AU2005309411B2

AU2005309411B2 - Mesoporous metal oxide

Info

Publication number: AU2005309411B2
Application number: AU2005309411A
Authority: AU
Inventors: Carmine Torardi
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 2004-11-23
Filing date: 2005-11-23
Publication date: 2011-06-02
Anticipated expiration: 2025-11-23
Also published as: AU2005309411A1; EP1831106A1; WO2006058254A1; EP1831106A4

Description

WO 2006/058254 PCT/US2005/042817 TITLE MESOPOROUS METAL OXIDE FIELD OF THE INVENTION 5 This invention pertains to mesoporous metal oxides and processes for making mesoporous metal oxides. More particularly, the metal oxides are oxides of Ti, Zr, and Hf. BACKGROUND The control of particle microstructure is an important commercial 10 activity, useful, for example, in catalysis, electronics, optics, photovoltaics, and energy absorption applications. Control of particle microstructure allows control of physical and electronic properties, and is critical in the development of new functionalized materials. As an example, synthesis of small particle, high surface area inorganic oxides allows good particle 15 dispersion in polymer binder systems for uniform coatings with specific tailored properties, such as light absorption/transmittance, porosity, and durability. It is well known that products having attributes such as small particles, high-surface area, and high porosity (porosity being determined by pore volume and average pore diameter) can be commercially useful in 20 many applications including, without limitation, as catalysts or catalyst supports. Titanium dioxide is an important material because of its high refractive index and high scattering power for visible light, making it a good pigment in paints and coatings that require a high level of opaqueness. 25 TiO 2 is also active as a photocatalyst in the decomposition of organic waste materials because it can strongly absorb ultraviolet light and channel the absorbed energy into oxidation-reduction reactions. If the TiO 2 particles are made very small, less than about 100 nm, and if the photoactivity is suppressed by coating the TiO 2 particles, transparent films 30 and coatings can be made that offer UV protection. Therefore, TiO 2 is a versatile material with many existing, as well as potential, commercial applications. 1 Several processes have been reported that use titanium tetrachloride, TiC 4 , as a starting source of titanium. TiCI 4 dissolved in a solvent is neutralized with a base, such as NH 4 OH or NaOH, to precipitate a titanium-oxide solid that is washed to remove the salt byproducts, such as NH 4 CI and NaCI. However, for the reaction 5 between TiC1 4 and NH 4 0H, the inclusion of the salt byproduct, NH 4 CI, in the precipitated solid in order to control the physical properties of the titania product has not been known. US Pat. No. 6,444,189 describes an aqueous process for preparing titanium oxide particles using TiC14 and ammonum hydroxide followed by filtration and 10 thorough washing of the precipitate to make a powder with a pore volume of 0.1 cc/g and pore size of 100 A. Inoue et al. (British Ceramic Transactions 1998 Vol, 97 No. 5 p. 222 ) describe a procedure to make a washed amorphous TiO 2 gel by starting with TiCl 4 and a stoichiometric excess of NH 4 OH solution. Publication No. CN 1097400A reacts TiCi 4 with NH 3 gas in alcohol solution to precipitate NH 4 CI 15 salt, but the titanium product is an alkoxide. A hydrated TiO 2 is made by removing the NH 4 CI and hydrolyzing the separated liquid with water. SUMMARY OF THE INVENTION The invention relates to a process for producing a mesoporous oxide of titanium, zirconium or hafnium product, the process comprising: 20 precipitating an ionic porogen and a hydrous oxide of titanium, zirconium or hafnium from a reaction mixture comprising a compound comprising titanium, zirconium or hafnium, a base and a solvent, wherein the compound comprising titanium, zirconium or hafnium or the solvent, or both, are a source of the anion for the ionic porogen and the base is the source of the cation for the ionic porogen; 25 and 2 removing the ionic porogen from the precipitate by calcining to recover (i) a mesoporous titanium oxide product having a pore volume of at least 0.5 cclg and an average pore diameter of at least 200A, (ii) a mesoporous zirconium oxide product having a pore volume of at least 0.25 cc/g and an average pore diameter 5 of at least 1 OOA or (iii) a mesoporous hafnium oxide product having a pore volume of at least 0.1 cc/g and an average pore diameter of at least 1OOA, wherein the solvent is ethanol, n-propanol, i-propanol, dimethyl acetamide, alcoholic ammonium halide and aqueous ammonium halide or combinations thereof, and wherein the ionic porogen is an ammonium halide. 10 In yet another embodiment the invention relates to a process for producing a mesoporous oxide of titanium, zirconium or hafnium product, the process comprising: forming a mixture of a hydrolyzed compound comprising titanium, zirconium or hafnium in a liquid medium; 15 adding a sufficient quantity of an ammonium halide, to the mixture to saturate the liquid medium of the mixture; recovering the solid from the saturated liquid medium, the solid comprising a hydrolyzed compound comprising titanium, zirconium or hafnium having pores containing the saturated liquid medium; and 20 removing the saturated liquid medium from the solid by drying and calcining to recover (i) a mesoporous titanium oxide product having a pore volume of at least 0.5 cc/g and an average pore diameter of at least 200A, (ii) a mesoporous zirconium oxide product having a pore volume of at least 0.25 cc/g and an average pore diameter of at least 10oA or (iii) a mesoporous hafnium oxide product having 25 a pore volume of at least 0.1 cc/g and an average pore diameter of at least 100A. 3 In yet another embodiment, the invention relates to the use of the metal oxide product of the invention as a catalyst or catalyst support and a nanoparticle precursor. The metal oxide of this invention can be used in plastics, protective coatings, optical devices, electronic devices, photovoltaic cells or battery anodes, 5 specifically, lithium-battery anodes. BRIEF DESCRIPTION OF THE FIGURES Figure 1 depicts a scanning electron microscope (SEM) image of calcined powder of Comparative Example A. 4 WO 2006/058254 PCT/US2005/042817 Figure 2 depicts the X-ray powder diffraction pattern of the a product of the process to make TiO 2 using TiCl 4 and NH 4 0H in aqueous saturated NH 4 CI as described in Example 1. Figure 3 depicts a scanning electron micrograph of the product of 5 the process of Example 3. Figure 4 depicts a scanning electron micrograph of the product formed in Example 4. Figures 5 and 6 are scanning electron micrographs of the product formed in Example 5. 10 DETAILED DESCRIPTION The present invention is directed to a process for forming a mesoporous transition metal oxide of Group IVB of the Periodic Table of the Elements (CAS version). Specific oxides of Group IVB transition metals include titanium, zirconium and hafnium. 15 The disclosure herein while relating in particular, in many instances, to oxides of titanium is also applicable to the production of oxides of zirconium and hafnium. As used herein, the term "mesoporous" means structures having an average pore diameter from about 20 upto and including about 800 A 20 (about 2 to about 80 nm). As best shown in Figure 5, the microstructure product of this invention can be a sponge-like network of Group IVB metal oxide particles. As described herein, and as shown in the scanning electron micrographs of the Figures, the product of this invention comprises pores, the pores 25 being interstices within an agglomerate of metal oxide particles and/or crystals. Pore volumes and pore diameters referred to herein are determined by nitrogen porosimetry, and the surface areas are determined by BET. The process of this invention uses a porogen. A porogen is a 30 substance that can create porous structures by functioning as a template for the microstructure of the Group IVB metal oxide of this invention. The porogen can be removed to recover a mesoporous Group IVB metal oxide. 5 WO 2006/058254 PCT/US2005/042817 In one embodiment of the invention, the porogen is ionic. When the porogen is ionic it can be formed in situ from the Group IVB metal compound or the solvent, or both, and a base. The metal compound or the solvent can function as the source of the anion for the ionic porogen. 5 The base can function as the source of the cation for the ionic porogen. Alternatively, an ionic porogen can be added during the process, for example by addition of ammonium chloride to a mixture of a hydrolyzed compound comprising Ti, Zr or Hf and a liquid medium. When the process is a continuous one, the addition of the porogen to the mixture of 10 hydrolyzed compound comprising Ti, Zr or Hf and liquid medium is done by any convenient method. When the process is a batch process, any method of adding one material to another can be used. The ionic porogen can be a halide salt. Typically, the halide salt is an ammonium halide which can optionally contain lower alkyl groups. The 15 lower alkyl groups can be the same or different and can contain from 1 upto and including about 8 carbon atoms, typically less than about 4 carbon atoms. Longer chain hydrocarbons for the alkyl group of the ammonium halide can be detrimental in making a calcined product because of charring; however, the longer chain hydrocarbons, typically 20 over 4 up to and including about 10 carbon atoms, or even higher, would not be detrimental in making an amorphous product. Specific examples of ammonium halides containing lower alkyl groups include, without limitation, tetramethyl ammonium halide, and tetraethyl ammonium halide. The halide can be fluoride, chloride, bromide, or iodide. Even more 25 specifically, the halide is chloride or bromide. The ionic porogen can be a combination of halide salts such as a combination of ammonium halide, tetramethyl ammonium halide and tetraethyl ammonium halide. The porogen can be removed from the product of this invention to recover a mesoporous Group IVB metal oxide. Any suitable method for 30 removing the porogen can be used. Contemplated methods for removing the porogen include washing, calcining, subliming and decomposing. It has been found that the choice of technique for removing the porogen depends upon whether a substantially or completely crystalline material is 6 WO 2006/058254 PCT/US2005/042817 desired or whether an amorphous material is desired. When an amorphous material is desired the porogen can be removed by washing. When a crystalline material is desired the porogen can be removed by volatilizing, such as calcining. 5 A Group IVB metal starting material for the metal of the metal oxide is used. The Group IVB metal starting material can be a halide of a Group IVB metal or an oxyhalide of a Group IVB metal. Specific examples of useful Group IVB metal starting materials include titanium tetrachloride, titanium oxychloride, zirconium tetrachloride, zirconium oxychloride, such 10 as ZrOCl2-8H 2 0, hafnium tetrachloride or hafnium oxychloride, such as HfOC12-8H 2 0. The foregoing starting materials can be made by well known techniques. The oxychlorides can be made by mixing the metal tetrachloride with water. The Group IVB metal tetrachlorides and the zirconium and hafnium oxychlorides are commercially available. 15 It is believed that metal compounds containing organic groups will work in the process of this invention, however, a titanium alkoxide was found to form mesoporous metal oxides having a pore volume and an average pore diameter lower than preferred. A hydrous metal oxide intermediate forms, from the starting material 20 for the metal oxide, in the presence of base or aqueous solvent, depending upon the reaction mechanism. A base can be used to precipitate the hydrous metal oxide intermediate. A base can also serve as the source of cations for the porogen. Suitable bases for the practice of the invention can include, 25 without limitation thereto, NH 4 0H, (NH 4

)

2

CO

3 , NH 4

HCO

3 , (CH 3

)

4 NOH,

(CH

3

CH

2

)

4 NOH, or other base or mixture of bases that are removable from the product of the invention by washing or calcining. NH 4 0H is preferred. In one embodiment of the invention, a solvent can be used in the process of this invention. A suitable solvent will depend upon the reaction 30 mechanism, as discussed below. Solvents can be aqueous or organic, depending upon the Group IVB metal starting material. Suitable aqueous solvents include water (when additional salt is added as discussed below) or aqueous halide salt such as aqueous ammonium halide. Suitable 7 WO 2006/058254 PCT/US2005/042817 organic solvents include lower alkyl group alcohols and dimethylacetamide. Lower alkyl group alcohols which have been found to be particularly useful in producing metal oxides of this invention typically have upto and including 3 carbon atoms. Specific examples of lower alkyl 5 group alcohols include, without limitation, ethanol, isopropanol and n propanol. A suitable solvent can also be the aqueous or organic solvent containing dissolved halide salt (e.g., ammonium halide), preferably a saturated solution of halide salt. Solvents which have a low capacity to dissolve the porogen, such 10 as aldehydes, ketones and amines, may also be suitable solvents. For example, without limitation thereto, in order for ammonium halide formed in situ to precipitate and act as a porogen, organic solvents having a low capacity to dissolve the ammonium halide or the saturated aqueous ammonium halide can be used. 15 Other examples of suitable solvents include, without limitation thereto, aqueous acid solutions, for example, an acid halide solution. Examples of acid halide solutions include, without limitation thereto, solutions of HCl, HBr or HF. In general the suitability of a particular solvent or solvent system will 20 depend upon the reactants, the porogen, the reaction mechanism and the desired porosity of the product. In the process of this disclosure, the reaction mixture can be formed by the steps, in order, of combining the base and the solvent to form a solution or a mixture and adding the titanium, zirconium or hafnium starting 25 material to the solution or mixture. The choice of solvent will depend upon the reaction mechanism and the porosity desired. When organic solvents are combined with aqueous reagents, such as 50 wt% TiC1 4 in water and concentrated NH 4 0H, the resulting organic-water liquid portion of the reaction mixture will dissolve 30 more of the porogen than would be dissolved in the organic solvent alone. However, under the conditions of this invention, enough undissolved porogen must remain to ultimately produce a high-porosity metal-oxide 8 WO 2006/058254 PCT/US2005/042817 product. A solvent in which the metal starting material is soluble is typically used. In the process of this disclosure more than about 50 weight percent, specifically more than about 70 weight percent, even more specifically 5 more than about 90 weight percent, of the halide salt can precipitate from the reaction mixture, the weight percent being based on the total amount of the halide salt that can form from the reaction mixture. In a specific embodiment, high porosity titanium dioxide can be obtained by using a high level of precipitated ammonium chloride, which 10 acts as the porogen. This can be accomplished by performing the acid base reaction in a solvent system having limited ammonium-chloride solubility thereby precipitating more than about 50 wt % of the ammonium chloride, with precipitation of more than about 70 wt % being preferred, and precipitation of greater than about 90 wt% being most preferred. 15 In a specific embodiment of the invention, it has been found that using solvents with low NH 4 CI solubility can yield TiO 2 having a high surface area, a pore volume of about 0.3 up to and including about 1.0 cc/g, and average pore diameter greater than about 300A. A high water concentration in the reaction mixture will reduce pore 20 volume by dissolving water soluble porogen, thereby leaving less precipitated porogen available for creating pores. Water can be introduced to the process through the source of the metal or through the source of the base: for example, when the source of the metal is in an aqueous solution or when the base is in an aqueous 25 solution. It has been found that the solubility of ammonium halide in an organic-water combination or in saturated aqueous ammonium halide, and the influence of ammonium halide solubility on the porosity of the metal oxide can be affected by the form of the metal starting material. For 30 example, TiC1 4 can be introduced neat and anhydrous, or it can be combined with water to make an aqueous solution which can be referred to as TiOCl 2 solution. For the aqueous TiC1 4 , as the water:TiC1 4 weight ratio increases, ammonium halide solubility increases which will result in a 9 WO 2006/058254 PCT/US2005/042817 decrease in product porosity. Similar results would be obtained for aqueous solutions of base as the water:base ratio increases. Other solvent-specific factors can influence the pore volume of the metal oxide product; for example, different rates of precipitation of the 5 porogen and the metal-oxide, and different rates of crystallization of the porogen and the metal oxide. These factors can. impact the nature of the composite precipitate and the ability of the precipitated ammonium halide to produce the high porosity metal oxide product of this invention. The concentration of the metal starting material can be in the range 10 of about 0.01 M to about 5.0 M, preferably about 0.05 to about 0.5 M. The metal starting material may in the form of a neat liquid or solid, or, preferably, as an aqueous or organic solution. There are several ways in which the hydrolyzed metal compound and the porogen can be precipitated. 15 In one embodiment, a solvent is combined with the metal starting material to form a solution. The solvent-metal-halide solution is mixed with a base to precipitate the titanium and the porogen. For example without limitation thereto, in the synthesis of TiO 2 , titanium chloride as the neat liquid, or as an aqueous solution such as 50 wt.% TiC1 4 in water based on 20 the entire weight of the solution may be combined with the solvent. To the solvent-titanium-chloride solution so formed is added ammonium hydroxide to precipitate the hydrolyzed compound containing titanium and the porogen, ammonium chloride. In the process of this disclosure, the reaction mixture can also be 25 formed by combining the titanium, zirconium or hafnium starting material and the solvent to form a solution or mixture and adding the base to the solution or mixture. In another embodiment of the invention, a solvent is first combined with the base. The solvent-base mixture is combined with the metal 30 starting material to form a precipitate of the metal and the porogen. For example without limitation thereto, in the synthesis of TiO 2 , NH 4 0H may be combined with the solvent to form the solvent-base mixture which is combined with titanium chloride or titanium oxychloride to precipitate the 10 WO 2006/058254 PCT/US2005/042817 hydrolyzed compound containing titanium and the porogen, ammonium chloride. The porogen is then removed to form the mesoporous metal oxide product of the invention. 5 If the porogen is removed by washing with water, a very high surface area, high porosity, mesoporous network of amorphous or poorly crystalline, hydrous metal oxide remains. If the porogen is removed by calcining, a high surface area, high porosity, mesoporous network of metal oxide nanocrystals remains. 10 In another embodiment of the invention a sufficient quantity of a halide salt can be added, after precipitating the hydrolyzed metal oxide, to saturate the liquid medium. A solid recovered from the saturated liquid medium comprises a hydrolyzed metal compound having pores containing the saturated liquid medium. The saturated liquid medium is removed 15 from the solid to recover the mesoporous Group IVB metal oxide. Typically, the liquid medium is the liquid portion of the mixture of solvent, with or without dissolved salt, and hydrous metal oxide. As an example, without being limited thereto, a titanium starting material is combined with water to form a solution. To the solution so formed is 20 added a base to form a mixture comprising precipitated hydrous metal oxide and liquid medium. To that mixture is added halide salt to saturate the liquid medium. Thereafter, the mesoporous product is recovered by removing the saturated liquid medium. Typically, this is accomplished by drying to volatilize the liquid and calcining to remove the porogen which 25 remains after drying. In general, after combining the starting materials, as described above, they can be mixed, preferably at room temperature, for less than one second upto several hours. Normally, mixing for 5-60 minutes will suffice. The precipitate can be recovered by any convenient method 30 including settling, followed by decanting the supernatant liquid, filtration, centrifugation and so forth. If a very high surface area hydrous metal oxide is desired, the recovered solid, however collected, can be slurried with fresh water to 11 WO 2006/058254 PCT/US2005/042817 remove the porogen, optionally, followed by additional washing steps. The hydrous metal oxide recovered by washing the solid to remove the porogen is substantially or completely amorphous, as determined by X-ray powder diffraction, and has a very high surface area, typically at least 5 about 400 m 2 /g, typically in the range of about 400 to about 600 m 2 /g. The pore volume of the amorphous hydrous metal oxide can be at least about 0.4 cc/g, typically in the range of about 0.4 to about 1.0. The number of washing steps required to achieve the desired level of hydrous metal oxide purity will depend upon the solubility of the porogen, the amount of water 10 employed, and the efficiency of the mixing process. The recovered solid can be dried by any convenient means including but not limited to radiative warming and oven heating. As an example, a very high surface area, mesoporous hydrous oxide of titanium having a surface area of at least 400 m 2 /g and pore volume of at least about 0.4 cc/g may be synthesized 15 using the process of this invention. If a high surface area, mesoporous, nanocrystalline, metal oxide is desired, the hydrolyzed metal compound and porogen, however collected, can be calcined at a temperature that removes the porogen. Generally, the calcination temperatures are at least the sublimation or decomposition 20 temperature of the porogen. Typically the calcination temperatures will range from about 300*C to about 600 0 C, preferably between about 3500C and about 5500C, and more preferably between about 4000C and 5000C. In the case of preparing TiO 2 from TiCl 4 and NH 4 0H in saturated aqueous ammonium chloride, the 450*C-calcined product is composed of 25 agglomerated nanocrystals of anatase, although some rutile, brookite, or X-ray amorphous material may also be present. The size of the anatase nanocrystals is a function of the calcination temperature and calcination time. At a calcination temperature of 450*C, the average crystallite size can be from about 10-15 nm. 30 The calcined TiO 2 made by the process of the invention is characterized by a combination of high surface area, high pore volume, and large average pore diameter. By high surface is meant at least about 70 m 2 /g, high pore volume at least about 0.5 cc/g, preferably at least about 12 WO 2006/058254 PCT/US2005/042817 0.6 cc/g, and large average pore diameter at least about 200 A, preferably at least about 300 A. Generally, the pore volume will range from about 0.5 cc/g to about 1.00 cc/g, and the average pore diameter from about 200 A to about 500 A. 5 The crystalline titanium oxide product made by the process of this invention can comprise agglomerated nanocrystals predominantly, if not completely, having an anatase crystal structure. When the product is not completely anatase, a minor amount of rutile, brookite, and/or X-ray amorphous material may be present. 10 Calcined ZrO2 made by the process of the invention is also characterized by a combination of high surface area, high pore volume, and large average pore diameter. For ZrO 2 , the high surface is at least about 70 m 2 /g, high pore volume at least about 0.25 cc/g, and large average pore diameter of at least about 100 A, preferably at least about 15 150 A. Generally, the pore volume for ZrO 2 thus formed is between about 0.25 cc/g and about 0.5 cc/g, and the average pore diameter is between about 100 A and 200 A. Calcined HfO2 made by the process of the invention is also characterized by a combination of high pore volume and large average 20 pore diameter. For Hf0 2 , the high surface area is at least about 40 m 2 /g, high pore volume at least about 0.1 cc/g, and large average pore diameter at least about 100 A, preferably at least about 120 A. Generally, the pore volume for HfO 2 is between about 0.1 cc/g and about 0.25 cc/g, and the average pore diameter is between about 100 A and about 200 A. 25 The process of the invention may be performed in both batch and continuous modes. The solvent can be separated and recycled. The volatiles can be condensed, then recycled or disposed. The pH of the system is generally in the range of about 4 to about 10, preferably from about 5 to about 9, and most preferably between about 30 6 and about 8. In a continuous process, the pH of the system is generally controlled better than with a batch process because it is believed that the material produced is exposed to less environmental variability in pH. 13 WO 2006/058254 PCT/US2005/042817 In one embodiment of the invention the oxide of titanium, zirconium or hafnium further comprises a dopant which can be a transition metal, a Group IIA, IlIlA, IVA, or VA metal. Specifically, without limitation thereto, the dopant can be Ge, P, As, Sb, Bi, Ni, Cu, Al, Zr, Hf, Si, Nb, Ta, Fe, Sn, 5 Co, Zn, Mo, W, V, Cr, Mn, Mg, Ca, Sr, Ba, Ga, or In. Methods for incorporating dopants into the oxide would be apparent to those skilled in the art. For example, a dopant-containing compound could be added with the titanium, zirconium or hafnium-containing starting material. Compositions of matter of this invention can be used as a catalyst 10 or catalyst support. For example, the catalytic properties of TiO 2 are well known to those skilled in the catalyst art. Use of the compositions of matter of this invention as catalysts or catalyst supports would be apparent to those skilled in the catalyst art. Compositions of matter of this invention can be used as 15 nanoparticle precursors. The Group IVB metal oxide agglomerates formed by the process of this invention can be formed into nanoparticles by any suitable deagglomeration technique. As an example, product of this invention can be deagglomerated by combining the product with water and a suitable sufactant such as, without being limited thereto, 20 tetrasodiumpyrophosphate followed by sonication to break-up the agglomerates. However, other suitable techniques for breaking-up the agglomerates would be apparent to those skilled in the metal oxide powder art. Typically, deagglomeration is by sonication or media milling. The nanoparticle precursor of the invention can be deagglomerated to a 25 degree sufficient to form agglomerates considered to fall within the nanoparticle size range, typically having an average agglomerate size diameter which is less than about 200 nanometers. The deagglomerated titanium dioxide product of this invention, if photo passivated, can be especially useful for UV light degradation 30 resistance in plastics, sunscreens and other protective coatings including paints and stains. The titanium dioxide, hafnium oxide or zirconium oxide product of this invention can be photo passivated by treatment with silica and/or 14 WO 2006/058254 PCT/US2005/042817 alumina by any of several methods which are well known in the art including, without limit, silica and/or alumina wet treatments used for treating pigment-sized titanium dioxide. The titanium dioxide, hafnium oxide or zirconium oxide product of 5 this invention can also have an organic coating which may be applied using techniques known by those skilled in the art. A wide variety of organic coatings are known. Organic coatings employed for pigment-sized titanium dioxide may be utilized. Examples of organic coatings that are well known to those skilled in the art include fatty acids, such as stearic 10 acid; fatty acid esters; fatty alcohols, such as stearyl alcohol; polyols such as trimethylpropane diol or trimethyl pentane diol; acrylic monomers, oligomers and polymers; and silicones, such as polydimethylsiloxane and reactive silicones such as methylhydroxysiloxane. Organic coating agents can include but are not limited to carboxylic 15 acids such as adipic acid, terephthalic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, salicylic acid, malic acid, maleic acid, and esters, fatty acid esters, fatty alcohols, such as stearyl alcohol, or salts thereof, polyols such as trimethylpropane diol or trimethyl pentane diol; acrylic monomers, oligomers and polymers. In addition, silicon-containing 20 compounds are also of utility. Examples of silicon compounds include but are not limited to a silicate or organic silane or siloxane including silicate, organoalkoxysilane, aminosilane, epoxysilane, and mercaptosilane such as hexyltrimethoxysilane, octyltriethoxysilane, nonyltriethoxysilane, decyltriethoxysilane, dodecyltriethoxysilane, tridecyltriethoxysilane, 25 tetradecyltriethoxysilane, pentadecyltriethoxysilane, hexadecyltriethoxysilane, heptadecyltriethoxysi lane, octadecyltriethoxysilane, N-(2-aminoethyl) 3-aminopropylmethyl dimethoxysilane, N-(2-aminoethyl) 3-aminopropyl trimethoxysilane, 3 aminopropyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3 30 glycidoxypropyl methyldimethoxysilane, 3-mercaptopropyl trimethoxysilane and combinations of two or more thereof. Polydimethylsiloxane and reactive silicones such as methylhydroxysiloxane may also be useful. 15 WO 2006/058254 PCT/US2005/042817 The titanium dioxide product of this invention may also be coated with a silane having the formula: RxSi(R') 4 x 5 wherein R is a nonhydrolyzable aliphatic, cycloaliphatic or aromatic group having at least 1 to about 20 carbon atoms; 10 R' is a hydrolyzable group such as an alkoxy, halogen, acetoxy or hydroxy or mixtures thereof; and x= 1 to 3. 15 For example, silanes useful in carrying out the invention include hexyltrimethoxysilane, octyltriethoxysilane, nonyltriethoxysilane, decyltriethoxysilane, dodecyltriethoxysilane, tridecyltriethoxysilane, tetradecyltriethoxysilane, pentadecyltriethoxysilane, 20 hexadecyltriethoxysilane, heptadecyltriethoxysilane and octadecyltriethoxysilane. Additional examples of silanes include, R=8-18 carbon atoms; R'=chloro, methoxy, hydroxy or mixtures thereof; and x=1 to 3. Preferred silanes are R=8-18 carbon atoms; R'=ethoxy; and x=1 to 3. Mixtures of silanes are contemplated equivalents. The weight content of 25 the treating agent, based on total treated particles can range from about 0.1 to about 10 wt. %, additionally about 0.7 to about 7.0 wt. % and additionally from about 0.5 to about 5 wt %. The titanium dioxide particles of this invention can be silanized as described in U.S. Patent Nos. 5,889,090; 5,607,994; 5,631,310; and 30 5,959,004 which are each incorporated by reference herein in their entireties. The titanium dioxide product of this invention may be treated to have any one or more of the foregoing organic coatings. 16 WO 2006/058254 PCT/US2005/042817 Titanium dioxide product made according to the present invention may be used with advantage in various applications including without limitation, coating formulations such as sunscreens, cosmetics, automotive coatings, wood coatings, and other surface coatings; chemical mechanical 5 planarization products; catalyst products; photovoltaic cells; plastic parts, films, and resin systems including agricultural films, food packaging films, molded automotive plastic parts, and engineering polymer resins; rubber based products including silicone rubbers; textile fibers, woven and nonwoven applications including polyamide, polyaramid, and polyimides 10 fibers products and nonwoven sheets products; ceramics; glass products including architectural glass, automotive safety glass, and industrial glass; electronic components; and other uses in which photo and chemically passivated titanium dioxide will be useful. Thus in one embodiment, the invention is directed to a coating 15 composition suitable for protection against ultraviolet light comprising an additive amount suitable for imparting protection against ultraviolet light of photo passivated titanium dioxide nanoparticles made in accordance with this invention dispersed in a protective coating formulation. The oxide of hafnium or zirconium can be used in a protective 20 coating composition. One area of increasing demand for titanium dioxide nanoparticles is in cosmetic formulations, particularly in sunscreens as a sunscreen agent. Titanium dioxide nanoparticles provide protection from the harmful ultraviolet rays of the sun (UV A and UV B radiation). 25 A dispersant is usually required to effectively disperse titanium dioxide nanoparticles in a fluid medium. Careful selection of dispersants is important. Typical dispersants for use with titanium dioxide nanoparticles include aliphatic alcohols, saturated fatty acids and fatty acid amines. The titanium dioxide nanoparticles of this invention can be 30 incorporated into a sunscreen formulation. Typically the amount of titanium dioxide nanoparticles can be up to and including about 25 wt.%, typically from about 0.1 wt.% up to and including about 15 wt. %, even 17 WO 2006/058254 PCT/US2005/042817 more preferably up to and including about 6 wt.%, based on the weight of the formulation, the amount depending upon the desired sun protection factor (SPF) of the formulation. The sunscreen formulations are usually an emulsion and the oil phase of the emulsion typically contains the UV active 5 ingredients such as the titanium dioxide particles of this invention. Sunscreen formulations typically contain in addition to water, emollients, humectants, thickeners, UV actives, chelating agents, emulsifiers, suspending agents (typically if using particulate UV actives), waterproofers, film forming agents and preservatives. 10 Specific examples of preservatives include parabens. Specific examples of emollients include octyl palmitate, cetearyl alcohol, and dimethicone. Specific examples of humectants include propylene glycol, glycerin, and butylene glycol. Specific examples of thickeners include xanthan gum, magnesium aluminum silicate, cellulose gum, and 15 hydrogenated castor oil. Specific examples of chelating agents include disodium ethylene diaminetetraacetic acid (EDTA) and tetrasodium EDTA. Specific examples of UV actives include ethylhexyl methoxycinnamate, octocrylene, and titanium dioxide. Specific examples of emulsifiers include glyceryl stearate, polyethyleneglycol-100 stearate, and ceteareth-20. 20 Specific examples of suspending agents include diethanolamine-oleth-3 phosphate and neopentyl glycol dioctanoate. Specific examples of waterproofers include C30-38 olefin/isopropyl maleate/MA copolymer. Specific examples of film forming agents include hydroxyethyl cellulose and sodium carbomer. 25 To facilitate use by the customer, producers of titanium dioxide nanoparticles may prepare and provide dispersions of the particles in a fluid medium which are easier to incorporate into formulations. Water based wood coatings, especially colored transparent and clear coatings benefit from a UV stabilizer which protects the wood. 30 Organic UV absorbers are typically hydroxybenzophenones and hydroxyphenyl benzotriazoles. A commercially available UV absorber is sold under the trade name Tinuvin TM by Ciba. These organic materials, however, have a short life and decompose on exterior exposure. 18 WO 2006/058254 PCT/US2005/042817 Replacing some or all of the organic material with titanium dioxide nanoparticles would allow very long lasting UV protection. Photo passivated titanium dioxide of this invention may be used to prevent the titanium dioxide from oxidizing the polymer in the wood coating, and be 5 sufficiently transparent so the desired wood color can be seen. Because most wood coatings are water based, the titanium dioxide needs to be dispersible in the water phase. Various organic surfactants known in the art can be used to disperse the titanium dioxide nanoparticles in water. Many cars are now coated with a clear layer of polymer coating to 10 protect the underlying color coat, and ultimately the metal body parts. This layer has organic UV protectors, and like wood coatings, a more permanent replacement for these materials is desired. The clear coat layers are normally solvent based, but can also be water based. Such coatings are well known in the art. The titanium dioxide nanoparticles of 15 this invention can be modified for either solvent or water based systems with appropriate surfactants or organic surface treatments. When treated for reduced photo activity, the titanium dioxide particles of this invention can be beneficial in products which degrade upon exposure to UV light energy such as thermoplastics and surface 20 coatings. The oxide of hafnium, zirconium or titanium can be used in a thermoplastic composition. Titanium dioxide nanoparticles can also be used to increase the mechanical strength of thermoplastic composites. Most of these 25 applications also require a high degree of transparency and passivation so underlying color or patterns are visible and the plastic is not degraded by the photoactivity of the titanium dioxide nanoparticles. The titanium dioxide nanoparticles must be compatible with the plastic and easily compounded into it. This application typically employs organic surface modification of 30 the titanium dioxide nanoparticles as described herein above. The foregoing thermoplastic composites are well known in the art. 19 WO 2006/058254 PCT/US2005/042817 Polymers which are suitable as thermoplastic materials for use in the present invention include, by way of example but not limited thereto, polymers of ethylenically unsaturated monomers including olefins such as polyethylene, polypropylene, polybutylene, and copolymers of ethylene 5 with higher olefins such as alpha olefins containing 4 to 10 carbon atoms or vinyl acetate, etc.; vinyls such as polyvinyl chloride, polyvinyl esters such as polyvinyl acetate, polystyrene, acrylic homopolymers and copolymers; phenolics; alkyds; amino resins; epoxy resins, polyamides, polyurethanes; phenoxy resins, polysulfones; polycarbonates; polyether 10 and chlorinated polyesters; polyethers; acetal resins; polyimides; and polyoxyethylenes. The polymers according to the present invention also include various rubbers and/or elastomers either natural or synthetic polymers based on copolymerization, grafting, or physical blending of various diene monomers with the above-mentioned polymers, all as 15 generally well known in the art. Thus generally, the present invention is useful for any plastic or elastomeric compositions (which can also be pigmented with pigmentary TiO 2 ). For example, but not by way of limitation, the invention is felt to be particularly useful for polyolefins such as polyethylene and polypropylene, polyvinyl chloride, polyamides and 20 polyester. From the refractive index of compositions of matter of this invention it would be apparent to those skilled in the optics art that the compositions of this invention can be useful in optics. The TiO 2 product of this invention could be combined with polymethylmethacrylate polymer and made into an 25 optical device. Other techniques for incorporating the compositions of this invention into optical devices would be apparent to those skilled in the art of making optical devices. The oxide of hafnium or zirconium can be used in an optical device. Additionally, compositions of matter of this invention can be useful 30 in electronics. For example, the oxide of titanium, hafnium, or zirconium can be used in an electronic device or in a photovoltaic cell. For example the TiO 2 product of this invention could be used in photovoltaic devices. As an example, a TiO 2 product can be combined with a binder and cast 20 WO 2006/058254 PCT/US2005/042817 into a film on a conducting substrate by well-known techniques to form a component of an anode which can be used in a solar cell. Other suitable techniques for incorporating products of this invention into photovoltaic devices would be apparent to those skilled in the electronics art. TiO 2 5 products of this invention can provide high powder conversion efficiency in solar cell applications. Compositions of matter of this invention can be used in a battery as a major component of the anode. For example, the electrochemical properties of titanium in a lithium battery are well known to those skilled in 10 the battery art and the titanium dioxide product of this invention can be used in making an anode of a battery by techniques known to those skilled in the battery art. In one embodiment, the invention herein can be construed as excluding any element or process step that does not materially affect the 15 basic and novel characteristics of the composition or process. Additionally, the invention can be construed as excluding any element or process step not specified herein. Further, when an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper 20 preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is 25 intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range. The examples which follow, description of illustrative and preferred embodiments of the present invention are not intended to limit the scope 30 of the invention. Various modifications, alternative constructions and equivalents may be employed without departing from the true spirit and scope of the appended claims. 21 WO 2006/058254 PCT/US2005/042817 TEST METHODS The following test methods and procedures were used in the Examples below: Nitrogen Porosimetry: Dinitrogen adsorption/desorption 5 measurements were performed at 77.3 K on Micromeritics ASAP model 2400/2405 porosimeters (Micromeritics Inc., One Micromeritics Drive, Norcross GA 30093-1877). Samples were degassed at 1500C overnight prior to data collection. Surface area measurements utilized a five-point adsorption isotherm collected over 0.05 to 0.20 p/p0 and analyzed via the 10 BET method (described in S. Brunauer, P. H. Emmett and E. Teller, J. Amer. Chem. Soc., 60, 309 (1938)). Pore volume distributions utilized a 27 point desorption isotherm and were analyzed via the BJH method (described in E. P. Barret, L. G. Joyner and P. P. Halenda, J. Amer. Chem. Soc., 73, 373 (1951)). Values for pore volume represent the single point 15 total pore volume of pores less than about 3000 angstroms. Average pore diameter, D, is determined by D = 4V/A, where V is the single point total pore volume and A is the BET surface area. X-ray Powder Diffraction: Room-temperature powder x-ray diffraction data were obtained with a Philips X'PERT automated powder 20 diffractometer, Model 3040. Samples were run in batch mode with a Model PW 1775 or Model PW 3065 multi-position sample changer. The diffractometer was equipped with an automatic variable slit, a xenon proportional counter, and a graphite monochromator. The radiation was CuK(alpha) (45 kV, 40 mA). Data were collected from 2 to 60 degrees 2 25 theta; a continuous scan with an equivalent step size of 0.03 deg; and a count time of 0.5 seconds per step. Thermogravimetric Analysis: About 5-20 mg samples were loaded into platinum TGA pans. Samples were heated in a TA Instruments 2950 TGA under 60 ml/min air purge and 40 ml/min N 2 in the balance area (total 30 purge rate was 100 ml/min). Samples were heated from RT to 8000C at 1 0*C/min. The temperature scale of the TGA was previously calibrated at the 10*C/min rate using thermomagnetic standards. 22 WO 2006/058254 PCT/US2005/042817 Ionic Conductivity: Ionic conductivity was measured with a VWR traceable conductivity/resistivity/salinity concentration meter. The ionic conductivity of the wash sollutions was used to determine when the majority of the NH 4 Cl salt had been removed. 5 Particle Size Distribution (PSD): Particle size distribution was measured with a Malvern Nanosizer Dynamic Light Scattering Unit on suspensions containing 0.1 wt % TiO 2 . Index of Refraction: The index of refraction of samples was measured with a Metricon Prism Coupler, Model 2010, with four 10 wavelengths available (633, 980, 1310 and 1550 nm). This instrument interprets the amount of light coupled into a sample that is pressed into contact with a high index prism. The light enters the sample from the prism side and the angle of incidence is varied. The wavelength selected in the examples below was 1550 nm. The sample was placed against the 15 prism and held in close optical contact with the prism by a pneumatic ram. The sample surface was flat, smooth and clean, and of uniform thickness. The aligned laser light hit the optically contacted spot between the sample and the prism, and the index of refraction was obtained from a plot of intensity versus angle of incidence. 20 Photo Voltaic Power Efficiency: Photo voltaic power efficiency ("PVPE") was measured using photoelectrochemical techniques as described in section 2.5 of M. K. Nazeeruddin, et al., J. Am. Chem. Soc., Vol. 123, pp. 1613-1624, 2001. Data were obtained by using a 450 W xenon light source that was focused to give 1000 W/m 2 , at the surface of 25 the test cell, and measuring the output with a digital source meter. The information was analyzed after data acquisition. EXAMPLES In the following Examples and Comparative Examples, reaction products of a Group IVB metals were formed and characterized. Surface 30 area and porosity data are summarized in Table 1 and were obtained by the procedures described above. 23 WO 2006/058254 PCT/US2005/042817 All chemicals and reagents were used as received from: . TiC1 4 Aldrich Chemical Co., Milwaukee, WI, 99.9% ZrOCI 2 .8H 2 0 Alfa Aesar, Ward Hill, MA, 99.9% HfOCl 2 .8H 2 0 Alfa Aesar, Ward Hill, MA, 99.98% 5 ethanol Pharmco, Brookfield, CT, ACS/USP Grade 200 Proof

NH

4 0H EMD Chemicals, Gibbstown, NJ, 28.0-30.0 %

NH

4 CI EMD Chemicals, Gibbstown, NJ, 99.5 % n-propanol EMD Chemicals, Gibbstown, NJ, 99.99% isopropanol EMD Chemicals, Gibbstown, NJ, 99.5% 10 n-butanol EMD Chemicals, Gibbstown, NJ, 99.97% iso-butanol EMD Chemicals, Gibbstown, NJ, 99.0% tert-butanol EMD Chemicals, Gibbstown, NJ, 99.0% DMAc EMD Chemicals, Gibbstown, NJ, 99.9% (N, N' dimethylacetamide) 15 acetone EMD Chemicals, Gibbstown, NJ, 99.5% (reagent bottle) TiO 2 Degussa Inc., Parsipanny, NJ, P25 TSPP tetrasodiumpyrophosphate (CAS number 7722-88-5) All references herein to elements of the Periodic Table of the Elements are 20 to the CAS version of the Periodic Table of the Elements. COMPARATIVE EXAMPLE A This example illustrates that reaction of TiCl 4 and NH 4 0H in water alone does not produce a TiO 2 product, uncalcined or calcined, having the surface area and porosity properties of TiO 2 made by processes of this 25 invention. The precipitate formed from the reaction of TiC 4 and NH 4 0H is washed extensively to remove any trapped NH 4 CI byproduct. 20.0 g (14 mL) of 50% wt TiC1 4 in H 2 0 were added to about 200 mL deionized water while stirring with a Teflon coated magnetic stirring bar in a 400 mL Pyrex beaker. With stirring, 14.5 mL concentrated NH 4 0H (i.e., 30 -30 % wt = 14.8 M) were added to the titanium solution. The pH of the slurry, measured with multi-color strip pH paper, was about 7. The resulting slurry was stirred for 60 minutes at ambient temperature. 24 WO 2006/058254 PCT/US2005/042817 The solid was washed extensively with deionized water until the clear, colorless supernatant wash water had a low ionic conductivity value, 12 pS/cm. The solid was collected by suction filtration and dried under an IR heat lamp. An X-ray powder diffraction pattern showed the material to 5 be amorphous. Nitrogen porosimetry measurements of this uncalcined powder revealed a surface area of 398 m 2 /g, a pore volume of 0.37 cc/g, and an average pore diameter of 37 A. The powder was transferred to an alumina crucible and heated uncovered from room temperature to 450"C over the period of one hour, 10 and held at 450 0 C for an additional hour. The crucible and its contents were removed from the furnace and cooled naturally to room temperature. An X-ray powder diffraction pattern of the calcined material showed only the broad lines of anatase indicating an average crystal size of 16 nm. Nitrogen porosimetry revealed a surface area of 72 m 2 /g, a pore 15 volume of 0.17 cc/g, and an average pore diameter of 95 A. Figure 1 is a scanning electron microscope (SEM) image of the calcined powder, at a magnification of 50,000x, showing the product is compacted with low porosity. The porosimetry data of this Example are reported in Table 6. COMPARATIVE EXAMPLE B 20 This example also illustrates that reaction of TiCl 4 and NH 4 0H in water alone does not produce a TiO 2 product, uncalcined or calcined, having the surface area and porosity properties of a TiO 2 product of this invention. Here, the precipitate formed from the reaction of TiCl 4 and

NH

4 0H is collected and processed without the washing step used in 25 Comparative Example A to remove NH 4 CI byproduct. 20.0 g (14 mL) of 50% wt TiCl 4 in H 2 0 were added to about 200 mL deionized water while stirring with a Teflon coated magnetic stirring bar in a 400 mL Pyrex beaker. With stirring, 28 mL 1:1 NH 4 0H (i.e., 14-15 % wt = 7.5 M) were added to the titanium solution. The pH of the slurry, 30 measured with multi-color strip pH paper, was about 5. The resulting slurry was stirred for 60 minutes at ambient temperature. The unwashed solid was collected by suction filtration and dried under an IR heat lamp. An X-ray powder diffraction pattern showed the 25 WO 2006/058254 PCT/US2005/042817 lines of NH 4 CI and a trace of anatase. Nitrogen porosimetry measurements of this mixture revealed a surface area of 215 m 2 /g, a pore volume of 0.17 cc/g, and an average pore diameter of 31 A. The powder was transferred to an alumina crucible and heated 5 uncovered from room temperature to 450*C over the period of one hour, and held at 450*C for an additional hour. The crucible and its contents were removed from the furnace and cooled naturally to room temperature. An X-ray powder diffraction pattern of the calcined material showed broad lines of anatase as the most intense and also showed one line of 10 brookite with very low intensity. Nitrogen porosimetry revealed a surface area of 70 m 2 /g, a pore volume of 0.25 cc/g, and an average pore diameter of 146 A. The porosimetry data of this Example are reported in Table 6. COMPARATIVE EXAMPLE C 15 This example illustrates that reaction of TiCl 4 and NH 4 0H using acetone as the solvent does not result in a calcined TiO 2 having the surface area and porosity properties of a calcined TiO 2 product made by the process of this invention. 20.0 g (14 mL) of 50% wt TiCl 4 in H 2 0 were added to about 200 mL 20 acetone while stirring with a Teflon coated magnetic stirring bar in a 400 mL Pyrex beaker. With stirring, 28 mL 1:1 NH 4 0H (i.e., 14-15 % wt = 7.5 M) were added to the titanium solution. The pH of the slurry, measured with water moistened multi-color strip pH paper, was about 7. The resulting slurry was stirred for 60 minutes at ambient temperature. 25 The solid was collected by suction filtration and dried under an IR heat lamp to yield 14.5 g of white powder. An X-ray powder diffraction pattern showed only the lines of NH 4 CI. The powder was transferred to an alumina crucible and heated uncovered from room temperature to 4500C over the period of one hour, 30 and held at 4500C for an additional hour. The crucible and its contents were removed from the furnace and cooled naturally to room temperature. It was observed that the volume of powder after calcination was about half the volume of the starting precalcined powder. 26 WO 2006/058254 PCT/US2005/042817 An X-ray powder diffraction pattern of the calcined material showed broad lines of anatase as the most intense, and also showed some lines of rutile with very low intensity, as well as some amorphous material. Nitrogen porosimetry revealed a surface area of 75.8 m 2 /g, a pore volume 5 of 0.24 cc/g, and an average pore diameter of 129 A. The porosimetry data of this Example are reported in Table 6. COMPARATIVE EXAMPLE D This example describes that reaction of TiCl 4 and NH 4 0H in the three butanol isomers to form TiO 2 . 10 20.0 g (14 mL) of 50% wt TiCl 4 in H 2 0 were added to about 200 mL n-butanol, tert-butyl alcohol, and isobutyl alcohol, respectively, while stirring with a Teflon coated magnetic stirring bar in 400 mL Pyrex beakers. With stirring, 29 mL 1:1 NH 4 0H (i.e., 14-15 % wt = 7.5 M) were added to each of the three titanium solutions. The pH of the slurries was 15 measured with water moistened multi-color strip pH paper and observed to be in the range of - 6-7. The slurries were stirred for 60 minutes at ambient temperature. The solids were each collected by suction filtration and dried under an IR heat lamp to give yields of 14.7 g, 13.3 g, and 13.1 g, respectively. 20 X-ray powder diffraction patterns showed only the lines of NH 4 CI for the n butanol and tert-butyl alcohol reactions, and a trace of anatase in addition to NH 4 CI for the isobutyl alcohol reaction. The powders were transferred to alumina crucibles and heated, uncovered, from room temperature to 4500C over the period of one hour, 25 and held at 450 0 C for an additional hour. The crucibles and their contents were removed from the furnace and cooled naturally to room temperature. X-ray powder diffraction patterns of the calcined materials showed the crystalline phases reported in Table 1: 27 WO 2006/058254 PCT/US2005/042817 TABLE 1 Butanol solvent Crystalline phases determined by XPD n-butanol anatase, trace of brookite tert-butyl alcohol anatase isobutyl alcohol anatase, NH 4 CI, small amount of rutile Nitrogen porosimetry revealed the following surface areas, pore volumes, and average pore diameters reported in Table 2: 5 TABLE 2 surface area pore vol. (cc/g) ave. pore diam. (m 2 /g) (A) (1) n-butanol 82 0.4 193 (II) tert-butyl 74 0.37 202 alcohol (1ll) isobutyl 109 0.28 105 alcohol As shown in Table 2, the TiO 2 product formed in accordance with the procedure of this Comparative Example D, wherein the solvent was each of the three different butanol isomers, did not have the porosity 10 properties of TiO 2 produced by the process of this invention. The porosimetry data of this Example are also reported in Table 6. EXAMPLE 1 This example illustrates that reaction of TiC 4 and NH 4 0H in aqueous saturated NH 4 CI can produce a calcined mesoporous 15 nanocrystalline TiO 2 powder having a high surface area and high porosity. 20.0 g (14 mL) of 50% wt TiCl 4 in H 2 0 were added to about 250 mL aqueous NH 4 CI solution, made by dissolving 73 g NH 4 CI in 200 g deionized H 2 0, with stirring with a Teflon coated magnetic stirring bar in a 400 mL Pyrex beaker. With continued stirring, 30 mL 1:1 NH 4 0H (i.e., 14 20 15 % wt or 7.5 M) were added to the titanium-chloride/ammonium chloride solution. The pH of the slurry, measured with multi-color strip pH paper, 28 WO 2006/058254 PCT/US2005/042817 was about 7. The resulting slurry was stirred for 60 minutes at ambient temperature. The solid was collected by suction filtration and dried under an IR heat lamp to yield 14.9 g of white powder. The powder was then 5 transferred to an alumina crucible and heated uncovered from room temperature to 450 0 C over the period of one hour, and held at 450*C for an additional hour to ensure removal of the volatile NH 4 CI. The crucible and its contents were removed from the furnace and cooled naturally to room temperature. 10 An X-ray powder diffraction pattern of the calcined material showed only broad lines of anatase and from the width of the strongest peak an average crystal size of 12 nm was estimated (see Figure 2). Nitrogen porosimetry revealed a surface area of 88 m 2 /g, a pore volume of 0.72 cc/g, and an average pore diameter of 325 A. The porosimetry data of this 15 Example are reported in Table 6. EXAMPLE 2 This example illustrates that reaction of TiC 4 and NH 4 0H in absolute ethanol can produce a calcined mesoporous nanocrystalline TiO 2 powder having a high surface area and high porosity. 20 15 mL concentrated NH 4 0H were added to about 200 mL absolute ethanol while stirring with a Teflon coated magnetic stirring bar in a 400 mL Pyrex beaker. With stirring, 20.0 g (14 mL) of 50% wt TiCl 4 in H 2 0 were added to the basic solution. The pH of the slurry, measured with water moistened multi-color strip pH paper, was about 8. The resulting 25 slurry was stirred for 60 minutes at ambient temperature. The solid was collected by suction filtration and dried under an IR heat lamp. The powder was transferred to an alumina boat and heated uncovered from room temperature to 450 0 C over the period of one hour, and held at 450*C for an additional hour. The furnace with the boat and its 30 contents were cooled naturally to room temperature. An X-ray powder diffraction pattern of the calcined material showed only the broad lines of anatase. Nitrogen porosimetry revealed a surface area of 84 m 2 /g, a pore 29 WO 2006/058254 PCT/US2005/042817 volume of 0.78 cc/g, and an average pore diameter of 371 A. The porosimetry data of this Example are reported in Table 6. EXAMPLE 3 This example illustrates that adding NH 4 0H to a solution of TiCl 4 in 5 n-propanol can produce a calcined mesoporous nanocrystalline TiO 2 powder having a high surface area and high porosity. 20.0 g (14 mL) of 50% wt TiCl 4 in H 2 0 were added to about 200 mL n-propanol while stirring with a Teflon coated magnetic stirring bar in a 400 mL Pyrex beaker. With stirring, 28 mL 1:1 NH 4 0H (i.e., 14-15 % wt or 7.5 10 M) were added to the titanium solution. The pH of the slurry, measured with water moistened multi-color strip pH paper, was about 6. The resulting slurry was stirred for 60 minutes at ambient temperature. The solid was collected by suction filtration and dried under an IR heat lamp to yield 13.0 g of white powder. An X-ray powder diffraction 15 pattern showed only the lines of NH 4 CI. The powder was transferred to an alumina crucible and heated uncovered from room temperature to 450 0 C over the period of one hour, and held at 4500C for an additional hour to ensure removal of the volatile NH 4 CI. The crucible and its contents were removed from the furnace and cooled naturally to room temperature. 20 Surprisingly, the volume of powder after calcination was almost the same as that of the starting pre-calcined powder, even though the amount of

NH

4 CI in the starting mixture was - 65% by weight. Nitrogen porosimetry revealed a surface area of 89 m 2 /g, a pore volume of 0.65 cc/g, and an average pore diameter of 293 A. A Scanning 25 Electron Microscopy image at 30,000x magnification, Figure 3, shows porous agglomerates of TiO 2 crystals. The porosimetry data of this Example are reported in Table 6. EXAMPLE 4 This example illustrates that adding TiCl 4 to a solution of NH 4 0H in 30 n-propanol can produce a calcined mesoporous nanocrystalline TiO 2 powder having a high surface area and high porosity. 37.5 mL concentrated NH 4 0H were added to about 500 mL n propanol while stirring with a Teflon coated magnetic stirring bar in a 1 L 30 WO 2006/058254 PCT/US2005/042817 Pyrex beaker. With continued stirring, 35 mL of 50% wt TiC 4 in H 2 0 were added to the NH 4 0H-propanol solution. The resulting slurry with pH 7 was stirred for 60 minutes at ambient temperature. The solid was collected by suction filtration and dried under an IR 5 heat lamp. The voluminous powder was transferred to alumina boats and heated uncovered, under flowing air in a tube furnace, from room temperature to about 450 0 C over the period of one hour, and held at about 450 0 C for an additional hour to ensure removal of the volatile NH 4 CI. The furnace was allowed to cool naturally to room temperature, and the fired 10 material was recovered. An X-ray powder diffraction pattern of the calcined material showed the broad lines of anatase and a trace of rutile. Nitrogen porosimetry revealed a surface area of 86 m 2 /g, a pore volume of 0.93 cc/g, and an average pore diameter of 435 A. Figure 4 is a Scanning Electron 15 Microscopy image of the product of this Example at 50,000x magnification showing very porous agglomerates of TiO 2 crystals. The porosimetry data of this Example are reported in Table 6. EXAMPLE 5 This example, where NH 4 0H is added to a solution of TiC 4 in n 20 propanol in the presence of a surfactant, describes a calcined mesoporous nanocrystalline TiO 2 powder having a high surface area and high porosity. 20.0 g (14 mL) of 50% wt TiCl 4 in H 2 0 were added to about 200 mL of 5% wt Pluronic P123 (BASF Corp) surfactant in n-propanol while stirring with a Teflon coated magnetic stirring bar in a 400 mL Pyrex beaker. With 25 stirring, 29 mL 1:1 NH 4 0H (i.e., 14-15 % wt or 7.5 M) were added to the titanium solution. The resulting slurry was stirred for 60 minutes at ambient temperature. The solid was collected by suction filtration and dried under an IR heat lamp to yield 14.1 g of white powder. The powder was transferred to 30 an alumina crucible and heated uncovered from room temperature to 450 0 C over the period of one hour, and held at 4500C for an additional hour to ensure removal of the volatile NH 4 CI template. The crucible and its contents were removed from the furnace and cooled naturally to room 31 WO 2006/058254 PCT/US2005/042817 temperature. An X-ray powder diffraction pattern of the calcined material showed broad lines of anatase (14 nm average crystal size), and a very small amount of rutile. Nitrogen porosimetry revealed a surface area of 91 m 2/g, a pore volume of 0.63 cc/g, and an average pore diameter of 276 A. 5 Figures 5 and 6 are scanning electron microscopy images with magnifications of 25,000x and 50,000x, respectively, showing very porous agglomerates of TiO 2 particles. The porosimetry data of this Example are reported in Table 6. EXAMPLE 6 10 This example illustrates that reaction of neat TiCl 4 and NH 4 0H in n propanol results in a calcined mesoporous nanocrystalline TiO 2 powder having a high surface area and high porosity. 10 g of 99.995 TiC14 were added to about 200 mL n-propanol while stirring with a Teflon coated magnetic stirring bar in a 400 mL Pyrex 15 beaker. With stirring, 16 mL concentrated NH 4 0H were added to the titanium solution. The thick slurry was thinned with an additional small portion of n-propanol. The pH of the slurry, measured with water moistened multi-color strip pH paper, was about 7-8. The resulting slurry was stirred for 60 minutes at ambient temperature. 20 The solid was collected by suction filtration and dried under an IR heat lamp to yield 16.1 g of white powder. An X-ray powder diffraction pattern showed only the lines of NH 4 CI. A TGA of this mixture exhibited a total weight loss of 74% up to - 300*C indicating that most of the NH 4 CI had been precipitated along with the TiO 2 . 25 The powder was transferred to an alumina crucible and heated uncovered from room temperature to 450*C over the period of one hour, and held at 450*C for an additional hour to ensure removal of the volatile

NH

4 CI. The crucible and its contents were removed from the furnace and cooled naturally to room temperature. An X-ray powder diffraction pattern 30 of the calcined material showed broad lines of anatase, a very small amount of brookite, and some amorphous material. Nitrogen porosimetry revealed a surface area of 89 m 2 /g, a pore volume of 0.56 cc/g, and an 32 WO 2006/058254 PCT/US2005/042817 average pore diameter of 251 A. The porosimetry data of this Example are reported in Table 6. EXAMPLE 7 This example illustrates that adding NH 4 0H to a solution of TiCl 4 in 5 isopropanol results in a calcined mesoporous nanocrystalline TiO 2 powder having a high surface area and high porosity. 20.0 g (14 mL) of 50% wt TiCl 4 in H 2 0 were added to about 200 mL isopropanol while stirring with a Teflon coated magnetic stirring bar in a 400 mL Pyrex beaker. With stirring, 30 mL 1:1 NH 4 0H (i.e., 14-15 % wt or 10 7.5 M) were added to the titanium solution. The resulting slurry was stirred for 60 minutes at ambient temperature. The solid was collected by suction filtration and dried under an IR heat lamp. An X-ray powder diffraction pattern showed only the lines of

NH

4 CI. 15 The powder was transferred to an alumina crucible and heated uncovered from room temperature to 450*C over the period of one hour, and held at 450*C for an additional hour to ensure removal of the volatile

NH

4 CI. The crucible and its contents were removed from the furnace and cooled naturally to room temperature. 20 An X-ray powder diffraction pattern of the calcined material showed only broad lines of anatase and some amorphous material. The average crystallite size of the anatase was estimated to be 11 nm from X-ray peak broadening analysis. Nitrogen porosimetry revealed a surface area of 78 m2/g, a pore volume of 0.74 cc/g, and an average pore diameter of 378 A. 25 The porosimetry data of this Example are reported in Table 6. EXAMPLE 8 This example illustrates that adding NH 4 0H to a solution of TiCl 4 in N,N' dimethylacetamide (DMAC) resulted in a calcined mesoporous nanocrystalline TiO 2 powder having a high surface area and high porosity. 30 20.0 g (14 mL) of 50% wt TiCl 4 in H 2 0 were added to about 200 mL N,N' dimethylacetamide (DMAC) while stirring with a Teflon coated magnetic stirring bar in a 400 mL Pyrex beaker. With stirring, 29 mL 1:1 33 WO 2006/058254 PCT/US2005/042817

NH

4 0H were added to the titanium solution. The resulting slurry was stirred for 60 minutes at ambient temperature. The solid was collected by suction filtration and dried under an IR heat lamp. The powder was transferred to an alumina crucible and heated 5 uncovered from room temperature to 450*C over the period of one hour, and held at 450*C for an additional hour to ensure removal of the volatile

NH

4 CI porogen. The crucible and its contents were removed from the furnace and cooled naturally to room temperature. An X-ray powder diffraction pattern of the calcined material showed only broad lines of 10 anatase with an average crystallite size of 13 nm. Nitrogen porosimetry revealed a surface area of 88 m 2 /g, a pore volume of 0.68 cc/g, and an average pore diameter of 313 A. The porosimetry data of this Example are reported in Table 6. EXAMPLE 9 15 This example illustrates that addition of NH 4 CI to the aqueous slurry formed by reaction of NH 4 0H with TiCl 4 results in a calcined mesoporous nanocrystalline TiO 2 powder having a high surface area and high porosity. 20.0 g (14 mL) of 50% wt TiCl 4 in H 2 0 were added to about 200 mL deionized H 2 0 while stirring with a Teflon coated magnetic stirring bar in a 20 400 mL Pyrex beaker. With stirring, 29 mL 1:1 NH 4 0H (i.e., 14-15 % wt or 7.5 M) were added to the titanium solution. The pH of the slurry was about 8. After a few minutes, 89 g NH 4 CI were added to the slurry, and the mixture was stirred for 60 minutes at ambient temperature. The solid was collected by suction filtration and dried under an IR 25 heat lamp. An X-ray powder diffraction pattern showed only the lines of

NH

4 CI. The powder was transferred to an alumina crucible and heated uncovered from room temperature to about 450*C over the period of one hour, and held at about 450"C for an additional hour to ensure removal of the volatile NH 4 CI. The crucible and its contents were removed from the 30 furnace and cooled naturally to room temperature. An X-ray powder diffraction pattern of the calcined material showed the broad lines of anatase and a very small amount of brookite. Nitrogen porosimetry revealed a surface area of 80 m 2 /g, a pore volume of 0.52 34 cc/g, and an average pore diameter of 260 A. The porosimetry data of this Example are reported in Table 6. COMPARATIVE EXAMPLE 10 This example illustrates that adding NH 4 0H to a solution of TiC 4 in n 5 propanol resulted in a washed and dried, uncalcined, mesoporous, TiQ 2 powder having a very high surface area and high porosity. 12.5 g TiCl 4 were added to about 200 mL n-propanol while stirring with a Teflon coated magnetic stirring bar in a 400 mL Pyrex beaker. With stirring, 19 mL concentrated NH 4 OH were added to the titanium solution. The resulting slurry was 10 stirred for 60 minutes at ambient temperature. The solid was collected by suction filtration and dried under an IR heat lamp. The mixture was slurried in 1 L deionized water, stirred for 15 minutes, and collected by suction filtration. The latter step was repeated, but this time stirring of the slurry was extended to 90 minutes. After overnight drying at room 15 temperature, a voluminous 7.7 g of powder was recovered. An X-ray powder diffraction pattern showed the washed TiO 2 to be amorphous. Nitrogen porosimetry measurements on this mixture revealed a surface area of 511 m 2 /g, a pore volume of 0.86 cc/g, and an average pore diameter of 68 A. The porosimetry data of this Example are reported in Table 6. 20 COMPARATIVE EXAMPLE E This example shows that calcination of the washed and dried TiO 2 product of Comparative Example 10, which no longer contains sufficient NH 4 CI porogen, does not give a nanocrystalline TiC 2 powder having the high surface area and high porosity of TiO 2 made by processes of this invention. 25 The washed and dried powder in Comparative Example 10 was transferred to an alumina crucible and heated uncovered from room temperature to 450"C over the period of one hour, and held at 450*C for an additional hour to ensure removal of the volatile NH 4 CI. The crucible and its contents were removed from the furnace and cooled naturally to room temperature. X-ray powder diffraction of 30 the calcined material showed only broad lines of anatase and some amorphous material. Nitrogen porosimetry revealed a surface area of 61 m 2 /g, a pore volume of 0.34 cc/g, and an average 35 pore diameter of 223 A. The porosimetry data of this Example are reported in Table 6. COMPARATIVE EXAMPLE 11 This example, where NH 4 0H is added to a solution of TiCl 4 in n-propanol in 5 the presence of a surfactant, describes a washed and dried, uncalcined mesoporous TiO 2 powder having a very high surface area and high porosity. Example 5 was repeated, but rather than drying and calcining, the filtered, undried product cake was slurried with 1 L deionized water, stirred for 75 minutes, and collected by suction filtration. This washing step was repeated two more 10 times. The filtered white powder was dried under an IR heat lamp. An X-ray powder diffraction pattern showed the washed and dried product to be amorphous. Nitrogen porosimetry revealed a surface area of 526 m 2 /g, a pore volume of 0.47 cc/g, and an average pore diameter of 35 A. The porosimetry data of this Example are reported in Table 6. 15 EXAMPLE 12 This example demonstrates the utility of the mesoporous, titanium dioxide product as a nanoparticle precursor. Micron size TiO 2 particles are deagglomerated by a factor of 100-500, e.g., particles having a d 5 s - 50 pm are reduced in size to have d 50 - 0.100 pm (100 nm). 20 TiO 2 powders from Examples 1, 4, and 5 above were dispersed by shaking in water containing 0.1 wt % TSPP surfactant. The particle size distributions for these powders before and after 20 minutes of sonication are shown in Table 3. TABLE 3 TiC 2 powder d 5 o (pm) as prepared d 5 o (pm) after 20 min. sonication Example 1 46.7 0.088 Example 4 11.3 0.110 Example 5 23.7 0.130 36 WO 2006/058254 PCT/US2005/042817 EXAMPLE 13 This example demonstrates the utility of the nanocrystalline, mesoporous titanium dioxide in a photovoltaic device. TiO 2 powder made as described in Example 3, was blended with a binder and cast into a film 5 on an electrically-conducting fluorine-doped tin-oxide (FTO) coated glass substrate. This anode was assembled into a dye-sensitized solar cell and tested as described in section 2.5 of "Engineering of Efficient Panchromatic Sensitizers for Nanocrystalline TiO2-Based Solar Cells", M. K. Nazeeruddin, et al., J. Am. Chem. Soc., volume 123, pp. 1613-1624, 10 2001. A control experiment using Degussa P25 TiO 2 was used for comparison. The cell containing TiO 2 of this invention exhibited a higher power conversion efficiency, relative to that of the control cell. The results are reported in Table 4. 15 TABLE 4 TiO 2 film Relative power conversion efficiency Example 3 1.13 Degussa 1.00 P25 EXAMPLE 14 This example demonstrates the utility of the nanocrystalline, mesoporous titanium dioxide in an optical device. The index of refraction 20 of a polymethylmethacrylate (PMMA) polymer film was modified by blending the PMMA polymer with TiO 2 powder from Example 4 to make composite films containing 5 % wt TiO 2 . The results are reported in Table 5. 37 WO 2006/058254 PCT/US2005/042817 TABLE 5 Film index of refraction at 1550 nm PMMA (two sample films) 1.479, 1.479 PMMA + TiO 2 from Example 4 1.512, 1.514 (two composite sample films) COMPARATIVE EXAMPLE F This example shows that reaction of ZrOCl 2 -8H 2 0 with NH 4 0H in 5 water does not result in calcined ZrO 2 as obtained via aqueous saturated

NH

4 CI solution. 11.0 g ZrOCl 2 -8H 2 0 were dissolved in 100 mL deionized H 2 0 while stirring with a Teflon coated magnetic stirring bar in a 250 mL Pyrex beaker. With stirring, 10 mL concentrated NH 4 0H were added to the 10 zirconium solution. The pH of the slurry, measured with multi-color strip pH paper, was about 10. The resulting slurry was stirred for 60 minutes at ambient temperature. The solid was collected by suction filtration and dried under an IR heat lamp. The powder was transferred to an alumina crucible and heated 15 uncovered from room temperature to 450*C over the period of one hour, and held at 4500C for an additional hour. The crucible and its contents were removed from the furnace and cooled naturally to room temperature. An X-ray powder diffraction pattern of the calcined material showed a mixture of the monoclinic and tetragonal forms of ZrO 2 with the 20 crystallites ranging 11-16 nm in size. Nitrogen porosimetry revealed a surface area of 63.4 m 2 /g, a pore volume of 0.13 cc/g, and an average pore diameter of 84 A. The porosimetry data of this Example are reported in Table 6. 38 WO 2006/058254 PCT/US2005/042817 EXAMPLE 15 This example, using ZrOCl 2 -8H 2 0 in aqueous saturated NH 4 CI solution, illustrates the synthesis of calcined ZrO 2 product in accordance with this invention. 5 11.0 g ZrOCl2-8H 2 0 were dissolved in 100 mL aqueous NH 4 CI solution saturated at room temperature, while stirring with a Teflon coated magnetic stirring bar in a 250 mL Pyrex beaker. With stirring, 20 mL 1:1

NH

4 0H:H 2 0 were added to the zirconium solution. The pH of the slurry, measured with multi-color strip pH paper, was about 10. The resulting 10 slurry was stirred for 60 minutes at ambient temperature. The solid was collected by suction filtration and dried under an IR heat lamp. The powder was transferred to an alumina crucible and heated uncovered from room temperature to 4500C over the period of one hour, and held at 4500C for an additional hour. The crucible and its contents 15 were removed from the furnace and cooled naturally to room temperature. An X-ray powder diffraction pattern of the calcined material showed only the tetragonal form of ZrO 2 with 7 nm crystals. Nitrogen porosimetry revealed a surface area of 84 m 2 /g, a pore volume of 0.31 cc/g, and an average pore diameter of 146 A. The porosimetry data of this Example are 20 reported in Table 6. EXAMPLE 16 This example, using ZrOCl2-8H 2 0 illustrates the synthesis of calcined product via addition of NH 4 CI after forming the ZrO 2 precipitate. 11.0 g ZrOCl 2 8H 2 0 were dissolved in 100 mL deionized H20 at 25 room temperature while stirring with a Teflon coated magnetic stirring bar in a 250 mL Pyrex beaker. With stirring, 10 mL concentrated NH 4 0H were added to the zirconium solution. After a few minutes, 45 g NH 4 CI were added to the slurry, and the mixture was stirred for 60 minutes at ambient temperature. 30 The solid was collected by suction filtration and dried under an IR heat lamp. The powder was transferred to an alumina crucible and heated uncovered from room temperature to 4500C over the period of one hour, 39 WO 2006/058254 PCT/US2005/042817 and held at 4500C for an additional hour. The crucible and its contents were removed from the furnace and cooled naturally to room temperature. An X-ray powder diffraction pattern of the calcined material showed only the tetragonal form of ZrO 2 with 7 nm crystals. Nitrogen porosimetry 5 revealed a surface area of 81.5 m 2 /g, a pore volume of 0.38 cc/g, and an average pore diameter of 187 A. The porosimetry data of this Example are reported in Table 6. COMPARATIVE EXAMPLE G Reaction of HfOCl 2 -8H 2 0 with NH 4 0H in water does not give Hf0 2 , 10 calcined, as obtained via aqueous saturated NH 4 CI solution. 10.0 g HfOCl 2 -8H 2 0 were dissolved in 200 mL deionized H 2 0 while stirring with a Teflon coated magnetic stirring bar in a 250 mL Pyrex beaker. With stirring, 3.5 mL concentrated NH 4 0H were added to the hafnium solution. The pH of the slurry, measured with multi-color strip pH 15 paper, was about 8-9. The resulting slurry was stirred for 60 minutes at ambient temperature. The solid was collected by suction filtration and dried under an IR heat lamp. The powder was transferred to an alumina crucible and heated uncovered from room temperature to 4500C over the period of one hour, 20 and held at 4500C for an additional hour. The crucible and its contents were removed from the furnace and cooled naturally to room temperature. An X-ray powder diffraction pattern of the calcined material showed it to be amorphous. Nitrogen porosimetry revealed a surface area of 62.5 m2/g, a pore volume of 0.05 cc/g, and an average pore diameter of 29 A. 25 The porosimetry data of this Example are reported in Table 6. EXAMPLE 17 This example, using HfOCl 2 8H 2 0 in aqueous saturated NH 4 CI solution, illustrates the synthesis of calcined HfO 2 product. 10.0 g HfOCl 2 -8H 2 0 were dissolved in 200 mL aqueous NH 4 CI 30 solution saturated at room temperature, while stirring with a Teflon coated magnetic stirring bar in a 250 mL Pyrex beaker. With stirring, 3.5 mL concentrated NH 4 0H were added to the hafnium solution. The pH of the 40 WO 2006/058254 PCT/US2005/042817 slurry, measured with multi-color strip pH paper, was about 8. The resulting slurry was stirred for 60 minutes at ambient temperature. The solid was collected by suction filtration and dried under an IR heat lamp. The powder was transferred to an alumina crucible and heated 5 uncovered from room temperature to 450*C over the period of one hour, and held at 450 0 C for an additional hour. The crucible and its contents were removed from the furnace and cooled naturally to room temperature. An X-ray powder diffraction pattern of the calcined material showed only the monoclinic form of HfO 2 with crystallites approximately 8-11 nm in 10 size. Nitrogen porosimetry revealed a surface area of 49.9 m 2 /g, a pore volume of 0.20 cc/g, and an average pore diameter of 161 A. The porosimetry data of this Example are reported in Table 6. EXAMPLE 18 This example, using HfOCl 2 -8H 2 0 illustrates the synthesis of 15 calcined product via addition of NH 4 CI after forming the HfO 2 precipitate. 10.0 g HfOCl2-8H 2 0 were dissolved in 200 mL deionized H 2 0 at room temperature while stirring with a Teflon coated magnetic stirring bar in a 250 mL Pyrex beaker. With stirring, 3.5 mL concentrated NH 4 0H were added to the zirconium solution. After a few minutes, 85 g NH 4 CI 20 were added to the slurry, and the mixture was stirred for 60 minutes at ambient temperature. The solid was collected by suction filtration and dried under an IR heat lamp. The powder was transferred to an alumina crucible and heated uncovered from room temperature to 450*C over the period of one hour, 25 and held at 450'C for an additional hour. The crucible and its contents were removed from the furnace and cooled naturally to room temperature. An X-ray powder diffraction pattern of the calcined material showed only the monoclinic form of HfO 2 with crystallites 8-10 nm in size. Nitrogen porosimetry revealed a surface area of 53.2 m 2 /g, a pore volume of 0.17 30 cc/g, and an average pore diameter of 130 A. The surface area and pore characteristics of the products of the examples are reported in the following Table 6. 41 TABLE 6 Example Material Surface . Pore Ave. Area, m 2 /g Vol. Pore (ccfg) Diam. (A) Comparative A uncalcined TiO 2 398 0.37 37 Comparative A calcined 72 0.17 95 Comparative B uncalcined 215 0.17 31 Comparative B calcined 70 0.25 146 Comparative C 75.8 0.24 129 Comparative D-I 82 0.4 193 Comparative D-1I 74 0.37 202 Comparative D-Ill 109 0.28 105 1 88 0.72 325 2 84 0.78 371 3 89 0.65 293 4 86 0.93 435 5 91 0.63 276 6 89 0.56 251 7 78 0.74 378 8 88 0.68 313 9 80 0.52 260 Comparative 10 511 0.86 68 Comparative E 61 0.34 223 Comparative 11 526 0.47 35 Comparative F Zr0 2 634 0.13 84 15 84 0.31 146 16 81.5 0.38 187 Comparative G HfO 2 62.5 0.05 29 17 49.9 0.20 161 18 53.2 0.17 130 The data of Table 6 show that this invention provides mesoporous products having high surface areas and high pore volumes and high average pore diameters. 5 While the surface area of the uncalcined 42 titanium-containing product of Comparative Examples A and B was high it was not as high as the uncalcined product of Comparative Example 10, Also, the pore volume and average pore diameter of the uncalcined product of Comparative Examples A and B was lower than that of titanium-containing product of 5 Comparative Example 10. While the surface area of the calcined product of Comparative Example D ill was higher than that of Examples 1-9 the pore volume and average pore diameter of the calcined product of Comparative Example D-Ill was much lower than that of the calcined product of Examples 1-9. Moreover, while the surface 10 area of the product of example D-l was slightly higher than Examples 7 and 9 and the pore volume and average pore diameter were lower. Where the terms "comprise", "comprises", "comprised" or "comprising" are used in this specification, they are to be interpreted as specifying the presence of the stated features, integers, steps or components referred to, but not to preclude 15 the presence or addition of one or more other feature, integer, step, component or group thereof. Further, any prior art reference or statement provided in the specification is not to be taken as an admission that such art constitutes, or is to be understood as constituting, part of the common general knowledge in Australia. 20 43

Claims

1. A process for making a mesoporous oxide of titanium, zirconium or hafnium, the process comprising: precipitating an ionic porogen and a hydrous oxide of titanium, zirconium or 5 hafnium from a reaction mixture comprising a titanium, zirconium or hafnium starting material, a base and a solvent, wherein the titanium, zirconium or hafnium starting material or the solvent, or both, are a source of the anion for the ionic porogen and the base is the source of the cation for the ionic porogen; and removing the ionic porogen from the precipitate by calcining to recover (i) a 10 mesoporous oxide of titanium having a pore volume of at least 0.5 cc/g and an average pore diameter of at least 200A, (ii) a mesoporous oxide of zirconium having a pore volume of at least 0.25 cc/g and an average pore diameter of at least 1 ooA or (iii) a mesoporous oxide of hafnium having a pore volume of at least 0.1 cc/g and an average pore diameter of at least I00A, wherein the solvent is 15 ethanol, n-propanol, i-propanol, dimethyl acetamide, alcoholic ammonium halide and aqueous ammonium halide or combinations thereof, and wherein the ionic porogen is an ammonium halide.

2. The process of Claim 1, wherein the ionic porogen is ammonium chloride. 20

3. The process of Claim 1, wherein the ionic porogen is ammonium halide, tetramethyl ammonium halide or tetraethyl ammonium halide or combinations thereof.

4. The process of any one of Claims 1 to 3, wherein the mesoporous oxide is crystalline. 25

5. The process of any one of Claims 1 to 4, wherein the oxide of titanium, zirconium or hafnium further comprises a dopant.

6. The process of Claim 5, wherein the dopant is a transition metal, a Group IIA, lilA, IVA, or VA metal.

7. The process of Claim 5 or Claim 6, wherein the dopant is Ge, P, As, 30 Sb, Bi, Ni, Cu, Al, Zr, Hf, Si, Nb, Ta, Fe, Sn, Co, Zn, Mo, W, V, Cr, Mn, Mg, Ca, Sr, Ba, Ga, or In. 44

8. The process of any one of Claims 1 to 7, wherein the titanium, zirconium or hafnium starting material is titanium tetrachloride, titanium oxychloride, zirconium tetrachloride, zirconium oxychloride octahydrate, hafnium tetrachloride or hafnium oxychloride octahydrate. 5

9. The process of any one of Claims 1 to 8, wherein the base is ammonium hydroxide, ammonium carbonate, ammonium bicarbonate, tetramethyl ammonium hydroxide or tetraethyl ammonium hydroxide or combinations thereof.

10. The process of any one of Claims 1 to 9, wherein the halide in the alcoholic ammonium halide and/or aqueous ammonium halide is chloride, 10 bromide, iodide or combinations thereof.

11. The process of any one of Claims 1 to 10, wherein the reaction mixture is formed by the steps, in order, of combining the base and the solvent to form a solution or a mixture and adding the titanium, zirconium or hafnium starting material to the solution or mixture. 15

12. The process of any one of Claims 1 to 10, wherein the reaction mixture is formed by combining the titanium, zirconium or hafnium starting material and the solvent to form a solution or a mixture and adding the base to the solution or mixture.

13. The process of any one of Claims 1 to 12, wherein; 20 (i) more than 50 weight percent; (ii) more than 70 weight percent; or (iii) more than 90 weight percent, of the ionic porogen precipitates from the reaction mixture, the weight percent based on the total amount of the halide salt that can form from the reaction 25 mixture.

14. A process for making a mesoporous oxide of titanium, zirconium or hafnium, the process comprising; forming a mixture of a solid hydrolyzed starting material comprising titanium, zirconium or hafnium and a liquid medium; 30 adding a sufficient quantity of an ammonium halide to the mixture to saturate the liquid medium of the mixture; 45 recovering the solid from the saturated liquid medium, the solid comprising a hydrolyzed intermediate comprising titanium, zirconium or hafnium having pores containing the saturated liquid medium; and removing the saturated liquid medium from the solid by drying and calcining 5 to recover (i) a mesoporous oxide of titanium having a pore volume of at least 0.5 cc/g and an average pore diameter of at least 200A, (ii) a mesoporous oxide of zirconium having a pore volume of at least 0.25 cc/g and an average pore diameter of at least 1 oA or (iii) a mesoporous oxide of hafnium having a pore volume of at least 0.1 cc/g and an average pore diameter of at least 1ooA. 10

15. The process of Claim 14, wherein the liquid medium is the liquid portion of the mixture which comprises a solvent.

16. The process of Claim 14, wherein the liquid medium comprises a dissolved salt.

17. The process of Claim 15, wherein the solvent is ethanol, n-propanol, 15 i-propanol, dimethyl acetamide, alcoholic ammonium halide and aqueous ammonium halide or combinations thereof.

18. The process of any one of Claims 14 to 17, wherein the halide is chloride, bromide or iodide or combinations thereof.

19. The process of any one of Claims 14 to 18, wherein the ammonium 20 halide is ammonium halide, tetramethyl ammonium halide or tetraethyl ammonium halide or combinations thereof.

20. The process of any one of Claims 14 to 19, wherein the ammonium halide is ammonium chloride.

21. The process of any one of Claims 14 to 20, wherein the mesoporous 25 oxide is crystalline.

22. The process of any one of Claims 14 to 21, wherein the oxide of titanium, zirconium or hafnium further comprises a dopant.

23. The process of Claim 22, wherein the dopant is a transition metal, a Group IIA, lIlA, IVA, or VA metal. 46

24. The process of Claim 23, wherein the dopant is Ge, P, As, Sb, Bi, Ni, Cu, Al, Zr, Hf, Si, Nb, Ta, Fe, Sn, Co, Zn, Mo, W, V, Cr, Mn, Mg, Ca, Sr, Ba, Ga, or In.

25. The process of any one of Claims 14 to 24, wherein the hydrolyzed 5 starting material comprising titanium, zirconium or hafnium is derived from titanium tetrachloride, titanium oxychloride, zirconium tetrachloride, zirconium oxychloride octahydrate, hafnium tetrachloride or hafnium oxychloride octahydrate.

26. The process of any one of Claims 1 to 25, wherein the mesoporous oxide of titanium is TiO 2 having a surface area at least 70 m 2 /g, a pore volume 10 measured by nitrogen porosimetry of at least 0.5 cc/g, and an average pore diameter of least 200 A.

27. . The process of any one of Claims 1 to 25, wherein the mesoporous oxide of zirconium comprises ZrO 2 having a surface area at least 70 m 2 /g, a pore volume of at least 0.25 cc/g, and an average pore diameter of at least 100 A. 15

28. The process of any one of Claims 1 to 25, wherein the mesoporous oxide of hafnium comprises HfO 2 having a surface area at least 40 m 2 /g, a pore volume of at least 0.1 cc/g, and an average pore diameter of at least 100 A.

29. A mesoporous oxide of titanium, zirconium or hafnium obtained by the process of any one of Claims 1 to 28. 20

30. The use of the mesoporous oxide product of claim 29 as a catalyst or catalyst support, as a nanoparticle precursor, in an optical device or an electronic device, or in a photovoltaic cell.

31. The oxide of titanium of Claim 29, which is treated with silica, alumina, both silica and alumina, or an organic coating agent. 25

32. The use of the oxide of titanium of Claim 29, in a lithium battery anode, thermoplastic composition or a protective coating composition.

33. The oxide of titanium of Claim 31, in which the organic coating agent is a silane, a siloxane, or a polysiloxane. 47