A kind of method of synthesizing titanium sol-gel paint under light induction
The invention belongs to titanium sol-gel paint and titanium dioxide nano material technical field, particularly a kind of method of synthesizing titanium sol-gel paint under light induction.
Mankind's activity makes atmospheric pollution and water pollute more and more serious.Discharge obnoxious flavoures such as a large amount of sulfurous gas, carbon monoxide as industrial coal.Along with the automobile industry development of China, the air severe contamination that lower valency nitride that motor vehicle exhaust is a large amount of and CO (carbon monoxide converter) gas make each big and medium-sized cities; Many on the other hand house decorative materials also can slowly discharge such as small molecules harmful organic substances such as aldehydes, phenols, alcohols, also have our human body, pet, food also to discharge bad smell, and our health in these invisible gas serious threats.People are faced with the shortage of Freshwater resources on the one hand, and great amount of water resources is subjected to serious pollution on the other hand.So improving the living environment of human and other life is whole world question of common concern.Because titanium dioxide nano-particle produces hole-electron pair during greater than the photon irradiation of its semiconductor energy gap at energy, the synergy of hole-electron pair not only has intensive oxidative degradation ability to the pollutent in the environment, but also have sterilizing function, so be the good functional materials of environment purification.
Can widespread use TiO
2The photocatalytic degradation function of nanoparticle need to solve two key issues, the supporting of first titanium dioxide optical catalyst layer; It two is active height of photocatalyst layer of titanium dioxide.
The titanium sol-gel is a kind of coating that is easy to be supported on the base material, and that the titanium sol-gel that existing titanium sol-gel process is prepared is supported on the titanium dioxide catalytic activity that substrate surface forms is low, so need just have good photocatalytic activity by sintering.Present titanium process for preparing sol-gel is that titanium organometallic compound catalytic hydrolysis under acid, alkali or water effect is formed the titanium sol-gel, and is dry then or be coated on substrate surface and form tiny non-crystal state TiO
2Nanoparticle, its catalytic activity is very low, improve its catalytic activity and need make it be transformed into the high TiO of crystallization degree usually at 400-500 ℃ sintering temperature
2Particle.As Mikula, M. etc. have reported with tetrabutyl titanate at water and HNO on " Materials science wall bulletin " magazine (1995, the 14 volumes, 615-616 page or leaf) [J.Mater.sci.lett.1995,14,615-616]
3Etc. preparation titanium sol-gel under the system, be supported on then on the base material, sinter TiO into 450 ℃ with good catalytic activity
2Hiroaki and for example, T. etc. are at " youth Ge Miuer " periodical (1997, the 13 volumes, the 360-364 page or leaf) [Langmuir 1997,13,360-364] are gone up and have been prepared the titanium sol-gel with isopropyl titanate, be supported on then on the quartz substrate, with just having good catalytic activity behind 500 ℃ of temperature sintering.Japanese Patent JP08 for another example, 299,789 disclose the titanium organic metal salt have been dissolved in the organic solvent, are coated on substrate surface then, and the titanium organic metal salt is hydrolyzed into aqueous TiO after the solvent evaporates
2Nanoparticle layers, TiO is burnt till in baking then
2The nano-particle catalyst layer.But these methods can only be applied to the substrate surface of heatproofs such as glass, pottery, metal.
The object of the present invention is to provide a kind of method of synthesizing titanium sol-gel paint under light induction, the titanium sol-gel paint of preparing can directly be supported on the substrate surface, obstructed oversintering directly becomes the TiO with good light catalytic activity
2Nanoparticle, with purify air effectively, waste water and clean surface.
The preparation method of titanium sol-gel paint of the present invention utilizes ultraviolet photon energy, induces and control the structure of colloidal growth, makes titanium sol-gel paint have property.Its preparation method is as follows:
At room temperature, by weight percentage, with titanic acid ester or titanate 1-50%, thinner 50-98%, hydrolyst 0.5-10% pipettes in the reactor and mixes, prepared titanium sol-gel paint with containing ultraviolet light source light according to 30 minutes-10 hours, above-mentioned weight percent sum is 100%.
Wherein titanic acid ester or titanic acid ester salt can be selected from and add following a kind of or several the mixing by arbitrary proportion: Ti (OC
4H
9)
4, Ti (OC
2H
5)
4, Ti (iso-OC
3H
7)
4Or TiCl
4Deng; Hydrolyst is: concentrated hydrochloric acid, nitric acid, sulfuric acid, Glacial acetic acid or water etc.; Thinner can be dehydrated alcohol or anhydrous methanol etc.Wherein containing ultraviolet light source is light sources such as basic, normal, high pressure mercury lamp.
The purposes of titanium sol-gel paint of the present invention:
This titanium sol-gel paint directly is supported on the base material makes titania functional material with nuisance in the empty G﹠W of photocatalytic degradation.
Wherein said base material is textiles, non-woven fabrics, paper, glass, pottery, steel, aluminium, stone material, timber, resin, plastics etc.
The coating process for preparing above-mentioned titania functional material is: the titanium sol-gel paint for preparing is coated on the base material with methods such as dipping, dip-coating, spraying, spin coating or diffusion are coated with, then at room temperature, the mobile diluent evaporates that allows by air is fallen, and is supported on the very long high Detitanium-ore-type TiO of crystallization degree that is transformed into of titanium sol-gel paint on the base material
2, this TiO that supported
2Base material have high catalytic activity.To base material wide adaptability.
The titanium sol-gel method is a kind of method that is widely used in the preparation nano material.It has the advantages such as composition of regulation system according to the above ratio, regulates the microstructure of titanium sol-gel, can make the functional materials of unique properties.
The titanium sol-gel paint that the present invention prepares under the irradiation of UV-light, on carrier, can directly become titanium dioxide with highlight catalytic active, can effectively utilize the ultraviolet degradation dyestuff of ultraviolet source as the 1# sample of embodiment 1, the results are shown in embodiment 1 (accompanying drawing 1A).With the high voltage mercury lamp of 400W as light source and sample pool at a distance of the 15cm place to 1 * 10
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-1The rhodamine B dyestuff degrade, a state from Figure 1A only needs 30 minutes to the b state, and the 2# sample of embodiment 1 is without the sample of ultraviolet lighting synthetic titanium sol-gel paint preparation, and catalytic activity is low, the a state is degraded to the b state from Figure 1B, then needs 10 hours.
The result shows from the Raman spectrometry, and the 1# sample crystallization degree of embodiment 1 is good, and TiO is arranged
2The characteristic peak 140cm of Detitanium-ore-type
-1Occur, and the 2# sample does not have tangible TiO
2(comparative result is seen accompanying drawing 2) appears in the Raman peak.
The 1# sample of embodiment 1 also can utilize the faint ultraviolet degradation aldehydes gas of luminescent lamp (seeing the 1# in the accompanying drawing 3) efficiently., the aldehydes gas of 16ppm can be reduced to about 1ppm in one hour, and the same terms 2# sample only reduces 5ppm as light source with the 20W luminescent lamp.Embodiment 3 shows with the 1# sample of embodiment 1 also can remove hydrogen sulfide (seeing accompanying drawing 4) at the ultraviolet lamp of 20W under as the situation of light source effectively.
Embodiment 4 has compared and utilizes tetrabutyl titanate to prepare TiO at different light time synthetic titanium sol-gel paint
2Sample is to aldehydes gas catalyzed degradation ability, the degradation results of comprehensive 2 pairs of acetaldehyde of embodiment, the mercury lamp illumination that shows 400W was the preferred time in 1 hour, and the catalytic activity difference of the catalytic activity of the sample that 2 hours, 5 hours titanium sol-gel of illumination makes and 1 hour sample is little.
Embodiment 5,6,8,9 has examined or check the different initial concentrations of tetrabutyl titanate, different hydrolyst and different methods and has been supported on the catalytic activity experiment for preparing sample on the different base materials.The system of the tetrabutyl titanate illumination of embodiment 5 usefulness 1% preparation in 30 minutes, dip-coating is on cotton, and getting area is 5 * 5cm
2Cloth was 8.67 * 10 with 50ml concentration in 6 hours
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-1Rhodamine B degrade substantially (seeing accompanying drawing 6).The tetrabutyl titanate of embodiment 6,5% is that the system that the light source illumination reaction prepared in 1 hour is spin-coated on the glass substrate with the 400W high voltage mercury lamp, and area is 5 * 5cm
2It is 8.67 * 10 that sample can be finished 50ml concentration in 4 hours substantially
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-1Rhodamine B degraded (seeing accompanying drawing 7), and the not sample degraded in more than 10 hour of illumination can not degrade fully (seeing accompanying drawing 8) of embodiment 7 the same terms.Embodiment 8, and the system of high density titanic acid ester preparation is supported on the cotton, can finish the degraded of above-mentioned identical rhodamine B substantially in 40 minutes.The system (embodiment 9) of the mixed with titanium acid esters preparation of high density is supported on the cotton, and its catalytic activity and embodiment 8 are approaching.The peptide collosol-gelatum system of embodiment 10 tetrachloro peptides hydrolysis preparation under photoinduction is supported on the sample for preparing on the dacron terylene cloth, and can finish 50ml concentration substantially at 1 hour is 8.75 * 10
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-1Rhodamine B degraded (the results are shown in accompanying drawing 9).Embodiment 5-10 carries out the condition of rhodamine B degradation experiment with embodiment 1.
By the synthetic titanium sol-gel of photoinduction, then this colloid is coated on the titanium dioxide that substrate surface directly becomes high catalytic activity, this preparation method's advantage is:
The one, coating process is simply various, as dip-coating, dipping, spin coating, spraying etc., does not need expensive equipment.
The 2nd, normal conditions just have high catalytic activity after being coated on temperature sintering on 400 ℃ of the sample needs that prepare on the base material with sol-gel method.The titanium sol-gel that the inventive method is prepared does not need sintering just to become the titanium dioxide of high catalytic activity, so simplified technology, has reduced cost.
The 3rd. because manufactured samples does not need sintering,, can be mass-produced so be applicable to various base materials.
The 4th. owing to be form and the base material effect of titanium sol-gel with coating, rather than with TiO
2Particle form is simply attached on the base material, so the titanium dioxide that forms combines firmly with base material.
The 5th. the catalytic activity height.
Description of drawings:
The TiO that Fig. 1 embodiment 1 forms on dacron terylene cloth
2Degraded to the dyestuff rhodamine B
A.1# sample is to the degraded ultraviolet absorption curve of dyestuff rhodamine B (a → b illumination 30 minutes);
B.2# sample is to the degraded ultraviolet absorption curve of dyestuff rhodamine B (a → b illumination 10 hours);
Fig. 2 embodiment 1 is supported on the dacron terylene cloth and forms TiO
2Raman spectrum;
The sample of Fig. 3 embodiment 2 under luminescent lamp to the degraded of aldehydes gas;
Under ultraviolet lamp, the degrade hydrogen sulfide experiment of the 1# sample of Fig. 4 embodiment 3;
The different light time synthetic titanium sol-gel paint of Fig. 5 embodiment 4 prepares TiO
2Sample is to acetaldehyde gas
The experiment of body catalyzed degradation;
The titanium sol-gel paint degradation experiment of the tetrabutyl titanate illumination of Fig. 6 embodiment 51% preparation in 30 minutes
(a → b illumination 6 hours);
Fig. 7 embodiment 6 is spin-coated on the TiO on the glass substrate
2To the degradation experiment of dyestuff (a → b illumination 4 hours);
The TiO of Fig. 8 embodiment 7 not illumination colloidal dispersions preparation
2Be supported on the glass substrate degradation experiment to dyestuff
(a → e illumination 10 hours);
The peptide collosol-gelatum system of Fig. 9 embodiment 10 tetrachloro peptides preparations be supported on the dacron terylene cloth sample its urge
Voltinism can be tested (a → b illumination 60 minutes).
Drawing reference numeral:
A, b, c, d, the e. curve of spectrum
F. the collection of illustrative plates of the dacron terylene cloth collection of illustrative plates collection of illustrative plates of sample h.2# of sample g.1#
Embodiment 1 (weight percent)
Tetrabutyl titanate with 10%, 89% dehydrated alcohol, 1% concentrated hydrochloric acid (concentration is 36.5%) pipettes in the reactor, and the high voltage mercury lamp with 400W in the time of stirring is light source illumination reaction 1 hour, makes titanium sol-gel paint.With area is 10 * 10cm
2The dacron terylene cloth directly immerse colloidal solution, rapidly take out to be placed on to dry in the air and make the 1# sample.To pipette with the reactant of above-mentioned weight percent concentration in the reactor, not illumination is stirred and was made titanium sol-gel paint in 1 hour, is 10 * 10cm with area then
2The dacron terylene cloth directly immerse and be coated with feed liquid, take out to be placed on to dry in the air rapidly and make the 2# sample.
1#, 2# sample are cut 5 * 5cm respectively
2Two, in the high voltage mercury lamp 15cm of distance 400W place's illumination, to 50ml 1 * 10
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-1Rhodamine B solution degrade.The result shows that the 1# sample only needs about 30 minutes with rhodamine B degrade substantially (comparative result is seen Figure 1A) fully by a → b, the 2# sample wants 10 hours ability to finish degraded (comparative result is seen Figure 1B) substantially by a → b, and its UV spectrum is by Shimadzu uv-1601pc spectrophotometer.
Measure the Raman structure (seeing accompanying drawing 2) of 1#, 2# sample with 2000 type Raman spectrographs (production of Britain Renishaw company).
Embodiment 2
Respectively getting two areas is 10 * 10cm
2With 1# and the 2# sample of embodiment 1, be that aldehydes gas in the 4L device carries out degradation experiment to volume respectively.Wherein the initial concentration of aldehydes gas is 16ppm in the experimental installation, the luminescent lamp of built-in 20W.Detect once (accompanying drawing 3 as a result) with gas-chromatography (SHIMADZUGC-17AG type) every 20 minutes concentration to aldehydes gas.
Embodiment 3
With the 1# sample titanium sol-gel paint of embodiment 1, use spraying method at plastics film surface preparation one deck TiO
2, getting two areas is 10 * 10cm
2Plastics film, gas decomposition apparatus with embodiment 2, select for use the 20W ultraviolet lamp as light source, initial concentration is degraded for the 40ppm hydrogen sulfide, detect once (the results are shown in Figure 4) every 20 minutes concentration hydrogen sulfide with gas-chromatography (SHIMADZUGC-17AG type)
Embodiment 4
With embodiment 1 reaction reagent system and concentration, the high voltage mercury lamp with 400W is light source illumination reaction 30 minutes, the gel-sol colloidal coating that prepared 3#, 4#, 5# in 2 hours, 5 hours respectively.And on dacron terylene cloth, support 3#, 4#, 5# sample with the dipping method.Respectively getting two areas respectively is 10 * 10cm
2Sample with the gas decomposition apparatus of embodiment 2, is degraded for the 16ppm aldehydes gas to initial concentration respectively, detects once (the results are shown in Figure 5) with gas-chromatography (SHIMADZUGC-17AG type) every the 20 minutes concentration to aldehydes gas.
Embodiment 5 (weight percent)
Tetrabutyl titanate with 1%, 98.5% dehydrated alcohol, 0.5% concentrated hydrochloric acid (concentration is 36.5%) pipettes in the reactor, and the mercury lamp with 400W in the time of stirring is light source illumination reaction 30 minutes, makes titanium sol-gel paint.With 10 * 10cm
2Cotton immerses titanium sol-gel paint, and takes out rapidly, places after 24 hours in air, and getting area is 5 * 5cm
2Cloth under the high voltage mercury lamp 15cm of distance 400W place's illumination, is 8.67 * 10 to 50ml concentration
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-1Rhodamine B degrade (the results are shown in accompanying drawing 6).
Embodiment 6 (weight percent)
Tetrabutyl titanate with 5%, 94% dehydrated alcohol, 0.5% concentrated hydrochloric acid (concentration is 36.5%), 0.5% water pipettes in the reactor, and the high voltage mercury lamp with 400W in the time of stirring is light source illumination reaction 1 hour, make titanium sol-gel paint, use spin-coating method at 5 * 5cm
2Coating one deck titanium sol-gel paint is placed after 24 hours in the air on the glass substrate, under the high voltage mercury lamp 15cm of distance 400W place's illumination, is 6.75 * 10 to 50ml concentration
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-1Rhodamine B degrade (the results are shown in Figure 7).
Embodiment 7
Each weight percentages of components without the colloidal dispersion of illumination preparation, uses spin-coating method at 5 * 5cm with embodiment 6
2Glass substrate on coating one deck titanium sol-gel paint, place after 24 hours in the air, under the high voltage mercury lamp 15cm of distance 400W place's illumination, be 6.75 * 10 to 50ml concentration
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-1Rhodamine B degrade (the results are shown in Figure 8).
Embodiment 8 (weight percent)
Tetrabutyl titanate with 20%, 79% dehydrated alcohol, 1% concentrated hydrochloric acid (concentration is 36.5%) pipettes in the reactor, and the high voltage mercury lamp with 400W in the time of stirring is light source illumination reaction 1 hour, makes titanium sol-gel paint.With 10 * 10cm
2Cotton immerses the titanium sol-gel paint system, and takes out rapidly, places after 24 hours in air, and getting area is 5 * 5cm
2Cloth under the high voltage mercury lamp 15cm of distance 400W place's illumination, is 8.75 * 10 to 50ml concentration
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-1Rhodamine B degrade (the results are shown in Figure 9).
Embodiment 9 (weight percent)
Tetrabutyl titanate with 20%, 30% tetraethyl titanate, 40% dehydrated alcohol, 10% concentrated nitric acid (concentration is 63%), pipette in the reactor, the high voltage mercury lamp with 400W in the time of stirring is light source illumination reaction 10 hours, makes titanium sol-gel paint coating.With 10 * 10cm
2Cotton immerses the titanium sol-gel paint system, and takes out rapidly, places after 24 hours in air, and getting area is 5 * 5cm
2Cloth under the high voltage mercury lamp 15cm of distance 400W place's illumination, is 8.75 * 10 to 50ml concentration
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-1The rhodamine B test (result is with embodiment 8) of under the 400w high voltage mercury lamp, degrading.
Embodiment 10
By weight percentage with 10% titanium tetrachloride, 85% dehydrated alcohol, 5% concentrated nitric acid (concentration is 63%) pipettes in the reactor, is light source illumination reaction 1 hour with the 400W high voltage mercury lamp in the time of stirring, makes titanium sol-gel paint.With 10 * 10cm
2Dacron terylene cloth immerses the titanium collosol-gelatum system, and takes out rapidly, places after 24 hours in air, and getting area is 5 * 5cm
2Cloth is 8.75 * 10 to 50ml concentration
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-1Rhodamine B degrade (the results are shown in accompanying drawing 9).