January 2002

Materials Letters 52 2002. 140146 www.elsevier.comrlocatermatlet

A chemical synthetic route for the preparation of fine-grained metal molybdate powders
Angana Sen, Panchanan Pramanik )
Department of Chemistry, Indian Institute of Technology, Kharagpur-721302, India Received 27 April 2001; accepted 30 April 2001

Abstract Nanocrystalline metal molybdates wi.e., AMoO4 , where A s CaII., CoII., CuII., NiII., and ZnII.x powders have been prepared from the complete evaporation of a polymer-based metal-complex precursor solution. The metal ions are in aqueous solution through complexion with triethanolamine TEA. and are dispersed in a polymeric reagent composed of an aqueous solution mixture of sucrose and polyvinyl alcohol PVA.. The mesoporous carbon-rich precursor powders has been obtained on complete dehydration of the precursor solution and generates the respective metal molybdate phase after complete removal of carbonaceous residue at a heat treatment temperature less than 500 8C. X-ray diffractometry XRD., Differential Thermal Analysis and Thermogravimetric Analysis TGrDTA., and Transmission Electron Microscopy TEM. have been used to characterize the preprecursors and the heat-treated final powders. The average particle sizes as measured from X-ray line broadening and transmission electron microscopy studies are around ; 1030 nm. The particles having sizes of the same order with that of crystalline indicates the poor agglomeration of crystallites. q 2002 Elsevier Science B.V. All rights reserved.
Keywords: Nanocrystalline metal molybdate powders; Sugar; PVA; Polymer matrix; Catalyst

1. Introduction Mixed metal oxides play a relevant role in many areas of modern technology. Mixed metal oxides are used as catalyst in a large variety of commercial processes such as cracking, dehydrogeneration, and hydrogenation in various chemical and petrochemical industries w13x. The catalytic properties of mixed metal oxides are largely dependent on their microstructure. In the nanoparticle phase, the surface to volume ratio increases drastically and the surface

Corresponding author.

atoms include an increasing fraction of the total particulate volume having high defect structures. Thus, they are expected to show drastically improved catalytic properties w4x. Several solution-based chemical synthesis methods have gained popularity for the preparation of the fine ceramic oxide powders w512x. It has been reported that polyvinylalcohol produces nanosized metal oxides from its nitrate or organic salts w1322x, but due to graphitization of PVA the process was further improved by sugar and complexing agents like EDTA, dietylenetriammine, diethanolamine, triethanolamine etc. w23x. In this paper we report a technically simple and versatile chemical method for the preparation of some fine-grained, homogeneous,

00167-577Xr02r$ - see front matter q 2002 Elsevier Science B.V. All rights reserved. PII: S 0 1 6 7 - 5 7 7 X 0 1 . 0 0 4 3 7 - 2

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highly pure transition metal molybdates at comparatively lower temperature. Among the mixed metal oxides some transition metal molybdates AMoO4 , where A s Ca, Co, Ni, Cu, Zn. are found to be very interesting due to their structural, electronic, and catalytic properties w24 34x. Calcium molybdate with a scheelite structure has been of practical interest because of their attractive luminescence property w35x. Cobalt and nickel molybdates are important components of industrial catalysts for the partial oxidation of hydrocarbons w30,36x and precursors in the synthesis of hydrodesulfurization HDS. catalyst w28,37x. This process involves complete dehydration of a solution comprising the metal molybdates complexed with triethanolamine, polyvinylalcohol and sucrose. The evaporation is always accompanied by the decomposition of the metal complexes. The decomposition results in a voluminous, black, fluffy mass of carbonaceous material, which on complete removal through aerial oxidation produces fine powders of metal molybdates.

2. Experimental In this preparative process of metal molybdates, the raw materials used are sodium molybdate 99%. of BDH Chemicals, India, metal nitrate salts where metals s CaII., CoII., CuII., NiII., ZnII.x, 99.9%. of E Merck India, triethanolamine of E Merck India, sucrose of E Merck India, polyvinyl alcohol i.e., PVA. of SDs Fine Chemical, India. The desired metal nitrates wi.e., CaNO 3 . 2r CuNO 3 . 2rCoNO 3 . 2rNiNO 3 . 2rZnNO 3 . 2 x were individually dissolved in deionised water. 10 ml of

0.01 M metal nitrate solutions were poured into equal volumes of an aqueous solution of sodium molybdate 0.01 M., maintaining the stoichiometric ratio 1:1. It precipitated out the respective metal molybdates from the solution. The metal molybdates were collected for filtration and were thoroughly washed with water to make it free of sodium ions. These precipitated molybdates of various metal ions were analyzed using an atomic absorption spectrophotometer to check for the metal ions and molybdate ion stoichiometries, which were found to be 1:1. The metal molybdate precipitate 10 mM. was then qualitatively transferred to a breaker containing 100 ml of distilled water. 40 mM of triethanolamine 4 mol per unit mol of metal cation. was added to the solution was between 11 and 12. A 40-mM aqueous solution of sucrose 4 mol per unit mol of metal cation. and 1 mM PVA 10 mol percent of monometer w.r.t. the total mol of the cation. dissolved in 5 ml of water were added to the previous solution under hot conditions to produce the homogeneous precursor solution. After addition of sucrose and PVA, the pH of the solution did not change. The details of the reagents required and their respective mole compositions are given in Table 1. The resultant homogeneous precursor solution was then heated at ; 250 8C. with continuous stirring and was eventually evaporated to dryness. Near the end of the evaporation the precursor solution transformed to a fluffy black organic mass. The effective surface area of this carbonaceous mass was about 250290 m2rg. The metal ions formed clusters with the molybdate ions and remained embedded in the resulting matrix of the mesoporous carbon. The carbon-rich mass that was easily crushed to constitute the precursor powders were subsequently heat-treated

Table 1 Mole ratios of various reagents required for the preparation of the various metal molybdate precursors System CuMoO4 NimoO4 CoMoO4 CaMoO4 ZnMoO4
a

Metal ions mol. 0.01 0.01 0.01 0.01 0.01

Sodium molybdate mol. 0.01 0.01 0.01 0.01 0.01

Triethanolamine 0.04 0.04 0.04 0.04 0.04

Sucrose mol. 0.04 0.04 0.04 0.04 0.04

PVAa mol. 0.001 0.001 0.001 0.001 0.001

Moles of vinyl alcohol monomer unit of PVA.

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at a temperature range between 300 and 500 8C along with variations in the period of time. The various virgin precursor powders of the metal molybdates were characterized before and after heat treatment. The overall chemical reactions that take place are as follows: A2qq Na 2 MoO4 AMoO4 q 2Naq A s Ca,Co,Ni,Cu,Zn . AMoO4 q N CH 2 CH 2 OH . 3 M N CH 2 CH 2 OH . 3 M N CH 2 CH 2 OH . 3
Aerial oxidation
2q 2q

1.

AMoO4

2.

AMoO4

AMoO4 nanosized.

The freshly precipitated molybdate of the various metal ions reaction 1.. after simple drying did not produce nanosized powder due to strong chemical agglomeration. Hence, this precipitated material was then dissolved in an aqueous solution of triethanolamine for further processing.

3. Results and discussion Thermogravimetric analysis TGA. and Differential thermal analysis DTA. of the precursor powders were carried out using a Shimadzu DT-40 thermal analyzer, at a heating rate of 10 8Crmin in air. The different crystalline forms of the powders were identified by X-ray powder diffraction XRD. using a Philips PW 1710 X-ray diffactometer with CuK a radiation. The average particle diameters of the heat-treated molybdate powders were measured using a Transmission Electron Microscope TEM. model: Philips Research Laboratories, Holland.. The DTA curve for the all the samples, prepared in the presence of sucrose and PVA, showed an exothermic peak between the temperature range 300 and 550 8C, which could be attributed to the catastrophic exothermic oxidation of the carbonaceous mass remaining from the PVA, sucrose and TEA. The entire thermal effect was accompanied by the evolution of various gases such as: CO, CO 2 , water-vapor, etc.. that was manifested by a single

step weight loss in the TG curve with an abroad peak. The DTArTG curve for the CaMoO4 precursors is depicted in Fig. 1 as a typical representative. The room temperature X-ray powder diffraction XRD. studies of the various virgin precursor powders and their corresponding heat-treated forms were carried out. The room temperature X-ray diffraction studies of the precursors of the samples CuMoO4 , CoMoO4 , and NiMoO4 prepared in the presence of sucrose and PVA showed diffraction lines characteristic of the respective metal molybdate phases. This indicates that the crystallization of the molybdate phases occur in the virgin sample itself i.e., during the complete evaporation of the precursor solution on the hot plate at temperatures ; 250 8C.. The X-ray diffractograms of the NiMoO4 and CoMoO4 precursor powders are depicted in Fig. 2. The X-ray diffractograms of the virgin precursors of the samples CaMoO4 and ZnMoO4 was, however, marked by the absence of the prominent diffraction lines reflecting their X-ray amorphous nature. The respective molybdate phase eventually crystallized in these samples on heat treatment of the virgin precursor powders. The X-ray diffractograms of the CaMoO4 precursors powders before and after heat treatment are depicted in Fig. 3. The respective heat-treatment temperatures required for the initiation of the crystalline phase and temperatures required to get the carbon-free metal molybdate powders are given in Table 2. After complete evaporation of the precursor solution, the residual carbonaceous mass started burning slowly in the presence of metal ions like Cu2q,

Fig. 1. Thermal studies of the CaMoO4 precursor powders prepared in the presence of sucrose and PVA.

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Table 2 Summary of the state of the various virgin precursors and the metal molybdate phase formation temperatures System CuMoO4 NiMoO4 CoMoO4 CaMoO4 ZnMoO4 X-ray phase of virgin precursor Crystalline Crystalline Crystalline Amorphous Amorphous Temperaturea 8C. ; 250 c ; 250 c ; 250 c 450r2 h 450r2 h Temperatureb 8C. 400r2 h 400r2 h 400r2 h 500r2 h 500r2 h

a The minimum heat treatment temperatures required for the formation of the desired metal molybdate phase from the amorphous virgin precursors. b The minimum heat treatment temperature required for getting the carbon-free metal molybdate powders. c Heat treatment temperature of ; 250 8C signifies the hot plate temperature during complete evaporation of the precursor solution.

Fig. 2. The X-ray diffractograms using CuK a radiation. of the virgin a. NiMoO4 precursor powders and b. CoMoO4 precursor powders prepared in the presence of sucrose and PVA.

Co 2q, and Ni 2q, generating heat. The presence of catalytic higher local temperature helped to easily produce crystalline of the metal molybdates easily from the amorphous material formed initially.

However, similar phenomena did not occur in the case of Ca2q- or Zn2q-containing systems due to poor catalytic activity of the Ca2q and Zn2q for oxidation of carbonaceous materials than that of Cu2q, Co 2q, Ni 2q. Thus, the in-situ temperature generated during oxidative decomposition of the carbonaceous materials was not sufficient for the crystallization of the molybdate phase in the virgin precursor materials obtained from Ca and Zn salts. Hence, the precursor powders appeared amorphous to X-rays. For this reason, higher calcination temperatures were required to get the desired metal molybdate phases of Ca2q and Zn2q from precursor powders.
Table 3 Summary of the particle sizes obtained from X-ray diffraction and TEM characterization studies System CuMoO4 NiMoO4 CoMoO4 CaMoO4 ZnMoO4
a

Crystallite size a nm. 22 16 10 27 25

Particle size b nm. 24 20 15 29 30

Fig. 3. The X-ray diffractograms using CuK a radiation. of the CaMoO4 system prepared in the presence of sucrose and PVA: a. virgin precursor powder, and b. after heat treatment at 500 8Cr2 h.

The average value of the crystallite sizes calculated using Scherrers formula applied to the various d h k l lines of the precursor powders heat-treated at 500 8Cr2 h. b Average of the smallest visible isolated particlercrystallite agglomerate as observed from TEM studies for the respective precursor powders heat-treated at 500 8Cr2 h.

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The crystallite size for the crystalline precursors and the heat-treatment powders were calculated from the X-ray line-broadening studies using Scherrers equation w38x. The details of the crystallite size for the various metal tungstate systems prepared with addition of sucrose and PVA in the precursor solution are summarized in Table 3. The bright field TEM micrographs reflected the basic powder morphology where the smallest visible isolated spot can be identified with the particler crystalline agglomerate. The bright field TEM micrograph for the heat-treated at 500 8Cr2 h. CoMo 4 precursor powders and heat-treated at 500 8Cr2 h. NiMoO4 precursor powders prepared in the presence sucrose and PVA are represented as typical examples in Fig. 4a and b., respectively. From the TEM studies of the metal molybdate powders prepared in

Fig. 5. Variation of particle size of CuMoO4 with the variation of sugar content.

Fig. 4. The bright field TEM micrograph of the a. CoMoO4 precursor powders, prepared in the presence of sucrose and PVA, after heat treatment at 500 8Cr2 h, b. NiMoO4 precursor powders, prepared in the presence of sucrose and PVA, after heat treatment at 500 8Cr2 h.

the presence of sucrose and PVA Fig. 4., it was observed that particles were almost spherical, with average particle diameters ranging between 10 and 30 nm. In this preparative method PVA and sucrose was added to form a highly porous carbonaceous material after complete evaporation of the precursor solution. The presence of PVA and sucrose mixture produces the finest particle with a narrow size distribution. Only PVA could fulfill the purpose but due to its graphite formation tendency, it was partially replaced by sucrose or any other polyhydroxy hydrocarbon. The sucrose or polyhydroxy hydrocarbon in the presence of PVA formed mesoporous carbonaceous residue, which volatilized through low temperature aerial oxidation. The effective surface areas of these carbonaceous masses were very high. It ranged between 250 and 290 m2rg. Only the polyhydroxy hydrocarbonrsucrose did not form these types of mesophases. This is probably due to chemical bonding of sucrose with PVA, in which sucrose tags onto the PVA backbone as the pendant group results in highly branched polymeric structure. This type of structure is very suitable for generation of mesoporous carbon; PVA and sucrose mixture can act as precursor for formation of a branch polymer, which easily transformed into a mesoporous material. The concentrations of PVA and sucrose were optimized using CuMoO4 for getting the smallest particle size with minimum formation of carbonaceous mass; it was found to be metal ion:sucrose metal ratio 1:4 and metal ion:monomer PVA ratio 1:0.1 and is presented in Figs. 5 and 6. The removal of residual carbon

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is TEA. It disperses the organic ions atomistically in a matrix produced by thermal decomposition of polymeric reagents composed of sucrose and PVA, through the formation of mesoporous carbonaceous mass embedded with nanoparticles of metal molybdates. After complete volatilization of the carbonaceous mass through aerial oxidation, a nanosized metal molybdate powder remains. The above developed method is technically simple, versatile and uses easily available laboratory reagents; hence, it is suitable for low-cost preparation of high-quality nanocrystalline metal molybdates.
Fig. 6. Variation of particle size of CuMoO4 with the variation of PVA content.

Acknowledgements The authors are grateful to the Council for Scientific and Industrial Research CSIR., New Delhi, India for the financial grant offered in support of this work.

becomes easy when transition metals having variable oxidation states are associated with it. Carbonaceous material is due to the high catalytic activities of the transitional metal ions Cu2q, Co 2q, Ni 2 . for aerial oxidation of the carbonaceous material. Before dispersion of the metal ions in the polymetric matrix, they were complexed with TEA, where TEA served as a chelating agent having efficient coordination properties, with the metal ions avoiding any intermittent precipitation from homogeneous solution. Complete dehydration of the precursor solutions resulted in a mesoporous carbon-rich mass embedded with the clusters of metal ion-molybdate ion in the matrix. The carbonaceous precursor powders, after heat treatment in air at temperatures between 200 and 500 8C, volatilized through the aerial oxidation carbon and it resulted in the formation of nanocrystals of the respective metal molybdates.

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4. Conclusion The fine-grained, homogeneous metal molybdate powders were prepared by calcination of a precursor mass obtained after complete dehydration of a solution comprising the metal molybdate complexed with triethanolamine, polyvinyl alcohol and sucrose. The principle was to keep the metal molybdates in solution through complexation, where metal ion forms water-soluble complex caption with TEA and molybdate ion remains as a salt of organic base, which

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