Efficient Catalytic Performance for Acylation-Nazarov Cyclization Based on an Unusual Postsynthetic Oxidization Strategy in a Fe(II)-MOF

Article abstract of DOI:10.1021/acs.inorgchem.8b01421

A rare example of SC-SC triggered by Cu²⁺ heterogeneous oxidation was demonstrated in a Fe(II)-based MOF {[Fe^II₃(L)₂(H₂O)₆]·3H₂O}_n (1), which occurred a slow conversion into an oxidized MOF 2 ({[Fe^III₃(L)₂(H₂O)₆]·3(OH)}_n) with retention of single crystallinity. The Fe^II → Fe^III progress of the reaction oxidation was proved by single crystal XRD, PXRD, XPS, ⁵⁷Fe M?ssbauer spectroscopy, and UV-vis. We used 1 and 2 as catalysts to catalyze the tandem Nazarov cyclization, and the results show that acylation products were only harvested when 1 was a catalyst, while the oxidized transformer 2 lead mainly to the formation of cyclization products under identical conditions. Through the test of different substrates, 2 can be a good heterogeneous catalyst candidate for the formation of cyclopentenone[b] benzenes. This work provides a new way to design efficient and hard-synthesized heterogeneous catalyst materials.

Full text of DOI:10.1021/acs.inorgchem.8b01421

Article
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
pubs.acs.org/IC
Efficient Catalytic Performance for Acylation-Nazarov Cyclization
Based on an Unusual Postsynthetic Oxidization Strategy in a Fe(II)-
MOF
†
†
†
‡
†
,†
Zhichao Shao, Mengjia Liu, Jian Dang, Chao Huang, Wenjuan Xu, Jie Wu,*
,†
and Hongwei Hou*
†The College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, Henan 450001, People’s Republic of
China
‡
Center for Advanced Materials Research, Zhongyuan University of Technology, Zhengzhou 450007, People’s Republic of China
*
S Supporting Information
ABSTRACT: A rare example of SC-SC triggered by Cu2+
heterogeneous oxidation was demonstrated in a Fe(II)-based
II
MOF {[Fe (L) (H O) ]·3H O} (1), which occurred a slow
3
2
2
6
2
n
III
conversion into an oxidized MOF 2 ({[Fe (L) (H O) ]·3(OH)} )
with retention of single crystallinity. The Fe → Fe progress of the
3
2
2
6
n
II
III
reaction oxidation was proved by single crystal XRD, PXRD, XPS,
5
7
Fe Mossbauer spectroscopy, and UV−vis. We used 1 and 2 as
̈
catalysts to catalyze the tandem Nazarov cyclization, and the results
show that acylation products were only harvested when 1 was a
catalyst, while the oxidized transformer 2 lead mainly to the
formation of cyclization products under identical conditions.
Through the test of different substrates, 2 can be a good
heterogeneous catalyst candidate for the formation of
cyclopentenone[b] benzenes. This work provides a new way to design efficient and hard-synthesized heterogeneous catalyst
materials.
INTRODUCTION
As functional carriers, the different chemical valences of
■
center metals are responsible for the discrepancy in material
Functional MOFs crystalline materials have recently been of
considerable interest due to porous characteristics, intriguing
topologies, and potential multifield applications (ferroelectric,
3
5,36
performance.
This feature may be most salient in the
37
activities of catalyst materials. The MOFs-based catalysts
have been rapidly developed because of high catalytic activity,
recyclable, and preeminent selectivity.
1
−15
gas adsorption, luminescence, magnetism, catalysis, etc.).
In particular, MOFs used for postsynthetic modification
PSM) and molecular reactor can fully highlight the functional
feature of MOFs carrier and emphasize the swappable trend of
38−42
Among them, the
efficient catalyst for acylation-Nazarov cyclization to form
cyclopentenone[b] has attracted the interests of researchers,
since cyclopentenone[b] is an important intermediate for the
synthetic natural medication. Encouraged by the above merits,
our laboratory has been interested in developing efficient MOF
catalysts for tandem Nazarov cyclization, and some porous
MOFs materials have been reported for the synthesis of
cyclopenta[b] pyrroles by treatment of pyrrole derivatives with
(
16−22
material performance.
In the previous reports about PSM,
the modification methods mainly involve modification of
2
3−25
26−29
linkers,
transformation of metal-containing nodes,
3
0,31
and effect of guest molecular.
Among them, the
postsynthetic oxidization (PSO) of metal ions as a simple
and direct method has attracted the attention and interest of
scholars, which can obtain unattainable highly valence ions
MOFs crystalline materials.
agent (such as oxygen, H O , OH radicals, I ) involves the
43,44
α,β-unsaturated carboxylic acids.
However, these catalysts
3
2,33
can not play a good catalytic role in the benzene system,
because the electron cloud density of benzene is relatively low,
and the activity of substrate is not positive. MOF catalysts
materials with a high valence state of Lewis acid will be an
excellent candidate to catalyze the Nazarov cyclization of the
benzene system substrate.
However, the strong oxidizing
•
2
2
2
drastic oxidation process, which easily causes the collapse of
3
4
structures and the loss of single crystallinity. Weak oxidant
examples (especially highly charged metal ions) were rarely
found. Therefore, exploration of the mild oxidation system is
imperative, which can help to maintain good conditions of the
MOFs material single crystal and regulate the functional
properties.
Received: May 23, 2018
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.8b01421
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Herein, we report the assembly of a three-dimensional (3D)
Table 1. Summary of Crystallographic Data for 1 and 2
II
Fe MOF, namely, {[Fe L (H O) ]·3H O} (1) (H L = 1-
3
2
2
6
2
n
3
compound
formula
1
C
2
C
aminobenzene-3,4,5-tricarboxylic acid). Upon SC-SC hetero-
2
+
II
H
18
26Fe N
3
2
O
21
H23Fe N O
18 3 2 21
geneous oxidation of Cu solution, the Fe MOF 1 transforms
III
F
w
773.9
770.9
to the Fe framework of {[Fe L (H O) ]·3(OH)} (2), which
3
2
2
6
n
T (K)
293(2)
293(2)
5
7
is confirmed by Fe Mossbauer, XPS, and variable temper-
̈
l (Mo−Ka)/Å
crystsyst
space group
a (Å)
b (Å)
c (Å)
α (deg)
β (deg)
γ (deg)
V (Å3)
Z
0.71073
monoclinic
Pn
11.6282(8)
7.6006(5)
14.2257(9)
90
101.488(2)
90
0.71073
monoclinic
Pn
11.675(7)
7.626(4)
14.289(9)
90
101.528(19)
90
ature susceptibility. The experimental results indicate that 1
and 2 showed a rare example of SC-SC oxidation behavior of
II
III
2+
Fe → Fe driven by free Cu ions. In addition, 1 and 2 are
used as catalysts for the formation of cyclopentenone[b]
benzenes with 1,3-dimethoxybenzene. The acylation products
were obtained when 1 as a catalyst, while 2 can effectively
catalyze the synthesis of the cyclization product under the
same conditions.
1232.1(4)
2
1246.5(13)
2
EXPERIMENTAL SECTION
■
Dcalcd (g cm−3)
F(000)
μ (mm−1)
GOF
2.086
788
1.853
1.068
2.054
782
1.831
1.040
In this work, the reagents and solvents were used in commercial
purchase without further purification. PXRD patterns were collected
on a PANalytical X’Pert PRO diffractometer. The element content
(
C, N, and H) was obtained by a FLASH EA 1112 elemental analyzer.
Thermal stability were measured on a Netzsch STA 449C thermal
analyzer. Solid ultraviolet diffuse reflection were carried out by
JASCO-750 UV−vis spectrophotometer. The IR spectra were
R1 (I > 2σ(I))
0.0513
0.1546
0.0587
0.1723
wR (I > 2σ(I))
2
1
obtained on a Bruker Tensor 27 spectrophotometer. H NMR
spectra were verified with a Bruker Avance 400 spectrometer.
RESULTS AND DISCUSSION
Crystal Structure. We conducted single crystal X-ray
diffraction analysis of MOF 1, and the result shows that 1
crystallizes in the monoclinal crystal system and Pn space
■
Mo
with a Co source.
Preparation of MOFs. Synthesis of {[Fe L (H O) ]·3H O} (1). A
ssbauer data were tested with a Wissel Mossbauer spectrometer
̈ ̈
57
II
3
2
2
6
2
n
total of 0.1 mmol FeSO ·7H O (0.027 g), 0.05 mmol H L (0.011 g),
4
2
3
2+
group. In each basic structural unit, there are three Fe , two
and 0.1 mmol NaOH (0.004 g) were added into acetonitrile (2 mL)
3
−
L , six coordinated H O, and three free H O. The
and H O (3 mL). The system was stirred and sealed in a 10 mL glass
2
2
2
coordination models of Fe1 and Fe2 display similar octahedron
configurations, and the Fe ions are surrounded by six oxygen
atoms from two L and three H O moleculars (Figure 1). For
vial at 100 °C for 2 day. Single crystals appear as yellow clumps with a
2
+
yield of 84% based on H L. The theoretical value of elemental analysis
3
3
−
(
%) for C H Fe N O : C, 28.01; H, 3.34; N, 3.60. The
1
8
26
3
2
21
2
experimental value: C, 28.87; H, 3.21; N, 3.69. IR: 3540m, 1593s,
Fe3, the ion is also surrounded by six atoms, and the equatorial
plane is occupied by four O atoms from carboxyl group and
two N from the amino group in the axial sites. The
coordination length in 1 is examined, and the results show
that Fe−O lengths both are from 2.076 to 2.318 Å and the
length of Fe−N is 2.280(7) and 2.191 Å. These values are
1
391m, 1313m, 1217m, 1091s, 835w, 774w, 660w.
III
Synthesis of {[Fe L (H O) ]·3(OH)} (2). The yellow clump
3
2
2
6
n
crystals were immersed in acetonitrile solution of Cu(NO ) ·3H O.
3
2
2
The system was placed in a 10 mL glass vial at 80 °C for 2 day.
Crystal color changed from yellow to brown. The theoretical value of
elemental analysis for C H Fe N O (2) is C, 27.91; H, 2.97; N,
1
8
26
3
2
21
48−50
similar to other reported Fe complexes.
3
1
.61. The experimental value is C, 28.47; H, 2.45; N, 3.80. IR: 3424m,
614m, 1556m, 1461m, 1389s, 1303s, 1107w, 835w, 732w, 655w.
Single Crystal X-ray Crystallography. The structures of 1 and 2
3−
The L in 1 is completely deprotonated and attached to
2
three metal ions. The three carboxylic groups acting as μ -
1
1
1
1
0
1−
1
1
were tested on a Bruker D8 VENTURE diffractometer with Mo Kα
radiation (λ = 0.71073 Å). The SAINT program was used to control
the integration of the diffraction data, polarization effects, and the
η :η , μ -η :η , and μ η :η modes, respectively. As shown in
2
+
Figure 1, three Fe ions are connected to each other to form a
trinuclear unit [Fe (CO ) ] by two carboxylate groups. The
different trinuclears are interconnected each other via the
carboxyl and amino to afford a 3D supramolecular framework.
For a better understanding of this supramolecular framework,
3
2 2
45
intensity corrections for the Lorentz. We used the SADABS
46
program to perform semiempirical absorption correction and solved
structures by immediate ways and refined by a full matrix least-squares
2
47
technique relied on F with the SHELXL-1997 software package.
3−
the structure of 1 is further analyzed. Ligand L , trinuclear
Fe (CO ) ] unit can be considered as 3-connecting nodes
The hydrogen atoms were generated geometrically and refined
isotropically using the riding model. The summary of crystallographic
data for 1 and 2 is listed in Table 1. Corresponding bond lengths (Å)
and bond angles (deg) are provided in Table S2.
General Process of a Tandem Acylation-Nazarov Cycliza-
tion. A mixture of 1,3-dimethoxybenzene (1.0 mmol, 1.0 equiv), α,β-
unsaturated carboxylic acid (4a−d; 1.5 mmol), catalyst (0.1 equiv
calculated according to the content of Fe), trifluoroacetic anhydride
[
3
2 2
and 6-connected nodes, respectively. Then the structure can be
simplified to a 3D (3,6)-connected network and corresponding
(
6) (6) (3) (3)
to the Schlafli symbol is 4 6 8 4 .
̈
Study of 1 → 2 Transformation. In order to obtain Fe-
MOF material with high valence state, the single crystals of 1
were dried and immersed in Cu(NO ) solution at 80 °C for 2
3
2
(
TFAA, 4.0 mmol), and 10 mL of 1,2-dichloroethane (DCE) were
added in a 25 mL round-bottom flask. Then the system was heated at
0 °C for 5 h and gradually cooled to room temperature. The DCE
days. The crystal of 1 is transformed to oxidized complex with
a good single crystallinity. In the process, the color of the
crystal changes slowly from yellow to brown. Corresponding,
the color of the solution became shallow and white precipitate
was generated and observed after adding NaCl to the oxidation
system, suggesting concentration of Cu decrease and part of
them may changed into Cu , which was proved by ultraviolet
9
was removed in vacuo and the grease was extracted by 15 mL of
EtOAC. The EtOAC phase was merged and washed with saturated
aqueous NaHCO , dried by Na SO , filtered, and evaporated under
3
2
4
2
+
reduced pressure. The crude residue were refined by column
chromatography on silica gel.
+
B
DOI: 10.1021/acs.inorgchem.8b01421
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Inorganic Chemistry
Article
Figure 1. View of 3D network of 1.
Figure 2. Elemental mapping images of 1 and 2.
spectra (Figure S2) and cyclic voltammograms curve (Figure
S3). In order to rule out the decrease of Cu2 coming from
deposit or adsorption, EDS spectra of 2 were measured. As
shown in Figure 2, the color of Cu is not uniformly distributed
in the crystal shape, and the content of Cu is only 0.11%. In
order to further prove the result, the atomic absorption
experiment of 2 was carried out, the results show that there is
+
2
+
0
.18% Cu in 2, which is similar to the result of EDS spectra.
2+
Therefore, the decrease of Cu is not coming from deposit or
adsorption. Moreover, some important controlled experiments
were also conducted: (1) when H O was used as oxidant,
2
2
similar brown crystals were obtained without good single
2
+
crystalline state; (2) the trace amounts of oxygen in Cu
solution was removed in advance, then MOF 1 was added in
the system under N protection. The oxidation results were not
2
Figure 3. Transformation of 1 → 2.
affected; (3) when the free radicals blocking agent was injected
to the system, the yellow crystal 1 was still oxidized to MOF 2.
These experimental results show that Cu2 plays the role of
oxidant in the mild oxidation system.
+
which corresponds to the formation of hydroxide. Because the
difference of valence may cause changes in magnetic behavior
51,52
The single-crystal X-ray analysis of 2 is similar to 1, and the
PXRD pattern showed no obvious structural changes (as
shown in Figure 3). According to the final crystallographic
parameters, a slight increase of axis was observed in 2, along
of MOFs material,
the variable temperature magnetic
susceptibilities of 1 and 2 were collected at a 1 kOe dc field
over 300−2 K. In Figure S5, for 1, the χ T value at 300 K
M
3
−1
II
(15.24 cm K mol ) is higher to three spin-only Fe ions,
3
with an increase of more than 14 Å of cell volume. In the IR
suggesting strong spin−orbit coupling interaction. Upon
cooling, the χ T value decreases slowly to 9.60 cm K mol
M
3
−1
spectra of 1 and 2 (Figure S12), the peak of 3300m changed,
C
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Inorganic Chemistry
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Figure 4. 57Fe Mo
ssbauer spectra and XPS of 1 and 2.
̈
at 30 K, and then the value declines rapidly. This phenomenon
Table 2. Screening of the Reaction Conditions
31,53
may be due to zero-field splitting.
For 2, the χ T is 10.24
M
3
−1
T
yield (%) of
yield (%) of
cm K mol at 300 K, which decreases more quickly than that
b
b
entry catalysis TFAA solvent (°C)
5a
6a
3
−1
of 1. The minimum is 2.07 cm K mol at 2 K. We infer that
the difference in magnetic behavior is mainly attributable to a
reduction of the number of electrons, which weakened the
antiferromagnetic coupling effect.
a
1
2
3
4
5
4
5
6
7
8
9
1
2
2
yes
yes
yes
yes
yes
yes
yes
no
DCM
DCM
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
60
60
25
90
90
90
90
90
90
90
90
n.o.
11
n.o.
n.o.
53
27
5<
n.o.
n.o.
56
30
38
60
39
61
37
a
a
5
7
FeCl2
Fe Mo
divalent, while the valence of Fe changed to III in 2. In Figure
, for 1, a quadrupole doublet with the isomer shift (δ) and
̈
ssbauer spectroscopy show that Fe atoms of 1 are
FeCl3
ZnCl2
no
1
2
4
II
quadrupole splitting (ΔEQ) characteristic of Fe was observed
a
a
n.o.
n.o.
(Table S1). There are only two doublets at 300 K, and doublet
a
a
no
yes
yes
was characterized by the quadrupole splitting with ΔEQ = 3.27
a
1
2
n.o.
73
90
21
−
1
−1
and 2.95 mm s and isomer shift δ = 1.11 and 1.07 mm s .
II
These values are corresponding to the HS state of Fe (S =
a
b
31,54
−1
Not observed. Yields are calculated based on 3.
2
).
As for 2, the characteristic of ΔEQ = 0.89 mm s and
δ = 0.39 mm s is assigned to Fe . In addition, we also
conducted XPS and solid diffuse reflectance spectrometry on 2,
−
1
III
whole tandem reaction was supported. For comparison, the
homogeneous catalysts ZnCl and FeCl as common Lewis
III
and the results both showed that the existence of Fe was
2
3
credible (Figure S4).
acid catalysts were used for this reaction under the same
reaction conditions. The target product 5a only were obtained
in yields of 27% and 53%, respectively. Thus, heterogeneous
catalyst 2 clearly showed superior activity in implementing the
tandem acylation-Nazarov cyclization reaction with high
selectivity.
Catalytic Performance of 1 and 2. Before the catalytic
experiment, the solvent-resistance properties of 1 and 2 were
examined by suspending samples in different organic solvents
and pH for 24 h. After this process, we first looked at the
appearance of the crystal through optical microscope, and the
color and shape of the crystal have not changed significantly.
Then, the crystal is filtered and verified for structural integrity
by PXRD spectrum. As shown in Figures S7 and S8, the
primary frameworks were intact throughout the process. In
addition, the thermal analysis were carried out (Figure S6),
and the framework of 1 and 2 begins to collapse at 300 °C.
The rest of the weight is consistent with the theoretical
formation of Fe O . As a result, 1 and 2 have good chemical
To further investigate the catalytic performance of 1 and 2 in
Nazarov cyclization, other α,β-unsaturated carboxylic acids
(4b−d) were introduced as substrates, and the tandem
reaction conducted successfully and supported the cyclization
of 1,3-dimethoxybenzene. As shown in Table 3, the same as
expected, heterogeneous catalyst 2 could effectively catalyzed
Nazarov cyclization and 5b−d is produced. The target product
of cyclopentenone[b]benzene were got in yields ranging from
52% to 73%. The yields decrease in the order 5a (73%) > 5b
(60%) > 5c (56%) > 5d (50%), corresponding to the increase
of substrate sizes 4a (3.83 Å) < 4b (3.92 Å) < 4c (4.51 Å) <
4d (4.91 Å). It indicated that the substrate sizes play vital roles
in the heterogeneous catalyzed reaction. In addition, 1 shows
high selectivity to acylated products with high yield (6a (90%)
> 6b (85%) > 6c (81%) > 6d (78%)). We deduced that the
high catalytic activities of 1 and 2 were mainly came from their
high density Lewis acid sites and the fixed framework channels.
The characteristics of the structure have the following
advantages: (i) Structural analysis shows that there is a
2
3
and thermal stability; it cannot be broken down in the process
of catalysis.
To better verify the catalytic performance of MOF1 and 2
for acylation-Nazarov cyclization reaction, we chose 1,3-
dimethoxybenzene and 4a as reaction substrates to compare
their activities under different reaction conditions (as shown in
Table 2). According to the analysis of yield under different
conditions, the most suitable reaction solvent is DCE, and the
reaction time is 5 hours at reflux. Noticeable, TFAA is
indispensable in this system. As shown in Table 1, 1 showed a
high specificity of acylation products selectivity (Table 1, entry
2
8
). On the contrary, 2 could effectively catalyze the generation
pathway (5.0 × 16.4 Å ) in the framework, such tunnels are
of cyclization productsin yields of 73% (Table 1, entry 9), the
favorable for the entry of the reaction substrate. (ii) The
D
DOI: 10.1021/acs.inorgchem.8b01421
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Table 3. Catalytic Efficiency for Different Substrates
a
b
Not observed. Yields are calculated based on 3 and the average of two runs.
trinuclear [Fe (CO ) ] units exhibit excellent catalytic activity
Fe center in MOFs catalyst. The coordination interaction with
MOF catalyst plays the effect of activation for carbonyl group
from α,β-unsaturated acid, and makes carbon atoms more
electrophilic. Then, electrophilic carbon atoms is attacked by
1,3-dimethoxybenzene to provide intermediate II. The lost of
trifluoroacetic acid unit let III been generated. Subsequently,
the electrons rearrangement of III lead to hydrogen atom
leaves and give the acylation products IV. Furthermore, the Fe-
based MOFs catalyst activated the unsaturated olefinic bond
continuously and generated a pentadienyl cation, followed by
4π conrotatory electrocyclization, generating the benzocyclo-
pentanone V, and Fe-based MOFs was rereleased for
participating in the next catalytic cycle. Noteworthy, the
frameworks of the two catalysts are similar, but the catalytic
effect showed a great difference. The differences can be
3
2 2
for the cyclization reaction, because there is coupling synergy
between iron ions. At the same time, the trinuclear provides a
platform for improving the density of lewis acid sites. (iii)
There are free water molecules around the metal center, which
are a good leaving group. These groups are conducive to
exposing the metal catalytic site to the reaction substrate
during the reaction process. Therefore, Fe-based MOFs 1 and
2
can be good candidates as heterogeneous catalyst. In order to
prove more accurately that the reaction occurs within the
crystals, the control experiment was compared with large
crystals of 2 and grinding 2. The similar yield was presented,
which eliminates the catalytic activity only come from the
surface metal sites. In addition, solid catalysts were removed
after 1 h and the conversion has not been improved.
2
+
A tentative catalytic mechanism of mechanism Fe-based
MOFs for Nazarov cyclization is proposed in Figure 5. First, a
substitution reaction took place between TFAA and α,β-
unsaturated acid to give mixed anhydride, which formed I with
attributed to that the metal center (Fe ) in MOF 1 is not
strong enough as a lewis acid for activating the unsaturated
3
+
olefinic bond. The highly charged Fe center in 2 has a strong
ability to receive electronically, which can promote 4π
conrotatory electrocyclization and make acylation IV can
55
easily be converted.
In order to better investigate the potential application value
of catalysts, the recycling experiment was carried out on behalf
of 4a to determine the reusability of the catalyst. Interestingly,
the catalyst is easy to be separated by magnetic attraction after
the reaction is completed. Compared with centrifugation and
filtration methods in previous reports, this characteristic is
beneficial for the recovery of the catalyst. The recycling
experiment results showed that the catalytic efficiency did not
display significant decline after five runs (Figure 6 and Figure
S10). Furthermore, we tested the recovered catalyst by PXRD,
the spectrum was very similar to that of simulation by single
crystal data. The consistency of PXRD patterns before and
after the catalysis indicated that the framework was intact and
not collapsed (Figure S9), which proved the stability and
reusability of the two catalysts after at least five runs, and 1 and
Figure 5. Suggested mechanism.
E
DOI: 10.1021/acs.inorgchem.8b01421
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Inorganic Chemistry
Article
Figure 6. Reusability test for catalytic performance of 2.
2
can be a good heterogeneous catalyst candidate for organic
Notes
synthesis.
The authors declare no competing financial interest.
CONCLUSIONS
■
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■
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ASSOCIATED CONTENT
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O. M. The Chemistry of CO Capture in an Amine-Functionalized
Corresponding Authors
E-mail: wujie@zzu.edu.cn.
E-mail: houhongw@zzu.edu.cn.
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Metal− Organic Framework under Dry and Humid Conditions. J. Am.
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Jie Wu: 0000-0001-7746-6640
Hongwei Hou: 0000-0003-4762-0920
Funding
This work was financially supported by the National Natural
Science Foundation (21371155 and 21671174) and the
Natural Science Foundation of Henan province
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