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WO2013076321A1 - Procédé d'obtention de particules de dioxyde de titane en phase anatase - Google Patents

Procédé d'obtention de particules de dioxyde de titane en phase anatase Download PDF

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Publication number
WO2013076321A1
WO2013076321A1 PCT/ES2011/070814 ES2011070814W WO2013076321A1 WO 2013076321 A1 WO2013076321 A1 WO 2013076321A1 ES 2011070814 W ES2011070814 W ES 2011070814W WO 2013076321 A1 WO2013076321 A1 WO 2013076321A1
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WIPO (PCT)
Prior art keywords
procedure according
alcohol
racterizado
titanium
hours
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/ES2011/070814
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English (en)
Spanish (es)
Inventor
Daniel FERNANDEZ HEVIA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Inael Electrical Systems SA
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Inael Electrical Systems SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Inael Electrical Systems SA filed Critical Inael Electrical Systems SA
Priority to PCT/ES2011/070814 priority Critical patent/WO2013076321A1/fr
Publication of WO2013076321A1 publication Critical patent/WO2013076321A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • 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
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Definitions

  • the present invention belongs to the field of synthesis of titanium dioxide particles with controlled morpho logy ⁇ to promote exposure of ultra reactive faces or to obtain microspheres self assembled bladas high crystallinity.
  • Said invention relates to a sustainable method of synthesizing particles of titanium dioxide in anatase phase.
  • the procedure is carried out by non-hydrothermal route, at atmospheric pressure and low temperatures (below 100 ° C), and allows its industrial implementation quickly, efficiently, and safely, through moderate economic investments, using raw materials abundant, economical, and environmentally acceptable, and exploiting natural and energy resources in an efficient, controlled and sustainable manner.
  • the invention also relates to the particles obtained by the method of the invention and the use thereof in the generation of hydrogen from water.
  • Titanium dioxide is a common constituent of minerals found in igneous rocks such as iron-titanium oxide, perovskites, and replacing the iron in some species of silicates such as pyroxene and divi ⁇ us.
  • rutile tetragonal
  • anatase tetragonal centered on the faces
  • brookite orthorhombic
  • A-TIO 2 crystals have existed, so far, in the form of octahedral bipyramids with the vast majority of their surface formed by thermodynamically favorable crystalline faces (faces ⁇ 101 ⁇ ), which, in turn, are the more inert and less reactive and, therefore, less interesting from the point of view of any of the aforementioned applications.
  • sol-gel method is described to prepare dioxide environment titanium anatase temperature from a titanium precursor and a solvent consisting of water, alcohol and an acid or base catalyst .
  • precipitates derived from sol-gel method are usually amorphous in nature and require a subsequent heat treatment for crystallization indu ⁇ cir thereof.
  • the method does not seek morphological control aimed at the exposure of ultra-reactive surfaces, or the obtaining of self-assembled microspheres, therefore being radically different from the invention claimed herein.
  • the hydro ⁇ thermal treatment makes it difficult to control the morphology of the particles, since the titanium cations that participate Breads in the reaction are susceptible to nucleophilic attack by water, resulting in too rapid hydrolysis and causing the particles to grow uncontrollably.
  • the method does not seek a specific morphological control ⁇ cally aimed at exposing ultrareactivas surfaces, nor obtaining self - assembled microspheres high crystallinity is achieved, and is therefore radically different from the invention claimed in the present document.
  • the inventors have found a process pa ⁇ ra preparing particles of titanium dioxide with morpho ⁇ controlled logy, leading either to obtaining nanoparticles with increased exposure ultrareac faces ⁇ tions (001), or to obtain of self-assembled microspheres from agglomerates of nanoparticles.
  • the process is non-hydrothermal, and comprises a solution of a titanium precursor at atmospheric pressure and at temperatures below 110 ° C thus avoiding extreme reaction conditions and the need to use high-cost sealed and pressurized reactors and high energy consumption.
  • the first aspect of the invention relates to a process for synthesizing titanium dioxide particles in the anatase phase, in unsealed or pressurized containers, which comprises the steps of:
  • a second aspect of the invention relates to nanoparticles obtained by the method des ⁇ Crito above, where step a) is performed in the presence of a surfactant and in a temperature range which is between 70 ° C and 90 ° C and which also includes the stages of:
  • step d disposal of organic remains; e) ⁇ tion of an aqueous suspension of the nanoparticles obtained in step d); f) preparation of a solution of hexachloroplatinic acid IV, H 2 PtCl 6 in distilled water with a metal filler content between 0.5% and 0.95% by weight; g) mixing of the suspension aqueous of step e) with the platinum solution of step f) and with a C2-C4 alcohol; h) illumination of the mixture of step g) with a lamp in the region below 410 nm in the presence of a nitrogen purge; i) centrifugation and j) drying.
  • a third aspect of the invention relates to the use of nanoparticles as described above ⁇ mers catalyzes the synthesis of hydrogen from water.
  • the use of the particles makes hydrogen synthesis more efficient than with the use of other known catalysts, with higher yields in a wide range of pH conditions, reagent concentration and irradiation.
  • the synthesis of hydrogen in the presence of the particles of the invention is cheaper and less polluting than the already known processes of hydrogen synthesis from water.
  • Example 1 shows an electronic microscopy by scanning field emission (MECEB) of the departed ⁇ particles obtained in Example 1 of the present inven ⁇ .
  • MECEB scanning field emission
  • Figure 2 shows an X-ray diffractogram of titanium dioxide synthesized at I) 60 ° C, for 4 hours; II) at 76 ° C for 4 hours and III) at 76 ° C for 4 hours plus calcination at 300 ° C for 2 hours.
  • 3 shows an electronic microscopy by scanning field emission (MECEB) of the particles obtained ⁇ departed 76 ° C for 4 hours calcination at 300 ° C for 2 hours.
  • MECEB scanning field emission
  • FIG. 4 shows a MECEB of the titanium dioxide particles obtained in example 2 of the invention.
  • titanium precursor refers to an organic titanium molecule that participates in the reaction to generate another titanium molecule.
  • titanium precursors are titanium halides such as titanium tetrachloride, titanium alkoxide such as titanium butoxide and tetradimethyl amino titanium.
  • titanium precursor is titanium butoxide.
  • C2-C4 alcohol refers to straight chain alcohols or branched ⁇ gives having from 2 to 4 carbon atoms. Examples of these alcohols include, but are not limited to, ethanol, butanol or isopropanol. Preferably the alcohols are ethanol and butanol.
  • surfactant refers to both anionic surfactants such as fatty acid salts of 5 to 30 carbon atoms, for example sodium lauryl sulfate and other fatty acid sulfate salts, oleic acid and cationic surfactants such as alkylamines of 8 to 22 carbon atoms, for example oleylamine and mixtures thereof.
  • Preferably it is a mixture of oleic acid and oleila ⁇ mine.
  • nanoparticle refers to particles with at least one of the dimensions of a size smaller than 10 m.
  • the first aspect of the invention relates to a method of synthesizing particles of titanium dioxide in anatase phase, in unsealed or pressurized containers which comprise ⁇ of the steps of:
  • reaction time is between 6 hours and 10 hours.
  • microspheres of size greater than 1 ⁇ in diameter are obtained, approximately between 2 ⁇ and 4 ⁇ in diameter.
  • the spheres are very homogeneous.
  • the crystallinity of the particles obtained by the process according to the first aspect of the invention can be improved by removing the remains cos ⁇ Organi. Therefore, in a embodiment of the first aspect of the invention, the process further comprises a step of eliminating the organic residues.
  • the removal of organic residues is carried out by a calcination step at a temperature between 300 ° C and 400 ° C for a time between 2 hours and 4 hours.
  • waste disposal is done by sonication.
  • irradiation of ultraviolet rays is carried out by irradiation of ultraviolet rays.
  • step a) if step a) is carried out in the presence of a surfactant, and in a temperature range between 70 ° C and 90 ° C, nanoparticles of carbon dioxide are obtained. truncated anatase titanium phase at its ends.
  • a surfactant in the presence of a surfactant, and in a temperature range between 70 ° C and 90 ° C, nanoparticles of carbon dioxide are obtained. truncated anatase titanium phase at its ends.
  • surfactants has been designed so that they are economical, naturally abundant, simple to process, and environmentally benign.
  • Anatase phase titanium dioxide nanoparticles exhibit high exposure of reactive faces ⁇ 001 ⁇ . These faces were considered far as unstable and impossible to synthesize in significant quantities, although its nature ultra-reactive to highly desirable, both from a scientific point of view, as a technology for numerous applica ⁇ tions.
  • microspheres may include a step of removing organic waste.
  • the titanium precursor is titanium butoxide
  • the surfactant is a solution of oleic acid and oleylamine in absolute or pure ethanol with a stoichiometry l: x: y where 4 ⁇ x ⁇ 7 and 3 ⁇ y ⁇ 6, where x refers to oleic acid and oleylamine.
  • step a) is performed in concentric vessels covered airtight ⁇ where precur is ⁇ sor titanium into the inner chamber, the surfactant and alcohol C 2 -C 4 , and in the outer vessel is a C 2 -C 4 alcohol with a purity between 90% and 98%.
  • the outer cup alcohol diffuses very lentamen ⁇ dishing mix inner vessel so that the reaction control and the morphology of the synthesized nanoparticles is allowed.
  • the variables with which the morphology of the particles can also be controlled are the temperature of the C 2 -C 4 alcohol and the titanium precursor.
  • reaction temperature is between 70 ° C-81 ° C.
  • the temperature is between 70 ° C and 85 ° C and alcohol is ethanol.
  • the temperature is between 85 ° C and 90 ° C and the alcohol is butanol.
  • the nanoparticles of the invention can be cu ⁇ O pen platinum so that they can be used as catalysts in the process of producing hydrogen from water.
  • step a) is carried out in the presence of surfactants and includes a step of removing organic residues and further comprising the steps of: d) forming a aqueous suspension of the particles obtained in the organic waste removal stage;
  • step f) mixing the aqueous suspension of step d) with the platinum solution of step e) and with a C 2 -C 4 alcohol;
  • Crystallinity can be improved by
  • the nanoparticles obtained in example 2 were platinized.
  • Hexachloroplatinic acid solution different (IV) H 2 PtCl 6
  • the solution is mixed with an aqueous suspension of the nanoparticles of example 2 of the present invention.
  • the concentration of nanoparticles must be in the range of l-2g Ti0 2/1.
  • Isopropanol was added as a sacrificial agent with donor functions, with a final concentration in the range 0.2-0.4M.
  • Photodeposition was carried out by lighting between 4h and 8h with a mercury lamp (300-500W) and a photon flow 2-3 ⁇ 10 ⁇ 7 Einstein s _1 L _1 in the region below 410 nm. A constant nitrogen purge is maintained throughout the process and, finally, mind, the product is recovered by centrifugation and dried at 283K for 8-12h.
  • the reaction was carried out by illuminating with controlled UV radiation a liquid mixture containing, 2g of the platinized nanoparticles synthesized per liter of emulsion, 25% sacrificial agent, in this example methanol.
  • the pH was maintained between 4.5 to 7.5.
  • the first injection was made to the gas chromatograph by means of a gas valve. Chromatograms were taken every 30 minutes. The experiment is maintained for 8 hours.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

Procédé de synthèse de particules de dioxyde de titane en phase anatase, dont la morphologie est contrôlée en vue de favoriser l'exposition de facettes ultraréactives et/ou d'obtenir des microsphères auto-assemblées à cristallinité élevée, par voie non hydrothermale, à pression atmosphérique et à basse température (<100°C), dans des récipients non étanches ni sous pression. Ce procédé est réalisé à des températures modérées, inférieures à 100°C, à des pressions atmosphériques, se prête à une implantation industrielle rapide, efficace et sûre, par le biais d'investissements modérés, et comprend l'utilisation de ressources naturelles et énergétiques limitées, économiques et ménageant l'environnement.
PCT/ES2011/070814 2011-11-24 2011-11-24 Procédé d'obtention de particules de dioxyde de titane en phase anatase Ceased WO2013076321A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/ES2011/070814 WO2013076321A1 (fr) 2011-11-24 2011-11-24 Procédé d'obtention de particules de dioxyde de titane en phase anatase

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/ES2011/070814 WO2013076321A1 (fr) 2011-11-24 2011-11-24 Procédé d'obtention de particules de dioxyde de titane en phase anatase

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WO2013076321A1 true WO2013076321A1 (fr) 2013-05-30

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050013766A1 (en) * 1999-02-04 2005-01-20 Kawasaki Jukogyo Kabushiki Kaisha Processes for producing anatase titanium oxide and titanium oxide coating material
WO2008005055A2 (fr) * 2005-12-29 2008-01-10 The Board Of Trustees Of The University Of Illinois Nanoparticules contenant de l'oxyde de titane

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050013766A1 (en) * 1999-02-04 2005-01-20 Kawasaki Jukogyo Kabushiki Kaisha Processes for producing anatase titanium oxide and titanium oxide coating material
WO2008005055A2 (fr) * 2005-12-29 2008-01-10 The Board Of Trustees Of The University Of Illinois Nanoparticules contenant de l'oxyde de titane

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PAYAKGUL W. ET AL.: "Effects of reaction medium on the synthesis of TiO2 nanocrystals by thermal decomposition of titanium (IV) n-butoxide", CERAMICS INTERNATIONAL, vol. 31, 2005, pages 391 - 397, XP027796148 *
VERMA A. ET AL.: "Thermal treatment effect on nanostructured TiO2 films deposited using diethanolamine stabilized precursor sol", ELECTROCHIMICA ACTA, vol. 52, 2007, pages 2701 - 2709, XP005856541 *

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