One-pot synthesis of ordered mesoporous transition metal-zirconium oxophosphate composites with excellent textural and catalytic properties

Article abstract of DOI:10.1039/c4nj01227e

A series of ordered mesoporous transition metal-zirconium oxophosphate composites (M-X-ZrPO, X = Cr, Mn, Fe, Co, Ni, Cu, Zn) were designed and synthesized via a facile and general one-pot evaporation-induced self-assembly (EISA) method. N₂-physisorption and TEM characterization showed that all the final materials possessed ordered mesoporous structure accompanied by large specific surface area (170-220 m² g^-1), big pore volume (0.2-0.4 cm³ g^-1) and uniform pore size (5.6-7.8 nm). Moreover, the introduced transition metals homogeneously dispersed in the mesoporous skeleton and effectively improved the mesostructure. The catalytic performance of M-X-ZrPO was evaluated in the liquid phase oxidation of ethylbenzene. The introduced transition metals obviously enhanced the catalytic performance of M-ZrPO. M-Mn-ZrPO showed excellent catalytic activity with 91.6% conversion of ethylbenzene and 87.0% selectivity of acetophenone. After five cycles, there was no notable decrease in catalytic activity. Therefore, it was a promising catalyst for the oxidation of ethylbenzene.

Full text of DOI:10.1039/c4nj01227e

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Oneꢀpot synthesis of ordered mesoporous transition metalsꢀzirconium
oxophosphate composites with excellent textural and catalytic properties
Zhichao Miaoa,b, Huahua Zhaoa, Jian Yanga, Jun Zhaoa, Huanling Songa,c, Lingjun
Choua,c*
Abstract
A series of ordered mesoporous transition metalsꢀzirconium oxophosphate
composites (MꢀXꢀZrPO, X = Cr, Mn, Fe, Co, Ni, Cu, Zn) were designed and
synthesized via a facile and general oneꢀpot evaporationꢀinduced selfꢀassembly (EISA)
method. N2ꢀphysisorption and TEM characterizations showed that all the final
materials possessed ordered mesoporous structure accompanying with large specific
surface area (170ꢀ220 m2·gꢀ1), big pore volume (0.2ꢀ0.4 cm3·gꢀ1) and uniform pore
size (5.6ꢀ7.8 nm). Moreover, the introduced transition metals homogeneously
dispersed in the mesoporous skeleton and effectively improved the mesostructure.
The catalytic performance of MꢀXꢀZrPO was evaluated in liquid phase oxidation of
ethylbenzene. The introduced transition metals obviously enhanced the catalytic
performance of MꢀZrPO. The MꢀMnꢀZrPO showed excellent catalytic activity with
91.6% conversion of ethylbenzene and 87.0% selectivity of acetophenone. After five
cycles, there was no notable decrease in catalytic activity. Therefore, it was a
promising catalyst for oxidation of ethylbenzene.
Keywords: oneꢀpot; ordered mesoporous materials; nanocomposites; partial
oxidation.
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1. Introduction
Ordered mesoporous materials (OMMs) have attracted continuous attention since
the discovery of M41S family in 1992.1,2 Owing to their superior textural properties,
such as high surface areas, regular pore frameworks with large pore size and volume,
OMMs have been widely developed and investigated the potential applications in
fields of catalysis, separation, drug delivery and sorption.3ꢀ6 As for synthetic methods,
the “hard template” and “soft template” are common methods to obtain OMMs.7,8 The
evaporationꢀinduced selfꢀassembly (EISA) method, which is a typical “soft template”
method and usually employed nonionic surfactants as structureꢀdirecting agents
(SDAs), is extensively investigated in preparing mesoporous metal oxides and
composites and the obtained mesoporous materials, such as Alꢀbased materials, metal
phosphates and TiO2 based materials, showed outstanding catalytic performance in the
CO2 reforming of CH4, acidꢀcatalyzed reactions and photocatalytical applications.9ꢀ13
This method is flexible, but expensive metal alkoxides are commonly utilized as
precursors and mineral acids need to be precisely controlled as acid modifier to
manage the alcoholysis process of metal precursors in the EISA process.14 All these
might limit the utilization of OMMs on a large scale.
Transition metals, which have unoccupied 3d orbits, are good electron acceptors
and widely used in many fields, such as redox reactions, adsorption, solar cell and
photocatalysis.15ꢀ19 Transition metals materials with abundant ordered mesoporous
pores can greatly increase the accessible active sites, which might improve their
applications in these fileds. For the applications in catalytic fields, transition metals
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extensively act as active sites for the oxidation reactions. The CrꢀMCMꢀ41,
MnꢀTiꢀSBAꢀ15, CoꢀSBAꢀ16 and CuꢀTUDꢀ1 materials were synthesized and
employed as catalyst in the oxidation of ethylbenzene, hydroxylation of benzene and
phenol.20ꢀ23 In consideration of the extensive applications of mesoporous transition
metals materials, the facile oneꢀpot method, which can be applied to the synthesis of
ordered mesoporous composites with different kinds of transition metals, has potential
to be investigated.
Herein, we employed a facile and general oneꢀpot EISA method to synthesize
ordered mesoporous transition metalsꢀzirconium oxophosphate composites
(MꢀXꢀZrPO). Cheap and common metal chlorides were chosen as the precursors of
transition metals. Simultaneously, the metal chlorides served as acid modifiers and no
mineral acids were added in the ethanol solution. Different kinds of transition metals
were successfully introduced into the skeleton of mesostructure. The mesostructure
and textural properties were detailed investigated by N2ꢀphysisorption and TEM
characterizations. The UVꢀvis diffuse reflectance spectra were employed for
characterizing the oxidation states and coordination of transition metals in MꢀXꢀZrPO.
The obtained materials were employed as catalyst in the liquid phase oxidation of
ethylbenzene. The heterogeneity and reusability of catalyst were also investigated.
More details about the characterizations of these mesoporous materials and their
catalytic properties are described specifically in the following text.
2. Experimental Section
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2.1 Synthesis of M-X-ZrPO.
MꢀXꢀZrPO was synthesized via an oneꢀpot EISA method with F127 employed as
structureꢀdirecting agents (SDAs).24 In a typical procedure, 1.2 g of F127, 4.5 mmol
of ZrOCl2·8H2O, 0.5 mmol of metal chlorides (CrCl3·6H2O, MnCl2·4H2O,
FeCl3·6H2O, CoCl2·6H2O, NiCl2·6H2O, CuCl2·2H2O and ZnCl2) and 3.75 mmol of
PO(OCH3)3 were dissolved in 15 mL of anhydrous ethanol and vigorous stirred for 6
h without adding any mineral acids. Then the solution mixture was transferred to a
drying oven to undergo the EISA process at 60 oC for 48 h and 100 oC for 24 h. The
asꢀsynthesized xerogel was calcined at 500 oC for 6 h with a heating rate of 1 oC·minꢀ1
in air to remove SDAs. The obtained ordered mesoporous transition metalsꢀzirconium
oxophosphate composites were denoted as MꢀXꢀZrPO (X = Cr, Mn, Fe, Co, Ni, Cu,
Zn) and the nominal molar ratio of X% was 10% (molar ratio of X% = Xmol / (Xmol
+
Zrmol) × 100%). In order to investigate the role of ordered mesostructure in promoting
catalytic performance, the MnꢀZrPO material without adding F127 was synthesized as
the aforementioned method and denoted as MnꢀZrPOꢀnoF127.
2.2 Characterization.
The nitrogen adsorption and desorption isotherms were recorded on an AutosorbꢀiQ
analyzer (Quantachrome Instruments U.S.). The specific surface area was calculated
via BrunauerꢀEmmettꢀTeller (BET) method in the relative pressure range of 0.05ꢀ0.3;
pore volume was calculated from adsorption isotherm at a relative pressure of 0.990;
pore size distribution was calculated by BarrettꢀJoynerꢀHalenda (BJH) method.
Powder Xꢀray diffraction (XRD) measurements were performed on an X’Pert Pro
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Multipurpose diffractometer (PANalytical, Inc.) with Cu Kα radiation (0.15406 nm)
at room temperature from and 10.0° to 80.0°.
Transmission electron microscopy (TEM) images, selected area electron diffraction
(SAED) and energyꢀdispersive Xꢀray spectroscopy (EDX) measurements were
performed on the TECNAI G2 F20 highꢀresolution transmission electron microscopy
under a working voltage of 200 kV.
The element compositions were analyzed by XꢀRay Fluorescence (XRF)
spectrometer on a Magix PW2403 (PANalytical, Inc.).
UVꢀvisible (UVꢀvis) diffuse reflectance spectra were recorded on a PE Lambda
650S instrument coupled with a diffuse reflectance accessory in the range of 190ꢀ850
nm.
2.3 Catalytic activity
The liquid phase oxidation of ethylbenzene was carried out in a round bottom flask
fitted with water condenser. Initially, MꢀXꢀZrPO (300 mg), acetonitrile (15 mL),
ethylbenzene (9 mmol) and tertꢀButyl hydroperoxide (36 mmol) were added to a 50
mL round bottom flask (the mass ratio of ethylbenzene to catalyst was 3.2). Then the
reaction mixture was stirred at 80 oC for 24 h and the products were centrifuged and
extracted with ether. The conversion of ethylbenzene and selectivity of products were
monitored by a gas chromatography (GC) instrument (Agilentꢀ7890A; equipped with
a flame ionization detector (FID) and HPꢀ5 column (30 m × 0.32 mm × 0.25 ꢁm))
using octane as external. Gas chromatographyꢀmass spectroscopy (GCꢀMS)
instrument (5975c vl MSD with tripleꢀaxis detector, GC Agilentꢀ7890A) was
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employed to identify the reaction products. The separated catalyst was washed with
ether and activated at 400 oC for 3 h for regeneration.
3. Results and discussion
Ordered MꢀXꢀZrPO materials were synthesized via the facile EISA method
employing F127 as SDAs (shown in Scheme 1). The ZrOCl2·8H2O, metal chlorides
and PO(OCH3)3 were chosen as precursors of metals and phosphorus. All the
precursors and F127 were dissolved in the ethanol solvent and the transparent solution
was gotten. Then the solution was transferred to an oven to undergo the EISA process.
In this process, the solution turned into xerogel and the hydrophobic segments of
F127 formed the cylindrical cores and all the precursors uniformly dispersed around
the cores.25 The F127 played a crucial role in the formation of mesoporous pores. The
gotten xerogel was calcined under air atmosphere to remove the F127. At last, the
MꢀXꢀZrPO materials were obtained.
The ordered mesostructure of obtained MꢀXꢀZrPO materials was characterized by
N2ꢀphysisorption technique. The N2 adsorptionꢀdesorption isotherms and
corresponding pore size distributions of MꢀXꢀZrPO materials are presented in Fig.1.
All the MꢀXꢀZrPO samples exhibited typical IV isotherms and wellꢀdefined H1
hysteresis loops (IUPAC) with sharp capillary condensation steps at the relative
pressure (p/po) of 0.4ꢀ0.8, indicating the existence of cylindrical mesoporous pores,
which would be confirmed by the TEM images. The pore sizes of these samples were
narrowly distributed at around 4ꢀ10 nm, implying the existence of uniform
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mesoporous system. Moreover, the textural parameters, such as specific surface area,
pore size and volume of MꢀXꢀZrPO gotten from the N2 adsorptionꢀdesorption
isotherms are shown in Table 1. All the materials had excellent textural properties
with large specific surface area (170ꢀ220 m2·gꢀ1), big pore volume (0.2ꢀ0.4 cm3·gꢀ1)
and uniform pore size (5.6ꢀ7.8 nm). It was noteworthy that the introduced transition
metals did not destroy the mesostructure. On the contrary, compared with MꢀZrPO,
the mesostructure of MꢀXꢀZrPO was improved with the introduction of transition
metals. Moreover, the MnꢀZrPOꢀnoF127 was synthesized and employed as a
comparison. Compared with MꢀMnꢀZrPO, the MnꢀZrPOꢀnoF127 material showed
poor textural properties (specific surface area (41.9 m2·gꢀ1), pore size (2.52 nm) and
volume (0.07 cm3·gꢀ1)). Hence, the F127 played an essential role in constructing
ordered mesoporous framework.
The XRD measurement of MꢀXꢀZrPO was conducted to investigate the states of
introduced transition metals species. As shown in Fig. 2, it was interesting that they
only exhibited two broad and weak diffraction peaks in all the parents. The absence of
obvious diffraction peaks of transition metals indicated that the introduced metals
species were highly dispersed in the mesoporous skeleton. This might be on account
of that transition metals atoms in the materials were segregated by zirconium and
phosphorus atoms owing to the peculiar traits of oneꢀpot EISA method. We deduced
that the highly dispersed transition metals might be the reason for successful
preservation of ordered mesostructure. Meanwhile, this could offer abundant active
sites for the reactants.
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In order to further confirm the presence of ordered mesopores in MꢀXꢀZrPO, TEM
(Fig. 3) images of the samples were taken. For all the samples, highly ordered
cylindrical pores view along [110] and [001] orientations were observed, revealing a
high degree of periodicity in large domains. These results of TEM observation agreed
quite well with the N2ꢀphysisorption characterization, which predicted the existence
of cylindrical pores in these materials. Moreover, no obvious particles or aggregations
of transition metals species were observed outside or inside of the channels for all the
samples, illustrating the high dispersion of transition metals species in the materials.
Therefore, it was concluded that metal species were highly dispersed in the
mesoporous pore walls. This phenomenon further explained the absence of obvious
diffraction peaks in XRD patterns of MꢀXꢀZrPO. In addition, the EDX measurement
and SAED pattern of MꢀMnꢀZrPO were studied as representatives. As shown in Fig.
3h, the characteristic peaks of Zr, P and Mn elements were obviously observed in the
EDX profile of MꢀMnꢀZrPO, implying that all the elements were successfully
introduced into the framework of mesostructure. In addition, all the transition metals
molar ratios gotten from EDX measurement were shown in Table 1 and the values
kept consistent with the ratios gotten from XRF characterizations and nominal values.
This might be owing to that transition metals were homogeneously dispersed in the
wall of mesostructure. For the corresponding SAED pattern of MꢀMnꢀZrPO (shown in
Fig. 3i), there were no apparent electron diffraction rings, implying that the wall of
mesoporous framework was amorphous, and further demonstrating the conclusion
gotten from XRD.
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The UVꢀvis diffuse reflectance spectra (shown in Fig. 4) were employed for
characterizing the oxidation states and coordination of transition metals in MꢀXꢀZrPO.
As our previous report about MꢀZrPO, the obvious adsorption band at 205 nm was
designated to the ZrꢀOꢀP coordination and the weak band at about 300 nm could be
attributed to Zr4+ interacting with the phosphate counter anions in the framework.24 As
the introduction of transition metals, additional bands appeared in the UVꢀvis spectra.
For the MꢀCrꢀZrPO material, the bands at 270 and 370 nm were contributed to the
ligandꢀmetal charge transfer (LMCT) O2ꢀ→Cr6+. The bands at 470 and 640 nm were
owing to the A2g→T1g and A2g→T2g transitions of Cr3+ in octahedral symmetry,
respectively.26,27 For the spectra of MꢀMnꢀZrPO, the band at 270 nm showed the
charge transfer transition of O2ꢀ→Mn3+ with tetrahedral coordination. The broad band
at about 500 nm was assigned to the dꢀd transition of Mn2+ in crystal field transition
(6A1g→4T2g).21,28 The MꢀFeꢀZrPO showed an obvious band at 300 nm, which was
owing to the LMCT that involved the isolated Fe3+ ions in tetrahedral coordination.
The band at 470 nm was attributed to the oxygen to metal charge transfer (Fe3+).29 In
the spectra of MꢀCoꢀZrPO, the bands at 520, 580 and 640 nm were designated to the
4A2(F)→4T1(P) transition characteristic of Co2+ ions in the isolated state with
tetrahedral coordination.22,30 The bands at 420 and 550 nm in the spectra of
3
3
MꢀNiꢀZrPO were assigned to the two spinꢀallowed A2g→3T1g(P) and A2g→3T1g(F)
of octahedrally coordinated Ni2+ ions (d8).31 For the MꢀCuꢀZrPO, the bands at 260 nm
was assignable to the LMCT transitions between surface oxygen and isolated Cu2+
ions and the broad band at 600ꢀ850 nm was owing to dꢀd transitions of Cu2+ in a
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tetragonally distorted octahedral environment.32 No obvious absorption bands were
observed in the spectra of MꢀZnꢀZrPO due to completely filled d10 electronic
configuration of Zn2+ metal.33
The catalytic performance of MꢀXꢀZrPO was investigated in liquid phase oxidation
of ethylbenzene (EB) (shown in Scheme 2). In this reaction, the acetophenone (AP)
was detected as the main product and a possible reaction mechanism was presented in
Scheme 3.34 The results of catalytic performance were shown in Fig. 5(1). The
MꢀZrPO showed poor catalytic performance, and only showed 9.7% conversion of
EB and 16.9% selectivity of AP. With the introduction of transition metals, the
catalytic performance was successfully improved, especially for the MꢀCrꢀZrPO and
MꢀMnꢀZrPO, which showed the best activity (~90.0% conversion of EB and ~90.0%
selectivity of AP). The sequence of catalytic activity was Cr, Mn, Cu, Co, Fe, Ni, Zn
and this might be due to the different redox properties of transition metals. Moreover,
it was noteworthy that the MnꢀZrPOꢀnoF127, which had poor mesostructure, only
showed 37.2% conversion of EB and 24.3% selectivity of AP. This indicated that the
excellent mesoporous structure was in favor of improving the catalytic performance
of MꢀXꢀZrPO.
On account of the excellent catalytic performance of MꢀMnꢀZrPO, it was further
employed for investigating the heterogeneity and reusability of catalyst. As shown in
Fig. 5(2), the conversion of EB and selectivity of AP were gradually increased with
time and reached the maximum at 24 h with the existing of catalyst. However, after
filtering the catalyst from the reaction system at 3 h, there was no obvious increase in
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conversion of EB and selectivity of AP even when the time reached up to 30 h.
Meanwhile, as shown in Table 1, compared with the fresh catalyst, the Mn contents
showed little change in the used catalyst (MꢀMnꢀZrPOꢀused). All these indicated that
the MꢀMnꢀZrPO was truly a heterogeneous catalyst and no obvious Mn species
leached into liquid phase in the reaction process.
The MꢀMnꢀZrPO was recycled for five runs and the results were shown in Fig. 5(3).
There was no significant decrease in catalytic performance, showing the MꢀMnꢀZrPO
could be reused as heterogeneous catalyst in the liquid phase oxidation of EB. In
addition, the regenerated catalyst was characterized by N2ꢀphysisorption and TEM
(shown in Fig. 6). The results manifested that the ordered mesoporous structure with
excellent textural properties and amorphous pore wall structure was successfully
maintained. The catalyst showed excellent stability and the mesostructure suffered
little influence in the reaction process. The high catalytic activity and stability of
MꢀMnꢀZrPO might be owing to that the transition metals introduced from the EISA
method were highly dispersed and firmly confirmed in the skeleton of mesoporous
materials. The sintering and leaching of metal species in the calcination and reaction
process could be largely avoided.
4. Conclusion
In this paper, a facile and general oneꢀpot EISA method, which was suitable for
different kinds of transition metals, was employed to synthesize a series of ordered
MꢀXꢀZrPO composites. All the transition metals species were homogeneously
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dispersed in the skeleton of mesostructure and the ordered mesostructure with
excellent textural properties were successfully maintained. The obtained ordered
mesoporous materials exhibited excellent catalytic activity and reusability in the
liquid phase oxidation of ethylbenzene. Therefore, the MꢀXꢀZrPO might be excellent
candidates of catalyst for selective oxidation reaction such as oxidation of
ethylbenzene.
Acknowledgements
The authors sincerely acknowledge the financial supported by the “Strategic
Priority Research Program” of the Chinese Academy of Sciences, Grant No.
XDA09030101 and the National Natural Science Foundation of China (No. 21133011,
201373244).
Notes and references
a State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute
of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, People’s
Republic of China.
b University of Chinese Academy of Sciences, Beijing 100049, People’s Republic of
China.
c Suzhou Institute of NanoꢀTech and NanoꢀBionics, Chinese Academy of Sciences,
Suzhou 215123, People’s Republic of China.
*Corresponding author: eꢀmail: ljchou@licp.cas.cn (L. J. Chou), Tel: +86 0931
4968066; Fax: +86 0931 4968129
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1. C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli and J. S. Beck, Nature,
1992, 359, 710ꢀ712.
2. J. S. Beck, J. C. Vartuli, W. J. Roth, M. E. Leonowicz, C. T. Kresge, K. D.
Schmitt, C. T. W. Chu, D. H. Olson and E. W. Sheppard, J. Am. Chem. Soc., 1992,
114, 10834ꢀ10843.
3. D. E. De Vos, M. Dams, B. F. Sels and P. A. Jacobs, Chem. Rev., 2002, 102,
3615ꢀ3640.
4. M. E. Davis, Nature, 2002, 417, 813ꢀ821.
5. G. Wang, A. N. Otuonye, E. A. Blair, K. Denton, Z. Tao and T. Asefa, J. Solid
State Chem., 2009, 182, 1649ꢀ1660.
6. D. D. Asouhidou, K. S. Triantafyllidis, N. K. Lazaridis, K. A. Matis, S. S. Kim
and T. J. Pinnavaia, Micropor. Mesopor. Mater., 2009, 117, 257ꢀ267.
7. Y. Shi, Y. Wan and D. Zhao, Chem. Soc. Rev., 2011, 40, 3854ꢀ3878.
8. D. Gu and F. Schuth, Chem. Soc. Rev., 2014, 43, 313ꢀ344.
9. W. Cai, J. Yu, C. Anand, A. Vinu and M. Jaroniec, Chem. Mater., 2011, 23,
1147ꢀ1157.
10. L. Xu, H. Song and L. Chou, Catal. Sci. Technol., 2011, 1, 1032ꢀ1042.
11. S. K. Das, M. K. Bhunia, A. K. Sinha and A. Bhaumik, ACS Catal., 2011, 1,
493ꢀ501.
12. A. Dutta, A. K. Patra, S. Dutta, B. Saha and A. Bhaumik, J. Mater. Chem., 2012,
22, 14094ꢀ14100.
13

New Journal of Chemistry
Page 14 of 26
View Article Online
DOI: 10.1039/C4NJ01227E
13. J. Wang, H. Li, H. Li, C. Zuo and H. Wang, J. Phys. Chem. C, 2012, 116,
9517ꢀ9525.
14. S. M. Grant and M. Jaroniec, J. Mater. Chem., 2012, 22, 86ꢀ92.
15. B. Han, H. Wang, Y. Kong and J. Wang, Mater. Lett., 2013, 100, 159ꢀ162.
16. J.ꢀH. Shan, L. Chen, L. B. Sun and X. Q. Liu, Energ. Fuel, 2011, 25, 3093ꢀ3099.
17. E. Ramasamy and J. Lee, Energy Environ. Sci., 2011, 4, 2529ꢀ2536.
18. J. H. Pan, X. Zhang, A. J. Du, H. Bai, J. Ng and D. Sun, Phys. Chem. Chem.
Phys., 2012, 14, 7481ꢀ7489.
19. S. Shen, J. Chen, R. T. Koodali, Y. Hu, Q. Xiao, J. Zhou, X. Wang and L. Guo,
Appl. Catal., B., 2014, 150ꢀ151, 138ꢀ146.
20. S. K. Mohapatra and P. Selvam, J. Catal., 2007, 249, 394ꢀ396.
21. P. Visuvamithiran, K. Shanthi, M. Palanichamy and V. Murugesan, Catal. Sci.
Technol., 2013, 3, 2340ꢀ2348.
22. Y. Dong, X. Zhan, X. Niu, J. Li, F. Yuan, Y. Zhu and H. Fu, Micropor. Mesopor.
Mater., 2014, 185, 97ꢀ106.
23. M. P. Pachamuthu, V. V. Srinivasan, R. Maheswari, K. Shanthi and A.
Ramanathan, Catal. Sci. Technol., 2013, 3, 3335ꢀ3342.
24. Z. Miao, L. Xu, H. Song, H. Zhao and L. Chou, Catal. Sci. Technol., 2013, 3,
1942ꢀ1954.
25. Z. X. Li, F. B. Shi, Y. Ding, T. Zhang and C. H. Yan, Langmuir, 2011, 27,
14589ꢀ14593.
26. D. Shee and A. Sayari, Appl. Catal., A., 2010, 389, 155ꢀ164.
14

Page 15 of 26
New Journal of Chemistry
View Article Online
DOI: 10.1039/C4NJ01227E
27. J. Baek, H. J. Yun, D. Yun, Y. Choi and J. Yi, ACS Catal., 2012, 2, 1893ꢀ1903.
28. A. Kumar, D. Nepak and D. Srinivas, Catal. Commun., 2013, 37, 36ꢀ40.
29. N. S. Sanjini and S. Velmathi, RSC Adv., 2014, 4, 15381ꢀ15388.
30. H. Cui, Y. Zhang, Z. Qiu, L. Zhao and Y. Zhu, Appl. Catal., B., 2010, 101, 45ꢀ53.
31. T. E. Klimova, D. Valencia, J. A. MendozaꢀNieto and P. HernándezꢀHipólito, J.
Catal., 2013, 304, 29ꢀ46.
32. C. S. Chen, Y. T. Lai, T. W. Lai, J. H. Wu, C. H. Chen, J. F. Lee and H. M. Kao,
ACS Catal., 2013, 3, 667ꢀ677.
33. P. C. Sahoo, Y. N. Jang, Y. J. Suh and S. W. Lee, J. Mol. Catal. A: Chem., 2014,
390, 105ꢀ113.
34. A. V. Biradar and T. Asefa, Appl. Catal., A., 2012, 435ꢀ436, 19ꢀ26.
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Table 1. Textural properties of MꢀXꢀZrPO derived from nitrogen physisorption and
molar ratios of transition metals gotten from XRF and EDX.
Specific
surface area
(m2·gꢀ1)
Pore
size
Pore
Nominal
molar
Ratios
from
Ratios
from
Sample
volume
(cm3·gꢀ1)
(nm)
ratios
XRF
EDX
MꢀZrPO
MꢀCrꢀZrPO
160.0
216.6
189.1
192.7
200.6
193.4
206.3
177.0
164.5
41.9
5.64
6.55
6.54
5.65
6.56
6.55
7.77
6.56
6.56
2.52
0.26
0.28
0.28
0.22
0.29
0.30
0.37
0.29
0.27
0.07
—
—
—
0.100
0.100
0.100
0.100
0.100
0.100
0.100
0.100
0.100
0.095
0.102
0.103
0.102
0.103
0.098
0.097
0.099
0.106
0.092
0.090
0.103
0.107
0.089
0.095
0.094
0.091
0.135
MꢀMnꢀZrPO
MꢀFeꢀZrPO
MꢀCoꢀZrPO
MꢀNiꢀZrPO
MꢀCuꢀZrPO
MꢀZnꢀZrPO
MꢀMnꢀZrPOꢀused
MnꢀZrPOꢀnoF127
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Figure captions:
Figure 1. (1) N2 physisorption isotherms and (2) pore size distributions of MꢀXꢀZrPO:
(a) MꢀZrPO, (b) MꢀCrꢀZrPO, (c) MꢀMnꢀZrPO, (d) MꢀFeꢀZrPO, (e) MꢀCoꢀZrPO, (f)
MꢀNiꢀZrPO, (g) MꢀCuꢀZrPO and (h) MꢀZnꢀZrPO.
Figure 2. XRD patterns of MꢀXꢀZrPO: (a) MꢀZrPO, (b) MꢀCrꢀZrPO, (c) MꢀMnꢀZrPO,
(d) MꢀFeꢀZrPO, (e) MꢀCoꢀZrPO, (f) MꢀNiꢀZrPO, (g) MꢀCuꢀZrPO and (h)
MꢀZnꢀZrPO.
Figure 3. TEM images of MꢀXꢀZrPO: (a) MꢀCrꢀZrPO, (b) MꢀMnꢀZrPO, (c)
MꢀFeꢀZrPO, (d) MꢀCoꢀZrPO, (e) MꢀNiꢀZrPO, (f) MꢀCuꢀZrPO and (g) MꢀZnꢀZrPO;
EDX measurement (h) and SAED pattern (i) of MꢀMnꢀZrPO.
Figure 4. UVꢀvis diffuse reflectance spectra of MꢀXꢀZrPO: (a) MꢀZrPO, (b)
MꢀCrꢀZrPO, (c) MꢀMnꢀZrPO, (d) MꢀFeꢀZrPO, (e) MꢀCoꢀZrPO, (f) MꢀNiꢀZrPO, (g)
MꢀCuꢀZrPO and (h) MꢀZnꢀZrPO.
Figure 5. Liquid phase oxidation of ethylbenzene: (1) catalyzed by MꢀXꢀZrPO and
MnꢀZrPOꢀnoF127; (2) catalyzed by MꢀMnꢀZrPO at different time; (3) the
recyclability of MꢀMnꢀZrPO.
Figure 6. (1) isotherms; (2) pore size distribution; (3) and (4) TEM images and SAED
pattern of MꢀMnꢀZrPOꢀused.
Scheme 1. Schematic illustration for the MꢀXꢀZrPO synthesized from EISA method.
Scheme 2. Liquid phase oxidation of ethylbenzene over MꢀXꢀZrPO catalyst.
Scheme 3. A possible reaction mechanism of liquid phase oxidation of ethylbenzene
over MꢀMnꢀZrPO catalyst.
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Figure 1
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Figure 2
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Figure 3
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Figure 4
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Figure 5
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Figure 6
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Scheme 1
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Scheme 2
Scheme 3
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The image for TOC
A series of ordered M-X-ZrPO materials were successfully synthesized via a facile
and general one-pot evaporation-induced self-assembly (EISA) strategy.