A series of crystalline organic polymer-inorganic hybrid material zinc-phosphonate-phosphates synthesized in the presence of templates for superior performance catalyst support

Article abstract of DOI:10.1016/j.inoche.2014.08.006

New types of organic copolymer-inorganic hybrid material zinc-phosphonate-phosphates are prepared with amines as templates. Notably, crystalline samples are obtained not with traditional methods but with simple reactions. Moreover, the samples are provide

Full text of DOI:10.1016/j.inoche.2014.08.006

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Inorganic Chemistry Communications 48 (2014) 36–39
Contents lists available at ScienceDirect
Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
A series of crystalline organic polymer–inorganic hybrid material
zinc-phosphonate-phosphates synthesized in the presence of templates
for superior performance catalyst support
b
c,
d
Jing Huang a, , Jiali Cai , Chang Ming Li , Xiang Kai Fu
⁎
⁎
a
Research Center for Advanced Computation, School of Physics and Chemistry, Xihua University, Chengdu 610039, PR China
College of Rongchang, Southwest University, Chongqing 402460, PR China
Institute for Clean Energy & Advanced Materials, Southwest University, Chongqing 400715, PR China
College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, PR China
b
c
d
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 17 June 2014
Received in revised form 2 August 2014
Accepted 6 August 2014
Available online 7 August 2014
New types of organic copolymer–inorganic hybrid material zinc-phosphonate-phosphates are prepared with
amines as templates. Notably, crystalline samples are obtained not with traditional methods but with simple re-
actions. Moreover, the samples are provided with the potential application as superior performance catalyst
supports.
© 2014 Elsevier B.V. All rights reserved.
Keywords:
Zinc poly(styrene-phenylvinylphosphonate)-
phosphate
Salen Mn(III)
Heterogeneous catalysts
Asymmetric epoxidation
Hybrid material
Introduction
inorganic hybrid material zinc phosphonate-phosphate are prepared
in the presence of templates (Scheme 1). The question as to whether
Since the first synthesis of aluminium phosphate zeolites in 1982 [1],
considerable interests have been focused on various metal phosphate
materials [2]. Metal phosphonates exhibit a variety of open frameworks
such as layered and microporous structures [3]. Materials with open
framework and microporous structures are expected to find their use
as hybrid composite materials in electro-optical and sensing applica-
tions in the future [4]. Research in the field of zirconium phosphates
and zirconium phosphonates is very intense, which have involved
mainly adsorbent [5–7], inorganic ion exchangers [8,9], intercalation
chemistry [10,11], sensor and proton conductivity [12] and catalysis
[13–15]. Our group has devoted ourselves to these in the last decades.
Zirconium oligostyrenylphosphonate-phosphate (ZSPP) and zirconium
poly(styrene-phenylvinylphosphonate)-phosphate (ZPS-PVPA) were
prepared and used as catalyst supports. The immobilized catalysts dis-
play higher conversions, enantioselectivities and reusabilities than
those achieved with the homogeneous catalysts under the same reac-
tion conditions [16–22]. In addition, zinc phosphates have been proven
to be very versatile in the formation of organic–inorganic hybrid mate-
rials [23,24]. In this work, a series of new types of organic copolymer–
or not crystalline zinc-phosphonate-phosphate hybrid materials could
also be synthesized without the appending of templates and the roles
of the templates as well as the feasibility for the superior catalyst perfor-
mance supports are all examined here.
Results and discussion
The sodium content in sample 1e is 1.7%, which is 0.2% lower than
that of theoretical values. This could be attributed to the surface-
bound or intercalated water leading to the augment of the molecular
weight.
According to FT-IR spectra (Fig. S1), the strong and wide absorption
bands extending from 3100 to 3700 cm−1 and centering at 3500 cm−1
are assigned to the \OH, which verify the presence of H-bound interac-
tions between the aminonium ion and pendant HPO−4 group. The prom-
inent bands at 1145, 1089, and 986 cm−1 are attributed to R\PO23−
stretching vibrations. The absorptions at 1201, 1144, and 1077 cm−1
are due to the phosphonate and phosphate stretching vibrations.
On account of the TG curves (Fig. S2), samples 1a–1f lose 2.0–3.5 mol
equivalents of surface-bound or intercalated water below 200 °C. There
are two types of weight loss for these samples. According to samples 1a–
1d, the surface-bound or intercalated water is firstly lost, followed by
⁎
Corresponding authors.
E-mail address: hj41012@163.com (J. Huang).
http://dx.doi.org/10.1016/j.inoche.2014.08.006
1387-7003/© 2014 Elsevier B.V. All rights reserved.

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J. Huang et al. / Inorganic Chemistry Communications 48 (2014) 36–39
37
Scheme 1. Synthesis of 1.
the decomposition of the templates, and then the sharp weight loss is in
the temperature range of 200–600 °C, owing to the decomposition of
the appended organic fragments. Finally, the small weight loss between
600 °C and 1000 °C is due to phase changes from layer to cubic Zn2P2O7
and NaZnPO4. While for samples 1e and 1f, the weight loss processes are
similar to those of 1a–1d apart from the absence of the decomposition of
the templates. On the other hand, organic reactions are usually carried
out below 200 °C. Therefore, the samples are provided with enough
thermal stabilities as catalyst supports.
XRD patterns (Fig. S3) indicate that 1a–1f are in crystalline states
and could be served as mesoporous materials. Simultaneously, the in-
terlayer distances of samples 1a–1f are approximately 11 Å, which are
broader than those of inorganic zinc phosphate Zn3(PO4)2 (10.61 Å). It
may be that the styrene-phenylvinylphosphonic acid copolymer chains
in the samples make the zinc layer stretched and becoming broader.
Moreover, pores or channels of various sizes and shapes are formed by
appropriate modification of the styrene-phenylvinylphosphonic acid
copolymer chain, further giving birth to a significant impact on the ex-
cellent catalytic activity. The interlayer distance of sample 1f is a little
narrower than that of the other samples, owing to the ammonium
dihydrogen phosphate as the inorganic phosphate resource.
The diffuse reflectance UV–vis spectrums for samples 1a–1f (Fig. S4)
show a strong absorption around 227 nm, which may be assigned to the
π–π* transition of the phenyl groups. Another strong absorption is
shown around 326 nm. The phenomenon may be originated in two
aspects of reasons. For samples 1a–1d, this may be attributed to the
involvement of the charge transfer transitions from the N atoms of the
templates to the empty 4s orbitals of the Zn2+ ions, while for samples
1e and 1f, this perhaps is due to the O atoms of the phosphate or phos-
phonate to the empty 4s orbitals of the Zn2+ ions.
Based on the desorption isotherm (Fig. 1), sample 1c indicates a hi-
erarchical distribution of pore size. The pore diameters of the particles
are mainly between 15 Å and 30 Å, and some other particles vary
from 3 nm to 30 nm as well as few particles are over 30 nm in diameter.
Meanwhile, the size of solvated Mn(salen)Cl complex is estimated to be
2.05–1.61 nm by MM2 based on the minimized energy [25]. On the
basis of this, sample 1c could provide enough room to accommodate
the solvated chiral Mn(III) salen complex. In addition, the local environ-
ment inside the mesopores and pore size of the support definitely put
effect on the enantioselectivity of the epoxidation. It is the crucial prop-
erty that makes these samples being superior performance catalyst
supports.
Compared with sample 1e, different templates played different im-
pacts on samples 1a–d such as the physical properties of 1a–f in Table 1.
In Fig. 2, the different morphologies of the samples are attributed to
the templates and inorganic phosphate resources. As seen in sample 1a,
it is consisted irregularly of many platy layers, owing to the presence of
the parts of zinc phosphonate in it. The anomalous clusters are induced
by accumulation of the fraction of zinc phosphate in it. With regard to
sample 1c, the mixed powders of atypical particles and hexagonal bipyr-
amid particles as well as anomalous suborbicular particles could be
discerned, and for sample 1e, there are regular neat plate layers which
are mainly aggregation of the parts of zinc phosphate in it, while the
anomalous roughly spherical segments are congregation of the propor-
tion of zinc poly(styrene-phenylvinylphosphonate) in it. The appear-
ances shed light not only on the intricate relationship among the open
framework phosphates of different dimensionalities, but also on the
mechanism of formation of the complex structures. Meanwhile, the
supports possess various caves, holes, porous and channels. Some mi-
cropores and secondary channels would increase the surface area of
the catalyst and provide enough chance for substrates to access to the
catalytic active sites. While for sample 1f, it is abnormally made up of la-
mellar sections and clusters. In a word, both various templates and dif-
ferent inorganic phosphate resources play vital impacts on the
appearances of the samples and further influence the structure of the
catalysts as well as the catalytic abilities.
TEM photographies of sample 1a (Fig. 3) manifest that the configu-
ration is filiform in structure and the sample consists of many irregular
particles, while for sample 1e (Fig. 4), the structure of the support is
spheroid and their sizes are about 70–80 nm. The channels, holes and
cavums could be observed clearly. Meanwhile, the average diameter
of these secondary channels among the layers of the supports is around
50–60 nm. Based on the interlayer distance of the sample determined
Table 1
The physical properties of 1a–f.
Sample
Surface
Pore volume
Average pore
diameter (nm)
area (m2/g)
(×10−2 cm3/g)
1a
1b
1c
1d
1e
1f
3.8
4.6
5.1
4.4
4.8
4.9
1.5
1.8
2.0
1.9
1.2
1.3
2.1
3.1
3.6
3.3
3.4
3.5
Fig. 1. The nitrogen adsorption–desorption isotherm and pore distribution of sample 1c.

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38
J. Huang et al. / Inorganic Chemistry Communications 48 (2014) 36–39
Fig. 2. SEM images of samples (1) 1a, (3) 1c, (5) 1e and (6) 1f.
by XPRD, it could be deduced that each particle is made up of stacks of
25–30 layers. Therefore, more chances would be provided for substrates
to transfer to the internal catalytic active sites and further result in the
superior catalytic ability.
The activities of the catalysts (Scheme 2) for asymmetric epoxida-
tion of unfunctional olefins are presently in progress. The primary re-
sults are summarized in Table 2. Obviously, the activities of catalysts
A, C and D are more superior than that of catalyst B, which is partly
due to the templates. Further researches are under way.
Conclusions
In summary, a series of crystalline organic polymer–inorganic hybrid
materials zinc-phosphonate-phosphates have been synthesized with
amines as the templates. Owing to the templates and inorganic phos-
phate resource, the samples show versatile properties and could be
used as superior performance catalyst supports. Furthermore, chiral
salen Mn(III) deposited compounds are stable, effective and promising
catalysts and may be provided with potential industry application.
Fig. 3. TEM images of sample 1a (A and B).
Fig. 4. TEM images of sample 1e (A and B).

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J. Huang et al. / Inorganic Chemistry Communications 48 (2014) 36–39
39
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Scheme 2. Synthesis of the catalyst.
Table 2
Asymmetric epoxidation of α-methylstyrene and indene catalyzed by heterogeneous
catalysts with m-CPBA/NMOm as oxidant systems.
Entry
Substrate
Catalyst
Time
Con. (%)
ee (%)
1
2
3
4
5
6
α-Methylstyrene
Indene
A
A
B
B
C
D
6
6
6
6
6
6
99.2
99.4
62
56
96.2
98.8
99.5
99.6
59
18
94.7
87.6
Indene
α-Methylstyrene
α-Methylstyrene
α-Methylstyrene
A = the immobilized chiral salen Mn(III) catalysts on p-phenylenediamine modified
sample 1a.
B = the immobilized chiral salen Mn(III) catalysts on p-phenylenediamine modified ZPS-
IPPA (zirconium poly (styrene-isopropylenephosphonate)-phosphate).
C = the immobilized chiral salen Mn(III) catalysts on p-phenylenediamine modified
sample 1b.
D = the immobilized chiral salen Mn(III) catalysts on p-phenylenediamine modified
sample 1f.
m
Reactions were carried out at −20 °C in CH2Cl2 (4 ml) with α-methylstyrene (1 mmol)
or indene (1 mmol), n-nonane (internal standard, 1 mmol), NMO (5 mmol), homogeneous
(5 mol%) or heterogeneous salen Mn(III) catalysts (5 mol%) and m-CPBA (2 mmol). The con-
version and the ee value were determined by GC with chiral capillary columns (HP19091G-
B213, 30 m × 0.32 mm × 0.25 μm).
Acknowledgment
This work was financially supported by the Fundamental Research
Funds for the Central Universities (XDJK2013C120), the Xihua Universi-
ty Key Projects (Z1223321), Sichuan Province Applied Basic Research
Projects (2013JY0090) and the Department of Education of Sichuan
Province Projects (13ZB0030).
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3D zinc phosphonate with helical channels, Angew. Chem. Int. Ed. 43 (2004)
6482–6485.
[24] J. Huang, X.K. Fu, G. Wang, C. Li, X.Y. Hu, Novel layered crystalline zinc poly (styrene-
phenylvinyl phosphonate)-phosphate synthesized by a simple route in a THF–water
medium, Dalton Trans. 40 (2011) 3631–3639.
Appendix A. Supplementary material
[25] H.D. Zhang, C. Li, Asymmetric epoxidation of 6-cyano-2,2-dimethylchromene on Mn
(salen) catalyst immobilized in mesoporous materials, Tetrahedron 62 (2006)
6640–6649.
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.inoche.2014.08.006.
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