EP1341609A1 - Herstellung von fest-verbunden photokatalytisch aktiv tiandioxidbeschichtung mitnicht-gekierten, organisch-dotierten vorläufern - Google Patents

Herstellung von fest-verbunden photokatalytisch aktiv tiandioxidbeschichtung mitnicht-gekierten, organisch-dotierten vorläufern

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Publication number
EP1341609A1
EP1341609A1 EP01993506A EP01993506A EP1341609A1 EP 1341609 A1 EP1341609 A1 EP 1341609A1 EP 01993506 A EP01993506 A EP 01993506A EP 01993506 A EP01993506 A EP 01993506A EP 1341609 A1 EP1341609 A1 EP 1341609A1
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EP
European Patent Office
Prior art keywords
weight
ranging
formulation
concentrations
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.)
Withdrawn
Application number
EP01993506A
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English (en)
French (fr)
Inventor
Valter Uiversità degli Studi di Torino MAURINO
Claudio Università degli Studi di Torino MINERO
Ezio Università degli Studi di Torino PELIZETTI
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.)
Neomat SA
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Neomat SA
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Application filed by Neomat SA filed Critical Neomat SA
Priority to EP01993506A priority Critical patent/EP1341609A1/de
Publication of EP1341609A1 publication Critical patent/EP1341609A1/de
Withdrawn legal-status Critical Current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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • 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

Definitions

  • the invention concerns a process for the coating of inorganic transparent supports with , a functional material consisting of thin films containing Ti0 2 according to the preamble of claim 1.
  • a functional material consisting of thin films containing Ti0 2 according to the preamble of claim 1.
  • Such films under light irradiation, can catalyze several redox processes. These processes result in several applications like pollutant abatements in gaseous and water streams, water potabilization, deodorizing and antibacterial functions for indoor air conditionings, self cleaning architectural ornaments and elements.
  • Photocatalytic Purification and Treatment of Water and Air Elsevier, Amsterdam, 1993
  • Practical examples of photocatalytic applications include the organic material mineralization in industrial waste, water potabilization, the recovery of noble metals from water, air cleaning in general, and in particular in indoor thermal and environmental air conditioning, deodorization, the manufacturing of architectural ornaments and elements (glass and shop windows, windows) that requires less duty for cleaning, the fabrication of lamp ' s and. shielding of them, accumulating less dirt.
  • the photocatalytic materials have disinfecting properties, which make them useful for keeping germ free the medical rooms.
  • the electronic carriers can recombine, or migrate to the, surface where, either by direct electron transfer or by trapping on surface sites and their subsequent reaction, react with the solvent (e.g. water if it is present) or organic and inorganic species adsorbed or transported to the interface. Some of these species are oxidized and some reduced, as oxygen and other electron scavengers do. In the presence of oxygen numerous organic substances are oxidized until full mineralization is achieved, so that carbon dioxide and inorganic ions are formed.
  • the main advantage of the photocatalytic process lies in his ability to mineralize organic compounds, overcoming the deficiencies of other cleaning technologies that simply transfer the pollutants from one phase to another one.
  • the role of the consecutive and parallel kinetic processes on the overall performance of the process has been subject of several theoretical and experimental studies (see for example ,
  • the main issues on the practical application of the photocatalytic processes concern: a) the activity of the catalyst (or its photon efficiency) , that is alleged insufficient for available semiconductor materials, b) the availability of a low cost semiconductor firmly anchored on a transparent support, c) the stability of the photocatalytic coating to exposure to alkaline media and surfactants, d) the homogeneity of the films and their transparency, that are an important issue for applications where efficient transmission of visible light, uniform features and aesthetic prerequisites are needed.
  • Deposition methods such as sputtering and chemical vapor deposition are costly and not suitable for support on any shape.
  • the deposition on the materials concerned in the present invention of previously prepared powders of titanium dioxide see for example the EP patent publications Nos.
  • the present invention pertains to a process to coat transparent inorganic supports (for example alkaline and borosilicate glass, quartz, fused silica) with thin films of titanium dioxide in the anatase crystalline form having relevant photocatalytic activity, and the use of organic dopants to improve the photocatalytic activity.
  • transparent inorganic supports for example alkaline and borosilicate glass, quartz, fused silica
  • organic dopants to improve the photocatalytic activity.
  • the coatings realized with the present methodology show 0.05 to 10 ⁇ film thickness, are resistant to atmospheric factors and abrasion, are thoroughly and absolutely homogeneous, and transmissive on average over 80% in the visible spectrum.
  • the process consists of the deposition on the support of a stable liquid precursor made of inorganic or metal-organic compounds of Ti (IV) partially or totally hydrolyzed, and surfactants, and/or acids, and a suitable organic doping, in particular s- triazine derivatives, included to improve the photocatalytic activity and mechanical resistance, followed by a thermal treatment to achieve the film densification.
  • a stable liquid precursor made of inorganic or metal-organic compounds of Ti (IV) partially or totally hydrolyzed, and surfactants, and/or acids, and a suitable organic doping, in particular s- triazine derivatives, included to improve the photocatalytic activity and mechanical resistance, followed by a thermal treatment to achieve the film densification.
  • the claimed procedure allows avoiding the gelification of the precursor, running away the need of further re-peptization of the gel as usually required in the common sol-gel methods.
  • the liquid precursor is stable in air, and storable for some months without alteration.
  • the films realized through the reported procedure do not decrease significantly either their photocatalytic activity or the adhesion to the support after treatment with alkaline solutions embodying also surfactants.
  • the doping with s-triazine derivatives results in an average improvement of the photocatalytic activity of 2-3 times with respect to non-doped films.
  • the present invention concerns the manufacture of homogeneous and transparent (in the visible spectrum) coating films of titanium dioxide in the anatase crystalline form on inorganic transparent supports, like different types of glasses, quartz, fused silica, through the deposition by dip- ⁇ oating, spray or roll of liquid precursors of which the composition is disclosed.
  • the invention improves on the issues previously discussed, and leads to photocatalytic activities superior to those obtained in the absence of nitrogen-containing dopants that are included in the formulation below disclosed.
  • the process requires no interlayer or binder between the support and the photocatalytic film.
  • the liquid precursor is prepared by hydrolysis or partial or total solvolysis of compounds of tetravalent titanium under conditions in which the gelation is avoided.
  • concentrations of Ti(IV) range from 0.1% to 35% by weight.
  • Titanium compounds included in the formulation are alkoxides, and in particular tetrabutoxy-ortho-titanate, tetrapropoxy- ortho-titanate, tetraisopropoxy-ortho-titanate, or halides, in particular the tetrachloride, or other kind of complexes like bis (ammonium lactate) dihydroxyde titanium (IV) .
  • the solvolysis is carried out from 1 min to 36 hours, at temperatures ranging from 5°C to the solvent boiling point, eventually under pressure (1-20 atm) at temperatures ranging from 0°C to 120 °C.
  • the solvolysis is necessary to form compounds of Ti(IV) that are less volatile than the original compounds, unable to vaporize during the subsequent thermal treatment, and showing good film sticking properties, and sufficient thickness to the support. Otherwise, the precursor could be partially or completely vaporized and lost during the thermal treatment, with formation of irregular and/or discontinuous or no coatings .
  • the water concentration needed by the hydrolysis ranges from 0.1% to 30% by weight.
  • the solvents needed in the formulation of the liquid precursors are alcohols, also polyfunctional and containing oxygen in ether bonds, carrying 1-10 carbon atoms and 1-6 oxygen atoms, or lactones containing 4-6 carbon atoms, or their mixtures in all proportions.
  • the solvent choice is based on the procedure used for the deposition (dip-coating, spray, roll-coating) and the desired depth of the resulting coating film of titanium dioxide.
  • the gelation of the liquid precursor either contemporary to the preparation step or when the precursor is stored before deposition renders it incompatible with the deposition with dip-coating, spray or roll-coating, especially if thin films below 10 ⁇ are desired.
  • an inorganic or organic acid is added at concentrations ranging from 0.1% to 20% by weight and/or a surfactant of type nonionic, or cationic, or anionic, or zwitterionic and their mixtures in all proportions, at concentrations ranging from 0.01% to 50% by weight .
  • a surfactant of type nonionic, or cationic, or anionic, or zwitterionic and their mixtures in all proportions at concentrations ranging from 0.01% to 50% by weight .
  • the presence of surfactant and/or the acid as the additional effect of inhibiting the formation in the liquid precursor of titanium dioxide particles having diameter larger than 100 nr ⁇ , that will form coating films less resistant to the abrasion and less uniform.
  • the disclosed formulation leads to the formation of polymeric titanates that under the thermal treatments hereafter disclosed form compact and non porous anatase films showing excellent adhesive properties on the supports above specified.
  • the gelation processes and formation of particulate titanium dioxide are inhibited by the presence of the acid and/or the surfactant at temperatures ranging from -10°C to 100 °C. At ambient temperature the disclosed formulation renders the precursor stable- against gelation and particle formation and settling for 6 to 12 months, depending on the composition.
  • inorganic acids the following are suitable: nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, hydrochloric acid, perchloric acid and their mixtures in all proportions.
  • organic acids are adequate those with linear or branched chains, also with 2 or 3 carboxylic groups and/or containing hydroxyl-, and/or chloro-, and/or fluoro-, and/or __ bromo- groups, or benzoic acid and its derivatives, and/or other carboxylic acid with aromatic structure.
  • Non-ionic surfactants alkyl- or alkylarylethoxylate and their mixtures in all proportions for example the commercial- products Brij 30, Brij 35, Triton X100
  • alkyl or alkylethoxysulphate anionic surfactants for example sodium dodecyl sulphate
  • alkylbenzene sulphonate and/or cationic surfactants, e.g. ⁇ etyltrimethylammonium bromide, and/or zwitterionic surfactants, like betaine derivatives
  • cationic surfactants e.g. ⁇ etyltrimethylammonium bromide, and/or zwitterionic surfactants, like betaine derivatives
  • the s-triazine ring which is characteristic of compounds like melamine, cyanuric acid, cyanurates, cyanuric chloride, was found to have a positive influence on. the photocatalytic activity when added as dopant to the precursor formulation.
  • melamine placed in a sealed vial is stable to red heat, see for example E. M. S olin, L. Rapoport, s-Triazines, in: A. Weissenberg Ed., The Chemistry of Heterocyclic Compounds, Vol. 13A, Wiley Interscience, New York, 1958) .
  • the s-triazine derivative doping gives the photocatalytic film a good stability against treatment with alkaline media and surfactants, concerning both adhesion on the support and the photocatalytic activity.
  • the photoactivity of the doped film is increased by a factor 1.5-3 when in the precursor formulation is introduced a selected s-triazine derivative in concentration ranging from 0.1 to 20% by weight.
  • the coating with the precursor made by the above cited procedures is followed by a thermal treatment lasting 10-200 min at temperatures ranging from 300°C to 800°C, in the presence of a gas phase containing oxygen in the range 1% to 50% by volume, in order to fully convert the precursor in micro ⁇ rystalline anatase Ti0 2 , and obtain a coating with good mechanical and chemical stability.
  • the formulations and procedures here disclosed allow the manufacture of .homogeneous and transparent (in the visible spectrum) coating films of titanium dioxide in the anatase cristalline form on inorganic transparent supports.
  • the coating films show relevant photocatalytic activity.
  • the formulations disclosed allow the preparation of liquid, non- gelled and stable precursors for film fabrication with low cost coating procedures (dip, spray or roll coating) .
  • the absence of gelification avoids the need of further re- peptization of the gel, as usually required in the common, sol-gel methods.
  • the liquid precursor is stable in air, and storable for some months without alteration.
  • the supported films obtained show very good mechanical properties, adesiveness to the support and scratching resistance without the intervention of an in-between layer.
  • a thermal aging could improve the precursor performance by completing the hydrolysis and/or solvolysis of the original titanium compound.
  • the exemplified formulation does not gel nor nucleate solid particles within 6-12 months if stored in the dark and in a closed container at ambient temperature ( ⁇ 25°C) .
  • Table 1 Example of film coating on inorganic transparent support according to the disclosed procedure, showing the weight % of Ti (IV) starting compound, acid, surfactant and solvent, the coating procedure and details of the thermal treatment.
  • Figure 1 reports the results of the tests on photocatalytic activity showed by a Ti0 2 film prepared according to claim 8 (without s-triazine derivative doping) .
  • the activity was checked by measuring the degradation rate of a model organic compound in aqueous solution (see the legend of Figure 1 for details) .
  • Figure 2 shows a scheme of the experimental setup employed for the photoactivity tests in the liquid media.
  • the film adhesion on the support, and the abrasion resistance are not adversely affected by a treatment with hot concentrated sulfuric acid and aqueous sodium carbonate (10% by weight in water) .
  • the film is not scratched by a pen eraser, and it is not removed by a series of 20 abrasions with fine grit paper (1000 mesh) under a 3 kg cm "2 load.
  • These coating properties are crucial in the above cited applications of photocatalytic films (e.g. purification and/or detoxification of water and wastewater) , where abrasion form liquids and/or solid suspended matter can remove a loose coating, or for application where washings with commercial detergents (acid or alkaline surfactant solutions) can not be excluded.
  • Figure 3 shows test results on the photocatalytic activity .in gaseous phase.
  • the film activity was measured through the disappearance rate of gaseous toluene (5-100 ppbv) in a gas- solid photorea ⁇ tor. See figure 4 for a scheme of the test apparatus.
  • the degradation rate of toluene follows a pseudo- first order kinetic law for concentration up to 100 ppbv with a decay constant not dependent from the substrate concentration. Thus the degradation rate increases linearly with the increase of the substrate concentration in the concentration range explored. Control experiments carried out irradiating the Pyrex glass support without catalyst film, showed no appreciable decrease of substrate concentration even after 70 hours of irradiation.
  • Figure 5 reports the Raman spectrum of the Ti0 2 coating. It is worth to note the exclusive presence of the Raman lines of the anatase cristalline, form (136, 389, 509, 631 cm “1 ), whereas emissions from rutile are absent (440 and 620 cm “1 ) .
  • the reported spectrum exactly matches the spectrum of microcrystalline anatase specimen. The line width indicates a icrocristalline habit of the film, excluding the presence of a large portion of amorphous zones.
  • the spectrum was collected with a dispersive confocal Raman microspectrometer (see Figure 5 caption for details) .
  • the photoactivity of the doped film is increased by a factor 1.5-3 when in the precursor formulation is introduced a selected s-triazine derivative in concentration ranging from 0.1 to 20% by weight.
  • the s-triazine derivative doping gives also the photocatalytic film a good stability against treatment with alkaline media and surfactants, both for the adhesion on the support, and the photocatalytic activity.
  • Table 2 reports the preparation procedure of a Ti0 2 - coating doped with cyanuric chloride, according to claim 8.
  • Figure 6 compares the photoactivity tests of doped and undoped films prepared according to claim 8 (undoped film is prepared from a precursor without cyanuric chloride) .
  • the pseudo- irst order kinetic constants for phenol disappearance are 0.14 and 0.35 hours '1 for the undoped and doped film, respectively.
  • the photocatalytic activity is increased by a factor of 2.5 under the reported experimental conditions .
  • the s-triazine derivative doping endows the photocatalytic film with good stability against treatment with alkaline media and surfactants, concerning both adhesion on the support, and the photocatalytic activity.
  • Figure 7 shows the test results on the photocatalytic activity of doped Ti0 2 films, prepared according to claim 8, before and after one and two treatments (24 hours immersion at a temperature of 25+5 °C) with a solution containing Na 2 C0 3 (100 g L" 1 ) and sodium dodecyl sulfate (50 g L "1 ) .
  • the first basic treatment the decrease in the photocatalytic activity was under 10% of the initial one.
  • the second treatment did not lead to a further decrease in the photocatalytic activity.
  • the adhesion on substrate and the resistance to abrasion of the doped films are not adversely affected also by treatment with concentrated sulfuric acid or with Na 2 C0 3 10%.
  • Figure 1 Results of the ' tests on the photocatalytic activity of a Ti0 2 film coated on Pyrex glass with a liquid substrate.
  • the film was prepared with a non-gelled precursor having a composition according to claim 8, but without s-triazine derivative dopant .
  • Substrate aqueous phenol solution (l.OxlO -4 M) .
  • Ti0 2 film with an active surface of 16 cm 2 irradiated with a fluorescent lamp (TL K 05 40 W Philips, radiation intensity incident on the film 30 Wm "2 . See figure 2 for a scheme of the experimental set-up) .
  • ( ⁇ ) Control specimen (Pyrex sheet without Ti0 2 film) .
  • Figure 2. Experimental setup employed for the tests on photocatalytic activity with liquid substrates. The volume of the liquid in the cell is 35 cm 3 . For other data see Figure 1 caption.
  • Figure 3 Test results on the photocatalytic activity of a- Ti0 2 film coated on Pyrex glass with a gaseous substrate.
  • the film was prepared with a non-gelled precursor having a composition according to claim 8, but without s-triazine derivative dopant.
  • Substrate toluene in air (20% 0 2 , 1.94% H 2 0, 70 L) at the concentration reported.
  • the active surface of the Ti0 2 film was 360 cm 2 , irradiation was carried out with a medium pressure Hg lamp (Philips mod. HPR 125 W HG, radiation intensity incident on the film 25 Wm" 2 ) . See figure 4 for a scheme of the experimental setup.
  • Tests on the control specimen Panrex glass sheet without photo ⁇ atalyst
  • FIG. 4 Experimental setup employed for the evaluation of the photocatalytic activity of Ti0 2 films in the degradation of volatile organic compounds and permanent gases in the gaseous phase.
  • the gas/solid photoreactor has a volume of 70 liter, is connected to an analytical apparatus (gas- chro atograph with a quadrupolar mass selective detector, equipped with a preconcentration system, allowing detection limit of the order of few pptv for most volatile organic compounds) , and to a dynamic diluter for gaseous mixture preparation.
  • an analytical apparatus gas- chro atograph with a quadrupolar mass selective detector, equipped with a preconcentration system, allowing detection limit of the order of few pptv for most volatile organic compounds
  • FIG. 6 Comparison of the photocatalytic activity ot Ti0 2 films undoped ( ⁇ ) and doped with a s-triazine compound ( ⁇ ) (cyanuric chloride) .
  • Substrate aqueous phenol solution (l.OxlO "4 M) .
  • Other conditions as in figure 1.
  • Figure 7 s-Triazine derivative doped Ti0 2 film stability against alkaline treatments.
  • Substrate aqueous phenol solution (1.0x10 " * M) .
  • Other conditions as in figure 1. Ti0 2 film before ( ⁇ ) and after 24 ( ⁇ ) and 48 hours (•) of treatment with a solution containing Na 2 C0 3 100 g L "1 and sodium dodecyl sulfate 50 g L "1 .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
EP01993506A 2000-11-09 2001-11-09 Herstellung von fest-verbunden photokatalytisch aktiv tiandioxidbeschichtung mitnicht-gekierten, organisch-dotierten vorläufern Withdrawn EP1341609A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP01993506A EP1341609A1 (de) 2000-11-09 2001-11-09 Herstellung von fest-verbunden photokatalytisch aktiv tiandioxidbeschichtung mitnicht-gekierten, organisch-dotierten vorläufern

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP00203953A EP1205243A1 (de) 2000-11-09 2000-11-09 Herstellung von fest verbundenen photocatalytisch aktivierten Titaniumdioxydfilmen aus nicht-gelierten organisch-dotierte Vorausläufern
EP00203953 2000-11-09
EP01993506A EP1341609A1 (de) 2000-11-09 2001-11-09 Herstellung von fest-verbunden photokatalytisch aktiv tiandioxidbeschichtung mitnicht-gekierten, organisch-dotierten vorläufern
PCT/EP2001/013009 WO2002038272A1 (en) 2000-11-09 2001-11-09 Preparation of firmly-anchored photocatalitically-active titanium dioxide coating films with non-gelled organic-doped precursors

Publications (1)

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EP1341609A1 true EP1341609A1 (de) 2003-09-10

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EP00203953A Withdrawn EP1205243A1 (de) 2000-11-09 2000-11-09 Herstellung von fest verbundenen photocatalytisch aktivierten Titaniumdioxydfilmen aus nicht-gelierten organisch-dotierte Vorausläufern
EP01993506A Withdrawn EP1341609A1 (de) 2000-11-09 2001-11-09 Herstellung von fest-verbunden photokatalytisch aktiv tiandioxidbeschichtung mitnicht-gekierten, organisch-dotierten vorläufern

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EP00203953A Withdrawn EP1205243A1 (de) 2000-11-09 2000-11-09 Herstellung von fest verbundenen photocatalytisch aktivierten Titaniumdioxydfilmen aus nicht-gelierten organisch-dotierte Vorausläufern

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AU (1) AU2002226331A1 (de)
WO (1) WO2002038272A1 (de)

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FI117754B (fi) * 2004-02-06 2007-02-15 Kemira Pigments Oy Titaanidioksidituote, sen valmistusmenetelmä ja käyttö fotokatalyyttinä
ITPR20040059A1 (it) 2004-08-06 2004-11-06 Vacuum Surtec Srl Procedimento per depositare strati sottili di biossido di titanio su superfici di supporto e manufatti realizzati mediante detto procedimento.
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US7833935B2 (en) 2006-11-08 2010-11-16 Rockwood Italia S.P.A. Iron oxide containing precipitated crystalline titanium dioxide and process for the manufacture thereof
US7655274B2 (en) † 2007-11-05 2010-02-02 Guardian Industries Corp. Combustion deposition using aqueous precursor solutions to deposit titanium dioxide coatings
JP5964585B2 (ja) 2008-03-31 2016-08-03 ハンツマン ピグメンツ エス．ピー．エー． 光触媒活性を有する顆粒体およびその製造方法
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US8647652B2 (en) 2008-09-09 2014-02-11 Guardian Industries Corp. Stable silver colloids and silica-coated silver colloids, and methods of preparing stable silver colloids and silica-coated silver colloids
DE102009017409A1 (de) * 2008-10-04 2010-04-08 Friedrich-Alexander-Universität Erlangen-Nürnberg Azin-modifizierter Titandioxid-Photokatalysator und Verfahren zu seiner Herstellung
US8545899B2 (en) 2008-11-03 2013-10-01 Guardian Industries Corp. Titanium dioxide coatings having roughened surfaces and methods of forming titanium dioxide coatings having roughened surfaces
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