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CN1692982A - Nanometer catalyst for used under sunlight and its prepn. method - Google Patents

Nanometer catalyst for used under sunlight and its prepn. method Download PDF

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Publication number
CN1692982A
CN1692982A CN 200510042115 CN200510042115A CN1692982A CN 1692982 A CN1692982 A CN 1692982A CN 200510042115 CN200510042115 CN 200510042115 CN 200510042115 A CN200510042115 A CN 200510042115A CN 1692982 A CN1692982 A CN 1692982A
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China
Prior art keywords
film
room temperature
sheet glass
out light
catalytic
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Granted
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CN 200510042115
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Chinese (zh)
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CN1318136C (en
Inventor
李晓俊
王晓丽
刘丰
李静
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HENGGUAN PLASTIC RUBBER CO Ltd SHANDONG
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HENGGUAN PLASTIC RUBBER CO Ltd SHANDONG
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Priority to CNB2005100421158A priority Critical patent/CN1318136C/en
Publication of CN1692982A publication Critical patent/CN1692982A/en
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Publication of CN1318136C publication Critical patent/CN1318136C/en
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Abstract

A catalyzing nanofilm able to play its catalysis role under sunlight is prepared from TiO2 as carrier and cadmium sulfide as active component through proportional mixing, coating it on glass, heating treating in tubular furnace, and maintaining the temp for 2 hr.

Description

A kind of light-catalysed nano-catalytic film and preparation method thereof that under sunshine, carries out
(1) technical field
The present invention relates to a kind of nano-photo catalytic film that is used to purify air, be specifically related to a kind of light-catalysed nano-catalytic film and preparation method thereof that under sunshine, carries out.
(2) background technology
Preceding 20 years of 21 century was the critical period of international development nano material, and nanometer technology will be brought new opportunity to the every field development.Serious day by day along with environmental problem in the world wide, nano-photocatalyst material are widely studied and at present as novel environment-friendly materials.Self-cleaning glass as one of them branch is with titanium dioxide (TiO 2) be main body, adopt eco-friendly surface sensitizing technology, airborne greasy dirt and other harmful substance are realized that efficient pollution-free transforms.
Traditional self-cleaning glass is with coating TiO 2Single composition is main, because titanium dioxide (TiO 2) energy gap be 2ev, its photocatalysis characteristic is only limited to ultraviolet band, and the sunshine that is used for catalytic degradation mainly is distributed in the 0.25-2.5 mu m range, at this wave band ultraviolet light only about 2%, thereby titanium dioxide (TiO 2) directly to utilize sunshine to carry out the efficient of photocatalytic degradation lower, can't be with a wide range of applications.
In order to address this problem, people are once at TiO 2In utilize precious metal element, rare earth element etc. to carry out doping vario-property, wish to cause the red shift of ABSORPTION EDGE.Though obtain certain effect, light-catalyzed reaction still need be carried out under high-pressure sodium lamp or uviol lamp, can't fundamentally improve the efficient of titanium dioxide photocatalytic degradation under sunshine.
(3) summary of the invention
For solving the deficiency that prior art exists, the invention provides a kind of light-catalysed nano-catalytic film and preparation method thereof that under sunshine, carries out, this film can be by light-catalyzed reaction, common trace harmful gases in air is converted into harmless product, formaldehyde that can the human lives place is common, hydrogen sulfide, methyl mercaptan, ammonia etc. have the trace harmful gases of foul odour to be eliminated, to purify air.
The present invention realizes by following measure:
As carrier, is active component with the cadmium sulfide with titanium dioxide, coats laminated film at glass surface, and the mol ratio of titanium dioxide and cadmium sulfide is 45%; Laminated film is heat-treated under room temperature-450 ℃ in tube furnace, and 450 ℃ of following constant temperature 2 hours promptly.
Be coated with the pure TiO that a layer thickness is 28-34nm on the above-mentioned gained composite membrane surface again 2Film, and be coated with pure TiO 2Hole material polyethylene glycol or the trifluoroacetic acid that add 5% percentage by weight in the thin-film process.Titanium dioxide crystal form is the anatase type.
Under sunshine, carry out light-catalysed nano-catalytic film and preparation method thereof, comprise the steps:
(1) in the aqueous solution of the CdS solution that contains 0.1mol/L-0.2mol/L ammonium titanium fluoride and 0.3mol/L-0.5mol/L boric acid and 0.22mol/L-0.25mol/L, adds 0.5mgTiO 2Crystallite must react stoste after the stirring;
(2) will at room temperature leave standstill 5h-6h respectively through the vertical reactant liquor of putting into of sheet glass after rare nitric acid, absolute ethyl alcohol and the distilled water supersound washing of percentage by weight 5%, and take out the washing back and dry naturally;
(3) sheet glass after drying places tube furnace, heat-treats under room temperature-450 ℃, when reaching 450 ℃, 450 ℃ of following constant temperature 2 hours;
(4) sheet glass of handling well is put into the polyethylene glycol of 0.1mol/L-0.2mol/L ammonium titanium fluoride and 0.3mol/L-0.5mol/L boric acid and 5% percentage by weight or the aqueous solution of trifluoroacetic acid and left standstill 5h-6h, take out the washing back and dry naturally;
(5) sheet glass after drying places tube furnace, heat-treats under room temperature-450 ℃, when reaching 450 ℃, 450 ℃ of following constant temperature 2 hours, promptly obtains a kind of porous photocatalytic film of stable performance.
In order to reduce the stripping quantity of film surface cadmium, reduce the decay of film light catalytic activity, can continue following steps:
(6) the laminated film surface after heat treatment is coated with the pure TiO of last layer thickness 28-34nm 2Film, and be coated with pure TiO 2Hole material polyethylene glycol or the trifluoroacetic acid that add percentage by weight 5% in the thin-film process.
Quantity of cadmium release is the important safety sanitary index of silicate product.The existence of cadmium is owing to contain due to the cadmium in the composition that the product surface processing procedure is introduced, and as if improper process control or improper use, very easily causes the excessive stripping of cadmium in use.Therefore product in this experiment will consider the influence that quantity of cadmium release uses film because introduced cadmium element in the surface coating process in test process.
Standard GB 12651-92 " the ceramic lead that contacts with food, quantity of cadmium release tolerance limit " is a state compulsory standard, and its scope of application has covered all domestic ceramics wares.Standard code: the good fortune stripping quantity of any single product does not allow to surpass 0.5ppm.
The present invention adopts AAS to measure the cadmium amount of stripping.Method of testing: the solvent that can touch when glass contacts with air during according to practical application has only water, has acid rain under with serious pollution situation.Therefore be solvent with water when measuring, water is mixed with pH value is 5 dilute acid soln to the acid rain composition in the imitation atmosphere.Diluted acid is poured in the beaker that fills glass substrate,, in 20 ℃ ± 2 ℃ environment temperature, soaked 24 hours, measure its quantity of cadmium release until till overfall 5mm place.
Cubage quantity of cadmium release with the cadmium in the diluted acid of test.The cadmium of unit glass surface stripping (Cd) in test, its result mg/dm 2Be expressed as follows: ρ A (M)=ρ (M) x V/1000xl/A.
In the formula: the cadmium of ρ A (M)-stripping; ρ (the M)-concentration of cadmium in extract, mg/L; V adds the volume of the water in the beaker, mL one by one; The surface area of A-test, dm 2Represent the concentration (Cd) of cadmium stripping and with mg/dm with mg/L 2The cadmium content (Cd) of representation unit surface institute stripping.The seepage discharge of cadmium is as the criterion to be lower than national standard.
Nano-photo catalytic film of the present invention is used for sealing or the elimination of hemi-closure space pernicious gas, the nano-photo catalytic reaction with sunshine as excitation source.
Nano-photo catalytic film reaction condition is: the employing sunshine is an excitation source, is 1-5h at optical response time.Catalytic film is carried on glass surface, is placed in the closed container of printing opacity.In container and a fan is arranged, the gas flow that makes internal tank is to reach concentration balance.
The present invention compared with prior art excellent results is as follows:
1. Zhi Bei film is transparent, with the base material strong adhesion.
2.UV move to the visible light direction and to work, under sunshine, just can carry out photocatalysis.
3. photocatalysis film is active high, and after the light-catalyzed reaction, air quality reaches the level close with outdoor air.
4. nano-photo catalytic film coating process is simple, does not require special installation
(4) specific embodiment
Embodiment 1:
(1) aqueous solution that will contain the CdS solution of 0.2mol/L ammonium titanium fluoride and 0.5mol/L boric acid and 0.25mol/L adds 0.5mgTiO 2Crystallite must react stoste after the stirring; (2) will pass through rare nitric acid respectively, absolute ethyl alcohol and the vertical reactant liquor of putting into of sheet glass after the distilled water supersound washing, at room temperature leave standstill 6h, taking out the washing back dries naturally, (3) sheet glass after drying places tube furnace, under room temperature-450 ℃, heat-treat, and 450 ℃ of following constant temperature 2 hours; (4) then, the aqueous solution of this slide of handling well being put into again 0.1mol/L ammonium titanium fluoride and 0.3mol/L boric acid and 5% (percentage by weight) polyethylene glycol leaves standstill 6h, taking out the washing back dries naturally, (5) in tube furnace, under room temperature-450 ℃, heat-treat then, and, obtain a kind of porous photocatalytic film of stable in properties 450 ℃ of following constant temperature 2 hours.Relevant test data is as follows: at 0.0256m 3In the closed container, the initial concentration that makes formaldehyde is 25ppm, and behind solar light irradiation reaction 5h, the photodissociation rate of formaldehyde is 81%; The initial concentration that makes hydrogen sulfide is 18ppm, and behind solar light irradiation reaction 5h, the photodissociation rate of hydrogen sulfide is 94%; The initial concentration that makes methyl mercaptan is 12ppm, and behind solar light irradiation reaction 5h, the photodissociation rate of methyl mercaptan is 89%; The initial concentration that makes ammonia is 23ppm, and behind solar light irradiation reaction 5h, the photodissociation rate of ammonia is 77%.
Embodiment 2:
(1) aqueous solution that will contain the CdS solution of 0.1mol/L ammonium titanium fluoride and 0.3mol/L boric acid and 0.22mol/L adds 0.5mgTiO 2Crystallite must react stoste after the stirring; (2) will pass through rare nitric acid respectively, absolute ethyl alcohol and the vertical reactant liquor of putting into of sheet glass after the distilled water supersound washing, at room temperature leave standstill 6h, taking out the washing back dries naturally, (3) sheet glass after drying places tube furnace, under room temperature-450 ℃, heat-treat, and 450 ℃ of following constant temperature 2 hours; (4) then, the aqueous solution of this slide of handling well being put into again the trifluoroacetic acid of 0.2mol/L ammonium titanium fluoride and 0.5mol/L boric acid and 5% percentage by weight leaves standstill 6h, taking out the washing back dries naturally, (5) in tube furnace, under room temperature-450 ℃, heat-treat then, and, obtain a kind of porous photocatalytic film of stable in properties 450 ℃ of following constant temperature 2 hours.Relevant test data is as follows: at 0.0256m 3In the closed container, the initial concentration that makes formaldehyde is 23ppm, and behind solar light irradiation reaction 5h, the photodissociation rate of formaldehyde is 80%; The initial concentration that makes hydrogen sulfide is 21ppm, and behind solar light irradiation reaction 5h, the photodissociation rate of hydrogen sulfide is 92%; The initial concentration that makes methyl mercaptan is 16ppm, and behind solar light irradiation reaction 5h, the photodissociation rate of methyl mercaptan is 87%; The initial concentration that makes ammonia is 22ppm, and behind solar light irradiation reaction 5h, the photodissociation rate of ammonia is 75%.
Embodiment 3: as described in embodiment 1, different is after step (5), continues the pure TiO that the laminated film surface of step (6) after heat treatment is coated with last layer thickness 30nm 2Film, and be coated with pure TiO 2A hole material polyethylene glycol that adds percentage by weight 5% in the thin-film process.

Claims (5)

1. one kind is carried out light-catalysed nano-catalytic film under sunshine, it is characterized in that, titanium dioxide is active component as carrier with the cadmium sulfide, coats laminated film at glass surface, and the mol ratio of titanium dioxide and cadmium sulfide is 45%; Laminated film is to heat-treat under room temperature-450 ℃ in tube furnace, and obtained in 2 hours at 450 ℃ of following constant temperature.
2. as claimed in claim 1ly under sunshine, carry out light-catalysed nano-catalytic film, it is characterized in that, scribble the pure TiO of a layer thickness 28-34nm on the gained laminated film surface again 2Film, and be coated with pure TiO 2Hole material polyethylene glycol or the trifluoroacetic acid that add 5% percentage by weight in the thin-film process.
3. as claimed in claim 1ly under sunshine, carry out light-catalysed nano-catalytic film, it is characterized in that titanium dioxide crystal form is the anatase type.
4. a preparation method who carries out light-catalysed nano-catalytic film under sunshine comprises the steps:
(1) in the aqueous solution of the CdS solution that contains 0.1mol/L-0.2mol/L ammonium titanium fluoride and 0.3mol/L-0.5mol/L boric acid and 0.22mol/L-0.25mol/L, adds 0.5mgTiO 2Crystallite must react stoste after the stirring;
(2) will pass through rare nitric acid respectively, absolute ethyl alcohol and the vertical reactant liquor of putting into of sheet glass after the distilled water supersound washing at room temperature leave standstill 6h, take out the washing back and dry naturally;
(3) sheet glass after drying places tube furnace, heat-treats under room temperature-450 ℃, when reaching 450 ℃, 450 ℃ of following constant temperature 2 hours;
(4) sheet glass of handling well is put into the polyethylene glycol of 0.1mol/L-0.2mol/L ammonium titanium fluoride and 0.3mol/L-0.5mol/L boric acid and 5% percentage by weight or the aqueous solution of trifluoroacetic acid and left standstill 6h, take out the washing back and dry naturally;
(5) sheet glass after drying places tube furnace, heat-treats under room temperature-450 ℃, when reaching 450 ℃, 450 ℃ of following constant temperature 2 hours, promptly obtains a kind of porous photocatalytic film of stable performance.
5. the preparation method who carries out light-catalysed nano-catalytic film under sunshine as claimed in claim 4 is characterized in that, comprises that also step (6) is coated with the pure TiO of last layer thickness 28-34nm on the laminated film surface 2Film, and be coated with pure TiO 2Hole material polyethylene glycol or the trifluoroacetic acid that add 5% percentage by weight in the thin-film process.
CNB2005100421158A 2005-03-02 2005-03-02 Nanometer catalyst for used under sunlight and its prepn. method Expired - Fee Related CN1318136C (en)

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CN1318136C CN1318136C (en) 2007-05-30

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100348318C (en) * 2005-11-28 2007-11-14 浙江大学 Nanometer, composite semiconductor photocatalyst, and its prepn. method
CN100351013C (en) * 2006-02-27 2007-11-28 西安交通大学 CdS/Ti-MCM-41 loaded platinum photo catalyst and its preparation method
CN100448780C (en) * 2007-01-19 2009-01-07 北京工业大学 A method for making the surface of cadmium sulfide film hydrophilic by using light
CN110655141A (en) * 2019-09-20 2020-01-07 蚌埠学院 Method for repairing water microecosystem by using CdS glass colored glaze

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60118239A (en) * 1983-11-29 1985-06-25 Toshiba Corp Semiconductor photocatalyst
KR100304349B1 (en) * 1998-09-09 2001-11-30 김충섭 Photocatalyst for generating cadmium sulfide hydrogen and its production method and hydrogen production method using the same
KR100301281B1 (en) * 1999-06-18 2001-09-13 김충섭 The Manufacturing Method of CdS Photocatalyst for Hydrogen Production and Method for Producing Hydrogen by use of the same
CN1269565C (en) * 2004-05-26 2006-08-16 鞍山市环境保护研究所 SiO2/TiO2 composite nanometer photocatalysis membrane for treating indoor light pollution air and preparing method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100348318C (en) * 2005-11-28 2007-11-14 浙江大学 Nanometer, composite semiconductor photocatalyst, and its prepn. method
CN100351013C (en) * 2006-02-27 2007-11-28 西安交通大学 CdS/Ti-MCM-41 loaded platinum photo catalyst and its preparation method
CN100448780C (en) * 2007-01-19 2009-01-07 北京工业大学 A method for making the surface of cadmium sulfide film hydrophilic by using light
CN110655141A (en) * 2019-09-20 2020-01-07 蚌埠学院 Method for repairing water microecosystem by using CdS glass colored glaze

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