts with benzaldehyde at H atmosphere, the
2
conversion is only 79.5%, intermediates of nitrobenzene used as reactants, the
conversion is close to that of nitrobenzene, suggesting the hydrogenation of
nitrobenzene to aniline is the rate-determining step in the coupling reaction (Table S3
entry 2-4). The mechanism of the reaction of nitrobenzene with benzaldehyde or
furfural to synthesize imines is shown in Scheme 1. Firstly, nitrobenzene was reduced
to aniline by hydrogen over the hydrogenation site, which is the rate-determining step;
secondly, the aniline and benzaldehyde or furfural undergo dehydration and coupling
reaction to form the imine over acid site. Therefore, selective reduction active site and
dehydration active site should be necessary for a selective reduction coupling catalyst.
Scheme 1. The reaction mechanism of selective reduction coupling reaction to
synthesize imine over CoS @MoS catalyst
2
2
3
.3 Characterizations of the catalysts

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The CoS @MoS samples were characterized via XRD patterns (Fig. 1),
2
2
o
o
diffraction peaks at 2θ= 33.0 and 58.2 corresponds to the (100), and (110) planes of
hexagonal MoS (JCPDF 96-101-0994). The broadening and weak diffraction peaks
2
show that the crystallinity of MoS particles is poor and most of them present small
2
o
particles. Besides, there is no obvious diffraction peak at about 14 corresponding to
(
002) plane, suggesting single or a few layer structures of MoS [25, 26]. The other
2
diffraction peaks can match well with CoS (JCPDF 00-041-1471). When Co/Mo
2
mole ratio less than 0.5, there is no obvious diffraction peaks of CoS , meaning that
2
CoS is highly dispersed. With the Co/ Mo ratio increases to 0.75, the diffraction
2
peaks of CoS become sharp and obvious, suggesting that CoS particles grow up.
2
2
Further increasing this ratio to 1, peaks of CoS particles are stronger and sharper,
2
suggesting larger crystal CoS particles. When preparation temperature of catalysts
2
o
with Co/ Mo ratio of 0.75 increased from 160 to 200 C, the peaks of MoS showed
2
no apparent change, suggesting the high dispersion, however, the CoS peak intensity
2
increased remarkably, illustrating the increase of particles size.

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Fig 1. XRD patterns of MoS and CoS @MoS samples with different Co/Mo ratio
2
2
2
from 0.25 to 1 and CoS @MoS samples with Co/Mo=0.75 prepared at different
2
2
temperature.
The electronic properties of Mo, Co and S in the CoS @MoS -180-0.75 catalyst
2
2
was investigated using XPS technique in Fig. 2. The pattern of Mo 3d, Co 2p and S
p in the sample was decomposed by Peakfit software to determine the chemical
constitution. In Mo 3d, two characteristic peaks at 228.5 and 231.7 eV belong to 3d5/2
2

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4
+
and 3d3/2 of Mo in MoS , the doublet peaks at 232.4 and 235.2 eV are attributed to
2
6
+
the Mo which were formed by the no complete sulfidation of Mo precursor or by
exposure in air before XPS injection. In S 2p pattern, the major peaks at 161.3 and
2
-
1
62.6 eV are the characteristic peaks of S and the peaks at 162.4 and 163.7 eV
2
−
2−
indicated the presence of bridging S2 or apical S . In Co 2p pattern, the peaks at
7
78.6 and 793.7 eV belong to CoS , the major peaks at 778.9 and 793.9 eV can be
2
assigned to the cobalt in CoMoS [27]. The evidence for the existence of CoMoS
phase is as follows: firstly, the binding energy of Co 2p in CoS @MoS -180-(0.25,
2
2
0
.5, 0.75, 1) has a positive shift (0.2-0.3 eV) comparing with pure CoS sample, see
2
Fig. 2 and Fig. S3. Secondly, the characteristic differences of binding energy among
Co 2p, Mo 3d and S 2p also can prove the existence of CoMoS phase (Table S4) [23].
Another two peaks at 781.1 and 797.5 eV are the satellite peaks of Co 2p, which was
widely reported by literatures [28]. In addition, two broadened peaks at about 786.0
eV and 802.5 eV belongs to cobalt salts [29].

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Fig 2. XPS spectra showing the binding energies of molybdenum, sulfur and cobalt in
the CoS @MoS -180-0.75 and Co 2p in pure CoS and CoS @MoS -180-0.75
2
2
2
2
2
TEM technique is applied to reveal the morphology and microstructure of MoS2
and CoS @MoS catalysts in Fig. S4. The TEM images clearly show the generation
2
2
of typical layered structure with d-spacing of 0.65 nm, corresponding to (002) planes
of hexagonal MoS sheets. When Co/ Mo mole ratio is less than 0.5, no obvious CoS
2
2
phase can be observed. When Co/ Mo mole ratio is 0.75, separated CoS particles can
2
be seen. When Co/ Mo ratio increased to 1, the agglomeration of CoS can be easily
2
observed.
The textural properties of CoS @MoS nanocomposites were presented in Table
2
2
2
3
S5. MoS shows a lower surface area of 30.1 m / g and pore volume of 0.08 cm / g.
2

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When Co/ Mo mole ratio is 0.25, the surface area and pore volume decreased to 15.6
2
3
m /g and 0.05cm /g, respectively. The reason for this phenomenon may be that the
smaller CoS particles stay in pores of MoS , partly blocking the pores. Further
2
2
increase the Co/Mo ratio, the surface area and pore volume increase correspondingly.
From the comparison experiments, it is observed that the coupling reaction
activity is low for single MoS , CoS or their mechanical mixture. Good catalytic
2
2
performance is found only over the solvethermal synthetic nanocomposite. By the
XPS, the formation of CoMoS phase is evidenced for the nanocomposite catalysts.
According to references [30, 31], the CoMoS phase is formed by Co decorated the
edge of MoS sheets which enhance the hydrogenation and hydrodesulfurization
2
activity. We thus suggest that the formed CoMoS in CoS @MoS nanocomposite
2
2
enhances the hydrogenation of nitrobenzene to aniline which is the rate-determined
step. Formation of CoMoS phase are influenced by the ratio of Co/Mo, particle size
and the interface between CoS and MoS . It is found by XRD and HRTEM that with
2
2
the increase of Co/Mo ratio and preparing temperature, the average size of CoS2
increased and that of MoS has no apparent change. It is deduced that the CoS and
2
2
MoS in CoS @MoS -180-0.75 catalyst may sufficiently form CoMoS phase owing to
2
2
2
the matched particle size. The ratio of CoS and the surface area may less effect on
2
the hydrogenation of nitrobenzene and its derivatives. NH -TPD was applied to
3
characterize the strength of acidity and distribution of acidic sites of the catalysts (Fig.
o
3
). Two adsorption peaks are observed at low temperature (130 C) and high

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o
temperature (318 C) for MoS catalysts, corresponding to the weak and mediated
2
strong acid sites, respectively. With the addition of Co, desorption peak of high
temperature is inhibited and moved to low temperature. However, the NH desorption
3
peak of low temperature showed no apparent change, suggesting that the weak acidic
sites are not apparently influenced by the introduction of CoS . Using aniline reacted
2
with benzaldehyde as the acid catalyzed model reaction, it is observed that the yields
of imine are similar for all catalysts (Table S6), which suggests that the weak acidity
site may play the key role in the dehydration to produce imines.
CoS @MoS -180-1
2
2
CoS @MoS -180-0.75
2
2
CoS @MoS -180-0.5
2
2
CoS @MoS -180-0.25
2
2
MoS2
100
200
300
o400
500
600
Temperature/ C
Fig 3. NH -TPD profiles of the MoS and CoS @MoS samples with different Co/
3
2
2
2
Mo mole ratio
In addition, in order to further verify the catalytic performance of the catalyst for
reduction coupling reaction. The industrial supported (sulfide or non-sulfide)
CoMo/γ-Al O catalysts [32] and the reported Co-Mo-S-0.39-180 catalyst [21] with
2
3

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high activity and selectivity for aromatic nitro compounds were selected and
compared with CoS @MoS -180-0.75 catalyst (Table S7). The results show that the
2
2
two industrial catalysts have poor catalytic activity. The Co-Mo-S-0.39-180 catalyst
has high catalytic activity, but the selectivity of the target product imine is lower. The
CoS @MoS -180-0.75 catalyst has similar activity and higher selectivity for imines.
2
2
4
. Conclusions
In summary, a series bifunctional CoS @MoS catalysts was synthesized by
2
2
one-pot solvothermal method. Catalyst with Co/Mo ratio of 0.75 and prepared at 180
o
C shows the best performance for selective reduction coupling of nitrobenzene with
o
benzaldehyde to imine under mild conditions (60 C and 1.5 MPa H ). Moreover, this
2
catalyst shows good versatility for various nitroaromatics and aldehydrates. The
mechanism study reveals that the hydrogenation of nitroaromatics to anilines is the
rate-determining step. CoMoS is suggests as the active centers for reduction reaction
and the weak acid of MoS is the dehydration reaction site. The suitable Co/Mo mole
2
o
ratio (nCo/Mo=0.75) and preparation temperature (180 C) lead to formation of
sufficient CoMoS phase, which facilitates reductive coupling reaction to synthesize
imines.
Acknowledgments
This work was supported financially by the National Natural Science Foundation of
China (No. 21473231 and No. 21603256).

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References
[
[
[
[
1] P. Zhou, Z.H. Zhang, Chemsuschem, 10 (2017) 1892-1897.
2] B. Chen, L.Y. Wang, S. Gao, ACS Catal., 5 (2015) 5851-5876.
3] R.D. Patil, S. Adimurthy, Asian J. Org. Chem., 2 (2013) 726-744.
4] L. Ravishankar, S.A. Patwe, N. Gosarani, A. Roy, Synth. Commun., 40 (2010)
3
177-3180.
[
[
(
[
5] M. Hosseini-Sarvari, Chin. Chem. Lett., 22 (2011) 547-550.
6] F.W. Zhang, C. Zhao, S. Chen, H. Li, H.Q. Yang, X.M. Zhang, J. Catal., 348
2017) 212-222.
7] C.F. Zhang, J.M. Lu, M.R. Li, Y.H. Wang, Z. Zhang, H.J. Chen, F. Wang, Green
Chem., 18 (2016) 2435-2442.
8] R.V. Jagadeesh, A.E. Surkus, H. Junge, M.M. Pohl, J. Radnik, J. Rabeah, H.M.
Huan, V. Schunemann, A. Bruckner, M. Beller, Science, 342 (2013) 1073-1076.
9] F.G. Cirujano, A. Leyva-Perez, A. Corma, F. Xamena, Chemcatchem, 5 (2013)
38-549.
[
[
5
[
[
10] L.L. Santos, P. Serna, A. Corma, Chem.-Eur. J., 15 (2009) 8196-8203.
11] B. Zhang, X.W. Guo, H.J. Liang, H.B. Ge, X.M. Gu, S. Chen, H.M. Yang, Y.
Qin, ACS Catal., 6 (2016) 6560-6566.
12] Y.F. Zheng, K. Ma, H. Li, J. Li, J.G. He, X. Sun, R. Li, J.M. Ma, Catal. Lett.,
28 (2009) 465-474.
[
1
[
[
13] R. Ren, J.T. Ma, Rsc Advances, 5 (2015) 74802-74810.
14] Y.Z. Xiang, Q.Q. Meng, X.N. Li, J.G. Wang, Chem. Commun., 46 (2010)
5
918-5920.
15] J. Huang, L. Yu, L. He, Y.M. Liu, Y. Cao, K.N. Fan, Green Chem., 13 (2011)
672-2677.
16] Y. Yamane, X.H. Liu, A. Hamasaki, T. Ishida, M. Haruta, T. Yokoyama, M.
Tokunaga, Org. Lett., 11 (2009) 5162-5165.
[
2
[
[
(
[
17] E.A. Artiukha, A.L. Nuzhdin, G.A. Bukhtiyarova, V.I. Bukhtiyarov, Rsc Adv., 7
2017) 45856-45861.
18] B. Ma, X.L. Tong, C.X. Guo, X.N. Guo, X.Y. Guo, F.J. Keil, Rsc Adv., 6 (2016)
5
5220-55224.
19] B. Ma, Y.Y. Wang, X.L. Tong, X.N. Guo, Z.F. Zheng, X.Y. Guo, Catal. Sci.
Technol., 7 (2017) 2805-2812.
20] L. Huang, P.F. Luo, M. Xiong, R.Z. Chen, Y. Wang, W.H. Xing, J. Huang, Chin.
J. Chem., 31 (2013) 987-991.
[
[
[
[
21] I. Sorribes, L. Liu, A. Corma, ACS Catal., 7 (2017) 2698-2708.
22] F. Huang, R. Meng, Y. Sui, F. Wei, J. Qi, Q. Meng, Y. He, J. Alloys Compd.,
7
[
42 (2018) 844-851.
23] Y.-R. Liu, X. Shang, W.-K. Gao, B. Dong, J.-Q. Chi, X. Li, K.-L. Yan, Y.-M.
Chai, Y.-Q. Liu, C.-G. Liu, Appl. Surf. Sci., 412 (2017) 138-145.

ACCEPTED MANUSCRIPT
[
24] A.K. Chakraborti, S. Bhagat, S. Rudrawar, Tetrahedron Lett., 45 (2004)
7
641-7644.
25] J. Wang, Y.J. Zhang, J.Y. Diao, J.Y. Zhang, H.Y. Liu, D.S. Su, Chin. J. Catal.,
9 (2018) 79-87.
26] H. Matte, A. Gomathi, A.K. Manna, D.J. Late, R. Datta, S.K. Pati, C.N.R. Rao,
Angew. Chem.-Int. Edit., 49 (2010) 4059-4062.
27] I. Naboulsi, B. Lebeau, C.F.L. Aponte, S. Brunet, M. Mallet, L. Michelin, M.
Bonne, C. Carteret, J.L. Blin, Appl. Catal. , A, 563 (2018) 91-97.
28] A.A. Pimerzin, D.I. Ishutenko, A.V. Mozhaev, V.M. Kapustin, E.A.
[
3
[
[
[
Chernysheva, A.V. Maximova, A.A. Pimerzin, P.A. Nikulshin, Fuel Process.
Technol., 156 (2017) 98-106.
[
29] X.P. Dai, K.L. Du, Z.Z. Li, M.Z. Liu, Y.D. Ma, H. Sun, X. Zhang, Y. Yang, ACS
Appl. Mater. Interfaces, 7 (2015) 27242-27253.
30] Usman, T. Kubota, Y. Araki, K. Ishida, Y. Okamoto, J. Catal., 227 (2004)
23-529.
[
5
[
[
31] M.Y. Sun, J. Adjaye, A.E. Nelson, Appl. Catal., A, 263 (2004) 131-143.
32] H. Ge, X.-D. Wen, M.A. Ramos, R.R. Chianelli, S. Wang, J. Wane, Z. Qin, Z.
Lyu, X. Li, ACS Catal., 4 (2014) 2556-2565.
Graphical abstract:
Highlights:




Imines synthesized over CoS @MoS nanocomposite under mild condition
2 2
Good adaptability for different nitroaromatics and aromatic aldehyde derivatives
CoMoS phase is the active sites of hydrogenation of nitrobenzene derivatives
Weak acid site responds for the dehydration between aniline and aldehyde