WO2006058254A1 - Oxyde metallique mesoporeux - Google Patents

Oxyde metallique mesoporeux Download PDF

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Publication number
WO2006058254A1
WO2006058254A1 PCT/US2005/042817 US2005042817W WO2006058254A1 WO 2006058254 A1 WO2006058254 A1 WO 2006058254A1 US 2005042817 W US2005042817 W US 2005042817W WO 2006058254 A1 WO2006058254 A1 WO 2006058254A1
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Prior art keywords
titanium
oxide
zirconium
hafnium
mesoporous
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PCT/US2005/042817
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English (en)
Inventor
Carmine Torardi
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E.I. Dupont De Nemours And Company
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Priority claimed from US10/995,968 external-priority patent/US20060110316A1/en
Priority claimed from US11/170,878 external-priority patent/US7601326B2/en
Priority claimed from US11/171,055 external-priority patent/US20060110317A1/en
Priority claimed from US11/170,991 external-priority patent/US7601327B2/en
Priority claimed from US11/172,099 external-priority patent/US20060110318A1/en
Application filed by E.I. Dupont De Nemours And Company filed Critical E.I. Dupont De Nemours And Company
Priority to AU2005309411A priority Critical patent/AU2005309411B2/en
Priority to EP05852224A priority patent/EP1831106A4/fr
Publication of WO2006058254A1 publication Critical patent/WO2006058254A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G27/00—Compounds of hafnium
    • C01G27/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3669—Treatment with low-molecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3676—Treatment with macro-molecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3684—Treatment with organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter

Definitions

  • 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.
  • control of particle microstructure is an important commercial 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.
  • synthesis of small particle, high surface area inorganic oxides allows good particle 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 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.
  • 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 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. Several processes have been reported that use titanium tetrachloride, TiCU, 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.
  • a base such as NH 4 OH or NaOH
  • the salt byproducts such as NH 4 CI and NaCI.
  • 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 TiCI 4 and ammonum hydroxide followed by filtration and thorough washing of the precipitate to make a powder with a pore volume of 0.1 cc/g and pore size of 100 A.
  • lnoue et al. (British Ceramic Transactions 1998 VoI, 97 No. 5 p. 222 ) describe a procedure to make a washed amorphous TiO 2 gel by starting with TiCI 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 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.
  • the invention relates to a process for making a mesoporous oxide of titanium, zirconium or hafnium product, comprising: precipitating an ionic porogen and a hydrolyzed compound comprising titanium, zirconium or hafnium; and removing the ionic porogen from the precipitate to recover a mesoporous oxide of titanium, zirconium or hafnium, the ionic porogen being in sufficient amount to produce (i) a mesoporous titanium oxide product having a pore volume of at least about 0.5 cc/g and an average pore diameter of at least about 200A, (ii) a mesoporous zirconium oxide product having a pore volume of at least about 0.25 cc/g and an average pore diameter of at least about 100A or (iii) a mesoporous hafnium oxide product having a pore volume of at least about 0.1 cc/g and an average
  • the invention in another embodiment, relates to a process for producing a mesoporous oxide of titanium, zirconium or hafnium product, the process comprising: 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; and removing the ionic porogen from the precipitate to recover (i) a mesoporous titanium oxide product having a pore volume of at least about 0.5 cc/g and an average pore diameter of at least about 200A, (ii) a mesoporous zirconium oxide product having a pore volume of at least about 0.25 cc/g and an
  • 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; adding a sufficient quantity of a halide salt 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 removing the saturated liquid medium from the solid to recover (i) a mesoporous titanium oxide product having a pore volume of at least about 0.5 cc/g and an average pore diameter of at least about 200A, (ii) a mesoporous zirconium oxide product having a pore volume of at least about 0.25 cc/g and an average pore diameter of at least about 100A or (iii) a mesop
  • the composition of matter of this invention comprises a mesoporous titanium dioxide product having a microstructure characterized by a surface area of at least about 70 m 2 /g, a pore volume of least about 0.5 cc/g, and an average pore diameter of least about 200 A, a composition of matter comprising ZrO 2 having a microstructure characterized by a surface area at least about 70 m 2 /g, a pore volume of at least about 0.25 cc/g, and an average pore diameter of at least about 100 A and a composition of matter comprising HfO 2 having a microstructure characterized by a surface area at least about 40 m 2 /g, a pore volume of at least about 0.1 cc/g, and an average pore diameter of at least about 100 A.
  • the invention relates to a process for making a mesoporous amorphous hydrous oxide of titanium, comprising: precipitating an ionic porogen and a hydrolyzed compound comprising titanium; and removing the ionic porogen from the precipitate to recover a mesoporous hydrous oxide of titanium, the ionic porogen being in sufficient amount to produce a mesoporous hydrous oxide of titanium having a surface area of at least about 400 m 2 /g and a pore volume of at least about 0.4 cc/g.
  • the invention relates to a mesoporous amorphous hydrous oxide of titanium having a microstructure characterized by a surface area of at least about 400 m 2 /g and a pore volume of at least about 0.4 cc/g.
  • 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, specifically, lithium-battery anodes.
  • Figure 1 depicts a scanning electron microscope (SEM) image of calcined powder of Comparative Example A.
  • Figure 2 depicts the X-ray powder diffraction pattern of the a product of the process to make TiO 2 using TiCI 4 and NH 4 OH in aqueous saturated NH 4 CI as described in Example 1.
  • Figure 3 depicts a scanning electron micrograph of the product of 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.
  • 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.
  • 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.
  • mesoporous means structures having an average pore diameter from about 20 upto and including about 800 A (about 2 to about 80 nm).
  • the microstructure product of this invention can be a sponge-like network of Group IVB metal oxide particles.
  • the product of this invention comprises pores, the pores 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.
  • a porogen is a 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.
  • the porogen is ionic.
  • the porogen 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.
  • the base can function as the source of the cation for the ionic porogen.
  • 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.
  • the addition of the porogen to the mixture of hydrolyzed compound comprising Ti, Zr or Hf and liquid medium is done by any convenient method.
  • any method of adding one material to another can be used.
  • the ionic porogen can be a halide salt.
  • the halide salt is an ammonium halide which can optionally contain lower alkyl groups.
  • the 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 over 4 up to and including about 10 carbon atoms, or even higher, would not be detrimental in making an amorphous product.
  • 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 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 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 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. 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.
  • useful Group IVB metal starting materials include titanium tetrachloride, titanium oxychloride, zirconium tetrachloride, zirconium oxychloride, such as ZrOCb SH 2 O, hafnium tetrachloride or hafnium oxychloride, such as HfOCI 2 -8H 2 O.
  • 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. 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 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, without limitation thereto, NH 4 OH, (NH 4 J 2 CO 3 , NH 4 HCO 3 , (CH 3 ) 4 NOH,
  • a solvent can be used in the process of this invention.
  • a suitable solvent will depend upon the reaction 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 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 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 may also be suitable solvents.
  • suitable solvents include, without limitation thereto, aqueous acid solutions, for example, an acid halide solution.
  • acid halide solutions include, without limitation thereto, solutions of HCI, HBr or HF.
  • 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 material to the solution or mixture.
  • solvent will depend upon the reaction mechanism and the porosity desired.
  • organic solvents such as 50 wt% TiCI 4 in water and concentrated NH 4 OH
  • the resulting organic-water liquid portion of the reaction mixture will dissolve more of the porogen than would be dissolved in the organic solvent alone.
  • a solvent in which the metal starting material is soluble is typically used.
  • more than about 50 weight percent, specifically more than about 70 weight percent, even more specifically 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.
  • high porosity titanium dioxide can be obtained by using a high level of precipitated ammonium chloride, which 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.
  • solvents with low NH 4 CI solubility can yield T ⁇ O 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 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 solution.
  • solvent-specific factors can influence the pore volume of the metal oxide product; for example, different rates of precipitation of the 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 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.
  • 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.
  • titanium chloride as the neat liquid, or as an aqueous solution such as 50 wt.% TiCU in water based on the entire weight of the solution may be combined with the solvent.
  • ammonium hydroxide to precipitate the hydrolyzed compound containing titanium and the porogen, ammonium chloride.
  • the reaction mixture can also be 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.
  • a solvent is first combined with the base.
  • the solvent-base mixture is combined with the metal starting material to form a precipitate of the metal and the porogen.
  • NH 4 OH may be combined with the solvent to form the solvent-base mixture which is combined with titanium chloride or titanium oxychloride to precipitate the hydrolyzed compound containing titanium and the porogen, ammonium chloride.
  • the porogen is then removed to form the mesoporous metal oxide product of the invention. 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.
  • 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 from the solid to recover the mesoporous Group IVB metal oxide.
  • the liquid medium is the liquid portion of the mixture of solvent, with or without dissolved salt, and hydrous metal oxide.
  • a titanium starting material is combined with water to form a solution.
  • a base is added to form a mixture comprising precipitated hydrous metal oxide and liquid medium.
  • halide salt is added to saturate the liquid medium.
  • 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 remains after drying.
  • the starting materials 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 including settling, followed by decanting the supernatant liquid, filtration, centrifugation and so forth.
  • the recovered solid can be slurried with fresh water to 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 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 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.
  • 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 using the process of this invention.
  • the hydrolyzed metal compound and porogen can be calcined at a temperature that removes the porogen.
  • the calcination temperatures are at least the sublimation or decomposition temperature of the porogen.
  • the calcination temperatures will range from about 300 0 C to about 600 0 C, preferably between about 350 0 C and about 550 0 C, and more preferably between about 400 0 C and 500 0 C.
  • the 450°C-calcined product is composed of 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 45O 0 C, the average crystallite size can be from about 10-15 nm.
  • the calcined Ti ⁇ 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
  • 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.
  • Calcined Zr ⁇ 2 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.
  • the high surface is at least about 70 m 2 /g
  • high pore volume at least about 0.25 cc/g
  • large average pore diameter of at least about 100 A, preferably at least about 150 A.
  • the pore volume for Zr ⁇ 2 thus formed is between about 0.25 cc/g and about 0.5 cc/g
  • the average pore diameter is between about 100 A and 200 A.
  • Calcined Hf ⁇ 2 made by the process of the invention is also characterized by a combination of high pore volume and large average pore diameter.
  • 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.
  • 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.
  • 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 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.
  • the oxide of titanium, zirconium or hafnium further comprises a dopant which can be a transition metal, a Group HA 1 IMA, IVA, or VA metal.
  • the dopant can be 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.
  • Methods for incorporating dopants into the oxide would be apparent to those skilled in the art.
  • 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 or catalyst support.
  • the catalytic properties of " I ⁇ O 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 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.
  • product of this invention can be deagglomerated by combining the product with water and a suitable sufactant such as, without being limited thereto, tetrasodiumpyrophosphate followed by sonication to break-up the agglomerates.
  • a suitable sufactant such as, without being limited thereto, tetrasodiumpyrophosphate followed by sonication to break-up the agglomerates.
  • deagglomeration is by sonication or media milling.
  • the nanoparticle precursor of the invention can be deagglomerated to a 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 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 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 this invention can also have an organic coating which may be applied using techniques known by those skilled in the art.
  • organic coatings employed for pigment-sized titanium dioxide may be utilized.
  • organic coatings that are well known to those skilled in the art include fatty acids, such as stearic 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 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.
  • silicon-containing compounds are also of utility.
  • 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, tetradecyltriethoxysilane, pentadecyltriethoxysilane, hexadecyltriethoxysilane, heptadecyltriethoxysilane, octadecyltriethoxysilane, N-(2-aminoethyl) 3-aminopropylmethyl dimethoxysilane, N-(2-aminoethyl) 3-aminoprop
  • R is a nonhydrolyzable aliphatic, cycloaliphatic or aromatic group having at least 1 to about 20 carbon atoms;
  • R 1 is a hydrolyzable group such as an alkoxy, halogen, acetoxy or hydroxy or mixtures thereof;
  • silanes useful in carrying out the invention include hexylthmethoxysilane, octyltriethoxysilane, nonyltriethoxysilane, decylthethoxysilane, dodecyltriethoxysilane, tridecyltriethoxysilane, tetradecyltriethoxysilane, pentadecyltriethoxysilane, hexadecyltriethoxysilane, heptadecyltriethoxysilane and octadecyltriethoxysilane.
  • the weight content of the treating agent, based on total treated particles can range from about
  • 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 5,959,004 which are each incorporated by reference herein in their entireties.
  • Titanium dioxide product of this invention may be treated to have any one or more of the foregoing organic coatings.
  • 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 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 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.
  • coating formulations such as sunscreens, cosmetics, automotive coatings, wood coatings, and other surface coatings
  • chemical mechanical planarization products such as sunscreens, cosmetics, automotive coatings, wood coatings, and other surface coatings
  • the invention is directed to a coating 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 coating composition.
  • Titanium dioxide nanoparticles provide protection from the harmful ultraviolet rays of the sun (UV A and UV B radiation).
  • 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 incorporated into a sunscreen formulation.
  • 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.
  • the sunscreen formulations are usually an emulsion and the oil phase of the emulsion typically contains the UV active 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.
  • preservatives include parabens.
  • emollients include octyl palmitate, cetearyl alcohol, and dimethicone.
  • humectants include propylene glycol, glycerin, and butylene glycol.
  • Specific examples of thickeners include xanthan gum, magnesium aluminum silicate, cellulose gum, and hydrogenated castor oil.
  • chelating agents include disodium ethylene diaminetetraacetic acid (EDTA) and tetrasodium EDTA.
  • UV actives include ethylhexyl methoxycinnamate, octocrylene, and titanium dioxide.
  • emulsifiers include glyceryl stearate, polyethyleneglycol-100 stearate, and ceteareth-20.
  • suspending agents include diethanolamine-oleth-3- phosphate and neopentyl glycol dioctanoate.
  • waterproofers include C30-38 olefin/isopropyl maleate/MA copolymer.
  • film forming agents include hydroxyethyl cellulose and sodium carbomer. 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.
  • Organic UV absorbers are typically hydroxybenzophenones and hydroxyphenyl benzotriazoles.
  • a commercially available UV absorber is sold under the trade name TinuvinTM by Ciba. These organic materials, however, have a short life and decompose on exterior exposure. 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 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.
  • 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 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 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 the titanium dioxide nanoparticles as described herein above.
  • the foregoing thermoplastic composites are well known in the art.
  • 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 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 and chlorinated polyesters; polyethers; acetal resins; polyimides; and polyoxyethylenes.
  • olefins such as polyethylene, polypropylene, polybutylene, and copoly
  • 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 generally well known in the art.
  • the present invention is useful for any plastic or elastomeric compositions (which can also be pigmented with pigmentary Ti ⁇ 2 ).
  • the invention is felt to be particularly useful for polyolefins such as polyethylene and polypropylene, polyvinyl chloride, polyamides and polyester.
  • compositions of matter of this invention can be useful in optics.
  • the Ti ⁇ 2 product of this invention could be combined with polymethylmethacrylate polymer and made into an 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.
  • compositions of matter of this invention can be useful in electronics.
  • the oxide of titanium, hafnium, or zirconium can be used in an electronic device or in a photovoltaic cell.
  • the Ti ⁇ 2 product of this invention could be used in photovoltaic devices.
  • a TiO 2 product can be combined with a binder and cast 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.
  • " ⁇ O 2 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.
  • the electrochemical properties of titanium in a lithium battery are well known to those skilled in 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.
  • the invention herein can be construed as excluding any element or process step that does not materially affect the 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.
  • Nitrogen Porosimetrv Dinitrogen adsorption/desorption measurements were performed at 77.3 K on Micromeritics ASAP model 2400/2405 porosimeters (Micromeritics Inc., One Micromeritics Drive,
  • X-ray Powder Diffraction Room-temperature powder x-ray diffraction data were obtained with a Philips X'PERT automated powder 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- theta; a continuous scan with an equivalent step size of 0.03 deg; and a count time of 0.5 seconds per step.
  • Thermoqravimetric 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 purge rate was 100 ml/min). Samples were heated from RT to 800 0 C at 10°C/min. The temperature scale of the TGA was previously calibrated at the 10°C/min rate using thermomagnetic standards.
  • 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 CI salt had been removed.
  • Particle Size Distribution Particle Size Distribution was measured with a Malvern Nanosizer Dynamic Light Scattering Unit on suspensions containing 0.1 wt % TiO 2 .
  • the index of refraction of samples was measured with a Metricon Prism Coupler, Model 2010, with four 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 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. Photo Voltaic Power Efficiency: Photo voltaic power efficiency
  • PVPE photoelectrochemical polymer
  • This example illustrates that reaction Of TiCI 4 and NH 4 OH 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 invention.
  • the precipitate formed from the reaction Of TiCI 4 and NH 4 OH is washed extensively to remove any trapped NH 4 CI byproduct.
  • COMPARATIVE EXAMPLE B This example also illustrates that reaction Of TiCI 4 and NH 4 OH 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.
  • the precipitate formed from the reaction of TiCI 4 and NH 4 OH is collected and processed without the washing step used in Comparative Example A to remove NH 4 CI byproduct.
  • the unwashed solid was collected by suction filtration and dried under an IR heat lamp.
  • An X-ray powder diffraction pattern showed the 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 uncovered from room temperature to 45O 0 C over the period of one hour, and held at 45O 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 broad lines of anatase as the most intense and also showed one line of 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 This example illustrates that reaction of TiCI 4 and NH 4 OH 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.
  • 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 450 0 C 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.
  • 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 of 0.24 cc/g, and an average pore diameter of 129 A. The porosimetry data of this Example are reported in Table 6.
  • This example describes that reaction Of TiCI 4 and NH 4 OH in the three butanol isomers to form TiO 2 .
  • 20.0 g (14 mL) of 50% wt TiCI 4 in H 2 O 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.
  • the pH of the slurries was 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.
  • Nitrogen porosimetry revealed the following surface areas, pore volumes, and average pore diameters reported in Table 2:
  • reaction Of TiCI 4 and NH 4 OH in aqueous saturated NH 4 CI can produce a calcined mesoporous nanocrystalline TiO 2 powder having a high surface area and high porosity.
  • 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 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 0 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 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 Example are reported in Table 6.
  • This example illustrates that reaction Of TiCI 4 and NH 4 OH in absolute ethanol can produce a calcined mesoporous nanocrystalline TiO2 powder having a high surface area and high porosity.
  • 15 ml_ concentrated NH 4 OH were added to about 200 ml_ absolute ethanol while stirring with a Teflon coated magnetic stirring bar in a 400 ml_ Pyrex beaker.
  • 20.0 g (14 ml_) of 50% wt TiCI 4 in H 2 O were added to the basic solution.
  • 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 0 C for an additional hour.
  • the furnace with the boat and its 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 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.
  • This example illustrates that adding NH 4 OH to a solution Of TiCI 4 in n-propanol can produce a calcined mesoporous nanocrystalline TiO 2 powder having a high surface area and high porosity.
  • 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 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 45O 0 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. 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 Electron Microscopy image at 30,00Ox magnification, Figure 3 shows porous agglomerates of TiO 2 crystals. The porosimetry data of this Example are reported in Table 6.
  • This example illustrates that adding TiCI 4 to a solution of NH 4 OH in n-propanol can produce a calcined mesoporous nanocrystalline TiO 2 powder having a high surface area and high porosity.
  • the solid was collected by suction filtration and dried under an IR 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 material was recovered.
  • 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 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 template.
  • 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 (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.
  • Figures 5 and 6 are scanning electron microscopy images with magnifications of 25,00Ox and 50,00Ox, respectively, showing very porous agglomerates Of TiO 2 particles. The porosimetry data of this Example are reported in Table 6.
  • EXAMPLE 6 This example illustrates that reaction of neat TiCI 4 and NH 4 OH in n- propanol results in a calcined mesoporous nanocrystalline TiO 2 powder having a high surface area and high porosity.
  • a TGA of this mixture exhibited a total weight loss of 74% up to ⁇ 300 0 C indicating that most of the NH 4 CI had been precipitated along with the TiO 2 .
  • 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 45O 0 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 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 average pore diameter of 251 A. The porosimetry data of this Example are reported in Table 6.
  • This example illustrates that adding NH 4 OH to a solution Of TiCI 4 in isopropanol results in a calcined mesoporous nanocrystalline TiO 2 powder having a high surface area and high porosity.
  • This example illustrates that adding NH 4 OH to a solution of TiCU in N 1 N' dimethylacetamide (DMAC) resulted in a calcined mesoporous nanocrystalline TiO 2 powder having a high surface area and high porosity.
  • 20.0 g (14 mL) of 50% wt TiCI 4 in H 2 O were added to about 200 mL
  • N 1 N' dimethylacetamide (DMAC) while stirring with a Teflon coated magnetic stirring bar in a 400 mL Pyrex beaker. With stirring, 29 mL 1:1 NH 4 OH were added to the titanium solution. The resulting slurry was stirred for 60 minutes at ambient temperature.
  • DMAC dimethylacetamide
  • 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 0 C over the period of one hour, and held at 45O 0 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 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 This example illustrates that addition of NH 4 CI to the aqueous slurry formed by reaction of NH 4 OH with TiCI 4 results in a calcined mesoporous nanocrystalline TiO 2 powder having a high surface area and high porosity.
  • 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.
  • the powder was transferred to an alumina crucible and heated uncovered 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 crucible and its contents were removed from the furnace and cooled naturally to room temperature.
  • This example illustrates that adding NH 4 OH to a solution Of TiCI 4 in n-propanol resulted in a washed and dried, uncalcined, mesoporous, TiO 2 powder having a very high surface area and high porosity.
  • TiCI 4 12.5 g TiCI 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 stirred for 60 minutes at ambient temperature.
  • Example 10 The washed and dried powder in Example 10 was transferred to an alumina crucible and heated uncovered from room temperature to 45O 0 C over the period of one hour, and held at 450 0 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.
  • 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 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.
  • Micron size TiO 2 particles are deagglomerated by a factor of 100-500, e.g., particles having a d 50 ⁇ 50 ⁇ m are reduced in size to have d 50 ⁇ 0.100 ⁇ m (100 nm).
  • 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.
  • This example demonstrates the utility of the nanocrystalline, mesoporous titanium dioxide in a photovoltaic device.
  • Ti ⁇ 2 powder made as described in Example 3 was blended with a binder and cast into a film on an electrically-conducting fluorine-doped tin-oxide (FTO) coated glass substrate.
  • FTO fluorine-doped tin-oxide
  • 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, 2001.
  • a control experiment using Degussa P25 Ti ⁇ 2 was used for comparison.
  • the cell containing Ti ⁇ 2 of this invention exhibited a higher power conversion efficiency, relative to that of the control cell.
  • the results are reported in Table 4.
  • 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 0 C over the period of one hour, and held at 45O 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 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 reported in Table 6.
  • ZrOCI 2 -8H 2 O illustrates the synthesis of calcined product via addition of NH 4 CI after forming the ZrO 2 precipitate.
  • 11.O g ZrOCI 2 -8H 2 O were dissolved in 100 mL deionized H2O at room temperature while stirring with a Teflon coated magnetic stirring bar in a 250 mL Pyrex beaker. With stirring, 10 mL concentrated NH 4 OH 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. 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, and held at 45O 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 tetragonal form of ZrO 2 with 7 nm crystals.
  • Nitrogen porosimetry 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.
  • 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 0 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 it to be amorphous.
  • Nitrogen porosimetry revealed a surface area of 62.5 m 2 /g, a pore volume of 0.05 cc/g, and an average pore diameter of 29 A. The porosimetry data of this Example are reported in Table 6.
  • 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 0 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 only the monoclinic form of Hf ⁇ 2 with crystallites approximately 8-11 nm in 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.
  • HfOCI 2 -8H 2 O illustrates the synthesis of calcined product via addition of NH 4 CI after forming the HfO 2 precipitate.
  • 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 45O 0 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 8-10 nm in size.
  • Nitrogen porosimetry revealed a surface area of 53.2 m 2 /g, a pore volume of 0.17 cc/g, and an average pore diameter of 130 A.

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Abstract

La présente invention a trait à des oxydes métalliques mésoporeux et des procédés de fabrication d'oxydes métalliques mésoporeux. Des oxydes métalliques et des oxydes dérivés qui peuvent être préparés sont les oxydes de Ti, Zr, et Hf. Les produits d'oxydes métalliques peuvent être cristallins ou amorphes. Les utilisations finales des oxydes métalliques de l'invention comprennent de manière non limitative, des matières plastiques, des revêtements, des éléments optiques, des éléments électroniques, des éléments photovoltaïques, des catalyseurs, des supports de catalyseur, des précurseurs de nanoparticules, et des composants d'anodes de batterie au lithium.
PCT/US2005/042817 2004-11-23 2005-11-23 Oxyde metallique mesoporeux WO2006058254A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2005309411A AU2005309411B2 (en) 2004-11-23 2005-11-23 Mesoporous metal oxide
EP05852224A EP1831106A4 (fr) 2004-11-23 2005-11-23 Oxyde metallique mesoporeux

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
US10/995,968 US20060110316A1 (en) 2004-11-23 2004-11-23 Mesoporous metal oxide
US10/995,968 2004-11-23
US11/170,991 2005-06-30
US11/170,878 US7601326B2 (en) 2004-11-23 2005-06-30 Mesoporous oxide of zirconium
US11/171,055 US20060110317A1 (en) 2004-11-23 2005-06-30 Mesoporous amorphous oxide of titanium
US11/172,099 2005-06-30
US11/170,991 US7601327B2 (en) 2004-11-23 2005-06-30 Mesoporous oxide of hafnium
US11/170,878 2005-06-30
US11/172,099 US20060110318A1 (en) 2004-11-23 2005-06-30 Mesoporous oxide of titanium
US11/171,055 2005-06-30

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EP1990315A1 (fr) 2007-05-08 2008-11-12 E.I. Du Pont De Nemours And Company Procédé de fabrication de particules de dioxyde de titane
WO2009061707A1 (fr) * 2007-11-05 2009-05-14 E. I. Du Pont De Nemours And Company Dioxyde de titane anatase stable à température élevée
WO2009085908A1 (fr) * 2007-12-20 2009-07-09 E. I. Du Pont De Nemours And Company Dioxyde de titane luminescent dopé au samarium
WO2010106146A1 (fr) 2009-03-20 2010-09-23 Basf Se Procédé de production de matériaux en dioxyde de titane à surfaces de contact et stabilité thermique élevées
CN101294928B (zh) * 2008-06-13 2011-09-07 北京化工大学 MoO3-SnO2基掺杂的纳米复合金属氧化物及其制备方法

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US5532057A (en) * 1990-09-26 1996-07-02 The United States Of America As Represented By The Secretary Of The Navy India-stabilized ziroconia coating for composites
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1990315A1 (fr) 2007-05-08 2008-11-12 E.I. Du Pont De Nemours And Company Procédé de fabrication de particules de dioxyde de titane
US7858066B2 (en) 2007-05-08 2010-12-28 E.I. Du Pont De Nemours And Company Method of making titanium dioxide particles
WO2009061707A1 (fr) * 2007-11-05 2009-05-14 E. I. Du Pont De Nemours And Company Dioxyde de titane anatase stable à température élevée
WO2009085908A1 (fr) * 2007-12-20 2009-07-09 E. I. Du Pont De Nemours And Company Dioxyde de titane luminescent dopé au samarium
CN101294928B (zh) * 2008-06-13 2011-09-07 北京化工大学 MoO3-SnO2基掺杂的纳米复合金属氧化物及其制备方法
WO2010106146A1 (fr) 2009-03-20 2010-09-23 Basf Se Procédé de production de matériaux en dioxyde de titane à surfaces de contact et stabilité thermique élevées

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