CN1448214A - Nano titanium dioxide photocatalyst,prep. and use thereof - Google Patents
Nano titanium dioxide photocatalyst,prep. and use thereof Download PDFInfo
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Abstract
The nanometer titania photocatalyst includes semiconductor material doped nanometer titania substrate and conjugated organic matter coated onto the substrate. It has nanometer level dispersivity, has no atomization, aging and other damage phenomena in polyethylene plastic and other material, and obvious antibiotic and mouldproof effect in low-light level area.
Description
Invention field
The present invention relates to a kind of nano titanium dioxide photocatalyst, more particularly, the present invention relates to a kind ofly mix and with the nano titanium dioxide photocatalyst of conjugated system organic matter surface modification with semi-conducting material, this photochemical catalyst not only can show good photocatalytic activity under ultraviolet light and radiation of visible light, and can show good photocatalytic activity under the low-light irradiation.The invention further relates to the preparation method and the application thereof of described nano titanium dioxide photocatalyst.
Prior art
As everyone knows, the titanium dioxide of titanium dioxide, especially nanoscale demonstrates oxidation activity or reducing activity, i.e. photocatalytic activity under illumination is penetrated.People are progressively utilizing the photocatalytic activity of ultraviolet-shielding type, visible light permeability, physical and chemical stability, the especially anatase-type nanometer titanium dioxide of nano titanium oxide to carry out the exploitation of application and development and functional material at present.
Yet lower without the nano titanium dioxide photocatalysis efficient of surface modification, excitation source is restricted, is difficult to be distributed to nanoscale, and the photolytic activity that exists lattice defect to cause reacts also and then cause outside release, the while Ti of nascent oxygen [O]
4+To Ti
3+Change the problem that causes the material efflorescence.Its main cause is that serious reunion takes place after high-temperature calcination nano titanium oxide, disperses processing difficulties during use, is difficult to adapt to the application of opposed polarity, different materials, varying environment.Simple nano titanium oxide n type semiconductor must be excited by ultraviolet source could to produce photocatalysis, use restricted very big.These problems all need the surface modification of titanium dioxide to solve.
Domestic and international disclosed technology has adopted methods (for example referring to Chinese patent application publication number CN1286649A) such as titanium dioxide surface coating porous calcium phosphate coating has been improved photocatalysis efficiency at present, but unexposed also carrying out surface modification with the conjugated system organic matter strengthens light absorption and photocatalysis by doped semiconductor materials, a photocatalysis light source broadening is to visible light, broadening does not also have many restrictions to the low-light of dark region in the application.
Summary of the invention
In view of above-mentioned prior art situation, the present inventor has carried out research extensively and profoundly in the nano titanium dioxide photocatalyst field, a kind ofly both good photocatalytic activity can be under ultraviolet light and visible light radiation, shown in the hope of obtaining, the nano titanium dioxide photocatalyst of good photocatalytic activity can be under the low-light irradiation of dark region, shown again.Found that by doped semiconductor materials in the preparation process of nano titanium oxide, the redox ability of nano titanium oxide is improved, and the nano titanium oxide that gained mixes is carried out surface modification by further employing conjugated system organic matter, can further strengthen photocatalysis efficiency and improve dispersive property.The present invention just is being based on above-mentioned discovery and is being accomplished.
Therefore, the purpose of this invention is to provide a kind of good photocatalytic activity that not only under ultraviolet light and radiation of visible light, has, and under the low-light irradiation of dark region, also have the nano titanium dioxide photocatalyst of good photocatalytic activity.
Another object of the present invention provides a kind of method for preparing above-mentioned nano titanium dioxide photocatalyst.
A further object of the present invention provides the application of above-mentioned nano titanium dioxide photocatalyst in various materials.
One aspect of the present invention provides a kind of nano titanium dioxide photocatalyst, and it nano titanium oxide that comprises the semi-conducting material doping is as matrix and coated conjugated system organic matter on described matrix surface.
The present invention provides a kind of method for preparing above-mentioned nano titanium dioxide photocatalyst on the other hand, the nano titanium oxide that the semi-conducting material that wherein uses the conjugated system organic matter that the metastable state chloridising is produced mixes carries out surface modification, obtains physical and chemical stability and good thermal stability, easy dispersion, safety non-toxic, is not subjected to the photochemical catalyst that light source limits, nanometer particle size distributes.
These and other purposes of the present invention, feature and advantage will be easy to be understood by those of ordinary skill after considering the present invention in conjunction with following accompanying drawing integral body.
The accompanying drawing summary
The particle diameter of unique description of drawings nano titanium dioxide photocatalyst of the present invention distributes.
Detailed Description Of The Invention
Nano titanium dioxide photocatalyst of the present invention uses the nano titanium oxide of semi-conducting material doping as matrix. In described matrix, used semi-conducting material can be those skilled in the art well-known those, such as the oxide of niobium, tungsten, chromium, indium, tin, strontium, iron, vanadium, gallium, germanium and zinc etc., the oxide of preferred iron, zinc, vanadium, tin etc. In described matrix, the weight ratio of titanium dioxide and semi-conducting material (take metal oxide) is 60: 40-96: 4, preferred 65: 35-90: 10. The matrix used particle size of the present invention is nanoscale, in the preferred 100nm, more preferably in the 50nm.
The present invention is matrix used preferred by the production of metastable state chloridising. Particularly, described metastable state chloridising comprises the steps:
1) hydrolysis: the mixing material that titanium tetrachloride raw water solution is obtained containing white precipitate;
2) sol gel reaction: in step 1) add alone or in combination the compound with oxidation susceptibility and/or reducing property in the gained mixing material, make the white precipitate dissolving, form uniform reaction solution, then heating makes the liquid slow evaporation under 50-150 ℃ temperature, forms sol-gel:
3) filtration washing: filter and water cyclic washing step 2) products therefrom is until pH is 6-8;
4) drying: with step 3) products therefrom is dry under the vacuum of-30 ℃ to 30 ℃ temperature and 5-15mmHg, obtains having of one's own the metastable state TiO 2 precursor of microparticle system; With
5) high-temperature calcination: with step 4) the gained presoma was 200-1000 ℃ temperature lower calcination 0.5-6 hour; Wherein in step 1) hydrolysis, in step 2) sol gel reaction or in step 1) and step 2) add the precursor of semi-conducting material in the two.
In above-mentioned metastable state chloridising, step 1) relates to the hydrolysis of raw material titanium tetrachloride.Used raw material can be the technical grade titanium tetrachloride in this step, also can be the pure titanium tetrachloride of reagent.From the cost angle, preferred technical grade titanium tetrachloride.Concentration to titanium tetrachloride there is no particular restriction, but preferably its molar concentration is controlled at 0.01-30mol/l, and preferred 0.05-10mol/l is more preferably in the scope of 0.09-5mol/l.The hydrolysis of step 1) can carry out under the pH value arbitrarily, and for example the pH value can be about 0-11, preferred 0-8, more preferably 0-5, most preferably 1-3.Preferably use alkali to carry out to a certain degree neutralization in this hydrolysing step, wherein operable alkali comprises for example ammonium hydroxide (MH
4OH), NaOH (NaOH), potassium hydroxide (KOH) etc., preferably ammonium hydroxide.Also without any restriction, for example its consumption can be the 0.1-10 mole based on every mole of titanium tetrachloride to the consumption of described alkali, preferred 0.5-5 mole, more preferably 1-3 mole.The temperature that hydrolysis carried out is not particularly limited, can under room temperature (about 30 ℃) or low temperature, carries out, but preferably at room temperature carry out.Because therefore the hydrolysis very exothermic of titanium tetrachloride needs to use conventional cooling means such as cooled with liquid nitrogen, refrigerated bath etc. to cool off.After hydrolysis is finished, obtain containing the mixing material of white precipitate.
In above-mentioned metastable state chloridising, step 2) relates to the formation of sol-gel.Particularly, the compound that will have oxidation susceptibility and/or reducing property under 10-180 ℃, preferred 30-100 ℃ temperature adds in the step 1) gained hydrolysate alone or in combination, white precipitate dissolves, form uniform reaction solution, under 50-150 ℃, preferred 70-100 ℃ temperature, heated reaction solution 1-10 hour then, liquid is slowly evaporated, form sol-gel.The oxidisability and/or the reproducibility compound that are used for this step comprise for example hydrochloric acid (HCl), ammonium sulfide ((NH
4)
2S), sulfuric acid (H
2SO
4), nitric acid (HNO
3), perchloric acid (HClO
4), sulfurous acid (H
2SO
3), stannous chloride (SnCl
2), frerrous chloride (FeCl
2), natrium nitrosum (NaNO
2), sodium dithionate (Na
2S
2O
42H
2O) etc.The consumption of oxidisability and/or reproducibility compound is the 0.01-10 mole based on every mole of titanium tetrachloride in this step, preferred 0.05-5 mole, more preferably 0.1-3 mole.Term used herein " oxidation susceptibility " and " reducing property " are relative concepts, promptly when the element oxidation number of compound used therefor hour, it is easy to lose electronics and is defined as reducing agent; And when the element oxidation number of compound used therefor was maximum, it was easy to obtain electronics and is defined as oxidant.
In above-mentioned metastable state chloridising, step 3) relates to step 2) filtration and the washing of gained sol-gel.The purpose of washing is in order to remove acid group and other impurity.Washing should be carried out repeatedly, is about 6-8 up to the pH of sol-gel value, preferred 6.5-7.5.
In above-mentioned metastable state chloridising, step 4) relates to the drying that the step 3) gained has washed sol-gel.This step is preferably carried out like this: will wash sol-gel and place under the vacuum of-30 ℃ to 30 ℃ temperature and 5-15mmHg dry 3-6 hour, remove moisture in the colloidal sol and possible solvent thus, obtain having of one's own the metastable state TiO 2 precursor of microparticle system.
In above-mentioned metastable state chloridising, step 5) relates to the high-temperature calcination of step 4) gained metastable state TiO 2 precursor.This step is more preferably carried out in the calciner of using always in this area under 500-980 ℃ the temperature preferably at 200-1000 ℃.Without any restriction, calcining can be carried out under oxygen or oxygen containing air atmosphere, also can carry out in the presence of inert gas such as nitrogen, ammonia, argon gas etc. to the atmosphere of calcining.Although calcining is optimal under oxygen atmosphere, consider production security, production cost and satisfying property of production, this calcining step adopts air atmosphere to carry out.Calcination time can be 0.5-6 hour.
In addition, in order to obtain the nm TiO 2-base body that semi-conducting material mixes, can be in hydrolysis, the step 2 of step 1)) sol gel reaction or step 1) and step 2) add the precursor of semi-conducting material in the two, as the inorganic acid salt or the acylate of niobium, tungsten, chromium, indium, tin, strontium, iron, vanadium, gallium, germanium and zinc etc., for example chloride, bromide, sulfate, nitrate, phosphate, acetate etc.Its consumption should make that the weight ratio of titanium dioxide and semi-conducting material (in metal oxide) is 60 in the gained matrix of calcining back: 40-96: 4, preferred 65: 35-90: 10.
The present invention's used wording " metastable state " in term " metastable state chloridising " and " metastable state TiO 2 precursor " is meant in the sol-gel preparation process in the inventive method, gel forms from heterogeneous non-equilibrium, astable system, through filtration, washing, vacuum drying, form unsettled on the thermodynamics, as to have microparticle system of one's own metastable state TiO 2 precursor.The phase transition temperature that this presoma changes to rutile-type from Detitanium-ore-type is less than 1000 ℃, be starkly lower than the phase transition temperature (the rutile-type phase transition temperature scope of conventional stable state titanium dioxide is about 1100-1400 ℃) of conventional stable state titanium dioxide, this is metastable physical property characteristic.In addition, its X-ray diffraction spectrum presents diffraction maximum broadening phenomenon, the large percentage of surface atom, and surperficial unsaturated bond is rich or the like, and these illustrate that all nano-TiO 2 precursor of the present invention belongs to the metastable state material.Therefore adopt " metastable state chloridising " term in this manual, be different from conventional chloridising.
In nano titanium dioxide photocatalyst of the present invention, the conjugated system organic matter of use is selected from maleic acid and salt, fumaric acid and salt thereof, alkene sulfonic acid (as vinyl sulfonic acid, acrylic sulfonic acid, allyl sulphonic acid etc.) and salt, DBSA and salt thereof, chooses the acrylic acid and the salt thereof that replace wantonly.The organic content of described conjugated system is 0.01-20% weight based on the weight of the nm TiO 2-base body that described semi-conducting material mixes, preferred 0.05-15% weight, more preferably 0.1-10% weight.
In the nano titanium dioxide photocatalyst of the present invention, the primary particle particle diameter is the 5-80 nanometer, preferred 10-30 nanometer, and soft aggregate most probable particle diameter is the 40-100 nanometer, preferred 60-80 nanometer.
In the preparation method of nano titanium dioxide photocatalyst of the present invention, by the nm TiO 2-base body that will be mixed by the semi-conducting material that the metastable state chloridising is produced and conjugated system organic matter abundant mixing in proportion in water, ageing is also dry and carry out the conjugated system organic matter and coat.Described matrix and the ratio of described organic matter in water should make the nano titanium dioxide photocatalyst that obtains after the drying contain 0.01-20% weight, preferred 0.05-15% weight, more preferably the conjugated system organic matter of 0.1-10% weight.Ageing and drying can be carried out 3-20 hour under preferred 95-120 ℃ the temperature at 80-150 ℃, preferred 5-15 hour.
After nano titanium dioxide photocatalyst of the present invention carries out surface modification through the semi-conducting material doping and with the conjugated system organic matter, its primary particle particle diameter remains on the 5-80 nanometer, preferred 10-30 nanometer, soft aggregate most probable particle diameter is distributed in the 40-100 nanometer, in the scope of preferred 60-80 nanometer.
Nano titanium dioxide photocatalyst of the present invention is except carrying out the light catalytic purifying under ultraviolet light and visible light environment, also has the antibacterial and mouldproof effect in the dark zone that loses light for a long time, and to the rotten safeguard procedures that provide of the mildew-resistant of material internal layer.Therefore, nano titanium dioxide photocatalyst of the present invention can be widely used in the disclosed all spectra of prior art, can be applicable to the mildew-resistant of low-light long acting antibiotic, degraded environmental contaminants, shielding ultraviolet rays in addition.Although do not wish to be bound by any theory, the inventor thinks that nano titanium dioxide photocatalyst of the present invention shows that under the low-light of ultraviolet and visible light and dark region good photocatalytic activity can make description below.By nano titanium oxide being carried out the doping vario-property of semi-conducting material, reduced the electron transition energy gap, produce the trap of electron-hole pair, make light induced electron-holoe carrier abundant, the reduction-oxidation ability is improved, the quantum size effect performance fully makes the light-catalyzed reaction that originally can not carry out carry out being carried out behind the doping vario-property with semi-conducting material.In addition, by the nano titanium oxide through the semi-conducting material doping vario-property further being carried out surface modification with the conjugated system organic matter, opened the reunion of nano titanium oxide, improved the stability of nano titanium oxide, the while efficiency of light absorption is strengthened and dispersive property improves, thereby the quantum size effect of making, the photocatalytic effect performance is more abundant, even therefore very faint excitation source (in the closed case of no light-illuminating), nano titanium dioxide photocatalyst of the present invention all produces tangible long acting antibiotic mildew-resistant, the effect of degradable organic pollutant, so that can be applied in the dark storehouse or material confining bed of no light-illuminating, widened application greatly.
Nano titanium dioxide photocatalyst of the present invention is in being applied to plastics, coating, PU leather products the time, and 24 hours room lights reach 99.9% to the killing rate of Escherichia coli, staphylococcus aureus, and bacillus subtilis black mutation killing rate is reached 97%.Escherichia coli, staphylococcus aureus killing rate reached 96% in 2 hours during low-light, bacillus subtilis black mutation killing rate is reached 93%, 24 hours PU leather mildew-resistant ranks reach zero level during low-light.The PE film hot strength of adding 1% photochemical catalyst is 17.8MPa, stand 72 hours senile experiments of UV-irradiation after, tensile strength values is 21.7MPa, intensity does not reduce, and as seen is not subjected to aging and destroys.Add the water-based exterior wall paint of 1% photochemical catalyst for another example, through the test of national chemical building material test center, the artificial ageing resistance performance all reaches 0 grade, testing result be 250 hours non-foaming, do not peel off flawless, 0 grade of efflorescence, 0 grade of variable color, value of chromatism (Δ E is 1.4) is 0 grade, the ageing-resistant performance performance is good.The polyester urethane resin that will contain 4% nano titanium dioxide photocatalyst soaked 10 hours in the 10%NaOH aqueous slkali, and the front and back performance variation is soaked in test, after found that material stands aqueous slkali soaking, stretching strength, tensile strength all do not have to reduce, after the interpolation nano titanium oxide is described, the experiment of alkali immersion corrosion does not weaken the mechanical property of materials, makes material present stronger alkaline-resisting behavior.
Compare with the titanium dioxide optical catalyst of prior art, nano titanium dioxide photocatalyst of the present invention has following advantage:
1) photocatalysis excitation source broadening is to the low-light of dark region;
2) stability of nano titanium oxide is improved, and has overcome photolytic activity reaction that lattice defect causes and and then has caused the outside release of nascent oxygen [O], Ti simultaneously
4+Easily to Ti
3+Change the problem that causes the material efflorescence;
3) nano-powder is dispersed to nanoscale and distributes, and can not cause efflorescence, breakoff phenomenon such as aging in materials such as vinyon, and the antibacterial and mouldproof effect is remarkable in the low-light district.
Embodiment
The present invention below will be described in more detail by reference example and Comparative Examples, but protection scope of the present invention is not limited to these embodiment.
The preparation embodiment of nano titanium dioxide photocatalyst Embodiment 1The preparation of nano titanium dioxide photocatalyst 1
Step 1:The preparation of the nm TiO 2-base body 1 of di-iron trioxide semiconductor doping
At room temperature 49 gram (0.3mol) ferric trichlorides (Beijing Raw Materials Company of Chemical Industry) are dissolved in the NH of 1000ml5% (weight per volume)
4In the OH aqueous solution.Adopt refrigerated bath then, 0.6mol technical grade titanium tetrachloride (Tianjin Chemical Plant) slowly is added drop-wise in this aqueous solution, under at the uniform velocity stirring, evenly produce white precipitate.Under agitation add 0.15mol perchloric acid (Beijing chemical industry two factories) then, make the white precipitate dissolving, obtain transparent liquid.Heat this liquid down at 95 ℃ and make its evaporation 2 hours, remove redundant moisture, obtain sol-gel.Filter the gained sol-gel and use 500ml water washing 4 times, making its pH is 7.With the sol-gel after the washing under 20 ℃ and 10mmHg dry 3 hours, obtain white micro mist, i.e. the metastable state TiO 2 precursor.Should the white micro mist in calcining furnace in 800 ℃ of calcinings 1 hour down, obtain the nm TiO 2-base body 1 that di-iron trioxide mixes, wherein the part by weight of di-iron trioxide and titanium dioxide is that the particle diameter of 24: 48 and matrix 1 is 30-60nm.
Step 2:The preparation of nano titanium dioxide photocatalyst 1
The matrix 1 that obtains in the step 1 is ground, be distributed in 200ml50 ℃ the pure water, add 6.5 gram acrylic sodium sulfonates (Beijing Raw Materials Company of Chemical Industry), fully mixing and dry 18 hours of 100 ℃ of following ageings, grind again, obtain nano-silica titanium photochemical catalyst 1 of the present invention.The particle diameter of this nano titanium dioxide photocatalyst 1 is 30-60nm and contains the 9 weight % acrylic sodium sulfonates of having an appointment.
Embodiment 2The preparation of nano titanium dioxide photocatalyst 2
Step 1:The preparation of the nm TiO 2-base body 2 that zinc oxide semi-conductor mixes
At room temperature 19 gram (0.15mol) zinc nitrates (Beijing Raw Materials Company of Chemical Industry) are dissolved in the NH of 1000ml5% (weight per volume)
4In the OH aqueous solution.Adopt refrigerated bath then, 0.6mol technical grade titanium tetrachloride (Tianjin Chemical Plant) slowly is added drop-wise in this aqueous solution, under at the uniform velocity stirring, evenly produce white precipitate.Under agitation add 0.15mol hydrochloric acid (Beijing chemical industry two factories) then, make the white precipitate dissolving, obtain transparent liquid.Heat this liquid down at 95 ℃ and make its evaporation 2 hours, remove redundant moisture, obtain sol-gel.Filter the gained sol-gel and use 500ml water washing 4 times, making its pH is 7.With the sol-gel after the washing under 20 ℃ and 10mmHg dry 3 hours, obtain white micro mist, i.e. the metastable state TiO 2 precursor.Should the white micro mist in calcining furnace in 860 ℃ of calcinings 1 hour down, obtain Zinc oxide doped nm TiO 2-base body 2, wherein the part by weight of zinc oxide and titanium dioxide is that the particle diameter of 12: 48 and matrix is 50-80nm.
Step 2:The preparation of nano titanium dioxide photocatalyst 2
The matrix 2 that obtains in the step 1 is ground, be distributed in 200ml50 ℃ the pure water, add 0.2 gram neopelex (Beijing Raw Materials Company of Chemical Industry), fully mixing and dry 10 hours of 100 ℃ of following ageings, grind again, obtain nano-silica titanium photochemical catalyst 2 of the present invention.The particle diameter of this nano titanium dioxide photocatalyst 2 is that the 50-80nm particle diameter distributes as shown in drawings) and contain the 0.33 weight % neopelex of having an appointment.
Embodiment 3The preparation of nano titanium dioxide photocatalyst 3
Step 1:The preparation of the nm TiO 2-base body 3 of tin ash semiconductor doping
At room temperature 8.5 gram (0.033mol) butters of tin (Beijing Raw Materials Company of Chemical Industry) are dissolved in the NH of 1000ml5% (weight per volume)
4In the OH aqueous solution.Adopt refrigerated bath then, 0.6mol technical grade titanium tetrachloride (Tianjin Chemical Plant) slowly is added drop-wise in this aqueous solution, under at the uniform velocity stirring, evenly produce white precipitate.Under agitation add 0.15mol nitric acid (Beijing Raw Materials Company of Chemical Industry) then, make the white precipitate dissolving, obtain transparent liquid.Heat this liquid down at 95 ℃ and make its evaporation 2 hours, remove redundant moisture, obtain sol-gel.Filter the gained sol-gel and use 500ml water washing 4 times, making its pH is 7.With the sol-gel after the washing under 20 ℃ and 10mmHg dry 5 hours, obtain white micro mist, i.e. the metastable state TiO 2 precursor.Should the white micro mist in calcining furnace in 900 ℃ of calcinings 2 hours down, obtain the nm TiO 2-base body 3 of doped sno_2, wherein the part by weight of tin oxide and titanium dioxide is that the particle diameter of 5: 48 and matrix is 20-50nm.
Step 2:The preparation of nano titanium dioxide photocatalyst 3
The matrix that obtains in the step 13 is ground, be distributed in 200ml50 ℃ the pure water, add 3.0 gram fumaric acid (Beijing Raw Materials Company of Chemical Industry), fully mixing and dry 12 hours of 100 ℃ of following ageings grinds again, obtains nano-silica titanium photochemical catalyst 3 of the present invention.The particle diameter of this nano titanium dioxide photocatalyst 3 is 20-50nm and contains 5.6 weight % fumaric acid.
The Application Example of nano titanium dioxide photocatalyst Embodiment 4
The nano titanium dioxide photocatalyst 1 that obtains among the embodiment 1 is sneaked in the cinnamic acrylic ester water-based emulsion (connection chemical plant, east, Beijing) with the concentration of 3 weight %, make water paint, brushing is on 50 * 100mm cement asbestos board, adopt the indoor natural light illuminate condition, at room temperature measure the degradation effect of PARA FORMALDEHYDE PRILLS(91,95) and ammonia, the result respectively as shown in Table 1 and Table 2.
The degradation efficiency of table 1 coating PARA FORMALDEHYDE PRILLS(91,95)
| Standing time (minute) | There is not TiO 2Make the concentration of formaldehyde (mg/m of time spent 3) | TiO is arranged 2Make the concentration of formaldehyde (mg/m of time spent 3) | Purification efficiency (%) |
| ????20 | ????1.21 | ????0.67 | ????45 |
| ????80 | ????1.12 | ????0.46 | ????59 |
| ????140 | ????0.88 | ????0.37 | ????58 |
| ????200 | ????0.88 | ????0.34 | ????61 |
| ????260 | ????0.71 | ????0.27 | ????62 |
Table 2 coating is to the degradation efficiency of ammonia
| Sequence number | Initial ammonia concentration (mg/m 3) | Reinforced ammonia concentration (mg/m after a day 3) | Purification efficiency (%) |
| ???1 | ????1.15 | ??????0.35 | ????70 |
| ???2 | ????1.15 | ??????0.45 | ????61 |
By the data in the last table as can be seen, nano titanium dioxide photocatalyst PARA FORMALDEHYDE PRILLS(91,95) of the present invention and ammonia have tangible degradation effect.
Embodiment 5
By following program the nano titanium dioxide photocatalyst 2 of preparation among the embodiment 2 is sneaked in the PE film with the concentration of 1 weight %:
1) nano titanium dioxide photocatalyst is pre-dispersed
Nano titanium dioxide photocatalyst 2 20 weight portions
PE resin 72 weight portions
Use banbury that above-mentioned material is fully mixed to banbury moment of torsion smooth decreasing (maximum temperature≤90 ℃) and through twin-screw mixer machine extruding pelletization.
2) preparation of PE film
Nano titanium dioxide photocatalyst 2 predispersions 5 weight portions after the granulation
Above-mentioned material is mixed in high speed dispersor, then by blown film unit blown film.According to condition, the PE film was 99.97%, the killing rate of staphylococcus aureus is reached 99.97% colibacillary killing rate through 24 hours indoor natural lights, and the killing rate of bacillus subtilis black mutation is reached 97.42%.The PE film is behind 100 hours senile experiment of UV-irradiation, indoor natural light is according to condition, colibacillary killing rate is 99.85%, the killing rate of staphylococcus aureus is reached 99.66%, the killing rate of bacillus subtilis black mutation is reached 95.22%.According to condition (black light at dark place), the PE film was 99.92%, the killing rate of staphylococcus aureus is reached 96.94% colibacillary killing rate through 24 hours low-lights, and the killing rate of bacillus subtilis black mutation is reached 92.75%.The test basis of above-mentioned test and analytical method be with reference to FZ/T01021-92 (antibacterial fabric performance test methods), the Quinn test method in GB15979-1995 (appendix B-product antibacterial and bactericidal property and stability test method) and the Ministry of Health of the People's Republic of China 1999 (disinfection technology standard-bacteriostatic test).
Embodiment 6
With the nano titanium dioxide photocatalyst 3 that obtains among the embodiment 3 with the concentration of 4 weight % and polyurethane resin (B.E Goodrich), micronizing Tissuemat E (Fine Chemical Factory of Beijing University of Chemical Technology), double solvents (dimethyl formamide/cyclohexanone/MEK/methyl propyl ketone, 4: 4: 1: 11) batching, form concentrated solution (liquid cream) through colloid mill (homogenizer) → planetary mixer → three-roll grinder, be applied to PAUR mildew-resistant synthetic leather.The PU leather printing ink that this nano titanium dioxide photocatalyst is made has the good sterilization effect to different moulds (as aspergillus flavus, aspergillus niger, multi-trunk natalensis, Penicillium citrinum, Trichoderma viride etc.).Add with the fungus-proof test result of the PU leather printing ink that does not add the nanometer titanium dioxide optical catalyst as shown in table 3.
The test of table 3 PU leather printing ink fungicidal properties
| Sample number into spectrum | The mildew-resistant grade |
| PU removes from office printing ink (1#) | ????????????????0 |
| PU removes from office printing ink (CK contrast) | ????????????????2 |
| Test strain: aspergillus niger, aspergillus flavus, Sai Shi aspergillus, Aspergillus terreus, aspergillus ustus, Chaetomium globosum, multi-trunk natalensis, Paecilomyces varioti, Penicillium citrinum, Trichoderma viride | |
PU leather printing ink (CK contrast) mildew resistance of not adding nano titanium dioxide photocatalyst is very poor, be easy to grow mold after making leather and fur products, leather is produced destruction, and add account for the nano titanium dioxide photocatalyst of the present invention of amount of resin 4% after, PU leather printing ink (1#) fungicidal properties is very strong, can prevent the generation that PU leather goes mouldy in early days, chaps, play the effect that improves the leather service property (quality) and increase the service life.
Embodiment 7
The nano titanium dioxide photocatalyst 3 that embodiment 3 is prepared is used for waste water degraded test with the concentration of 0.1% (weight).
Treatment Solution: without any pretreated 1 liter of magnificent medicine waste water (glass jar holds)
Laboratory sample: nano-TiO
2The consumption of photochemical catalyst is 1.5002 grams, and concentration is 0.1%
Experiment condition: the irradiation of 160W mercury lamp, 6 pipe ventilations apart from the about 30cm of light source, were handled 4 hours, surveyed COD changing value result of the test:
| Waste water former state COD value | Handle back COD value | Degradation rate (%) |
| ????27000 | ???13321 | ????50.66 |
Result of the test shows that about 0.1% nano titanium dioxide photocatalyst all has significantly degradation to polluting organic matter in the water as fat, benzene etc.
Claims (10)
1. nano titanium dioxide photocatalyst, the nano titanium oxide that comprises the semi-conducting material doping is as matrix and coated conjugated system organic matter on described matrix surface, wherein the weight ratio of titanium dioxide and semi-conducting material (calculating with metal oxide) is 60 in described matrix: 40-96: 4 and the particle size of described matrix be in the 100nm, the organic content of wherein said conjugated system is 0.01-20% weight based on the weight of the nm TiO 2-base body that described semi-conducting material mixes.
2. according to the nano titanium dioxide photocatalyst of claim 1, wherein the weight ratio of titanium dioxide and semi-conducting material (calculating with metal oxide) is 65 in described matrix: 35-90: 10 and the particle size of described matrix be in the 50nm, the organic content of wherein said conjugated system is 0.05-15% weight based on the weight of the nm TiO 2-base body that described semi-conducting material mixes.
3. according to the nano titanium dioxide photocatalyst of claim 1, wherein said matrix is produced by the metastable state chloridising.
4. according to the nano titanium dioxide photocatalyst of claim 1, wherein said semi-conducting material is selected from the oxide of tungsten, niobium, chromium, indium, tin, strontium, iron, vanadium, gallium, germanium and zinc.
5. according to the nano titanium dioxide photocatalyst of claim 1, wherein said conjugated system organic matter is selected from maleic acid and salt, fumaric acid and salt thereof, alkene sulfonic acid and salt thereof, DBSA and salt thereof, chooses the acrylic acid and the salt thereof that replace wantonly.
6. according to the nano titanium dioxide photocatalyst of claim 1, wherein the primary particle particle diameter is that 5-80 nanometer and soft aggregate most probable particle diameter are the 40-100 nanometer.
7. according to the nano titanium dioxide photocatalyst of claim 6, wherein the primary particle particle diameter is that 10-30 nanometer and soft aggregate most probable particle diameter are the 60-80 nanometer.
8. method for preparing according to each nano titanium dioxide photocatalyst among the claim 1-7 comprises: I) prepare the nm TiO 2-base body that semi-conducting material mixes as follows:
1) hydrolysis: the titanium tetrachloride raw water is separated the mixing material that obtains containing white precipitate;
2) sol gel reaction: in step 1) gained mixing material, add compound alone or in combination with oxidation susceptibility and/or reducing property, make the white precipitate dissolving, form uniform reaction solution, heating is slowly evaporated liquid under 50-150 ℃ temperature then, forms sol-gel;
3) filtration washing: filter and water cyclic washing step 2) products therefrom is 6-8 until pH;
4) drying: the step 3) products therefrom is dry under the vacuum of-30 ℃ to 30 ℃ temperature and 5-15mmHg, obtain having of one's own the metastable state TiO 2 precursor of microparticle system; With
5) high-temperature calcination: with step 4) gained presoma temperature lower calcination 0.5-6 hour at 200-1000 ℃; Wherein at the hydrolysis of step 1), in step 2) sol gel reaction or in step 1) and step 2) add the precursor of semi-conducting material in the two; And II) will be at I) in the matrix that obtains and conjugated system organic matter abundant mixing in proportion in water, ageing is also dry.
9. method according to Claim 8, the precursor of wherein said semi-conducting material is selected from chloride, bromide, sulfate, nitrate, phosphate and the acetate of niobium, tungsten, chromium, indium, tin, strontium, iron, vanadium, gallium, germanium and zinc.
10. according to Claim 8 or 9 method, wherein said conjugated system organic matter is selected from maleic acid and salt, fumaric acid and salt thereof, alkene sulfonic acid and salt thereof, DBSA and salt thereof, optional acrylic acid and the salt thereof that replaces.
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