Cu(I) Coordination Polymers as the Green Heterogeneous Catalysts for Direct C-H Bonds Activation of Arylalkanes to Ketones in Water with Spatial Confinement Effect

Article abstract of DOI:10.1021/acs.inorgchem.7b02106

To develop coordination polymers (CPs) as catalysts to selectively catalyze the reaction of C-H bond activation of arylalkanes to their homologous ketones, three new Cu(I)-based coordination polymers (Cu^I-CPs) [CuI(aas-TPB)]_n (1), [CuBr(ass-TPB)CH₃CN]_n (2), and {[Cu(ass-TPB)]Cl}_n (3) (TPB = N,N,N-tris(3-pyridinyl)-1,3,5-benzenetricarboxamide) were synthesized. Structural variations from a herringbone fashion one-dimensional framework of 1 to a two-dimensional framework of 2 containing a 48-membered macrocycle and a cationic three-dimensional framework of 3 filled with Cl^- anions were observed arising from the different halogen ions (I^-, Br^-, and Cl^-). 1-3 were used as the green heterogeneous catalysts to catalyze direct C-H bond activation reactions of arylalkanes to ketones under mild reaction conditions with water as solvent. Handy product separation, convenient reaction procedures, and recyclability of these catalysts make the catalytic system fascinating. Moreover, the Cu^I-CPs performed the reaction with high regioselectivity due to the unique spatial confinement effect of CPs.

Full text of DOI:10.1021/acs.inorgchem.7b02106

Article
pubs.acs.org/IC
Cite This: Inorg. Chem. XXXX, XXX, XXX-XXX
Cu(I) Coordination Polymers as the Green Heterogeneous Catalysts
for Direct C−H Bonds Activation of Arylalkanes to Ketones in Water
with Spatial Confinement Effect
Xiaolu Wang,†,# Mengjia Liu,†,# Yuqing Wang,† Hongyan Fan,† Jie Wu,*,† Chao Huang,*,‡
and Hongwei Hou*,†
†College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, P. R. China
‡Center for Advanced Materials Research, Zhongyuan University of Technology, Zhengzhou 450007, P. R. China
S
* Supporting Information
ABSTRACT: To develop coordination polymers (CPs) as
catalysts to selectively catalyze the reaction of C−H bond
activation of arylalkanes to their homologous ketones, three new
Cu(I)-based coordination polymers (CuI−CPs) [CuI(aas-TPB)]n
(1), [CuBr(ass-TPB)CH3CN]n (2), and {[Cu(ass-TPB)]Cl}n (3)
(TPB = N,N,N-tris(3-pyridinyl)-1,3,5-benzenetricarboxamide)
were synthesized. Structural variations from a herringbone fashion
one-dimensional framework of 1 to a two-dimensional framework
of 2 containing a 48-membered macrocycle and a cationic three-
dimensional framework of 3 filled with Cl− anions were observed
arising from the different halogen ions (I−, Br−, and Cl−). 1−3
were used as the green heterogeneous catalysts to catalyze direct
C−H bond activation reactions of arylalkanes to ketones under
mild reaction conditions with water as solvent. Handy product
separation, convenient reaction procedures, and recyclability of these catalysts make the catalytic system fascinating. Moreover,
the CuI−CPs performed the reaction with high regioselectivity due to the unique spatial confinement effect of CPs.
that are deficient in classic porous carbons and various other
solid supports. For example, synergistic interactions with
substrates can be facilitated by CPs via the sequential or
cooperative manner to obtain the tandem or cooperative
catalytic products without isolating intermediates.11 In
particular, when substrates have more than one reaction
functional group, the lack of reaction selectivity happens in
typical homogeneous system. By contrast, CPs can possess
spatial confinement effect and regioselectivity, taking into
consideration the uniformly distributed single active sites in
CPs with specific coordination geometry, symmetry, and steric
configuration, making these materials attractive catalytic
selectivity.12
However, for the chemical transformation of methylene
groups of arylalkanes to ketones, besides the traditional
oxidation using KMnO4 as an oxidant, the homogeneous,13
heterogeneous,14 and metal-free15 catalysts catalyze C−H bond
activation of arylalkanes to form the homologous ketones,
which have been rapidly developed in recent years. However,
these methods lack selectivity. Overoxidation products are
always afforded when substrates have more than one methylene
group, so that it is still a challenge to find strategies to realize
INTRODUCTION
■
Coordination polymers (CPs) made from metal ions linked by
organic ligands are the structurally and compositionally
diversified class of function materials of which the physical
and chemical properties are investigated intensively for
numerous applications including drug delivery,1 gas liquid/
solid separations,2 sensing,3 luminescence,4 catalysis,5 and so
on. In particular, by introducing catalytically competent
moieties via either self-assembly or postsynthetic modification
methods, solid CPs-based catalysts have provided a versatile
tunable platform to engineer molecular catalysts that are
immobilizing, well-defined, and perform a broad range of
organic transformations, such as the formations of C−C bond,
aldol condensations, oxidations, epoxidations, etc.6−9
The most vital virtue of CPs is that they can imitate the site-
isolation of many catalytic enzyme assembled in nature, because
the active catalytic sites are immobilizing and atomistically well-
defined, isolated with certain fixed azimuth and distance in the
solid.10 These active catalytic sites can not only increase
catalytic activity via eliminating multimolecular catalyst
deactivation approaches but also possess exceptional chemo-,
size-, shape-, and enantioselectivity. Interestingly, solid CP-
based catalysts often display higher activity than that of the
corresponding homogeneous catalysts. Besides, several groups
including ours have reported other virtues of CP-based catalysts
Received: August 15, 2017
© XXXX American Chemical Society
A
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selectivity. Enlightened by the virtues of CPs, especially its
spatial confinement effect and regioselectivity, we are interested
in developing the oxidation of alkanes catalyzed by CPs as
heterogeneous catalysts, and meanwhile high catalytic selectiv-
ity can be achieved.
1586 (m), 1541 (s), 1486 (vs), 1420(vs), 1292 (s), 948 (vw),
907(m), 810(vs), 698(s), 648(w), 645(w).
Typical Procedure for Direct C−H Bonds Activation of
Arylalkanes to Ketones in Water. Arylalkanes (1.0 mmol,
1.0 equiv), tert-butyl hydroperoxide (TBHP; 1.5 mmol, 1.5
equiv) and catalyst (0.05 mmol, 0.1 equiv based on Cu ion)
were added in water (5 mL). The resulting mixture was first
ultrasonically treated for 0.5 h and then stirred for 3.5 h in
room temperature in the air. For product separation, the
aqueous phase was extracted with ethyl acetate (EtOAc; 3 × 15
mL). The organic phases were combined, dried with anhydrous
Na2SO4, and concentrated in vacuo. The raw products were
refined by column chromatography on silica gel, and the pure
products were obtained.
Herein, a series of Cu(I)-based coordination polymers (CuI-
CPs) [CuI(aas-TPB)]n (1), [CuBr(ass-TPB)CH3CN]n (2),
and {[Cu(ass-TPB)]Cl}n (3) (TPB = N,N,N-tris(3-pyridinyl)-
1,3,5-benzenetricarboxamide) were prepared and characterized.
It shows that 1 and 2 are efficient heterogeneous catalysts and
display high regionselectivity for direct C−H bond activation
reactions of arylalkanes to ketones in H2O under room
temperature. In addition, we proposed a plausible mechanism
for the catalytic reaction, and the relationship of reactivity−
structure was further clarified.
Crystal Data Collection and Refinement. The data of
the complexes 1−3 were collected on a Rigaku Saturn 724
CCD diffractomer (Mo Kα, λ = 0.710 73 Å) at a temperature of
EXPRTIMENTAL SECTION
■
20
1 °C. Absorption corrections were used by multiscan
Materials and Physical Measurements. N,N,N-Tris(3-
pyridinyl)-1,3,5-benzenetricarboxamide (TPB) was synthesized
through a modified method in the literature.16 All chemical
reagents were purchased from commercial suppliers without
program. The Lorentz and polarization effects were corrected
by the data. The structures were solved by direct methods and
refined on F2 by the full-matrix least-squares technique with the
SHELXL-97.17 The hydrogen atoms were generated geometri-
cally and refined the using riding model. The details of the
crystal data for 1−3 are listed in Table S1, and selected bond
lengths and bond angles are listed in Table S2 in the
Supporting Information. Crystallographic data for 1−3 were
deposited at the Cambridge Crystallographic Data Centre with
CCDC reference numbers 988513, 988512, and 1565786,
respectively.
1
further purification. H and 13C nuclear magnetic resonance
(NMR) spectra were obtained on Bruker Avance-400
spectrometers. Fourier transform infrared (FT-IR) spectra
were performed on a Bruker-ALPHA spectrophotometer with
KBr pellets in the 400−4000 cm−1 region. Powder X-ray
diffraction patterns were achieved by using Cu Kα1 radiation
on a PANalytical X’Pert PRO diffractometer. High-resolution
mass spectrometry−electrospray ionization (HRMS-ESI) was
performed on a Micro Q-TOF mass spectrometer. Atomic
absorption spectroscopy (AAS) was performed on a Z28000
graphite-oven atomic absorption spectrophotometer.
Synthesis of [CuI(aas-TPB)]n (1). The mixture of CuI (5.7
mg, 0.03 mmol), TPB (17.6 mg, 0.04 mmol), and 7 mL of
acetonitrile was added in a 25 mL Teflon-lined stainless steel
container and heated at 120 °C for 3 d. After the mixture
cooled to room temperature at a rate of 5 °C/h, yellow block-
shaped crystals of 1 were obtained in a yield of 80% based on
CuI. Anal. Calcd for C24H18CuIN6O3: C, 45.84; H, 2.88; N,
13.36. Found: C, 45.82; H, 2.91; N, 13.74%. IR (KBr, cm−1):
3328 (m), 3250 (m), 2162 (vw), 1672 (s), 1653 (vs), 1597 (s),
1525 (vs), 1413 (vs), 1297 (s), 926 (vw), 898 (w), 858 (vw),
800 (s), 724 (w).
RESULTS AND DISCUSSION
■
Crystal Structure of 1. A single-crystal X-ray diffraction
study indicated that 1 crystallizes in the monoclinic space C2/c.
Each Cu(I) is coordinated by I1 and two nitrogen atoms (N1
and N4) of two ligands. The Cu(I) centers are bridged by
ligand TPB ligands with aas conformation (Scheme 1), and a
chain was constructed in the herringbone fashion along a-axis
(Figure 1a).
a
Scheme 1. Conformations of the Ligand TPB in 1−3
Synthesis of [CuBr(ass-TPB)CH3CN]n (2). The synthesis
of 2 was similar to that of complex 1, except that CuBr was
used instead of CuI. Yellow block-shaped crystals of 2 were
obtained when the mixture was cooled to room temperature at
the rate of 5 °C/h in a yield of 40% based on CuBr. Anal. Calcd
for C26H21CuBrN7O3: C, 50.13; H, 3.40; N, 15.74. Found: C,
50.15; H, 3.37; N, 15.72%. IR (KBr, cm−1): 3339 (m), 3258
(m), 2252 (vw), 1683 (vs), 1584 (s), 1525 (vs), 1410 (vs),
1285 (s), 937 (w), 866 (w), 802 (vs), 768 (s), 735 (vw), 722
(m).
a
a-Conformation means that the oxygen of amide and the nitrogen of
pyridyl are in the opposite side. s-Conformation means that the two
atoms of the ligand are in the same side.
Synthesis of {[Cu(ass-TPB)]Cl}n (3). The mixture of CuCl
(9.9 mg, 0.1 mmol), TPB (17.6 mg, 0.04 mmol), and 7 mL of
acetonitrile was placed in a 25 mL Teflon-lined stainless steel
container and heated at 120 °C for 3 d. The yellow block-
shaped crystals of 3 were obtained when the mixture was
cooled to room temperature at the rate of 5 °C/h in a 60%
yield based on CuCl. Anal. Calcd for C24H18CuClN6O3: C,
50.23; H, 3.27; N, 14.68. Found: C, 50.58; H, 3.34; N, 14.62%.
IR (KBr, cm−1): 3232 (m), 3180 (m), 2092 (vw), 1696 (s),
It is noteworthy that the amide group is an interesting
functional group due to the two types of hydrogen bonding
sites, the −CO group working as an electron donor and the
−NH moiety working as the electron acceptor. Thus, the
amides induce hydrogen bonding interactions with itself, with
the counteranions, and with the solvent. As expected, two-
dimensional (2D) extended structure of the complex molecules
is linked through the hydrogen-bonding interactions between
B
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Figure 1. (a) View of the one-dimensional (1D) chain of compound 1. Hydrogen atoms are omitted for clarity. (b) View of the 3D supermolecular
framework of 1 built from the 1D chains.
Figure 2. (a) View of the 2D network of compound 2. Hydrogen atoms are omitted for clarity. (b) View of the 3D supermolecular framework of 2.
the amide nitrogen atom (N5) and the carbonyl oxygen atom
(O2) of the next chain (N5−H5···O2 = 2.983 Å; Figure S1b).
Furthermore, these 2D structures are further immobilized by
π−π interactions between parallel pyridyl rings (center-to-
center distance of ca. 3.679 Å) to form the three-dimensional
(3D) supermolecular structure (Figure 1b).
conformation (Scheme 1). The Cu(I) ions bridge ligands to
construct a 48-membered macrocycle formed 2D network that
three C3-symmetric triangular facial ligands connect with three
Cu(I) centers (Figure 2a). In addition, the plane networks are
further packed by hydrogen bonds (N3−H3···Br1 = 3.578 Å,
N5−H5A···Br1 = 3.398 Å) to build a 3D zeolite-like framework
(Figure 2b and Figure S2b).
Crystal Structure of 2. X-ray diffraction revealed that 2
belongs to the triclinic space group P1 and contains a
Crystal Structure of 3. A single-crystal X-ray diffraction
study on 3 indicated that it crystallizes in the orthorhombic
space Pbca. Each Cu(I) is coordinated by N1, N4, and N6 from
three ligands. In 3, the C3-symmetic triangular ligand TPB in
ass conformation links Cu(I) ions forming a 2D framework
̅
fascinating zeolite-like network. Cu(I) is coordinated in a
distorted tetrahedral coordination environment with a bromine
atom and three nitrogen atoms (N1, N4, and N6) from three
ligands. The C3-symmetic triangular ligand is the ass
C
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Figure 3. (a) View of the 2D network of compound 3. Hydrogen atoms are omitted for clarity. (b) View of the 3D supermolecular framework of 3.
structure (Figure 3a). Overall, the cationic framework is filled
with Cl− ions (Figure 3b). On the basis of charge balance, the
asymmetric unit contains one Cl− ion occupied in the channels.
Furthermore, the −NH hydrogen bond with the Cl− anions
(N5−H5···Cl = 3.333 Å; N2−H2···Cl = 3.234 Å; N3−H3···Cl
= 3.326 Å) connecting these layers to generate the 3D
framework (Figure S3b). The framework of 3 is similar to a Ag-
MOF (MOF = metal−organic framework) reported by Tzeng
group.18
The Catalytic Effect of 1−3 for Direct C−H Bond
Activation of Hydrocarbons. We selected the optimized
conditions of the direct C−H functionalization reaction using
diphenylmethane as the substrate. The results of the
optimization experiment were shown in Table 1. After extensive
screening of the temperature, atmosphere, and solvents, the
optimized conditions were obtained in the presence of TBHP
as an oxidant and 5 mol % of crystal samples as catalysts in H2O
under air at room temperature for 4 h, producing the desired
ketone products in the yields of 70%, 97%, and 99%. It showed
that 1 worked as an excellent heterogeneous catalyst for the C−
H bond activation reaction, while CuI was a less effective
homogeneous catalyst with a yield of 19% under the same
conditions. 2 and 3 could also work as heterogeneous catalysts
for the reaction with the yields of 97% and 70%, respectively.
With inert gases such as nitrogen and argon, only a trace
amount of the desired compound was produced. The C−H
activation proceeded with moderate effectiveness in acetonitrile
(48%) and dioxane (51%), but dimethylformamide (DMF),
dimethylacetamide (DMA), diglyme, N-methyl pyrrolidone
(NMP), and toluene were unsuitable solvents. In view of
environment, efficiency, cost, simplicity, and stability, we
identified 1/TBHP/H2O/air as our standard conditions for
the C−H functionalization reactions.
Structurally diverse alkylarenes were employed in the
benzylic Csp3-H bond activation to investigate the scope of
the three CuI-CPs catalytic processes (Table 2). The catalytic
system proceeded smoothly to generate the corresponding
carbonyl compounds in moderate or excellent yields. 5a and 6a
were converted into the corresponding ketones with 1 in the
yields of 93% and 90%, respectively (Table 2, entries 4 and 7).
More importantly, to research the regioselectivity of 1−3 on
this reaction, substrates with two symmetrical benzylic sites,
such as 7a, 8a, 9a, and 10a (Table 2, entries10−21) were
employed. Amazingly, it showed that their respective
monoketones formed as the sole products by using CPs 1−3
as heterogeneous catalysts. Specifically, using 1 as catalyst, 7a,
8a, and 9a were selectively oxidized to their respective
monoketones with yields ranging from 88 to 98% for 4 h
(Table 2, entries10, 13, and 16). While for the bulky 10a, the
desired monoketone 10b was obtained in a moderate yield of
72% for 8 h. The yield of 10b is significantly lower than other
products (Table 2, entries 19−21), which indicates that the size
of channels of CPs and substrates plays a significant role in the
heterogeneous catalytic reaction. As an effective heterogeneous
catalyst, large open channels are needed for CPs to transport
organic substrates and products. It shows that the increasing
size of the substrates leads to the declining reaction rate but has
no effect on the reaction selectivity. In addition, when 2 and 3
were used as catalysts to perform these reactions under the
same conditions, the substrates were converted into the
respective sole monoketones with moderate yields. In contrast,
a
Table 1. Optimized Conditions of the Reaction
entry
catalyst
atmosphere
solvent
H2O
yield, %
1
CuI
1
air
air
air
air
air
N2
Ar
air
air
air
air
air
air
air
19
99
97
70
0
2
H2O
3
2
H2O
4
3
H2O
5
none
1
H2O
6
H2O
<5
<5
7
1
H2O
b
8
1
acetonitrile
dioxane
DMF
DMA
dilyme
NMP
toluene
48
b
9
1
51
10
11
12
13
14
1
<5
58
<5
<5
1
1
1
b
1
<5
a
Reagents and conditions: diphenylmethane (1.0 mmol), TBHP (1.5
b
mmol), and catalyst (0.05 mmol), room temperature, 4 h. Reaction
performed at refluxed temperature.
D
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a
Table 2. Direct C−H Bonds Activation of Arylalkanes to Ketones Catalyzed by 1−3
a
b
Reagents and conditions: arylalkanes (1.0 mmol), TBHP (1.5 mmol), and catalyst (0.05 mmol), H2O (5 mL), room temperature, air, 4 h. 8 h.
this reaction under a series of catalytic conditions (KAuCl4,
MnO2, ionic liquid, palladium complexes, ruthenium com-
plexes, etc.) generally provided a mixture of mono- and bis-
ketone compounds under strict operation conditions (high
temperature, toxic solvents, complex reagents, etc.).19 For
example, CuI, a commonly used homogeneous catalyst for the
direct C−H bond activation of diphenylmethane only gave
monoketone benzophenone in a yield of 19% under the same
reaction conditions (Table 1, entry 1). In addition, the similar
selectivity could only be found using Fe(III)/THA (thymine-1-
acetate) as catalysts and H2O2 as an oxidant.13a Compared to
other catalytic systems, CPs have great potential as
heterogeneous catalyst for the reaction not only because their
unique structural features, including crystallinity, active-site
uniformity, high surface area, and porosity, but also due to their
atomistically well-defined isolated active sites with uniformly
fixed configuration and suitable channel size throughout the
solid, which endow them with spatial confinement effect and
catalyze the reaction with regioselectivity. In addition, the
catalytic active sites of the CPs 1−3 are arranged periodically
with the distance of neighboring Cu(I) ions more than 6 Å,
which can effectively avoid synergic activity among Cu(I) ions,
yielding products with the high selectivity. Therefore, the
catalytic systems with CuI−CPs as catalysts in H2O under air at
room temperature not only remain environmental friendly
conditions but also express high selectivity in the reactions that
C−H bonds of arylalkanes are directly activated to ketones.
The mechanism for the oxidation of alkanes to the
corresponding ketones catalyzed by the Cu(I)-based CPs
were proposed based on previous report (Scheme 2).20 The
E
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Scheme 2. Proposed Mechanism for the Oxidation of Alkanes Catalyzed by CuI−CPs
t
intermediates of BuO· radical and HO-CuIIXL are first given
by ultrasonic treatment of TBHP with Cu(I)-based CPs.
Subsequently, the tBuO· radical abstracts one of allylic H atoms
from the substrate to produce the allylic radical I, which further
reacts with HO-CuIIXL to produce the corresponding
peroxyether II. Finally, II reacts with O2 to provide the
expected ketone. Therefore, the activity centers in 1 are
coordinated with I− anions, which may be easily cleaved and
form the transient state (Cu···I) to make contact with active
centers of substrates during the catalytic process. In contrast,
the lowest catalytic activity of 3 may be caused by the
dissociative Cl− anions, which are unfavorable for catalyzing
closely matched the simulated 2 and 3, respectively (Figures S2
and S3).
CONCLUSION
■
In summary, a series of catalytically active Cu(I)-based CPs 1−
3 were successfully regulated with different halogen ions (I−,
Br−, and Cl−) under the same reaction conditions. 1−2 could
not only be used as the efficient and green heterogeneous
catalysts to catalyze direct C−H bond activation reactions of
arylalkanes to ketones in water under room temperature but
also present spatial confinement effect, the reaction proceeding
with high regioselecticity. We also showed that the CPs
retained their integrated crystallinity after the catalysis. This
work provides important insights into CPs-catalyzed regiose-
lective reaction.
t
decomposition of TBHP into BuO· and HO· radicals.
To study whether the C−H functionalizations were
heterogeneous or homogeneous, atomic absorption spectros-
copy analysis of the filtrate showed the presence of slight
leaching (<1 ppm) of copper from the crystalline sampes of 1
during the reaction. Next, a filtration experiment was
conducted. After 25% conversion of 4a catalyzed by 1, we
use a sand core funnel to filtrate the catalysts from reaction
mixture. Then the filter liquor was stirred for 3 h. It was found
that the conversion was constant in the process. The
experiment data clearly demonstrated that 1 was a heteroge-
neous catalyst. Furthermore, the recyclability of the catalyst was
investigated with 1 and diphenylmethane in this reaction. In the
recyclability experiments, 1 could be easily recovered by
filtrating from the reaction mixture. The reused catalyst
indicated that only tiny catalyst was deteriorated after six
runs (Figure 4a). Besides, the PXRD patterns of the crystalline
ASSOCIATED CONTENT
■
S
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.7b02106.
Experimental details for all new compounds and all
reactions reported. Crystallographic information for
complexes 1−3 in CIF format and additional figures
and tables for structural, spectral, and computational
characterization (PDF)
Accession Codes
CCDC 1565786 and 988512−988513 contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge via www.ccdc.cam.ac.uk/data_request/
cif, or by emailing data_request@ccdc.cam.ac.uk, or by
contacting The Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
■
Corresponding Authors
*E-mail: houhongw@zzu.edu.cn. (H.H.)
*E-mail: wujie@zzu.edu.cn. (J.W.)
*E-mail: huangchao@zut.edu.cn. (C.H.)
Figure 4. (a) The recyclability of the catalyst of 1 in this reaction. (b)
Comparison of the PXRD patterns of 1 before and after recycle
experiments.
ORCID
Jie Wu: 0000-0001-7746-6640
Hongwei Hou: 0000-0003-4762-0920
Author Contributions
samples of 1 after the sixth round of reaction completely
matched the simulated 1 (Figure 4b) and displayed that the
framework did not collapse, which revealed that the framework
could retain integrated after at least six runs. Likewise, the
powder PXRD patterns of 2 and 3 after catalytic cycle also
#The authors X.L.W. and M.J.L. contributed equally to the
work and should be considered cofirst authors.
Notes
The authors declare no competing financial interest.
F
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ACKNOWLEDGMENTS
■
This work was funded by the National Natural Science
Foundation of China (Nos. 21771163, 21371155, and
21671174), the National Natural Science Foundation of
Henan Provience (No. 162300410243), and Project for the
Leading Young Teachers in Henan Provincial Institutions of
Higher Education of China.
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