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WO2004089543A1 - Procede de production d'un film d'oxyde metallique semi-conducteur - Google Patents

Procede de production d'un film d'oxyde metallique semi-conducteur Download PDF

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Publication number
WO2004089543A1
WO2004089543A1 PCT/EP2003/003333 EP0303333W WO2004089543A1 WO 2004089543 A1 WO2004089543 A1 WO 2004089543A1 EP 0303333 W EP0303333 W EP 0303333W WO 2004089543 A1 WO2004089543 A1 WO 2004089543A1
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WO
WIPO (PCT)
Prior art keywords
process according
titanium
acid
metal oxide
film
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/EP2003/003333
Other languages
English (en)
Inventor
Luca Martinotto
Andrea Pelizzoni
Xicola Agustin Sin
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.)
Pirelli and C SpA
Original Assignee
Pirelli and C SpA
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 Pirelli and C SpA filed Critical Pirelli and C SpA
Priority to PCT/EP2003/003333 priority Critical patent/WO2004089543A1/fr
Priority to PCT/EP2004/003220 priority patent/WO2004087318A1/fr
Priority to EP04723585A priority patent/EP1608463A1/fr
Priority to US10/551,172 priority patent/US7459320B2/en
Publication of WO2004089543A1 publication Critical patent/WO2004089543A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0219—Coating the coating containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis

Definitions

  • the present invention relates to a method for producing films com- prising semiconductive metal oxide.
  • Semiconductive metal oxide such as oxides of titanium, zirconium, hafnium, strontium, zinc, indium, yttrium, lanthanum, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, show a crystalline phase exhibiting photocatalytic functionality, and can be use in a variety of appli- cations.
  • Titania TiO 2
  • has several crystalline phases such as anatase, rutiie and brookite. Among these crystalline phases, the anatase one exhibits higher photocatalytic properties and photovoltaic effect and thus has attracted much attention in these fields.
  • Nanosized anatase titania film have been studied for applications such as solar cells, photocatalysts, antibacterial coating, electrochromic display, anti-reflecting coating and gas sensors.
  • Thin films based on nanoparticles of anatase titania show high photocatalytic activity depending on phase, crystal dimension and surface area, and porosity.
  • the sol-gel method is one of the most promising techniques to prepare thin films because it has a number of advantages such as low-temperature processing and the ability to prepare materials in various shapes, compared with the conventional preparation procedures of glass and ceramics.
  • as-prepared films by the sol-gel method are usually amorphous, and a high temperature process over 300°C is required to form anatase nanocrystals. Therefore, it is difficult to form anatase nanocrystals on the substrates with poor heat resistance such as organic polymers.
  • EP-A-0 859 385 discloses a method for manufacturing photovoltaic cells comprising polycrystalline oxides exhibiting semiconductor functionality.
  • Particles of the polycrystalline metal oxide can be prepared by hydrolysis of the corresponding metal alk- oxide followed by optional physical treatments such as growth and particle size control through digestion under hydrothermal conditions at temperatures in the range of from 150 to 250°C, followed by high temperature (200- 500°C) sintering and grinding of the resulting sintered product to the re- quired particle size. Said particles are then dye coated and suspended to yield a ink suspension, optionally containing additives, e.g.
  • dispersants which can enhance the even distribution of the ink particles on the substrate where the ink suspension is deposited to yield a uniform layer.
  • the so deposited layer is treated under mild and non-destructive conditions in- eluding temperatures below 180-150°C, possibly combined with non-destructive pressure e.g. below 20 bars, and/or evaporation under sub-atmospheric pressures. No specific examples are provided.
  • EP-A-1 167 296 (in the name of Kawasaki Jukogyo Kabushiki Kai- sha) relates to a process for producing anatase titanium oxide having photocatalytic activity and large specific surface area.
  • Anatase particles are prepared by a sol-gel method starting, for example, from a metal oxide or alkoxide heat treated in a closed vessel in the temperature range of 80 to 250°C. The examples show that a temperature of about 240°C is necessary to obtain the anatase phase while operating at atmospheric pressure.
  • EP-A-1 182 169 (in the name of Japan Science and Technology Corporation) relates to a process for producing anatase titania or composite oxide containing anatase titania wherein a gel containing a metal oxide is formed from a solution containing a hydrolysable titanium compound and an organic polymer (e.g. polyethylene glycol), and subsequently the gel is allowed to react with water at a temperature of 100°C or below.
  • a gel containing a metal oxide is formed from a solution containing a hydrolysable titanium compound and an organic polymer (e.g. polyethylene glycol), and subsequently the gel is allowed to react with water at a temperature of 100°C or below.
  • Applicant faced the problem of obtaining a process for preparing as film comprising a semiconductive metal oxide with a major amount of photocatalytic crystalline phase, said phase being nanosized and with a controlled porosity, by operating under non-destructive conditions so that said film can be deposited on a variety of substrates.
  • Such a goal is attained by preparing a semiconductive metal oxide with a major amount of nanosized photocatalytic crystalline phase, depositing a film thereof in the presence of a hydrosoluble organic polymer and a hydrolysable organic derivative of said metal, under non-destructive conditions.
  • the present invention relates to a process for preparing a film comprising a semiconductive metal oxide with a major amount of nanosized photocatalytic crystalline phase, said process comprising the steps of a) obtaining a semiconductive metal oxide with a major amount of photocatalytic crystalline phase; b) forming a suspension of semiconductive metal oxide in an aqueous solution containing at least a hydrosoluble organic polymer and a hydrolysable organic derivative of said metal; c) depositing the resulting suspension on a substrate to give a film; d) treating said film at a temperature ranging between about 30°C and about 100°C in water.
  • semiconductive metal oxides are oxides of titanium, zir- conium, hafnium, strontium, zinc, indium, yttrium, lanthanum, vanadium, niobium, tantalum, chromium, molybdenum, tungsten.
  • Preferred semicon- ductive metal oxide is titanium oxide (hereinafter referred to as "titania") with a major amount of anatase phase.
  • films provided with the method according to the invention comprises nanosized photocatalytic crystalline phase in a per- centage higher than 70% by weight, more preferably higher than 90% by weight, even more preferably, higher than 95% by weight.
  • Step a) of the present method may be carried out according to known technique.
  • the anatase phase may be obtained by treating a hydrolysable precursor with an anhydrous al- cohol, for example absolute ethanol, isopropanol or isobutanol, and water, and heating the resulting slurry at temperature ranging between about 300°C and about 700°.
  • anhydrous al- cohol for example absolute ethanol, isopropanol or isobutanol
  • a hydrolysable precursor can be selected from alkoxides, chlorides and bromides.
  • titania examples are tetra-isopropoxy tita- nium, tetra-n-butoxy titanium, tetrakis(2-ethylhexyloxy)titanium, tetrastearyl- oxy titanium, and titanium tetrachloride.
  • Hydrosoluble organic polymer useful in the present invention can be polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, polytetrame- thylene glycol, cellulose acetate, cellulose nitrate, hydroxypropylcellulose, polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride.
  • the hydrosoluble organic polymer is polyethylene glycol.
  • Preferred polyethylene glycol according to the invention has molecular weight ranging between 600 and 300,000, preferably between 3,000 and 10,000.
  • a hydrosoluble organic polymer according to the invention contains hydroxy groups
  • the percentage by weight of monomeric units bearing such groups is preferably lower than about 90%, more preferably lower than about 80%.
  • the hydrolysable organic derivative of said metal may be an ester derivative optionally containing one or more group/s selected from hydroxy, alkoxy, carbonyl and carboxy.
  • titanium it can be selected from titanium diisopropoxide bisacetyl acetonate, titanium dibutoxide bis2,4- pentanedionate, titanium lactate, titanium methacrylate triisopropoxide, titanium methacryloxyethylacetoacetate triisopropoxide, titanium oxide bispentanedionate, titanium oxide bistetramethylheptanedionate, titanium diisopropoxide bisethylacetoacetate, titanium diisopropoxide bistetramethylheptanedionate, titanium allylacetoacetatetriisopropoxide.
  • the hydrolysable organic titanium derivative is titanium diisopropoxide bisacetyl acetonate (hereinafter referred to as TiACAC).
  • the aqueous solution of step b) preferably comprises a stabilizer.
  • the stabilizer can be an organic acid such as acetic acid, citric acid, propionic acid, butyrric acid, butylacetic acid, vinylacetic acid, ossalic acid, succinic acid, maleic acid, adipic acid, stearic acid, lactic acid.
  • the stabilizer is acetic acid.
  • said aqueous solution shows a molar amount of stabilizer more than double with respect the hydrolysable organic derivative. More preferably the molar ratio hydrolysable organic derivative/stabilizer is of from about 1 :4 to about 1 :10.
  • the aqueous solution of step b) may be prepared from a first solution of hydrosoluble organic polymer and a second solution of a hydrolysable organic derivative of said metal.
  • said second solution has a molar ratio hydrolysable organic derivative/water of from about 1 :1 to about 1 : 100. More preferably, said ratio is of from about 1 :2 to about 1 :20.
  • step d) of the invention is performed at a temperature ranging between about 80°C and about 100°C.
  • the time of the treatment of step d) can range between about 2 hours and about 5 hours.
  • said step d) is preceded by a drying step. Said drying step can be per- formed at a temperature of about 70°C-90°C.
  • the process of the present invention yields films comprising a semi- conductive metal oxide with a major amount of nanosized photocatalytic crystalline phase, with porosity and thickness suitable for photocatalytic application on various kind of substrates. Due to the low temperature em- ployed the film can be deposited on substrates with low thermal resistance, such as those based on organic polymers, too. Examples of substrates with low thermal resistance are polyethyleneterephthalate (PET), polyethylene (PE) and polyvinylchloride (PVC).
  • PET polyethyleneterephthalate
  • PE polyethylene
  • PVC polyvinylchloride
  • hydrolysable organic derivative improves interconnections among the nanoparticles and enhance the electron percolation within the film.
  • said nanosized photocatalytic crystalline phase has a particle size ranging between about 1 and about 20 nm, preferably ranging between about 5 and about 10 nm.
  • the film provided by the method pf the invention shows a porosity of about 40-80%, preferably about 50-60%.
  • Titanium isopropoxide (8 ml, 97%, Aldrich) was added under stirring to absolute ethanol (92 ml, Carlo Erba Reagenti). The solution was drop- wise added, under vigorous stirring to a solution ethanol/distilled water (250 ml, 1 :1 by weight). The resulting colloidal suspension was kept under stir- ring for 10 minutes.
  • FWHM is the full width at half maximum of an individual peak , and q is the peak position.
  • the obtained powder (1.5 g) was admixed to a solution A (3.5 g) composed by solution B (1.4 g) and solution C (2.1 g), solutions B and C having the following composition:
  • Example 2 A film was prepared according to what taught in EP 1 182 169, example 2.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de préparation d'un film d'oxyde métallique semi-conducteur renfermant une proportion prépondérante d'une phase cristalline photocatalytique, d'ordre nanométrique, en la déposant en présence d'un polymère organique hydrosoluble et d'un dérivé organique hydrolysable dudit métal, dans des conditions non destructives.
PCT/EP2003/003333 2003-03-31 2003-03-31 Procede de production d'un film d'oxyde metallique semi-conducteur Ceased WO2004089543A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
PCT/EP2003/003333 WO2004089543A1 (fr) 2003-03-31 2003-03-31 Procede de production d'un film d'oxyde metallique semi-conducteur
PCT/EP2004/003220 WO2004087318A1 (fr) 2003-03-31 2004-03-26 Procede pour la production d'un dispositif photovoltaique
EP04723585A EP1608463A1 (fr) 2003-03-31 2004-03-26 Procede pour la production d'un dispositif photovoltaique
US10/551,172 US7459320B2 (en) 2003-03-31 2004-03-26 Method for producing a photovoltaic device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2003/003333 WO2004089543A1 (fr) 2003-03-31 2003-03-31 Procede de production d'un film d'oxyde metallique semi-conducteur

Publications (1)

Publication Number Publication Date
WO2004089543A1 true WO2004089543A1 (fr) 2004-10-21

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PCT/EP2003/003333 Ceased WO2004089543A1 (fr) 2003-03-31 2003-03-31 Procede de production d'un film d'oxyde metallique semi-conducteur
PCT/EP2004/003220 Ceased WO2004087318A1 (fr) 2003-03-31 2004-03-26 Procede pour la production d'un dispositif photovoltaique

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PCT/EP2004/003220 Ceased WO2004087318A1 (fr) 2003-03-31 2004-03-26 Procede pour la production d'un dispositif photovoltaique

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8106101B2 (en) * 2004-11-16 2012-01-31 The Hong Kong Polytechnic University Method for making single-phase anatase titanium oxide
JP5757736B2 (ja) * 2007-08-22 2015-07-29 クワンジュ インスティチュート オブ サイエンス アンド テクノロジー 湿式工程の可能な金属酸化物溶液、これの製造方法、及びこれを用いる有機太陽電池

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001104797A (ja) * 1999-09-20 2001-04-17 Lg Electronics Inc ナノサイズのアナターゼ型の二酸化チタン光触媒の製造方法並びに前記方法で製造された光触媒
EP1167296A1 (fr) * 1999-02-04 2002-01-02 Kawasaki Jukogyo Kabushiki Kaisha Procede de production d'oxyde de titane du type anatase et d'un materiau de revetement a base de dioxyde de titane
EP1182169A1 (fr) * 1999-02-04 2002-02-27 Japan Science and Technology Corporation Procede d'obtention de titane d'anatase ou d'oxyde composite contenant du titane d'anatase

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1167296A1 (fr) * 1999-02-04 2002-01-02 Kawasaki Jukogyo Kabushiki Kaisha Procede de production d'oxyde de titane du type anatase et d'un materiau de revetement a base de dioxyde de titane
EP1182169A1 (fr) * 1999-02-04 2002-02-27 Japan Science and Technology Corporation Procede d'obtention de titane d'anatase ou d'oxyde composite contenant du titane d'anatase
JP2001104797A (ja) * 1999-09-20 2001-04-17 Lg Electronics Inc ナノサイズのアナターゼ型の二酸化チタン光触媒の製造方法並びに前記方法で製造された光触媒
US6576589B1 (en) * 1999-09-20 2003-06-10 Lg Electronics Inc. Method for making anatase type titanium dioxide photocatalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MATSUDA A.: "Transparent Anatase Nanocomposite Films by the Sol-Gel Process at Low Temperatures", J. AM. CERAM. SOC., vol. 83, no. 1, 2000, pages 229 - 231, XP002251603 *

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