SciELO - Scientific Electronic Library Online

vol.16 issue1Polyvinyl pyrrolidone-assisted synthesis of crystalline manganese vanadate microtubesEffect of heat treatment on some mechanical properties of 7075 aluminium alloy author indexsubject indexarticles search
Home Pagealphabetic serial listing  

Services on Demand




Related links


Materials Research

Print version ISSN 1516-1439

Mat. Res. vol.16 no.1 São Carlos Jan./Feb. 2013  Epub Nov 22, 2012 

A novel vanadium n-propylamino phosphate catalyst: synthesis, characterization and applications



Rajini AnumulaI; Muralasetti NookarajuI; Kaliaperumal SelvarajII; Ingala Ajit Kumar ReddyI; Venkatathri NarayananI,*

IDepartment of Chemistry, National Institute of Technology, Warangal 506 004, Andhra Pradesh, India
IICatalysis Division, National Chemical Laboratory, Pune 411 008, Maharastra, India




A novel, lamellar type Vanadium n-propylamino phosphate catalyst is synthesized and characterized by using various physicochemical techniques such as Powder X-ray diffraction, Scanning electron microscopy/Energy dispersive X-ray analysis, Thermogravimetry/Differential thermal analysis, Fourier transform Infrared analysis, Electron spin resonance spectroscopy, Ultraviolet – Visible Diffuse reflectance spectroscopy, X-ray Photoelectron spectroscopy, 31P Magic angle spinning Nuclear Magnetic Resonance spectroscopy and Catalytic applications toward Octahydroquinazolinone synthesis. It is found that the n-propylamine is present as sandwich between Vanadyl phosphate layers. Most of the Vanadium is present as V4+ ions in tetrahedral co-ordination. Vanadium n-propylamino phosphate catalyses Octahydroquinazolinone synthesis more effeciently and the optimum conditions required for Octahydroquinazolinone synthesis are, Benzaldehyde (2 mmol), Dimedone (2 mmol), Urea (4 mmol), Methanol + Water (1:1, 5 mL) and Catalyst (0.05 g). A plausible mechanism is also proposed.

Keywords: vanadium, n-propylamino phosphate, octahydroquinazolinones, synthesis



1. Introduction

The Octahydroquinazolinones derivatives have attracted considerable attention, as they exhibit potent antibacterial activity against Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa1, and calcium antagonist activity2,3. In 1893, Italian chemist Pietro Biginelli was first reported, the acid catalyzed cyclocondensation reaction of an aldehyde, ethylacetoacetate and urea. This procedure known as Biginelli reaction. Recently, the Biginelli reaction has been found to employ in the synthesis of Octahydroquinazolinones, which involves Knoevenagel condensation, Michael addition and cyclization of aromatic aldehydes, urea and cyclic β-diketones4. Various Lewis acid catalysts such as Mn (OAc)3, LiBr, VCl3, La (OTf)3, ZrCl4, and InBr3, are employed in the synthesis of dihydropyrimidinones through Biginelli reaction. However the reagents/catalysts are found to be expensive, harmful and are difficult to handle especially in large scale. Literature survey reveals a number of homogeneous and heterogeneous catalytic systems used for synthesis of octahydroquinazolinone derivatives which includes TMSCl5, conc. H2SO4, Nafion-H6, VOSO4, conc. HCl in ethanol7, ammonium metavanadate8, ionic liquids9 and silica sulfuric acid10. However the procedures are having several drawbacks.

Vanadium containing micro porous molecular sieves was found to be active in a number of oxidation reactions. They are industrially important in a number of catalytic processes such as the selective oxidation of hydrocarbons, production of SO3, ammoxidation of hydrocarbons and reduction of nitric oxide11. Vanadium phosphates (VPO) are having many applications in catalysis, materials science and as heterogeneous catalysts in various organic reactions, because of the nontoxic nature and the ability to promote selective reactions. VPO constitute a interesting class of layered compounds exist in a wide range of structural forms due to the variable valency of Vanadium as well as the large diversity in VO6 octahedron bonding and PO4 structural units. Phases containing Vanadium in +5, +4 and +3 oxidation states and co-ordination geometry (tetrahedral, square pyramidal and octahedral) are known. In all the compounds the layers are held together by hydrogen bonding or by weak Vander Waal’s interactions and the layered compounds are amenable for intercalation reactions. VPO catalysts are extremely important in heterogeneous catalysis for the selective oxidations of methanol to formaldehyde12, benzyl alcohol to benzaldehyde13, esterification of oleic acid14, Ammoximation of aromatics and alkyl aromatics15, n-butane to maleic anhydride16, propane to acrylic acid17, oxidative dehydrogenation of ethane and propane18, epoxidations of allylic alcohols19.

The concept of using micelles and long chain surfactants as templates for the synthesis of novel mesoporous silicates was first introduced by a group of scientists at Mobil in 199220. From the literature studies, the neutral templating approach using amines as templates leads to the formation of lamellar VPO phases21. The role of organic structure directing agents has been discussed22 as an important role in the kinetics of nucleation and crystallization. The development of Vanadium containing materials with novel structures and well defined oxidation states of Vanadium is an important area of research in oxidation catalysts. Reports are available regarding the applications of Vanadium as a catalyst in organic synthesis such as synthesis of coumarins23, 3, 4-dihydropyrimidin-2(1H)-ones, bis-(indolyl) methane’s24, trimethylsilylation of alcohols25, tris (2, 4-dinitrophenoxo) compounds26 and mannich-type reactions27.

Recently, Venkatathri et al.28, reported a novel Manganese organophosphate and Titanium n-propylamino phosphate synthesized using amines as templates. The aim of the present study is to synthesis Vanadium n-propylamino phosphate and characterize it by various physico-chemical techniques such as, powder XRD, SEM/EDAX, TG/DTA, FT-IR, ESR, UV-Vis DRS, XPS and 31P MAS NMR. We are also used the above catalyst for the synthesis of Octahydroquinazolinone derivatives and studied the influence of various synthesis parameters.


2. Experimental

2.1. Materials

Vanadyl sulphate (98%, Loba Chemie, India), n-propyl amine (Spectrochem, India), Orthophosphoric acid (85%, Merck, India), aldehydes (Sisco, India) and dimedone (Oakwood, USA) were used without further purification.

2.2. Synthesis

A calculated quantity of 0.01 molar Vanadyl sulphate, was added to 1 molar orthophosphoric acid and stirred mechanically for 5-10 minutes to form a homogeneous mixture. To the well stirred mixture, a 4 molar n-propylamine was added and stirred well to get solid homogeneous Vanadium n-propylamino phosphate. The catalyst was ground well, washed with ether and dried at 40 ºC for 5-10 minutes. The resulting solid was subjected to various physico-chemical characterizations.

The Vanadium n-propylamino phosphate catalyst was analyzed by powder X-ray diffraction using a spectrometer (Philips X’pert Pro PW-3040 model, special detector – X’elerator) supported by small and wide angle goniometers with voltage and current of 40 kV and 30 mA respectively at room temperature in a 2q range of 0 to 50º. The morphology and surface elemental composition of the catalyst were investigated by using scanning electron microscope with EDAX attachment on a JEOL-JSM-5200 electron microscope. The thermal characteristics of the Vanadium n-propylamino phosphate has been studied by Thermo gravimetry/Differential thermal analysis (Diamond TG/DTA thermal analyzer) in a temperature range from 25 to 900 ºC with heating rate of 10 ºC/min in Nitrogen atmosphere. Fourier transform Infrared spectrum was recorded on a Shimadzu spectrophotometer using KBr pellet technique. Electron spin resonance spectrum was obtained from Bruker instrument. The co-ordination and oxidation state of Vanadium in Vanadium n-propylamino phosphate was examined by using diffuse reflectance UV–visible spectrometer (Shimadzu UV 2550) with 200 to 800 nm region and Barium sulphate was used as reference. X-ray photoelectron spectroscopy of Vanadium n-propylamino phosphate was obtained from ESCA-3000. 31P Magic angle spinning nuclear magnetic resonance spectrum were obtained from Bruker MSL-300 instrument.

In a typical reaction, benzaldehyde (2 mmol), dimedone (2 mmol) and urea (4 mmol) were taken in a round bottomed flask. To the above reaction mixture 0.05 g Vanadium n-propylamino phosphate catalyst was added. The reaction mixture was kept under stirring and reaction progress was monitored by TLC. The solid product was filtered and recrystallized with ethanol. The products were authenticated by melting point, FT-IR and 1H NMR.


3. Results and Discussions

The powder X-ray diffraction pattern (Figure 1) of Vanadium n-propylamino phosphate shows peaks at 7.02º, 8.7º, 13.1º, 13.8º, 17.4º, 19.0º, 21.1º, 22.4º, 24.3º, 25.2º, 26.2º and 32.1º, 2θ values and the corresponding d-spacing’s are 12.5 Å, 10.0 Å, 6.7 Å, 6.3 Å, 5.08 Å, 4.6 Å, 4.2 Å, 3.9 Å, 3.6 Å, 3.5 Å, 3.3 Å, and 2.7 Å. The peaks at 21.1º and 26.2º values indicates the presence of Vanadium ions29 predominantly in V4+ state with small amount in V5+[30] and peak at 19.0º indicates the presence of Vanadium phosphate31 layer. The peaks at 13.9º, 19º, 22º, 24º and 26.2º are due to the presence of VOPO4 phases32 in Vanadium n-propylamino phosphate.

The Scanning electron micrograph (Figure 2) shows homogeneous distribution of the material with plate like structures33 and 15-30 µm particle size. The Energy dispersive X-ray analysis (Figure 3) shows the presence of Vanadium ions on surface.



The Thermogravimetry/Differential thermal analysis (Figure 4) of Vanadium n-propylamino phosphate shows endothermic weight loss at 100-150 ºC are due to volatilization of physically adsorbed water molecules34. The exothermic weight loss at 230-500 ºC is due to the oxidative decomposition of organic molecules35.



The Fourier transform Infrared spectrum (Figure 5) of Vanadium n-propylamino phosphate shows a peak at 534 cm–1 associated with the V-O-V rotational vibrations29. Peak at 1468 cm–1 is due to the presence of hydrocarbon moiety (-CH2-CH2-)36. While the peak at 756 cm–1 was due to asymmetric stretching vibrations of V-O-V units37. A peak around 1220-1080 cm–1 corresponds to C-N stretching vibration38. Peak at 1396 cm–1 may be due to P-O stretching vibration39. Peak at 970 cm–1 is due to stretching vibration of V=O in the infrared spectrum40. The band at 436 cm–1 arises due to P-O bending vibrations. Peak at 878 cm–1 may corresponds to condensed P-N units41,42. The broad band at 3416 cm–1 may be due to N-H stretching vibrations43. Peak in the range of 1650-1590 cm–1 corresponds to N-H bending vibrations. The material may possess lamellar type of structure, explained by the profile of the absorption band due to the VOPO4 lattice vibration at 970 cm–1 was retained after the synthesis, suggesting the lamellar nature and intercalation compound was formed involving a V-P-O framework with the organic molecules44. The Vanadium phosphate layers may be sandwitched by n-propylamine (Figure 6)45,46.



The Electron spin resonance spectrum (Figure 7) of Vanadium n-propylamino phosphate exhibits a typical characteristic eight-line hyperfine patterns originated from the interaction of an unpaired electron with nuclear spin (I = 7/2) of 51V (natural abundance 99.8%). The well-resolved hyperfine patterns further indicate the paramagnetic center VO2+ is well dispersed in the sample. The EPR parameters (g ll = 1.931, g = 1.991, A ll = 180.5 G, A = 69.5 G) corresponds to V4+ in square pyramidal environment47.



The UV-Vis diffuse reflectance spectrum (Figure 8) of Vanadium n-propylamino phosphate shows a band at 250 nm due to VO2+ species present in tetrahedral coordination34. The band at 300-320 nm is in favour of high dispersion of V5+ ions in the lattice and due to (V=O) (π)t2 (d)e and (π)t1 (d)e electron transfer transitions48 resulting from V5+ in tetrahedral environment. Hence, UV-Vis diffuse reflectance spectrum explains V4+ and V5+ ions are co-existed in the catalyst. Presence of a broad peak at 410-460 nm is due to charge transfer transitions of V5+ species (V=O) in square pyramidal geometry49.



The X-ray photoelectron spectra (Figure 9a, b) of Vanadium n-propylamino phosphate shows the carbon 1s spectrum signal at 288 eV was attributed to carbon bonded to oxygen, Nitrogen and Hydrogen respectively50. The oxygen 1s spectrum shows signal at 534 eV is associated with the bridging oxygen of P-O-P bonds51. The binding energies for V-O-V and V=O structures have been reported to be closer to 531.6-530.9 and 530.3-529.9 eV, respectively52 concludes the presence of V-O-P bonds in Vanadium n-propylamino phosphate. The N 1s signal shows peak around 400-404 eV correlated with the photo activity in Visible light53 or may be due to presence of interstitial N2 in Vanadium n-propylamino phosphate54. The Vanadium ion shows peak at 525 eV corresponding to binding energy of V 2p1/2 electron indicates Vanadium exists as V4+ oxidation state and the peak became broadened55. The V2p XPS spectrum indicates, Vanadium exists as V4+ and V5+ oxidation states in Vanadium n-propylamino phosphate catalyst. Vanadium n-propylamino phosphate catalyst possesses V5+ species with trace amounts of V4+ species. The P 2p binding energy shows a peak around 137 eV attributed to presence of phosphorous oxide P2O5[56] in Vanadium n-propylamino phosphate or related to presence of V-O-P compounds containing mono-, di- and poly- hydrogen phosphate anions57.

Phosphorous solid state NMR spectroscopy is a powerful tool to distinguish different valence states of Vanadium surrounding the phosphorous atoms in different environments. 31P MAS NMR spectrum (Figure 10) of Vanadium n-propylamino phosphate shows two 31P peaks, with an intensity ratio of about 1:1 at 0 ppm is ascribed to the presence of phosphorous58 in tetrahedral environment59,60. According to Bunker et al.60 the peaks at 0 ppm is due to presence of PO2N2 tetrahedra. The 31P MAS NMR spectrum explains two kinds of tetrahedra are formed simultaneously, at the expense of the PO4 tetrahedral61. Phosphorous atoms at VOPO4, in the neighborhood of V5+ species, leads to narrow 31P MAS NMR signals in the range of ca. -22 to 4 ppm62.



4. Catalytic Properties

4.1. Influence of substituted aldehydes

In order to confirm the versatility of the catalyst, the standard reaction was carried out by using various aromatic aldehydes in methanol and water. [Table 1, entries 1 to 7]. In all the cases, the reactions proceed smoothly to afford the desired octahydroquinazolinone derivatives in 69-85% yields. The yields obtained were good to excellent without formation of side products. The aromatic aldehydes bearing electron withdrawing groups (p-NO2, p-Br) reacted at faster rate compared with aromatic aldehydes substituted with electron releasing groups (p-methyl, p-hydroxyl. The corresponding products and yields were illustrated in Table 1.



4.2. Influence of solvents

Influence of solvents (Table 2) on the synthesis of octahydroquinazolinones is studied in presence of 0.05 g Vanadium n-propylamino phosphate have been monitored using solvents tetrahydrofuran, chloroform, water, acetonitrile, ethanol, methanol and methanol + water (1:1) at 60 ºC. In comparison with other solvents, combination of methanol, water gave the products with higher yields. As protic solvents, methanol and water will solubilize dimedone and bring the reactants on the surface of the catalyst and enhance the yield. However, the reaction did not proceed in aprotic solvents like acetonitrile, chloroform and tetrahydrofuran.



4.3. Influence of the amount of catalyst

In order to optimize the amount of Vanadium n-propylamino phosphate catalyst for the synthesis of octahydroquinazolinone derivatives, the reaction was carried out by varying the amount of catalyst from 0.03 g to 0.1 g (Table 3). With increase in amount of Vanadium n-propylamino phosphate catalyst from 0.03 g to 0.1 g, no change in the reaction time was observed. The optimum amount of catalyst was found to be 0.05 g with respect to product yield and amount of catalyst. The yields of the products obtained were good to excellent without the formation of side products. The reactions carried out in the presence of Vanadium n-propylamino phosphate shows the formation of only octahydroquinazolinone derivatives.



4.4. Recyclability of the catalyst

Catalyst was recovered after the reaction by simple filtration, washed with dichloromethane, dried at ambient temperature and used for the next run. Recyclability of the catalyst (Table 4) for the standard reaction conditions at reflux temperature was investigated. The yields of the product obtained in the subsequent cycles are found to be 80, 65 and 50% (Table 4).



4.5. Mechanism

The role of Vanadium n-propylamino phosphate catalyst is to activate the aldehyde by binding the oxygen atom of aldehyde with vacant orbital of Vanadium (Figure 11) to achieve the stable oxidation state. Low acidity and neutrality of Vanadium n-propylamino phosphate catalyst exhibit higher selectivity toward the synthesis of octahydroquinazolinones derivatives.


5. Conclusions

A novel Vanadium n-propylamino phosphate catalyst is synthesized and found to have lamellar structure with Vanadyl phosphate layers and n-propylamine sandwich. It was prepared from n-propylamine, Vanadyl sulphate and Orthophosphoric acid. It is characterized in detail by various spectral and physicochemical techniques. The characterization shows that the Vanadium is incorporated mainly as V4+ species. The catalytic applications of this material toward octahydroquinazolinones synthesis is established. Influence of various reaction parameters such as different solvents, various amounts of catalyst and aldehydes on Octahydroquinazolinones synthesis have been studied.



The authors are thankful to the Director, National Institute of Technology, Warangal for constant encouragement through out the course of research work and one of the authors, A. R is thankful to the MHRD, Govt of India for a fellowship.



1. Kidwai M, Saxena S, Khan MKR and Thukral SS. Synthesis of 4-aryl-7,7-dimethyl-1,2,3,4,5,6,7,8-octahydroquinazoline-2-one/thione-5-one derivatives and evaluation as antibacterials. European Journal of Medicinal Chemistry. 2005; 40(8):816-819. PMid:16122583.        [ Links ]

2. Yarim M, Sarac S, Kilic SF and Erol K. Synthesis and in vitro calcium antagonist activity of 4-aryl-7,7-dimethyl/1,7,7-trimethyl-1,2,3,4,5,6,7,8-octahydroquinazoline-2,5-dione derivatives. Il Farmaco. 2003; 58(1):17-24.        [ Links ]

3. Yarim M, Sarac S, Ertan M, Kilic SF and Erol K. Synthesis, enantioseperation and pharmacological activity of 4-aryl-7,7-dimethyl-5-oxo-1,2,3,4,5,6,7,8-octahydroquinazoline-2-thiones. Arzneimittel-Forschung. 2002; 52:27-33.         [ Links ]

4. Hassani Z, Islami MR and Kalantari M. An efficient one-pot synthesis of octahydroquinazolinone derivatives using catalytic amount of H2SO4 in water. Bioorganic & Medicinal Chemistry Letters. 2006; 16(17):4479-4482. PMid:16806918.        [ Links ]

5. Kantevari S, Bantu R and Nagarapu L. TMSCl mediated highly efficient one-pot synthesis of octahydroquinazolinone and 1, 8-dioxo-octahydroxanthene derivatives. Arkivoc. 2006; 16:136-148.         [ Links ]

6. Lin H, Zhao Q, Xu B and Wang X. Nafion-H catalyzed cyclocondensation reaction for the synthesis of octahydroquinazolinone derivatives. Journal of Molecular Catalysis A: Chemical. 2007; 268(1-2):221-226.        [ Links ]

7. Ladani NK, Patel MP and Patel RG. An efficient three component one-pot synthesis of some new octahydroquinazolinone derivatives and investigation of their antimicrobial activities. Arkivoc. 2009; 7:292-302.         [ Links ]

8. Niralwad KS, Shingate BB and Shingare MS. Microwave-assisted one-pot synthesis of octahydroquinazolinone derivatives using ammonium metavanadate under solvent-free condition. Tetrahedron Letters. 2010; 51(28):3616-3618.        [ Links ]

9. Niralwad KS, Shingate BB and Shingare MS. Ultrasound-assisted one-pot Synthesis of octahydroquinazolinone derivatives catalyzed by acidic ionic liquid [tbmim]Cl2/AlCl3. Journal of the Chinese Chemical Society. 2010; 57:89-92.         [ Links ]

10. Mobinikhaledi A, Foroughifar N and Khodaei H. Synthesis of octahydroquinazolinone derivatives using silica sulfuric acid as an efficient catalyst. European Journal of Chemistry. 2010; 1(4):291-293.        [ Links ]

11. Venkatathri N. Synthesis, characterization and catalytic properties of vanadium aluminophosphate molecular sieves VAPO-31 and VAPSO-Amr from non-aqueous media. Applied Catalysis A: General. 2006; 310:31-39.        [ Links ]

12. Behera GC and Parida KM. Selective gas phase oxidation of methanol to formaldehyde over aluminum promoted vanadium phosphate. Chemical Engineering Journal. 2012; 180:270-276.        [ Links ]

13. Behera GC and Parida KM. Liquid phase catalytic oxidation of benzyl alcohol to benzaldehyde over vanadium phosphate catalyst. Applied Catalysis A: General. 2012; 413-414:245-253.        [ Links ]

14. Behera GC and Parida KM. Fascinating and challenging role of tungstate promoted vanadium phosphate towards solvent free esterification of oleic acid. Dalton Trans. 2012; 41(4):1325-1331. PMid:22130509.        [ Links ]

15. Cavani F, Foresti E, Trifiro F and Busca G. Nature of active species in the ammoxidation of toluene over V2O5/TiO2 catalysts prepared by flash-drying. Journal of Catalysis. 1987; 106(1):251-262.        [ Links ]

16. Cavani F and Trifiro F. Selective oxidation of light alkanes: interaction between the catalyst and the gas phase on different classes of catalytic materials. Catalysis Today. 1999; 51(3-4):561-580.        [ Links ]

17. Dasgupta S, Agarwal M and Datta A. Mesolamellar vanadium phosphate phases obtained by intercalation of a long chain alkylamine into different catalytically important VPO host lattices. Journal of Molecular Catalysis A: Chemical. 2004; 223(1-2):167-176.        [ Links ]

18. Centi G. Some prospects and priorities for future research on vanadyl pyrophosphate. Catalysis Today. 1993; 16(1):147-153.        [ Links ]

19. Sharpless KB and Michaelson RC. High stereo- and regioselectivities in the transition metal catalyzed epoxidations of olefinic alcohols by tert-butyl hydroperoxide. Journal of American Chemical Society. 1973; 95(18):6136-6137.        [ Links ]

20. Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC and Beck JS. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature. 1992; 359:710-712.        [ Links ]

21. Tanev PT and Pinnavaia TJ. A Neutral Templating Route to Mesoporous Molecular Sieves. Science. 1995; 267(5199):865-867. Pmid:17813916.        [ Links ]

22. Gabelica Z, Blom N and Derouane EG. Synthesis and characterization of zsm-5 type zeolites: III. A critical evaluation of the role of alkali and ammonium cations. Applied Catalysis. 1983; 5(2):227-242.        [ Links ]

23. Sunil Kumar B, Kumar PS, Srinivasulu N, Rajitha B, Thirupathi Reddy Y, Narsimha Reddy P et al. Vanadium(III) chloride as an effective catalyst for the Pechmann reaction. Chemistry of Heterocyclic Compounds. 2006; 42(2):172-175.        [ Links ]

24. Shirini F, Yahyazadeh A, Abedini M and Langroodi DI. Vanadium Hydrogen Sulfate Catalyzed Solvent-Free Synthesis of 3,4-Dihydropyrimidin-2(1H)-ones and Bis-(indolyl) methanes. Bulletin Korean Chemical Society. 2010; 31(6):1715-1718.        [ Links ]

25. Shirini F, Zolfigol MA, Abedini M and Sakhaei AR. Vanadium Hydrogen Sulfate (I): Chemoselective trimethylsilylation of alcohols and deprotection of trimethylsilyl ethers. Journal Chinese Chemical Society. 2008; 55:943-946. Available from: <>         [ Links ].

26. Sharma N, Sharma R, Kumari M and Chaudhary SC. Synthesis and characterisation of tris(2,4-dinitrophenoxo)monooxovanadium(V) and its complex salts. Turkish Journal of Chemistry. 2011; 35:45-59.         [ Links ]

27. Hwang DR and Uang BJ. A Modified Mannich-Type Reaction Catalyzed by VO(acac)2. Organic Letters. 2002; 4(3):463-466. PMid:11820905.        [ Links ]

28. Venkatathri N, Santhanaraj D and Shanthi K. Synthesis, characterization and catalytic properties of a novel Mn – organophosphate having MFI topology. Bulletin of the Catalysis Society of India. 2008; 7:97-104. Available from: <>         [ Links ].

29. Xue M, Chen H, Zhang H, Auroux A and Shen J. Preparation and characterization of V-Ag-O catalysts for the selective oxidation of toluene. Applied Catalysis A: General. 2010; 379(1-2):7-14.        [ Links ]

30. Pillai UR and Sahle-Demessie E. Selective oxidation of alcohols over vanadium phosphorus oxide catalyst using hydrogen peroxide. Applied Catalysis A: General. 2004; 276(1-2):139-144.        [ Links ]

31. Xue M, Chen H, Ge J and Shen J. Preparation and characterization of thermally stable high surface area mesoporous vanadium oxides. Microporous and Mesoporous Materials. 2010; 131(1-3):37-44.        [ Links ]

32. Abdelouahab FB, Olier R, Guilhaume N, Lefebvre F and Volta JC. A study by in situ laser Raman spectroscopy of VPO catalysts for n-butane oxidation to maleic anhydride I. Preparation and characterization of pure reference phases. Journal of Catalysis. 1992; 134(1):151-167.        [ Links ]

33. Kiely CJ, Burrows A, Sajip S, Hutchings GJ, Sananes MT, Tuel A et al. Characterisation of Variations in Vanadium Phosphate Catalyst Microstructure with Preparation Route. Journal of Catalysis. 1996; 162(1):31-47.        [ Links ]

34. Murgia V, Torres EMF, Gottifredi JC and Sham EL. Sol–gel synthesis of V2O5–SiO2 catalyst in the oxidative dehydrogenation of n-butane. Applied Catalysis A: General. 2006; 312:134-143.        [ Links ]

35. Venkatathri N. Synthesis, characterization and catalytic properties of Nanocrystalline V-MCM-41 molecular sieve from room temperature. Bulletin of the Catalysis Society of India. 2008; 7:129-136.         [ Links ]

36. Farias RFD and Airoldi C. Some insights into the reactivity of oxovanadium phosphate: Synthesis and characterization of an VOPO4-H2N(CH2)3NH2 coordination compound. Journal of Serbian Chemical Society. 2005; 70(11):1283-1290.        [ Links ]

37. Harreld JH, Dunn B and Nazar LF. Design and synthesis of inorganic–organic hybrid microstructures. International Journal of Inorganic Materials. 1999; 1(2):135-146.        [ Links ]

38. Ayyappan P, Asnani M, Ramanan A and Piffard Y. Hydrothermal synthesis of a new ethylenediammonium intercalated vanadyl phosphate, (H3NCH2CH2NH3)0.5[ O2PO4{P(OH)2}0.44] Proceedings of the Indian Academy of Sciences - Chemical Sciences. 2003; 115(1):33-40.         [ Links ]

39. Jiao X, Chen D, Pang W, Xu R and Yue Y. Solvothermal synthesis and characterization of silica-pillared titanium phosphate. Journal of Materials Chemistry. 1998; 8(12):2831-4.        [ Links ]

40. Shiels RA, Venkatasubbaiah K and Jones CW. Polymer and Silica Supported Tridentate Schiff Base Vanadium Catalysts for the Asymmetric Oxidation of Ethyl Mandelate – Activity, Stability and Recyclability. Advanced Synthesis & Catalysis. 2008; 350(17):2823-2834.        [ Links ]

41. Khainakova SA, Khainakovaa OA, Garcíaa JR, García-Grandaa S and Blancob JA. Different morphology of organic–inorganic hybrid nanomaterials based on titanium phosphate. Journal of Alloys and Compounds. 2012; 536S: S491-S494.        [ Links ]

42. Janke C, Schneider M, Bentrup U, Radnik J, Martin A, Scholz G et al. Impact of phosphorus and nitrogen on structure and catalytic performance of VZrPON oxynitrides in the ammoxidation of 3-picoline. Journal of Catalysis. 2011; 277(2):196-207.        [ Links ]

43. Shi Z, Zhang D, Li G, Wang L, Lu X, Hua J and Feng S. Hydrothermal synthesis and characterization of layered vanadium phosphite: [HN(C2H4)3N][(VO)2(HPO3)2(OH)(H2O)]·H2O. Journal of Solid State Chemistry. 2003; 172(2):464-470.        [ Links ]

44. Yamamoto N, Hiyoshi N and Okuhara T. Thin-Layered Sheets of VOHPO4·0.5H2O Prepared from VOPO4·2H2O by Intercalation−Exfoliation−Reduction in Alcohol. Chemistry of Materials. 2002; 14(9):3882.        [ Links ]

45. Machado MO, Farias RF and Airoldi C. Two different synthetic routes involving the reaction of dodecylamine or nicotinamide with crystalline lamellar vanadylphosphate. Journal of Physics and Chemistry of Solids. 2004; 65(10):1697-1703.        [ Links ]

46. Benziger JB, Guliants V and Sundaresan S. New precursors to vanadium phosphorus oxide catalysts. Catalysis Today. 1997; 33(1-3):49-56.        [ Links ]

47. Sen T, Rajamohanan PR, Ganapathy S and Sivasanker S. The Nature of Vanadium in Vanado-Silicate (MFI) Molecular Sieves: Influence of Synthesis Methods. Journal of Catalysis. 1996; 163(2):354-364.        [ Links ]

48. Chao KJ, Wu CN, Chang H, Lee LJ and Hu SF. Incorporation of Vanadium in Mesoporous MCM-41 and Microporous AFI Zeolites. Journal of Physical Chemistry B. 1997; 101(33):6341-6349.        [ Links ]

49. Back G, Yu J-S, Lee H and Lee Y-Ill. Synthesis and spectroscopic characterization of vanadium incorporated V-AlMCM-41 molecular sieves. Journal of the Korean Magnetic Resonance Society. 2006; 10:141-154.         [ Links ]

50. Yang J, Bai HZ, Tan XC and Lian JS. IR and XPS investigation of visible-light photocatalysis—Nitrogen–carbon-doped TiO2 film. Applied Surface Science. 2006; 253(4):1988-1994.        [ Links ]

51. Khattak GD, Mekki A and Wenger LE. X-ray photoelectron spectroscopy (XPS) and magnetic susceptibility studies of vanadium phosphate glasses. Journal of Non-Crystalline Solids. 2009; 355(43-44):2148-2155.        [ Links ]

52. Tripathi AM, Nair RG and Samdarshi SK. Visible active silver sensitized vanadium titanium mixed metal oxide photocatalyst nanoparticles through sol–gel technique. Solar Energy Materials & Solar Cells. 2010; 94(12):2379-2385.        [ Links ]

53. Chen XB and Burda C. Photoelectron Spectroscopic Investigation of Nitrogen-Doped Titania Nanoparticles. Journal of Physical Chemistry B. 2004; 108(40):15446-15449.        [ Links ]

54. Ananpattarachai J, Kajitvichyanukul P and Seraphin S. Visible light absorption ability and photocatalytic oxidation activity of various interstitial N-doped TiO2 prepared from different nitrogen dopants. Journal of Hazardous Materials 2009; 168:253-261. PMid:19282105.        [ Links ]

55. Nagaraju P, Lingaiah N, Balaraju A and Prasad PSS. Studies on vanadium-doped iron phosphate catalysts for the ammoxidation of methylpyrazine. Applied Catalysis A: General. 2008; 339(2):99-107.        [ Links ]

56. Fluck E and Weber D. P 2p binding energies in phosphorus (III) compounds, phosphonium salts and oxiacids of phosphorus. Z Naturforsch 1974; B29:603-607.         [ Links ]

57. Chary KVR, Kumar CP, Naresh D, Bhaskar T and Sakata Y. Characterization and reactivity of Al2O3–ZrO2 supported vanadium oxide catalysts. Journal of Molecular Catalysis A: Chemical. 2006; 243(2):149-157.        [ Links ]

58. Bourbigot S, Le Bras M, Delobel R. Carbonization mechanisms resulting from intumescence-part II. Association with an ethylene terpolymer and the ammonium polyphosphate-pentaerythritol fire retardant system. Carbon. 1995; 33(3):283-94.        [ Links ]

59. Park Y, Kim W, Park H, Tachikawa T, Majima T and Choi W. Carbon-doped TiO2 photocatalyst synthesized without using an external carbon precursor and the visible light activity. Applied Catalysis B: Environmental. 2009; 91(1-2):355-361.        [ Links ]

60. Bunker BC, Tallant DR, Balfe CA, Kirkpatrick RJ, Turner GL and Reidmeyer MR. Structure of Phosphorus Oxynitride Glasses. Journal of the American Ceramic Society. 1987; 70(9):675-681.        [ Links ]

61. Hutchings GJ, Lopez-Sanchez JA, Bartley JK, Webster JM, Burrows A, Kiely CJ et al. Amorphous Vanadium Phosphate Catalysts Prepared Using Precipitation with Supercritical CO2 as an Antisolvent. Journal of Catalysis. 2002; 208(1):197-210.        [ Links ]

62. Sananes MT, Tuel A and Volta JC. A Study by 31P NMR Spin-Echo Mapping of VPO Catalysts: I. Characterization of the Reference Phases. Journal of Catalysis. 1994; 145(2):251-255.        [ Links ]



Received: January 1, 2012
Revised: September 3, 2012




Creative Commons License All the contents of this journal, except where otherwise noted, is licensed under a Creative Commons Attribution License