US20030171446A1 - Surface cleaner - Google Patents

Surface cleaner Download PDF

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US20030171446A1
US20030171446A1 US10/168,933 US16893302A US2003171446A1 US 20030171446 A1 US20030171446 A1 US 20030171446A1 US 16893302 A US16893302 A US 16893302A US 2003171446 A1 US2003171446 A1 US 2003171446A1
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composition
groups
derivatives
sensitising agent
sol
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Barry Murrer
Robert Potter
Virginie Ogrodnik
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Reckitt Benckiser UK Ltd
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Assigned to JOHNSON MATTHEY PUBLIC LIMITED COMPANY reassignment JOHNSON MATTHEY PUBLIC LIMITED COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MURRER, BARRY ANTHONY, OGRODNIK, VIRGINIE, POTTER, ROBERT J.
Publication of US20030171446A1 publication Critical patent/US20030171446A1/en
Assigned to RECKITT BENCKISER (UK) LIMITED reassignment RECKITT BENCKISER (UK) LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: JOHNSON MATTHEY PUBLIC LIMITED COMPANY
Priority to US11/513,783 priority Critical patent/US7351294B2/en
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0063—Photo- activating compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2

Definitions

  • the present invention relates to sensitising agents and compositions effective to degrade soils deposited on a surface, methods employing said agents and compositions, and uses thereof.
  • compositions intended for general and specific uses are well known in the art. Such compositions will normally comprise one or more surfactants, solvents thickening agents, abrasive particles, bleaching agents, disinfectant/antibacterial agents, perfumes, preservatives and colouring agents. Although these compositions are effective at removing soils, inevitably resoiling occurs after cleaning and thus recleaning is required.
  • a means to reduce the frequency of cleaning and recleaning would thus be advantageous.
  • the present invention seeks to address these problems.
  • the present inventors have found, however, that the use of a sensitising agent in addition to the light absorbing material reduces the amount of energy required to be absorbed by said light absorber in order for charge separation to take place, and subsequently for the photocatalysed degradation of surface soils to occur.
  • the present inventors have found that ambient light, for example sunlight or artificial light is sufficient in the presence of a sensitising agent and a light absorbing material to induce such a degradation.
  • the present inventors have found, in addition, that the use of highly conjugated heterocyclic complexes such as polypyridine, macrocycle or phthalocyanines with various centrally coordinated atoms such as Ru, Fe and Si can be used to sensitise a light absorbing agent (such as titanium dioxide or zinc oxide) not only when the light absorbing agent is coated onto a surface, but also when the agent is in solution.
  • a light absorbing agent such as titanium dioxide or zinc oxide
  • Bendig et al J Photochem Photobiology A: Chemistry 108 (1997) 89, describe the sensitised photocatalytic oxidation of herbicides using tris(2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium (II) dichloride, tris(2,2′-bipridyl) ruthenium (II) dichloride and a methylated form of the latter.
  • sensitising agents carrying a negatively charged group can bind via electrostatic interaction, whereas positively charged groups will tend to be repelled.
  • pH greater than the PZC value for titania molecular moieties with positively charged groups will tend to bind more strongly with the TiO 2 surface.
  • sensitisation for sensitisation to be most effective at a particular working pH, on semiconductors such as titania, zinc oxide, tin oxide etc, charged groups of the appropriate sign should be present on the absorbing sensitiser-molecule to promote binding.
  • a sensitising molecule should preferably have a positively charged group or groups in its structure.
  • the present invention provides a composition
  • a composition comprising a photocatalyst and a metal complex sensitiser comprising a ligand with a conjugated ⁇ system which absorbs light substantially in the visible and/or the infrared region of the spectrum, effective to deposit a functional residue of said composition on a surface.
  • the term ‘functional residue’ in the context of the present invention means a residue or layer of photocatalytic composition provided on a surface whereby soils deposited on the residue or layer or soils which are present on the surface prior to the deposition of the residue or layer are subject to a photocatalytic or other photochemical oxidation, reduction, free radical or other photochemical reaction effective to substantially break down, or otherwise decompose the soil.
  • a photocatalytic or other photochemical oxidation, reduction, free radical or other photochemical reaction effective to substantially break down, or otherwise decompose the soil.
  • the cleaning process continues after the conventional act of soil removal is completed.
  • these reactions may also provide an ongoing antibacterial effect that continues after the physical cleaning process has been completed.
  • a functional residue of photocatalytic material is applied to a substantially clean or sterile surface then the rate of accumulation of soils on the surface will be reduced.
  • photocatalytic agent in the context of the present invention refers to an agent that has a favourable combination of electronic structure, light absorption properties, charge transport characteristics and excited-state lifetimes.
  • Primary light absorbers for photocatalysis include but are not limited to semiconductor materials.
  • the conduction band electrons may then reduce oxygen to reactive species such as .OH radicals, which can rapidly attack organic molecules, i.e.
  • D.+ may oxidise organic molecules.
  • the sensitising agent is working in a catalytic manner i.e it is not significantly altered itself during the photocatalytic cleaning process, and is therefore active over a long period of time.
  • Suitable photocatalytic agents include but are not limited to titanium dioxide (in the form of anatase and/or rutile and/or brookite), zinc oxide, tin oxide, cadmium sulphide, tungsten trioxide and molybdenum trioxide. Alternatively, combinations of two or more of these agents may be used. In a preferred embodiment the agent is titanium dioxide.
  • the photocatalytic composition further comprises a metal complex sensitiser.
  • the central atom of such sensitisers can be but is not limited to ruthenium, platinum, palladium, iridium, rhodium, osmium, rhenium, iron or copper, titanium or zinc.
  • suitable sensitising agents include but are not limited to heterocyclic complexes which contain polypyridine, macrocyclic or phthalocyanine ligands and optionally other ligand types wherein at least one of the nitrogen groups is displaced by other donor groups.
  • the complex is any one or more of ruthenium II, III or IV or mixed oxidation state chelating complexes containing nitrogen donor atoms or a ruthenium(II), (III), (IV) or a mixed oxidation state polypyridine complex.
  • the sensitising agent includes any one or more of the following groups: terpyridyls, bipyridyls, phthalocyanines, phorphyrins, tetra-aza-annulenes, pyrazines, phenanthrolines and derivatives thereof and compounds with substantially similar nitrogen based ring systems.
  • the sensitisng agent may further include any one or more of R 4 N+ or R 4 P+ groups wherein each R group may be the same or different and is any one or more of the following groups: hydrogen, halogen, amine, alkyl, aryl, arylalkyl, alkoxy, heterocyclic groups, or derivatives thereof, including acid and ester derivatives, any of which may be branched or unbranched, substituted or unsubstituted,
  • sensitising agents are specifically designed wherein the molecular structure functions in combination with semiconductors where the desired operating condition is such that the un-coated semiconductor surface presents adsorption sites with a negative charge. This will occur for instance where the composition containing said agent is of alkaline pH.
  • the sensitising agent may include a terpyridal group of general formula I shown below:
  • R1, R2 and R3 are positively charged groups which has the general formula II shown below:
  • R5-R7 are any one or more of the following groups: hydrogen, halogen, amine, alkyl, aryl, arylalkyl, alkoxy, heterocyclic groups, or derivatives thereof, including acid and ester derivatives, any of which may be branched or unbranched, substituted or unsubstituted,
  • the sensitising agent may include a bipyridyl group having the general formula III shown below:
  • R8 and R9 can be the same or different and is any one or more of the following groups: hydrogen, halogen, amine, alkyl, aryl, arylalkyl, alkoxy, heterocyclic groups, or derivatives thereof, including acid and ester derivatives, any of which may be branched or unbranched, substituted or unsubstituted,
  • R2 may be the same or different from R3 and is any one or more of the following groups: hydrogen, halogen, amine, alkyl, aryl, arylalkyl, alkoxy, heterocyclic groups, or derivatives thereof, including acid and ester derivatives, any of which may be branched or unbranched, substituted or unsubstituted,
  • sensitising agents of the present invention may include phtalocyanines of general formula IV below:
  • each R group may be the same or different and is any one or more of the following groups: hydrogen, halogen, amine, alkyl, aryl, arylalkyl, alkoxy, heterocyclic groups, or derivatives thereof, including acid and ester derivatives, any of which may be branched or unbranched, substituted or unsubstituted,.
  • sensitising agents may include tetra-aza-annulenes (TADAs) of general formula V shown below.
  • TADAs tetra-aza-annulenes
  • R1-R4 may be the same or different and is any one or more of the following groups: hydrogen, halogen, amine, alkyl, aryl, arylalkyl, alkoxy, heterocyclic groups, or derivatives thereof, including acid and ester derivatives, any of which may be branched or unbranched, substituted or unsubstituted,.
  • bipyridyl compounds tris(2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium (II) dichloride and tris(2,2′-bipridyl) ruthenium (II) dichloride can be dimerised using pyrazine derivitives such as pyrazine, pyrimidine and 4,4′-bipyridyl linking ligands using procedures well known in the art. Again as previously discussed these will be most suitable for use in operating conditions such that the un-coated semiconductor presents absorption sites with a negative charge
  • compositions of the present invention will most preferably be in the form of a liquid. They may also be in the form of an emulsion, suspension, or in particulate form.
  • the light absorbing agent will comprise no more than 50% w/v of the photocatalytic composition, more preferably the light absorbing agent will comprise no more than 10% w/v of the photocatalytic composition. More preferably still the light absorbing agent will comprise no more than 1% w/v of the photocatalytic composition. Yet more preferably the light absorbing agent will comprise no more than 0.1% w/v of the photocatalytic composition.
  • the sensitising agent will comprise no more than 1% w/v of the photocatalytic composition. More preferably the sensitising agent will comprise no more than 0.1% w/v of the photocatalytic composition.
  • compositions of the present invention are effective at a whole range of pH values from 1 to 14.
  • sensitising agents of the present invention which contain polypyridine, macrocyclic or phthalocyanine ligands and optionally other ligand types wherein at least one of the nitrogen groups is displaced by other donor groups
  • sensitising agent is ruthenium II, III or IV or mixed oxidation state chelating complexes containing nitrogen donor atoms, or a ruthenium(II), (III), (IV) or a mixed oxidation state polypyridine complex
  • these compounds perform most effectively at pHs corresponding to a positive charged surface-state of the semiconductor component e.g for titania this corresponds to a pH of less than 7.
  • a composition comprising sensitising agents described above and also titania preferably has a pH of less than 7, even more preferably of less than 6, more preferably still of less than 5.
  • compositions comprising a sensitising agent according to the present invention which includes any one or more of the following groups: terpyridyl, bipyridyls, phthalocyanines, phorphyrins, tetra-aza-annulenes, pyrazines, phenanthralines and derivitives thereof and compounds with substantially similar nitrogen based ring systems, and may further include any one or more of R 4 N+ or R 4 P+ groups wherein each R group is as hereinbefore described.
  • the preferred pH of the composition corresponds to the value where the semi-conductor component has a negatively charged surface. For titania this is pH 7 or greater. Even more preferred is a pH of greater than 8, more preferred still a pH of greater than 9.
  • the present invention provides a sensitising agent which includes any one or more of the following groups: terpyridyl, bipyridyl, phthalocyanine, phorphyrins, tetra-aza-annulenes, pyrazines, phenanthrolines and derivatives thereof and compounds with substantially similar nitrogen based ring systems
  • the sensitising agents listed above further includes any one or more of R 4 N+ or R 4 P+
  • R5-R7 are any one or more of the following groups: hydrogen, halogen, amine, alkyl, aryl, arylalkyl, alkoxy, heterocyclic groups, or derivatives thereof, including acid and ester derivatives, any of which may be branched or unbranched, substituted or unsubstituted,.
  • These groups may be derivatised to produce compounds containing positively-charged binding sites suitable for attachment to semiconductors as hereinbefore described.
  • the present invention provides the use of a sensitising agent according to the present invention for the sensitisation of a light absorbing agent on a surface such that soils present on the surface are substantially broken down and/or the rate of accumulation of such soils on a surface is significantly diminished.
  • the rate of accumulation of soils is significantly diminished in the context of the present invention means that the rate is significantly diminished as compared with a similar sample in which no sensitising agent has been applied.
  • the photocatalytically active composition may be doped with an additional element which has the effect of reducing the energy required to promote an electron of the photochemically active material to the conductance band.
  • Suitable doping agents may include but are not limited to platinum, palladium, cobalt, silver, copper, nickel or iron, tungsten, chromium. These may be present as the metals themselves, and/or as complexes and/or compounds thereof.
  • compositions of the present invention may further include a wetting agent which may be any one or more of the following: Igepal® CA-520 [polyoxyethylene(5) isooctylphenyl ether], Igepal® CA-630 [(octylphenoxy)polyethoxyethanol], Igepal® CA-730 [polyoxyethylene(12) isooctylphenyl ether].
  • concentration used will be between 0.5-5.0 wt %, even more preferably between 0.5 and 3 wt %, more preferably still between 0.5 and 2.0 wt %.
  • the photocatalytic compositions and/or sensitising agents of the present invention can be used in conjunction with those conventional ingredients of cleaning materials known to those skilled in the art. These may include but are not limited to water, anionic, non-ionic or amphoteric surfactants. Grease cutting, surfactant synergistic or other solvents may also be included as may antibacterial agents, suspending agents, colourants, perfumes, thickeners, preservatives and so on. Some or all of the ingredients may be of high volatility whereby a residue of photochemically active material can be left behind on a surface in a controlled manner.
  • the sensitising agent, or compositions according to the present invention may be applied to the surface in any appropriate form such as, for example, a liquid, cream, mousse, emulsion, microemulsion or gel form and may be dispensed either directly from the bottle or by means of for example an aerosol, pump action dispenser. These means will be known to those in the art.
  • compositions and/or sensitising agent according to the present invention once deposited on the surface should be substantially imperceptible to the user. This may be achieved by using materials, agents and compositions with a microscopic particle size.
  • the microscopic particle size also aids in achieving a uniform dispersion throughout the materials and/or compositions thus maximising the efficiency of the photochemical reaction.
  • the particle size is less than 100 nm, more preferably the particle size is less than 50 nm and more preferably still it is less than 20 nm
  • FIG. 1 represents the UV/Visible spectra of the ⁇ max of the target dye Gentian Violet disappearing with time as described in example 6.
  • Horizontal axis is wavelength in nm.
  • Vertical axis is absorbance in units measured using UV spectrometer (UV/vis spectrometer-UV 4-UNICAM)
  • GV Gentian Violet dye
  • FIG. 2 represents the activity of TiO2 sol (sol 1) as described in example 8.
  • Horizontal axis represents time and the vertical axis represents the change in absorbance measured using a (UV/vis spectrometer-UV 4-UNICAM)
  • ⁇ represents the activity of sensitised TiO2 at pH 3.28, ⁇ Activity of sensitised TiO2 at pH 2.08, ⁇ Activity of sensitised TiO2 at pH 2.72, X Activity of sensitised TiO2 at pH 4.02.
  • FIG. 3 represents the activity of TiO2 sol (sol 2) as described in example 8. Horizontal axis represents time and the vertical axis represents the change in absorbance measured using a (UV/vis spectrometer-UV 4-UNICAM)
  • ⁇ represents the activity of sensitised TiO2 at pH 2.00, ⁇ Activity of sensitised TiO2 at pH 2.64, ⁇ Activity of sensitised TiO2 at pH 4.12, X Activity of sensitised TiO2 at pH 3.39, * Activity of sensitised TiO2 at pH 5.00, ⁇ Activity of sensitised TiO2 at pH 5.98.
  • FIG. 4 represents the activity of TiO2 sol (sol 3) as described in example 8.
  • Horizontal axis represents time and the vertical axis represents the change in absorbance measured using a (UV/vis spectrometer-UV 4-UNICAM)
  • ⁇ represents the activity of sensitised TiO2 at pH 4.1, ⁇ Activity of sensitised TiO2 at pH 3.2, ⁇ Activity of sensitised TiO2 at pH 2.7, X Activity of sensitised TiO2 at pH 2.1, * Activity of sensitised TiO2 at pH 5.2, ⁇ Activity of sensitised TiO2 at pH 6.0, - Activity of sensitised TiO2 at pH 6.5-7.0.
  • FIG. 5 represents the activity of TiO2 sol (sol 4) as described in example 8.
  • Horizontal axis represents time and the vertical axis represents the change in absorbance measured using a (UV/vis spectrometer-UV 4-UNICAM)
  • ⁇ represents the activity of sensitised TiO2 at pH 2.74, ⁇ Activity of sensitised TiO2 at pH 2.12, ⁇ Activity of sensitised TiO2 at pH 3.38, X Activity of sensitised TiO2 at pH 4.00.
  • FIG. 6 represents the activity of sensitised TiO2 sol at different pH as described in example 9. Horizontal axis represents time and the vertical axis represents the change in absorbance measured using a (UV/vis spectrometer-UV 4-UNICAM)
  • ⁇ represents the activity of sensitised solution (1) at pH 6.7, ⁇ Activity of sensitised TiO2 at pH 5.2, ⁇ Activity of sensitised TiO2 at pH 8.8.
  • FIG. 7 represents the effect of the light source in photocatalytic activity as described in example 11.
  • Horizontal axis represents time and the vertical axis represents the change in absorbance measured using a (UV/vis spectrometer-UV 4-UNICAM)
  • ⁇ represents the ratio: TiO2:Ru:1:6, ⁇ Ratio: TiO2:Ru:1:4, ⁇ Ratio: TiO2:Ru:1:2.
  • OHP represents overhead projector
  • GV stands for Gentian Violet dye.
  • a nanocrystalline titanium dioxide sol was applied to the surface of a previously cleaned glass microscope slide by spin coating 0.5 ml of the titanium dioxide sol at 1500 rpm for 30 seconds. The glass slide was then fired at 450° C. for 30 minutes. Once cool the process was repeated two further times to give 3 coats of the nanocrystalline titanium dioxide. The slide was then immersed in an aqueous 1 ⁇ 10 ⁇ 6M solution of tris(2,2′-bipyridyl-4,4′-dicarboxylate)Ru(II)(dichloride) for 30 minutes to allow adsorption of the sensitising agent to the titanium dioxide.
  • the slide was removed, rinsed with water to remove any unbound ruthenium complex and then stained with a 0.3% Gentian Violet solution (N-4[Bis[4-dimethylamino)-phenyl]methylene]-2,5-cyclohexadien-1-ylidene]-N-methylmethanaminium chloride) in 20% ethanol by immersing in the dye for 5 minutes. Once again the slide was washed with water to remove any unbound dye.
  • Gentian Violet solution N-4[Bis[4-dimethylamino)-phenyl]methylene]-2,5-cyclohexadien-1-ylidene]-N-methylmethanaminium chloride
  • a nanocrystalline titanium dioxide sol thickened with methylcellulose was screen printed on to a series of cleaned glass microscope slides.
  • the printed titanium dioxide films were then fired at 450° C. for 30 minutes.
  • Half of the slides were then immersed in an aqueous 1 ⁇ 10 ⁇ 6 M solution of tris(2,2′-bipyridyl-4,4′-dicarboxylate)Ru(II)(dichloride) for 30 minutes to allow adsorption of the sensitising agent to the titanium dioxide.
  • the slides were then removed from the sensitising solution and washed with water to remove any unbound ruthenium complex. All the slides, both sensitised and unsensitised were then divided into two groups.
  • Gentian Violet solution N-4-[Bis[4-dimethylamino)-phenyl]methylene]-2,5-cyclohexadien-1-ylidene]-N-methylmethanaminium chloride
  • Acid Orange dye 4-[(2-hydroxy-1-napthalenyl)azo]-benzenesulfonic acid monsodium salt
  • a sensitised and unsensitised slide dyed with either the Gentian Violet or Acid Orange stains was placed in total darkness and used as a control for each treatment.
  • a second equivalent set was left exposed to daylight next to the window of a south-facing window.
  • a third and final set was also left exposed to the daylight through a south-facing window but these slides were covered with a 6 mm thick piece of Perspex which substantially absorbs the UV component of the light. Decolourisation of both the purple and orange colours was monitored as both the Gentian Violet and Acid Orange were decomposed photocatalytically. After 48 hours exposure to light the slides dyed with Gentian Violet and left directly on the open bench were partially decolourised. The slides stored under the Perspex had begun to decolourize but at a slower rate than those not under Perspex. By day 7 the dye on all the slides left just on the bench had either completely or almost completely disappeared. The slides under Perspex reached the same amount of decolourization on day 14. There was no change in the colour of the slides stored in the dark.
  • the mixture was stirred, the pH was checked (pH 8.8) then a nitric acid solution (1M) was added slowly to get pH close to 3.3. The mixture was stirred for 30-45 minutes then allowed to settle. The supernatant was removed and the volume was made up with de-ionised water to 3-3.5 L. The mixture was washed until the conductivity was below 500 ⁇ S. The supernatant was removed then nitric acid (1M, 23.2 ml) was added to the white mixture. The mixture was stirred for about 20 minutes then was left to age for about a week. In order to increase the peptisation step, the mixture can be heated gently to 60-70° C. for 30 minutes then allowed to settle.
  • Titanium-isopropoxide (Aldrich, 400 ml, 97%) was added rapidly to a beaker containing de-ionised water (1 L). The precipitated TiO 2 was decanted and washed 4 times with de-ionised water (4 ⁇ 500 ml) then filtered. The wet filtered solid was digested at 70° C. with concentrated nitric acid (16.7 ml) and de-ionised water (volume total 800 ml) for 30 to 1 h 30 min to produce a sol.
  • RuCl 3 ,xH 2 O (1.33 mmol Ru), 1-methyl-2-pyrrolidinone (15 ml) and 2,2′-dipyridyl-4,4′-dicarboxylate (4.1 mmol) were added into a round bottomed flask and then purged with Ar or N 2 . The mixture was heated to reflux in the dark for 1 h30 min. 1-methyl-2-pyrrolidinone (25 ml) was added to the flask and the reflux was continued for a further 2 hours under Ar or N 2 . The mixture was allowed to cool to room temperature and kept under Ar or N 2 overnight. The dark mixture was filtered.
  • the vial containing the mixture was placed onto an overhead projector (2 cm height from the glass, in order to reduce heat).
  • the pH of the sensitised sol (TiO 2 sol prepared by Kormann method) was found to be different at each step of the process. The results are summarised in Table 2. The pH was measured using a pH meter (HANNA Instruments-HI8424 microcomputer). TABLE 2 Effect of different steps of the process on activity. pH of the Time to decolourise Steps of the process sensitised sol 0.08 ml Gentian Violet Before dialysis 1.85 2 h 45 min After dialysis 2.95 2 h 20 min Sol dried using rotary- 3.16 4 h 40 min evaporator then re-suspended Sol dried using freeze-drier 3.08 2 h 45 min mixture then resuspended* still purple.
  • Buffer solutions were obtained by diluting the powder buffer (BDH chemicals) into the required amount of de-ionised water. Attempts to stabilise TiO 2 sols prepared from the hydrolysis of TiCl 4 (Kormann method) were made using buffer solution pH 7 and pH 9.2. Addition of buffer solution pH 7 into a TiO 2 sol (10 ml, 1 g/L) produced a precipitate at pH 7. Addition of a buffer solution pH 7 or pH 9.2, de-ionised water and solid TiO 2 produced cloudy solutions at different pHs (see Table 4). TABLE 4 Buffer solutions addition effect. No Sols Particle solutions Compositions pH size (nm) Observations 1 2 ml buffer pH7 6.8 208 nm Cloudy.
  • Solutions (1) and (4) were found to be cloudier than solutions (2) and (3).
  • the particle size was higher for (1) and (4) this may correspond to the cloudiness of the solutions.
  • PVA Poly(vinyl alcohol)
  • TiO 2 :Sensitiser or TiO 2 :Ru has been looked at for a particular TiO 2 sol (Kormann method, TiO 2 sol dialysed only).
  • the sol tested was obtained from hydrolysis of TiCl 4 followed by a dialysis.
  • the experiment involved variation of ruthenium and kept the TiO 2 fixed.
  • the target dye was decolourised quicker in 1:6 TiO 2 :Ru ratio than in 1:2 TiO 2 :Ru ratio
  • the target dye gentian violet (0.05 ml, 0.03 wt/v %) was decolourised within 3 hours in 1:6 TiO 2 :Ru ratio whereas in 1:4 TiO 2 :Ru ratio and 1:2 TiO 2 :Ru ratio the gentian violet decolourised within 4 and 5 hours, respectively.
  • a range of dyes have been tested as potential sensitising agent. They include: copper or iron complexes containing sulfonated phtalocyanine ligands, silicon complex containing phtalocyanine ligand and ruthenium complexes containing bipyridyl or functionalised bipyridyl complexes (e.g: carboxylate, phosphonate) ligands and anions (e.g.: Cl, NCS) and rose bengal.
  • TiO 2 sols have been tested for their activity including commercially available types from the Millennium Performance Chemicals, 85 Avenue Victor Hugo, 92563 Rueil-Malmaison Cedex, France.
  • the TiO 2 sol (made from isopropoxide route) containing PVA (MW: 15,000) was prepared as follows. PVA (0.10 g, MW:15,000) was diluted in hot de-ionised water (50 ml) then allowed to cool to room temperature. A known amount of concentrated TiO 2 sol was added to the PVA solution under vigorous stirring. The volume was completed to 100 ml with de-ionised water. Final TiO2 concentration 1 g/L.
  • a solution containing a TiO2 sol (Millennium TiO2 sol in basic medium, 10 g/L, 5.0 ml), tris(2,2′-bipyridyl-4,4′-dicarboxylate)ruthenium(II)(dichloride) (1.8 ml, 3.4 ⁇ 10 ⁇ 5 M), Igepal® CO-720 (0.18 g) and de-ionised water (3.2 ml) was stirred for few minutes using a rotamixer. The pH was adjusted to 10 by addition of a sodium hydroxide solution (0.1M). The mixture was wrapped into some aluminium foil and left standing overnight to equilibrate.
  • a TiO2 sol Millennium TiO2 sol in basic medium, 10 g/L, 5.0 ml
  • tris(2,2′-bipyridyl-4,4′-dicarboxylate)ruthenium(II)(dichloride) (1.8 ml, 3.4 ⁇ 10 ⁇
  • a solution containing a TiO2 sol (Millennium TiO2 sol in basic medium, 10 g/L, 5.0 ml), Igepal® CO-720 (0.18 g) and de-ionised water (5.0 ml) was stirred for few minutes using a rotamixer. The pH was adjusted to 10 by addition of a sodium hydroxide solution (0.1M).
  • Thin films of these solutions were prepared by spin coating 0.1 ml of these solutions at 100 to 500 rpm on a clean glass microscope slide for 80 seconds. The film was dried using a hot air gun and the process repeated to give a total of 2 coats on the microscope slide. A second slide was then prepared in exactly the same way. All slides were then immersed into a solution of 0.3% Gentian Violet in 20% ethanol for 5 minutes. The slides were removed, rinsed with water to remove any excess stain and allowed to air dry. One slide was kept in total darkness and the second was placed onto an overhead projector (Model Ensign. Lamp: 24V-250 W-3860 lux). The purple colour on the films faded after 3 hours 30 min. There was no change in the colour of the slide stored in darkness.
  • the titania sols have been characterised by TEM (transmission electron microscopy). The samples were prepared by pipetting a few drops of the sol onto holey carbon films. Gold grids were used to avoid support corrosion. The microscope used was a Philips CM20, operated at 200 kV.The results are summarised in Table 7. TABLE 7 TEM results of different source of titania. TiO 2 sol source TEM results Prepared as per example 1 of GB 1412 Irregularly shaped titania crystallites mainly 937 (Woodhead) (peptised at 60° C.) anatase with a size of 10 nm.
  • the TiO 2 sol (made from isopropoxide route) containing PVA (MW:15,000) was prepared as follows. PVA (0.10 g, MW:15,000) was diluted in hot de-ionised water (50 ml) then allowed to cool to room temperature. A known amount of concentrated TiO 2 sol was added to the PVA solution under vigorous stirring. The volume was completed to 100 ml with de-ionised water. Final TiO2 concentration 1 g/L. A mixture of TiO 2 sol containing PVA (1 ml, 1 g/L) and de-ionised water (4 ml) was stirred for about 1 minute using a rotamixer. Gentian violet (0.08 ml, 0.03 wt/v %) was added to the mixture.
  • the TiO 2 sol (made from isopropoxide route) containing PVA (MW15,000) was prepared as follows. PVA (0.10 g, MW 15,000) was diluted in hot de-ionised water (50 ml) then allowed to cool to room temperature. A known amount of concentrated TiO 2 sol was added to the PVA solution under vigorous stirring. The volume was completed to 100 ml with de-ionised water. Final TiO2 concentration 1 g/L.
  • a UV/Visible spectrum is taken at this stage.
  • the vials containing the mixtures were placed onto an overhead projector (2 cm height from the glass, in order to reduce heat). UV/Visible spectra were used to observe the colour change over a period of time.
  • TiO2 without dye has significantly slower photocatalytic activity when compared with sensitised TiO 2
  • a microscope slide containing a thin film of sensitised TiO 2 was added into a solution of 4-chlorophenol (99+%, Aldrich, 8 ml, 10 ⁇ 4 M).
  • the vial containing the solution and the slide was placed onto an overhead projector.
  • the degradation of 4-chlorophenol was monitored using UV/Visible analysis.
  • Zinc oxide was prepared according to the method outlined by Bruemann et al, J. Phys. Chem., (1987), 91, 3789.
  • the oxide suspension (made by stirring the ZnO solid into a sodium hydroxide solution at pH9) was then sensitised with 4,4′-dicarboxa late,tris (2,2′bibyridyl) Ru (II) dichloride according to the method outlined in previous examples.
  • Gentian violet dye was added to both the sensitised sample and the non-sensitised control sample, and the UV/visible spectrum was recorded as a function of time under illumination with white light (5,000 lux). The results demonstrate that the absorption peak associated with Gentian Violet decreases faster with the sensitised ZnO compared to the control.
  • Typical positively charged groups for use as binding sites include, but are not limited to R 4 N+ groups and R 4 P+ groups, where R is as hereinbefore described
  • Terpyridyl-based sensitisers with phosphonate chelating ligands have been used in conjunction with titania in dye-sensitised solar cells.
  • the terpyridyl group of general formula I can be synthesised with e.g. R1 as a positively charged unit.
  • R5-7 of formula II are methyl, is synthesised according to procedures where the intermediate is made by the method outlined in Recl.Trav. Chim. Pays. Bas, 1959, v78, 408.
  • This nitrated aryl group is then changed into the terpyridyl unit by the method outlined by McWhinne et al (J Organoetallic chem.., 1968, v11, 499).
  • the nitro group is then reduced to the amine by hydrazine hydrate under Pd/C catalysis followed by reaction with excess methyl iodide to form the quaternary nitrogen terpyridyl ligand desired.
  • terpyridyl molecule [described by general formula I] can be synthesised by reacting 2-acetylpyridine with 4-nitrobenzaldehyde in base followed by ring closure with ammonium acetate according to methods outlined by E Constable et al (J Chem Soc Dalton Trans, 1992, 2947), followed by reduction of the nitro group to the amine and quaternisation as described previously to form a compound described by formula I with R2 and R 3 as hydrogen and R1 as
  • Phthalocyanine dyes can be synthesised with amine nitrogen groups by e.g. Buchwald ammination of halide precursors to produce outer-ring derivatives such as (J Org Chem 2000, V65, 1158), the amine groups of which are then quarternised.
  • TADAs Tetra-aza-annulenes
  • TADAs of the general formula V can be derivatised at R1, R2, R3, and R4 by the general methods outlined above.
  • the bipyridyl compounds tris(2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium (II) dichloride and tris(2,2′-bipridyl) ruthenium (II) dichloride can be dimerised using pyrazine derivatives such as pyrazine, pyrimidine and 4,4′-bipyridyl linking ligands according to procedures detailed in (E A Seddon & K R Seddon, The Chemistry of Ruthenium, Elsevier, New York 1984, p 436).

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US20060019853A1 (en) * 2002-10-29 2006-01-26 Torsten Wieprecht Use of metal complex compounds as catalysts for oxidation using molecular oxygen or air
US20060104894A1 (en) * 2004-11-16 2006-05-18 Daoud Walid A Method for making single-phase anatase titanium oxide
US20070190765A1 (en) * 2005-12-29 2007-08-16 Rong-Cai Xie Quaternary oxides and catalysts containing quaternary oxides
US20070202334A1 (en) * 2005-12-29 2007-08-30 Rong-Cai Xie Nanoparticles containing titanium oxide
CN100340616C (zh) * 2006-01-17 2007-10-03 福州大学 复合灭菌涂料的制备方法
US20090068282A1 (en) * 2001-04-30 2009-03-12 Gunther Schlingloff Use of metal complex compounds as oxidation catalysts
US20100193449A1 (en) * 2009-02-02 2010-08-05 Jian-Ku Shang Materials and methods for removing arsenic from water
US20100294304A1 (en) * 2000-12-21 2010-11-25 Massholder Karl F Aqueous composition containing a semiconductor
US20110003684A1 (en) * 2004-11-16 2011-01-06 Walid Abdelhemld Daoud Method for making single-phase anatase titanium oxide
CN108452773A (zh) * 2018-03-07 2018-08-28 南昌航空大学 一种可同时吸附和检测三价铬离子并具有光催化活性的纳米功能材料的制备方法

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EP1217056A1 (de) * 2000-12-21 2002-06-26 Johnson Matthey Public Limited Company Fotokatalytisches Material
AUPR501901A0 (en) * 2001-05-16 2001-06-07 Sustainable Technologies International Pty Ltd Improved method for large scale manufacturing of dye-seusitised solar cells
GB2378185B (en) 2001-06-27 2003-12-17 Reckitt Benckiser Improvements in relation to organic compositions
BR0312694B1 (pt) 2002-07-11 2013-11-05 Uso de compostos de complexo de metal como catalisadores de oxidação, compostos de complexo de metal, agente de lavagem, limpeza, desinfecção ou alvejamento, bem como preparação sólida
GB2394720A (en) * 2002-10-30 2004-05-05 Reckitt Benckiser Nv Metal complex compounds in dishwasher formulations
GB2409207B (en) * 2003-12-20 2006-08-09 Reckitt Benckiser Nv Use of metal complex compounds as oxidation catalysts
DE102008020755A1 (de) * 2008-04-18 2009-10-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Luft-, Wasser- und Oberflächenreinigung unter Nutzung des photodynamischen Effektes
KR101021567B1 (ko) * 2009-05-25 2011-03-16 성균관대학교산학협력단 광촉매, 이의 제조방법 및 이를 이용한 휘발성 유기물의 분해 방법
JP2012179531A (ja) * 2011-02-28 2012-09-20 Silicon Plus Corp 色素増感光触媒、坦持型色素増感光触媒及び被膜形成用コーティング組成物
EP3060907A1 (de) * 2013-10-22 2016-08-31 Owens, Jeffery Ray Rose-bengal-test zum nachweis der oxidativen zersetzung von verunreinigungen
TWI707725B (zh) * 2019-06-27 2020-10-21 奇鼎科技股份有限公司 光催化分解材料之製備方法及使用光催化分解材料之濾網結構

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US4731194A (en) * 1982-12-13 1988-03-15 Henkel Kommanditgesellschaft Auf Aktien Silica-containing alkaline dispersions and their use in cleaning solid surfaces
US5376288A (en) * 1989-06-21 1994-12-27 Noro Nordisk A/S Detergent additive granulate and detergent
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US8172951B2 (en) * 2000-12-21 2012-05-08 Massholder Karl F Method of cleaning with an aqueous composition containing a semiconductor
US20100294304A1 (en) * 2000-12-21 2010-11-25 Massholder Karl F Aqueous composition containing a semiconductor
US20090068282A1 (en) * 2001-04-30 2009-03-12 Gunther Schlingloff Use of metal complex compounds as oxidation catalysts
US8044013B2 (en) * 2001-04-30 2011-10-25 Basf Se Use of metal complex compounds as oxidation catalysts
US20060019853A1 (en) * 2002-10-29 2006-01-26 Torsten Wieprecht Use of metal complex compounds as catalysts for oxidation using molecular oxygen or air
US20110003684A1 (en) * 2004-11-16 2011-01-06 Walid Abdelhemld Daoud Method for making single-phase anatase titanium oxide
US20060104894A1 (en) * 2004-11-16 2006-05-18 Daoud Walid A Method for making single-phase anatase titanium oxide
US7255847B2 (en) * 2004-11-16 2007-08-14 The Hong Kong Polytechnic University Method for making single-phase anatase titanium oxide
US8309167B2 (en) 2004-11-16 2012-11-13 The Hong Kong Polytechnic University Method for preparing an article with single-phase anatase titanium oxide
US8106101B2 (en) 2004-11-16 2012-01-31 The Hong Kong Polytechnic University Method for making single-phase anatase titanium oxide
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US7521394B2 (en) 2005-12-29 2009-04-21 The Board Of Trustees Of The University Of Illinois Nanoparticles containing titanium oxide
US20070202334A1 (en) * 2005-12-29 2007-08-30 Rong-Cai Xie Nanoparticles containing titanium oxide
US20070190765A1 (en) * 2005-12-29 2007-08-16 Rong-Cai Xie Quaternary oxides and catalysts containing quaternary oxides
US8541337B2 (en) 2005-12-29 2013-09-24 The Board Of Trustees Of The University Of Illinois Quaternary oxides and catalysts containing quaternary oxides
CN100340616C (zh) * 2006-01-17 2007-10-03 福州大学 复合灭菌涂料的制备方法
US20100193449A1 (en) * 2009-02-02 2010-08-05 Jian-Ku Shang Materials and methods for removing arsenic from water
CN108452773A (zh) * 2018-03-07 2018-08-28 南昌航空大学 一种可同时吸附和检测三价铬离子并具有光催化活性的纳米功能材料的制备方法

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