Mixed Metal Oxide Nanoparticles

Pramesh N. Kapoor Ajay Kumar Bhagi

University of Delhi, Delhi, India

Ravichandra S. Mulukutla
Nanoscale Materials, Inc., Manhattan, Kansas, U.S.A.

Kenneth J. Klabunde
Kansas State University, Manhattan, Kansas, U.S.A.

INTRODUCTION Mixed metal oxide (MMO) nanoparticles (also called heterometal oxide nanoparticles) can play an appreciable role in many areas of chemistry and physics. The unique electronic and magnetic properties obtained when combining two metals in an oxide matrix have been well studied.[1,2] However, the most common use for MMOs has been in the area of catalysis, and here they have found use both as the catalyst and as catalyst supports.[3,4] Specifically, MMO containing aluminum has found many opportunities in catalysis.[5 7] Mixed metal oxides are also used in many applications in the electronic industry as passive or active components in devices. These exhibit high dielectric, and ferro- or pyroelectric properties, e.g., BaTiO3, LiNbO3, KTaO3, Pb1xLaxTiyZr2O3, etc. The most remarkable MMO materials are surely the thermal-conducting superconductors based on YBa2Cu3O7x. The technological interest in MMOs such as silica titania and silica zirconia arises from their chemical resistance and their thermomechanical or optical properties. SiO2 TiO2 glasses and zircon, SrZrO4, are characterized by very low thermal expansion, which confer them a high thermal-shock resistance. SiO2 TiO2 and SiO2 ZrO2 glasses have high refractive indices and are wonderful catalysts or catalyst supports.[8] Owing to their refractoriness, these MMOs are difficult to produce by conventional melting techniques; thus, sol gel technique is used for their preparation. The homogeneity of binary oxide has great influence on structural evolution of the gels during the heat treatment. Magnesium aluminate spinel (MgAl2O4) is expected to have applications as a structural material at high temperatures because it has a high melting point and superior thermal and chemical properties. It is also of technological interest as a refractory material at elevated temperatures. It is important to realize that improved properties are recorded for ceramic materials at nanoscale and these materials are
Dekker Encyclopedia of Nanoscience and Nanotechnology DOI: 10.1081/E-ENN 120009136 Copyright D 2004 by Marcel Dekker, Inc. All rights reserved.

expected to find the most important place in technology in the coming years. In this article, we have covered the most important and recent methods of preparation of nanocrystalline MMOs. Special emphasis has been given on sol gel technique because of its popularity among researchers, resulting in homogeneous and pure MMO nanoparticles. Among physical methods, perhaps flame spray pyrolysis is gaining more importance in recent time. Structure, properties, and applications of MMO nanoparticles have also been discussed. This area of research is wide open and offers scope for development in synthetic and application fields.

SYNTHESIS OF MIXED METAL OXIDE NANOPARTICLES Developments in the field of MMO nanoparticles have produced many significant and interesting results in all areas investigated. This attracted attention toward the preparation of these potential new materials with variable composition having unique properties. Researches have explored and developed both physical and chemical methods by which such materials can be prepared.

Physical Methods Several physical aerosol methods have been reported for the synthesis of nanosized particles of ceramic materials. The most successful include gas condensation techniques,[9 12] spray pyrolysis,[13,14] thermochemical decomposition of metal organic precursors in flame reactors,[15,16] and some other aerosol processes named according to energy sources applied to reach the temperatures required for gas particle conversion. The experi2007

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mental details of these physical/aerosol methods have been outlined by Khaleel and Richards.[17] Vapor condensation method It involves two steps. In the first step, a metallic nanophase powder is condensed under an inert convection gas at high pressure, after the supersaturated vapor of metal is obtained inside a chamber. In the second step, the powder is oxidized by allowing oxygen into the chamber. It is a critical step in which the temperature is as high as 1000C because of the exothermic nature of the reaction. High temperature results in agglomeration into large particles, and often annealing process at high temperature is required for completion of oxidation. Nanoparticles result when supersaturation is achieved above the vapor source. A collection surface cooled by liquid nitrogen is used to collect the particles. Spray pyrolysis Some other techniques with slight modifications also work on same principle. They are aerosol thermolysis, evaporative decomposition of solutions, plasma vaporization of solutions, aerosol decomposition, flame pyrolysis, etc. A new broad name suggested for these techniques is flame spray pyrolysis (FSP) technology. The starting materials, or chemical precursors, are usually the appropriate salts, either in solution or in a sol or in suspension form. Aerosol droplets are generated by nebulizer or atomization technique of the starting chemical precursors. These droplets generated undergo evaporation with solute condensation within the droplet followed by drying and thermolysis of precipitate particles at high temperatures forming microporous particles. They are finally sintered to form dense particles. In this technique, various methods are used for atomization, including pressure, two-fluid, electrostatic, and ultrasonic atomizers. These methods give droplets of different sizes (2 15 mm) at various rates of atomization and various droplet velocities. Tal Materials Inc. uses a patented flame spray pyrolysis process developed at the University of Michigan for the direct, largescale production of inexpensive MMO nanopowders.[18,19] The preparation of a variety of nanosized MMO powders from the thermolysis/flame pyrolysis of a new polymer-matrix-based precursor solution has been reported by Pramanic et al.[20] Spinels such as MgAl2O4, CuFe2O4, NiFe2O4, CoFe2O4, ZnFe2O4; orthoferrites such as LaFeO3; NdFeO3; GdFeO3; SmFeO3; garnets such as Y3Al5O12, Gd3Al5O12, Gd3Fe5O12, Sm3Fe5O12; and composites such as Fe 2O3 NiO, Fe 2O3 CuO, and Fe2O3 TiO2 have been reported.

Thermochemical/flame decomposition of metal organic precursors This method is an example of another type of gas condensation technique. In this method, the starting material is a liquid chemical precursor. It is also known as chemical vapor condensation (CVC). It involves vaporization of chemical precursors, which are then oxidized with the help of a fuel oxidant mixture (propane O2 or methane O2). It combines the rapid thermal decomposition of a precursor carrier gas stream in a reduced pressure environment with thermophoretically driven deposition of the rapidly condensed product particles on a cold substrate.[16] The flame temperature varies between 1200 and 3000 K, which allows rapid gas phase chemical reactions. In rapid thermal decomposition of precursor in solution (RTDS), the precursor material dissolved in water undergoes rapid hydrothermal reactions in a near-critical and supercritical water environment. Due to the short residence time and extremely fast quenching rate, the particle growth in the reaction is limited. Both ultrafine metal oxides and MMOs using inexpensive watersoluble precursors are prepared using this method. Some examples of nanocrystalline powders produced using RTDS are (1) Fe3O4 (magnetite) having grain size less than 12 nm from FeSO4 / urea as precursors, (2) NiFe2O4 (trevorite) having grain size less than 10 nm from Fe(NO3)3 / Ni(NO3)2 / urea as precursors, and (3) NiO / ZrO2 having grain size nearly 10 nm from Ni(NO3)2 / ZrO(NO3)2. Chemical Methods The most potential and successful route for preparing homogeneous ceramic materials is liquid phase chemistry. The most widely used and perhaps most reliable method is the sol gel method. There are many other wet chemistry methods known, such as microemulsion techniques and precipitation from solutions. Another novel technique is the mechanochemical synthesis method, which involves solid-state chemistry reactions. Sol gel technique The synthesis of MMOs by sol gel technique is one of several liquid phase methods that is the most widely employed and has been widely reviewed.[21 28] Reviews on the preparation of aerogels have also appeared in the literature.[29,30] Mainly, three routes are used to prepare sol gel ceramic materials, which are distinguished by the nature of the starting material. They are (1) an aqueous solution of inorganic salt, (2) an aggregate of colloidal particles in a solvent, and (3) a network-forming species

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in organic or aqueous solution. The last route is the most acceptable because network formers can be tailor-made or modified to control the chemistry and processing of the gel, and ultimately its morphology. Usually, alkoxides, bimetallic-m-oxoalkoxides, and heterometallic (double, ter, tert-) alkoxides are used as precursors in alcoholic solutions. Other precursors include metal b-diketonates and metal carboxylates. Hydrolysis and condensation of metal alkoxides: The sol gel route is actually a two-step inorganic polymerization. In the first step, polymerization starts by hydrolysis at the metal alkoxy linkage yielding alcohol and new reactants, hydroxylated metal centers (M OH). MORn xH2 O ! MORnx OHx xROH
1

with other ligands when the exchange reaction takes place.[32] This results into a new precursor, which may undergo hydrolysis at a much slower rate. MORn xLOH ! MORnx OLx xROH
6

Thus, at times when alkoxy ligands are quickly removed by hydrolysis, then chelating ligands such as acetyl acetone or other b-diketones act as terminating agents that limit the condensation reaction.[33] The major steps involved in sol gel technique [21,22]for the preparation of MMOs as outlined in Fig. 1 are: 1. Preparation of a homogeneous solution of pure precursor in an organic solvent, which is miscible with water or the hydrolysis reagent. 2. Preparation of sol from solution by treating the homogeneous solution with H2O, or H2O with HCl/ NaOH/NH4OH. 3. Allowing the sol to convert into gel by polymerization (aging). 4. Shaping of gel into the desired form or shape followed by drying. In this step, solvent is removed. The manner in which the liquid phase is removed from wet gel determines whether the dried material is a highly porous aerogel or a denser xerogel. A xerogel is formed as the solvent evaporates from the wet gel, resulting in collapse of the wet-gel structure. If the network is compliant, the gel deforms because of capillary forces generated by the liquid phase as it recedes into the body of the gel. Supercritical drying (SCD) or ambient pressure upon wet gels results in

The mechanism of this reaction can be outlined as below:

2 In the second step, condensation or three-dimensional propagation occurs when hydroxylated species condense to form oxypolymers. Polycondensation involves alkoxylation, oxolation, or olation, a reaction that creates oxygen bridges and releases XOH species (where X =H or R). M OH MOR ! MOR ROH alkoxylation M OH MOH ! M M H2 O oxolation O M OH2 MOR ! MOHM ROH olation
3 4 5

The nature of the inorganic framework obviously then determines the relative rates of hydrolysis and condensation at different centers. The rates of hydrolysis and condensation depend upon the nature of metal in terms of its electrophilicity and ability to expand its coordination number.[31] The hydrolysis rates of transition metal alkoxides are very high, as metal centers are highly electrophilic and exhibit several coordination numbers. This sometimes complicates the problem, especially in the case when heterobimetallic alkoxides are used as precursor, as precipitation occurs at different rates and often instantaneously. One of the suitable ways to overcome this problem is the modification of precursor by reacting alkoxide

Fig. 1 Steps involved in sol gel method.

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Fig. 2 The method used to extract the pore fluid from a wet gel creates a dry solid with variable porosity: strong capillary forces create a xerogel, weak capillary forces create an ambigel, and zero capillary force creates an aerogel that nominally retains the low-density framework for the wet gel. (Reprinted with permission from Ref. [31].)

One can also use solvents with low surface tension so that pore liquid is exchanged with low-surface-tension solvents just before the ambient-pressure drying. The MMOs so obtained have been named as ambigels and are less porous than the corresponding SCD ceramics but have comparable surface area and pore volume (Fig. 2).[31] Finally, conversion of the shaped gel to the desired ceramic material by heating takes place at a much lower temperature than the conventional process of melting of oxides together. Another widely used method for obtaining MMO aerogels is the prehydrolysis route.[39,40] In this method, two alkoxides with different rates of hydrolysis are used as precursors for obtaining MMO aerogels. However, before mixing these together, the one with the lower rate of hydrolysis is hydrolyzed or partially hydrolyzed separately and then mixed with the other alkoxide solution. This is to avoid phase segregation caused by different rates of hydrolysis. Similarly, hydrolysis of metal alkoxide with faster rate of hydrolysis can be slowed by suit-

aerogels. Aerogels are actually nanoscale mesoporous materials of low density and high surface area. SCD preserves the porosity by bringing the solvent phase into its supercritical state (a state where no liquid vapor interface exist), so that capillary pressures do not develop. There are two SCD methods. The sol gel synthesis of (RuxTi1x)O2 (x = 0, 0.14, 0.20, 0.32) involves modification of an alkoxide preparation of TiO2 with a ruthenium chloride, RuCl3, refluxed in ethanol. Monolithic aerogels are formed using SCD method with CO2. These were characterized after annealing treatment at 400C, which removed the chloride and alkoxide. The resulting oxides consisted of $10 nm nanocrystallites of primarily phase-separated TiO2 and RuO2 (these rutile phases can form only a solid solution of a few mole percent RuO2 and TiO2). These MMO aerogels show surface areas of approximately 85 m2 g 1.[34] Ambient pressure method involves surface modifications as well as network strengthening.[35 38] Surface modification means, for example, that terminal silanols (Si OH) are replaced by nonreactive groups via silylation or esterification. These modifications inhibit condensation reactions, i.e., conversion of Si OH centers to Si O Si, which locks in structural collapse by sealing compressed pores shut. This allows the porous network to almost retain its original volume. Network strengthening is done by either aging of wet gel in mother liquor (including thermal treatment in water) or soaking it in a precursor alkoxide [such as Si(OR)4] during washing or aging steps.

Fig. 3 Preparation route for spinel MgAl2O4 precursor.

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able complexation. This is done to promote formation of M O M mixed bond, which increases the homogeneity of MMO aerogel. A nonhydrolytic sol gel route has also been used for preparation of MMO aerogels.[41] The M O M bridges are obtained by condensation of MX + M OR ! M OM + RX. In most cases, these reactions are thermally activated. Actually, the condensation completes with redistribution of the ligands, giving complicated halogenoalkoxides,[42] which ultimately leads to products after hydrolysis. The surface areas of oxides obtained after calcination was found to be quite high, but a low level of homogeneity on atomic scale was noticed. Syntheses of MgAl2O4 spinel and Mg2SiO4 spinel forsterite precursor from a heterogeneous alkoxide solution have been reported in the literature.[43,44] The preparation route is shown in Fig. 3. The obtained precursor was composed of a mixture of boehmite [AlO(OH)] and a mixed hydroxide [Mg4Al2(OH)14 3H2O]. The precursor was converted to a spinel phase through two steps: (1) decomposition of mixed hydroxide at $ 400C and (2) solid-state reaction between MgO (which has decomposed from mixed hydroxide) and g-Al2O3 (which had been converted from boehmite at higher temperature). To prepare almost-monolithic spinel powder, calcination at a temperature of 1300C was required. Powder that was calcined at 1000C showed extraordinary sinterability, and fully dense polycrystalline spinel could be obtained at sintering temperature as low as 1400C. Synthesis of La0.7Sr0.3MnO3 (LSMO)/silica hybrid nanocomposites have been reported by Huang et al.[45] Homogeneous granular mixtures can be obtained through sol gel chemical route in a single step. The precursors used are the following: (1) complexes of La3 + , Sr2 + , and Mn2 + with EDTA and (2) tetraethoxysilane (TEOS). Silica is produced by an ammonia-catalyzed method, whereas LSMO is obtained by thermal decomposition of the complex precursors. When hydrolysis of silicon alkoxide to form silica oxyalkoxy oligomers takes place in the LSMO precursor solution, both are formed in the same system. Thus, effective combination of both phases achieves a satisfactory level. The microstructure of the composites can be controlled mainly through the calcination temperature. When calcined at 800C, silica undergoes some interaction with LSMO, and Si O metal bonds are formed. These bonds establish the connection between silica network and LSMO surface. Synthesis of pure nanocrystalline Al2O3/MgO powder has been reported by Carnes et al.[46] The two Mg and Al alkoxide solutions were mixed in desired molar ratios and then allowed to react with a mixture of water in ethanol to yield a hydroxide gel. Upon solvent removal, a fine powder was obtained, which was then heat-treated under dynamic vacuum. The powder has excellent surface area

(790 830 m2/g) showing a completely amorphous XRD pattern. Bimetallic-m-oxoalkoxides as precursors for sol gel technique: Homogeneously dispersed bimetallic oxides in nanocrystalline form, of the type MAl2O4 (where M =Mg, Ca, Mn, Co, Fe, Ni, and Zn) were obtained by preparation of bimetallic-m-oxo-bridged (Al O M O Al) alkoxides [(RO)2Al O M O Al(OR)2], which upon thermal dehydration yield oxides [OAl O M O AlO] such that M is homogeneously dispersed in M and Al2 ions of empirical formula MAl2O4 in nanocrystalline form.[47] These materials were obtained in high-surface-area forms and were characterized by X-ray diffraction (XRD), electron microscopy (TEM), surface area analyses (BET), and solid-state 27Al NMR. Comparative studies of hydrolysis of m-alkoxo-bridged alkoxides yielded MMO phases of lower surface area. This method has proved advantageous over other traditional routes. One such method is coprecipitation of metal hydroxides followed by heat treatment at high temperature. Reverse microemulsion/micelle method It is a promising route for synthesis of MMO nanoparticles.[48 50] Surfactants dissolved in organic solvents form spheroidal aggregates called reverse micelles. The polar ends of surfactant molecules organize around small water pools ($ 100 A) in the presence of water. This leads to dispersion of aqueous phase in the continuous oil phase. These reverse micelles are used as water solutions of reactive precursors to prepare insoluble nanoparticles. Various reactive precursors such as alkoxides or metal salt mixtures can be used for synthesis of nanoparticles inside the micelles. Solvent removal followed by calcination lead to the final product. The above method was adopted to prepare the ZnFe 2 O 4 /TiO 2 nanocomposite. [51] In this method, ZnFe2O4 and TiO2 were prepared by coprecipitation and controlled hydrolysis methods, respectively. ZnFe2O4 was coprecipated from a mixed solution of Zn(NO3)2 and Fe(NO3)2 in a 1:2 molar ratio at pH 13 and temperature of 100C. TiO2 was precipitated from mixed solution with a volume ratio of Ti(OBu)4: C2H5OH:H2O  1:10:100 at pH 2. Both products were washed with deionized water. They were added separately to dodecyl benzene sulphonic acid (DBS), where ZnFe2O4 or TiO2 nanoparticles were capped with a layer of DBS. These then readily dispersed in organic solvents such as benzene or toluene. The capped ZnFe2O4 and TiO2 nanoparticles were mixed in various molar ratios, followed by extraction into toluene. Organic phase was removed by distillation, leaving mixed organic sol of ZnFe2O4/TiO2. This sol was distilled to remove toluene solvent and finally heated at 400C for

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2 hr to burn DBS, leaving behind nanocomposite ZnFe2O4 / TiO2 material. CoFe2O4 nanoparticles were also synthesized by this technique. It uses Co- and Fecontaining surfactants as metal sources.[52,53] Low-temperature wet chemical synthesis by precipitation from solutions It involves dissolving salt precursors, usually chloride, oxychloride, nitrate, etc., in water followed by addition of base solution (NaOH or NH4OH) to coprecipitate hydroxides. The hydroxide mixtures are calcined to obtain MMO powder. Its disadvantage is poor control of particle size and size distribution, as fast (uncontrolled) precipitation often causes formation of larger particles and not nanoparticles. Mechanistically, in this solvation sheets of water around metal ion are dehydrated under alkaline conditions, e.g., 2M3 H2 O6 ! M2 O3 6H 9H2 O
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nm have been prepared from Fe3 + , Fe2 + , and Mn2 + aqueous solution.

STRUCTURE AND MORPHOLOGY Control over structural and morphological properties are most crucial for performance of MMO nanoparticles in various applications. Mixed metal oxides are known to have different structural arrangement of constituent ions. The nature of these ions is important (size and charge) in the final adaptation of geometry; however, control over homogeneity, stoichiometry, phase, and crystallinity largely depend upon structure and reactivity of precursors in homogeneous solutions and their fate in subsequent processing steps. The stoichiometry and homogeneity depend upon the ability of mixed precursors especially on addition of water to form a single molecular species, so that the ions are distributed evenly. Structural and morphological challenges initiated the search for suitable methods of preparation of various MMO ceramics. Several new and modified methods have been proposed for preparation of numerous ceramic nanoparticles. For example, in a modified aerogel method,

The above scheme tells us the importance of alkaline conditions. [54] As an example, manganese ferrite (MnFe2O4) nanoscale particles ranging from 5 to 180

Fig. 4 Classification of the structures of A2BO4 ionic minerals as a function of cation radii. (Reproduced with permission from Treatise on Solid State Chemistry, Vol. 1, N.B. Hannay, ed., Plenum, New York, Copyright # 1973, Bell Telephone Laboratories, Inc.)

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addition of large amount of aromatic hydrocarbons to alcohol methoxide solutions before hydrolysis to form gel yields ceramic materials with extraordinarily large surface area in comparison to materials obtained without adding it. This is probably because of reduced surface tension of the solvent mixture, which facilitates solventremoved alcogel aerogel transformation.[55,56] Mixed metal oxide nanoparticles exhibit unusual surface morphologies and possess more reactive surface because of the presence of high concentrations of edge/ corner sites and other defects. Morphological studies indicate that the nanocrystals are more polyhedral and thus possess more defects. Such defects could be of the Frankel or Schottky type (vacancies) or may be manifested as unusual configurations of edges, corners, or crystal planes. A ceramic material with high surface area displays 30 40% of the ceramic moieties on the surface, which allows surface gas reactions to approach the stoichiometric range.[17] As MMOs contain a variety of cations, the prediction of structure simply on the basis of radius ratios of cations and oxide ions becomes complicated. This means some simpler approach is required. For example, take a list of known structures and the radii of the ions present in them. The radii of two of the ions present in a given compound are plotted against each other. This is graphically related to

arithmetic radius ratio approach. It is seen that compounds with similar structures are grouped together. In Fig. 4, compounds of the type A2BO4 (where B is a higher-valent metal than A) are plotted as a function of radii A and B. In these materials, oxide ions form a closed packed array (framework) and sizes of A and B decide how they fit in (sometimes major distortion in closest-packed structure is noticed). On the basis of fields in Fig. 4, one can predict structures of newly discovered ceramic materials with known rA and rB values.[57]

Spinel Structures It consists of a face-centered cubic arrangement of oxygen ions. A unit cell contains 32 O2 ions, 64 tetrahedral, and 32 octahedral sites, which are occupied by A2 + (A = Mg, Fe, Ca, Zn, etc.) and B3 + (B = Al, Fe, etc.) cations. The general formula of spinel is written as AII B2IIIO4 [where AII is a Group 2 metal ion or transition metal in + 2 oxidation state and BIII is a Group 3B (B, Al, Ga, In) cation or transition metal ion in + 3 oxidation state]. As a unit cell has 32 O2 ion and only 4 are present per molecule (from the formula), then spinel structure has 8 (64/8) tetrahedral and 4 (32/8) octahedral vacancies per molecule of AB2O4. When A2 + ions occupy one eighth of a tetrahe-

Fig. 5 XRD patterns of the ZnFe2O4/TiO2 composite with a molar ratio of Zn:Ti = 0.1 after annealing at various temperatures for 2 hr. A = anatase, R = rutile, S = spinel, $ = Fe2TiO5, # = ZnTiO3. (Reprinted with permission from Ref. [51].)

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dral (1 out of available 8) hole and B3 + ions occupy half (2 out of available 4) of an octahedral hole, the structure is called normal spinel, e.g., MgAl2O4. This is a very stable arrangement even in terms of coordination, having tetrahedral arrangement about a divalent cation and octahedral arrangement about a trivalent cation. In some cases, one half of B3 + ions exchange their positions with A2 + ions. This is called inverse spinel, e.g., NiFe2O4. In this arrangement, one eighth of tetrahedral sites are occupied by half of B3 + , whereas the rest of B3 + ions along with A2 + ions occupies half of the octahedral sites. If the general formula for normal spinel is written as (A)[B]2O4 to suggest ( ) and [ ] representing tetrahedral and octahedral coordination, then the general formula for inverse spinel is written as (B)[AB]O4. Many MMOs also have intermediate cation distribution between these two extremes. The general formula for these structure is then written as (A1xBx)[B2xAx]O4, where x is the inversion parameter (O < x < 1).[58,59] Nanocomposites of ZnFe2O4 and TiO2 were studied by Yuan and Zhang.[51] TiO2 (anatase phase) and ZnFe2O4 (spinel phase) with broad diffractions were recorded [Fig. 5a]. This means that in the composite, TiO2 and ZnFe2O4 crystallite phases separate each other, having small size. Fig. 5b and c shows composite begins to form at 600C. Anatase to rutile transformation takes place at 700C. [Fig. 5d and e]. The strongest peak (2q = 25.3) disappears and, simultaneously, two new peaks of phases ZnTiO3 and Fe2TiO5 appear. This shows the following solid-phase reaction might be taking place at annealing temperature. ZnFe2 O4 2TiO2 ! ZnTiO3 Fe2 TiO5
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orthorhombic. The truly cubic form is referred to as ideal perovskite having a unit cell edge of $ 4 A containing one ABO3. In perovskite structure, large cation A is surrounded by 12 oxide ions to form cuboctahedral coordination, while B cation is surrounded by 6 oxide ions in an octahedral coordination. Nanophase powders of YxZr1xO2x/2 have been prepared from a mixture of ZrO2 and Y2O3 powders.[60] It is shown that depending upon the starting powder mixture composition, the yttrium content in nanophases can be controlled to obtain tetragonal or cubic phases. Tetragonal or a mixture of tetragonal and cubic were observed for low yttria content (3.5 mol% yttria), and cubic for higher yttria contents (19, 54, and 76 mol% yttria). These powders were found to have a most probable grain size of about 10 12 nm, and the grains appeared as isolated single crystals with polyhedral shape. The grain shape appeared to be polyhedral and not too anisotropic. Lattice figures were parallel to surfaces, showing that (100) and (111) face dominates.[17]

PROPERTIES AND APPLICATIONS OF MIXED METAL OXIDE NANOPARTICLES Properties of MMO nanoparticles are mainly size dependent, and their chemical and physical properties are unique in comparison to corresponding bulk materials. The study of physical and chemical properties is interesting as it allows gradual transition from atomic or molecular to condensed matter systems. As the particle size decreases, the percentage of atoms residing on the surface increases. This makes MMO nanoparticles more reactive, as atoms/ions are more reactive than their bulk counterparts because of coordinative unsaturation. Because of this and high surface-to-volume ratio, it is not unusual to see unique behavior and characteristics of MMO nanoparticles, including insulating oxides. When strong chemical bonding is present, delocalization varies with size; this in turn can lead to different chemical and physical properties.[17]

Measurement of grain sizes in comparison with values of TiO2 and ZnFe2O4 shows the following: (1) As annealing temperature increases, the grain size of TiO2 increases. (2) In composite, an increase in temperature has the same effect of growth of ZnFe2O4 as it does on pure ZnFe2O4. TEM analysis proved particles are distributed homogeneously and particles grow with uniform sizes. Perovskite Structures Perovskite-phase MMO ceramics are important because of changes in their physical properties on application of an external electrical stimulus. These properties include feroelectric, pyroelectric, piezoelectric, and dielectric behavior. These have led to numerous applications in electromechanical transducers, light modulation, charge storage, nonvolatile memory applications, etc.[23,24] The class of MMOs having the formula ABO3 (such as CaTiO3) is called perovskite. The structure of this mineral was first thought to be cubic but later confirmed as

Acid Base Behavior (Catalysts) Several oxide composites have been found to be potential catalysts for a variety of important reactions because of different centers present in the same material and their basicity or acidity.[61,62] This behavior varies from one MMO to another. Some exhibit surface basic behavior and some surface acidic behavior, whereas mixtures show unusual properties. The mixing of two oxides can enhance the catalytic activity many fold because of synergistic

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effects, as seen in the mixed aerogel of titania/zirconia. The acid strength increases and active sites are more than pure titania and zirconia. This is probably because of oxide oxide interaction at molecular level, suggesting that co-gelling two metal oxides is an effective way to bring two oxides in close contact.[17] Unusual Adsorptive Properties Perhaps one of the greatest promises of MMO nanoparticles in chemistry is their ability to chemically adsorb a wide range of organic molecules or inorganic gases that are considered as hazardous environment pollutants. They not only adsorb but also dissociate these to nonhazardous substances on their surface. Carnes et al.[46] studied the adsorption of CCl4, SO2, and paraoxon on both Al2O3 and Al2O3/MgO. Reaction of Al2O3 and (1/1) Al2O3/MgO with CCl4 The reaction of CCl4 with Al2O3 and Al2O3/MgO was carried out to understand the destructive adsorption abilities of the metal oxides toward a model chlorocarbon at elevated adsorption temperatures. 2Al2 O3 3CCl4 ! 3CO2 2Al2 Cl6 2MgO CCl4 ! CO2 2MgCl2
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CONCLUSION Mixed metal oxide nanoparticles can provide great diversity of substances and phenomena. Different metals in their various oxidation states can combine in different ratios to produce a variety of materials. These new materials with variation in physical, chemical, and morphological properties can be exploited in various fields of science and technology. The compression of nanoscale ceramic particles yields more flexible solid objects, apparently because of the multitude of grain boundaries that exist. After further development of compression techniques so that highly densified nonporous MMO nanomaterials can be prepared, these may find uses as replacements for metals in many applications including electrochemistry. These materials, beyond doubt, would be environment friendly, not only by themselves but also as future water purifiers and destructive adsorbents. These MMO nanoparticles are finding use in antichemical/biological warfare, in air purification, and as an alternative to incineration of toxic substances. Mixed metal oxide nanoparticles would also be replacing many heterogeneous catalysts known today because of high surface area, which increases their efficiency many fold. Research on the effect of particle size (percent dispersion as a measure of the fraction of metal atoms on the surface and thus available to incoming reactants) and shape (crystal faces, edges, corners, defects that lead to enhanced surface reactivity) has been and continues to be a potential field. In general, the ability to prepare MMO nanoparticles for use in high surface area catalysis has certain inherent advantages, and further progress is sure to come in the near future. It has been proposed that further work in the area of nanophase ceramics may lead to increased flexibility, less brittleness, and greater strength. It may also be possible to form materials with a large fraction of atoms at grain boundaries, maybe in unique arrangements. It may also be possible to produce binary materials of normally immiscible oxides. This article has explored the synthetic, structural, and application prospects that MMO nanoparticles provide. Although relatively few examples have been chosen, all relevant areas have been covered.

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Thermodynamics predicts that the samples containing or being made of MgO will be more reactive than the Al2O3 samples.[31] However, surface area, crystallite size, and morphology play important roles. Sulfur dioxide adsorption on aluminum and aluminum/magnesium oxide Adsorption of SO2 was carried out to learn if the adsorption properties are different for nanocrystals (NC) when compared to commercial microcrystals (MC).[46] The experimental results showed that at atmospheric pressure and room temperature, SO2 adsorbed onto NCAl2O3 up to 3.5 molecules SO2/nm2; similarly, on CMAl2O3 there were 3.5 molecules SO2/nm2 adsorbed, and on NC- (1/1) Al2O3/MgO there were 6.8 molecules SO2/nm2, whereas on CM-MgO there were only 0.68 molecules SO2/nm2 adsorbed. These data indicate that NC-Al2O3/ MgO efficiently adsorb SO2 in slightly more than one layer. After adsorption, the samples were subjected to dynamic vacuum to remove the physisorbed species. The vacuum treatment removed most of the adsorbed SO2 from the CM-MgO, whereas the NC-Al2O3/MgO sample retained 3.9 chemisorbed molecules of SO2/nm2.

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