WO2006092442A1 - Particules d'oxyde de zinc a surface modifiee - Google Patents

Particules d'oxyde de zinc a surface modifiee Download PDF

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Publication number
WO2006092442A1
WO2006092442A1 PCT/EP2006/060449 EP2006060449W WO2006092442A1 WO 2006092442 A1 WO2006092442 A1 WO 2006092442A1 EP 2006060449 W EP2006060449 W EP 2006060449W WO 2006092442 A1 WO2006092442 A1 WO 2006092442A1
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WO
WIPO (PCT)
Prior art keywords
zno particles
modified
particles
zno
alkoxyalkylsilanes
Prior art date
Application number
PCT/EP2006/060449
Other languages
German (de)
English (en)
Inventor
Bernd Rohe
Michael Tausch
Original Assignee
Grillo-Werke Ag
Universität Duisburg-Essen
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 Grillo-Werke Ag, Universität Duisburg-Essen filed Critical Grillo-Werke Ag
Publication of WO2006092442A1 publication Critical patent/WO2006092442A1/fr

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Classifications

    • 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
    • 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
    • C09C1/04—Compounds of zinc
    • C09C1/043—Zinc oxide
    • 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

Definitions

  • the present invention is a process for the preparation of zinc oxide (ZnO) particles surface-modified with alkoxyalkylsilanes, surface-modified ZnO particles obtainable by the process according to the invention, the use of the ZnO particles according to the invention in heterogeneous catalysis and in photovoltaics, and with the inventive compounds ZnO particles coated photoelectrodes.
  • ZnO zinc oxide
  • Zinc oxide, ZnO, with a molar mass of 81.39 g / mol is a white, loose powder with a density of 5.65-5.68 g / cm 3 . It crystallizes in the wurtzite structure. In water it is insoluble, in acids and alkalis it dissolves under salt formation. Zinc oxide has a band gap of 3.2 eV and is assigned to the class of n-type semiconductors. Accordingly, zinc oxide can be electronically excited when exposed to wavelengths below 390 nm.
  • Nanoscale ZnO with a particle diameter of less than 100 nm can be prepared by precipitation reactions in the sol-gel process (Bruemann, DW, Kormann, C. Hoffmann, MR, J. Phys. Chem., 14, 1987, 91, 3789-3798 and Spanhel, L .; Anderson, MA; J. Am. Chem. Soc., 8, 1991, 113, 2826-2833).
  • the ZnO particles may be surface-modified with various substances after their preparation (Guo, L .; Yang, S. Yang, C .; Yu, P. Wang, J .; Ge, W .; Wong, GKL; Chem , 2000, 12, 2268-2274 and Armeiao, L. Fabrizio, M., Gialanella, S., Zordan, F. Thin Solid Films, 2001, 394, 90-96).
  • the technical production of nano-zinc oxide sols via the wet-chemical synthesis route is known.
  • the experimental procedure is based on 1 M methanolic zinc acetate solutions in which methanolic potassium hydroxide solution is added dropwise at 55 ° C. with stirring.
  • the resulting zinc oxide precipitate is washed four times with methanol and centrifuged, Subsequently, the zinc oxide gel is dispersed in dichloromethane or ethylene glycol / water / triethanolamine solution to sol (DE-A-10212121, DE-A-19907704, EP-A-1157064, DE-A-10118309, DE-A-19751448 ).
  • the disadvantage of the ZnO particles produced by the processes described in the prior art is their low surface area which renders them unsuitable for efficient use as a catalyst.
  • the technical problem to be solved is therefore the synthesis of surface-modified ZnO particles which have a high surface area and thus a high photocatalytic activity.
  • This problem is solved according to the invention by a method according to claim 1.
  • a process for the preparation of surface-modified zinc oxide (ZnO) particles characterized in that ZnO particles are suspended and / or dispersed in polar protic solvents and treated with alkoxyalkylsilanes, and the ZnO particles thus surface-modified with alkoxyalkylsilanes are Particles in aqueous medium are exposed to UV irradiation.
  • ZnO particles are suspended and / or dispersed in polar protic solvents and treated with alkoxyalkylsilanes, and the ZnO particles thus surface-modified with alkoxyalkylsilanes are Particles in aqueous medium are exposed to UV irradiation.
  • polar protic solvents are solvents whose molecules can give off protons and dissociate into protons and solvent anions, and on the other hand, a permanent electric dipole moment developed by charge shifts in atomic groups.
  • an inorganic oxide network of -O-Si-O-Si-O units is generated, which bridges the particles and keeps them at defined intervals.
  • This material has a high surface area - ⁇ ⁇ __
  • Organic compounds are efficiently absorbable and accessible to photocatalytic degradation processes.
  • the method is carried out according to claim 1 with the addition of H 2 O 2 and / or air supply during the UV irradiation.
  • UV light of a wavelength of less than 390 nm is preferably used.
  • the ZnO particles according to the invention can be nanoscale. "Nanoscale” in the sense of the present invention means that the ZnO particles have a diameter of at most 100 nm.
  • the polar protic solvent according to the invention is preferably selected from the group consisting of aliphatic, aromatic or cyclic monohydric or polyhydric alcohols or thioalcohols and aldehydes. Particularly preferred is methanol as a polar protic solvent according to the invention.
  • the inventive method is characterized in that the treatment of the suspended and / or dispersed ZnO particles with alkoxyalkylsilanes at a temperature of 40 0 C - 70 0 C, in particular at 60 0 C is performed.
  • ZnO particles surface-modified with alkoxyalkylsilanes may be exposed to UV radiation for 45-90 minutes, in particular for 60 minutes.
  • the alkoxyalkylsilanes are trimethoxyalkylsilanes.
  • the alkoxyalkylsilanes may be selected from the group consisting of methyltrimethoxysilane, isooctyltrimethoxysilane, trimethoxyvinylsilane, triethoxyoctylsilane, 3-methacryloxypropyltrimethoxysilane, isooctyltriethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, isobutylisopropyldimethoxysilane, Methacryloxypropylmethyldimethoxysilane, [3 ⁇ (2,3-epoxypropoxy) -propyl] -trimethoxysilane, N- (2-aminoethyl) -3-amino-propyl-trimethoxysilane, (3-methacryl
  • the alkoxyalkylsilanes are preferably used in a concentration of 0.1 to 15 mol%, in particular of 2 to 10 mol%.
  • surface-modified ZnO particles obtainable by the process according to the invention are claimed. These surface-modified ZnO particles have a surface area of at least 100 m 2 / g as measured by the BET method. This method will be explained below by way of example.
  • the surface-modified ZnO particles are characterized in that the Alkoxyalkylsilanmoleküle are covalently bonded to the ZnO particles, whereby in aqueous medium under UV irradiation, an inorganic network of -O-Si-O-Si-O- units which partially to form polycyclic silsesquioxane units.
  • the surface-modified ZnO particles according to the invention have a zinc content of at least 60%, in particular from 65% to 75%, as measured in accordance with DIN 55908.
  • the present invention relates to the use of the ZnO particles according to the invention as photocatalyst in heterogeneous catalysis.
  • the organochlorine compounds are aliphatic and aromatic hydrocarbons and dyes, Insecticides and nitrogen compounds. Furthermore, the organochlorine compounds may be selected from the group consisting of perchlorinated alkanes and alkenes, in particular tetrachloroethene, polychlorinated biphenyls, mono- or polychlorinated dioxins and singly or multiply chlorinated dibenzofurans.
  • the present invention is the use of the ZnO particles according to the invention as a coating of photoelectrodes in photogalvanic and photoelectric cells and also a photoelectrode which is coated with the ZnO particles according to the invention.
  • sample material is weighed into a U-tube attached to the instrument.
  • the samples are heated using a heating bag at a temperature of 105 0 C for about 20 minutes to remove any traces of water.
  • the U-tube is hooked into the measuring cell.
  • the devices measure the changes in a nitrogen-helium gas mixture (volume ratio 30:70).
  • the sample vessel is in liquid nitrogen cooled.
  • a portion of the gas mixture passed over the samples adsorbs to the sample material.
  • the adsorbed nitrogen is desorbed.
  • About the changes in the thermal conductivity of the gas mixture can be concluded about the ad- and desorbed amount of nitrogen on the surface of the sample.
  • the supernatant is filtered off with suction and replaced by 166.6 g of methanol. After stirring for 20 minutes and 75 minutes settling time, the supernatant is removed and replaced again with 83.3 g of methanol. After 40 minutes of stirring and 40 minutes settling time, the supernatant is discarded and replaced again by 83.3 g of methanol. After stirring for another 30 minutes, the solution is centrifuged (4300 rpm, 10 minutes).
  • the resulting gel is dried for 18 hours in a drying oven at 110 0 C.
  • the HPK 125W reaches its energy maximum at 365 nm, while it also develops a considerable amount of radiation at 435, 313, 253 and 404 nm.
  • the continuum from 200 to 600 nm reaches its peak at 260 nm with approximately 20% of the maximum energy measured in the line spectrum.
  • the reaction mixture and the UV lamp are cooled with water.
  • reaction mixture After 60 minutes irradiation time, the reaction mixture is drained and separated by centrifugation (10 min, 2000 U / min.). The precipitate is dried in an oven at 150 0 C for 24 hours, then triturated and weighed.
  • the immersion lamp reactor is charged with 180 ml of 0.1 molar sodium dihydrogenphosphate solution and 180 ml of 0.1 molar sodium hydroxide solution. 10, 30 or 100 mg of zinc oxide from example 3 are added to the buffer solution. The suspension is stirred with a magnetic stirrer. After a stirring time of 5 minutes, 5 ml of sample are drawn and then 0.15 ml of tetrachloroethene are added to the reactor.
  • the high-pressure mercury vapor lamp which is located centrally in a quartz tube in the reactor, is turned on. After 5, 10, 20, 40, 60, 80, 100, 120, 160 and 200 minutes each 5 ml of sample are removed.
  • the chloride content of the samples is determined by ion chromatography.
  • the catalytic activity of the ZnO particles (e) according to the invention is compared with that of the prior art titanium dioxide (b), a commercially available zinc oxide-based catalyst (d), non-surface-modified zinc oxide particles (c) and a blank test without use of a catalyst (a) compared.
  • the procedure is as follows.
  • An ITO (indium-tin-oxide) glass pane (6.5 ⁇ 3.5 ⁇ 0.3 mm) is coated with a paste of UV-modified ZnO network in ethanol about 35 ⁇ m thick, dried and left to stand for 60 min , long sintered at 450 0 C.
  • This photoelectrode delivers in a half-cell with 1 M potassium bromide solution against a half-cell of 1 M hydrochloric acid and a Pt electrode under irradiation with an Osram Ultravitalux lamp (300 W) photovoltage of about 350 mV.
  • the photoelectrode forms the negative pole.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

L'invention se rapporte à un procédé pour produire des particules d'oxyde de zinc (ZnO) dont la surface est modifiée par des alcoxyalkylsilanes. Cette invention concerne en outre les particules de ZnO à surface modifiée productibles au moyen dudit procédé, l'utilisation de ces particules de ZnO en catalyse hétérogène et en photovoltaïque, ainsi qu'une photoélectrode recouverte des particules de ZnO selon l'invention.
PCT/EP2006/060449 2005-03-03 2006-03-03 Particules d'oxyde de zinc a surface modifiee WO2006092442A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005010320.0 2005-03-03
DE200510010320 DE102005010320B4 (de) 2005-03-03 2005-03-03 Oberflächenmodifizierte Zinkoxidpartikel

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WO2006092442A1 true WO2006092442A1 (fr) 2006-09-08

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PCT/EP2006/060453 WO2006092443A1 (fr) 2005-03-03 2006-03-03 Particules d'oxyde de zinc a surface modifiee

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101059489B (zh) * 2007-05-24 2010-08-25 复旦大学 一种测定半导体电极光催化制氢活性的方法
WO2011023266A1 (fr) 2009-08-28 2011-03-03 Basf Se Nanoparticules modifiées
WO2011107577A2 (fr) 2010-03-05 2011-09-09 Basf Se Sels de zinc modifiés de diacides alcane en c4-8 et leur utilisation comme catalyseur de polymérisation
WO2013034489A1 (fr) 2011-09-09 2013-03-14 Basf Se Procédé de préparation de dicarboxylate de zinc

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105074952A (zh) 2013-04-03 2015-11-18 纳米格拉德股份公司 硅烷功能化缓冲层和包括该缓冲层的电子设备
JP6585595B2 (ja) 2013-12-12 2019-10-02 アファンタマ アクチェンゲゼルシャフト 溶液で処理できる金属酸化物バッファー層を含む電子機器
CN109251716A (zh) * 2018-06-29 2019-01-22 张家港康得新光电材料有限公司 紫外光固化防雾胶水及其制备方法
CN113248944A (zh) * 2020-06-24 2021-08-13 广西七色珠光材料股份有限公司 用于粉末涂料的珠光颜料、制备方法及其反应装置

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002062903A1 (fr) * 2001-01-09 2002-08-15 Silke Warchold Vitroceramique phosphorescente
EP1508599A1 (fr) * 2003-08-22 2005-02-23 Degussa AG Oxyde de zinc traitée en surface

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10212121A1 (de) * 2002-03-15 2003-09-25 Bayer Ag Verfahren zur Herstellung von nano-Zinkoxid-Dispersionen stabilisiert durch hydroxylgruppenhaltige anorganische Polymere

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002062903A1 (fr) * 2001-01-09 2002-08-15 Silke Warchold Vitroceramique phosphorescente
EP1508599A1 (fr) * 2003-08-22 2005-02-23 Degussa AG Oxyde de zinc traitée en surface

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101059489B (zh) * 2007-05-24 2010-08-25 复旦大学 一种测定半导体电极光催化制氢活性的方法
WO2011023266A1 (fr) 2009-08-28 2011-03-03 Basf Se Nanoparticules modifiées
WO2011107577A2 (fr) 2010-03-05 2011-09-09 Basf Se Sels de zinc modifiés de diacides alcane en c4-8 et leur utilisation comme catalyseur de polymérisation
WO2011107577A3 (fr) * 2010-03-05 2011-12-29 Basf Se Sels de zinc modifiés de diacides alcane en c4-8 et leur utilisation comme catalyseur de polymérisation
CN102869444A (zh) * 2010-03-05 2013-01-09 巴斯夫欧洲公司 C4-8-链烷二羧酸的改性锌盐及其用作聚合催化剂的用途
WO2013034489A1 (fr) 2011-09-09 2013-03-14 Basf Se Procédé de préparation de dicarboxylate de zinc

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DE102005010320B4 (de) 2007-02-15
DE102005010320A1 (de) 2006-09-07
WO2006092443A1 (fr) 2006-09-08

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