CN101322939A - Functional nano Ti2O/Cu2O heterophase Fenton thin film and preparation method as well as use - Google Patents
Functional nano Ti2O/Cu2O heterophase Fenton thin film and preparation method as well as use Download PDFInfo
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Abstract
The invention relates to a nanometer TiO2/Cu2O out-phase Fenton laminated film material which consists of a TiO2/Cu2O nanocomposite and an inorganic coating binder, wherein, the mass ratio between the TiO2/Cu2O nanocomposite and the inorganic coating binder is 1:1-1:500; the mass ratio between TiO2 and Cu2O in the TiO2/Cu2O nanocomposite is 1:0.01-1:100. The preparation method is as follows: nanometer TiO2 is taken as a crystal nucleus to induce the crystallization of Cu2O and the TiO2/Cu2O nanocomposite is prepared by an electrochemical process, chemical deposit or hydrothermal method; the composite prepared and the inorganic coating binder are mixed evenly and coated on the surface of substrate cleaned to prepare the TiO2/Cu2O laminated film and after the binder is totally solidified, the out-phase Fenton laminated film material is obtained. The nanometer TiO2/Cu2O out-phase Fenton laminated film material has better effect on sterilization, algae-killing, killing cancer cell, organic pollutant degradation, and the like, and is hopefully applied to indoor sterilization for building, degrading organics cleaning coating, outdoor self-cleaning coating for building, metal antifouling coating, public sterilization coating, special sterilization coating in hospital, daily chemical products, etc.
Description
Technical field
The present invention relates to have the visible light sterilization, kill the nano-TiO of functions such as algae, killing cancer cell and degradable organic pollutant
2/ Cu
2O heterophase Fenton thin film and preparation method and application.Belong to combining of semiconductor nano material complex technique and visible light catalytic oxidation technology, it is outdoor from aspects such as clean coating, metal nonpolluting coating, the sterilization coating of public place, the special sterilization coating of hospital, daily chemical products that the heterophase Fenton thin film of gained can be used on architecture indoor sterilization, degradation of organic substances cleaning coating, building.
Background technology
The photooxidation technology mainly utilizes strong oxidizer to produce to have the hydroxyl free radical (OH) of strong oxidability to come thorough mineralising organic pollution or kill bacteria, algae, belongs to high-level oxidation technology.Hydrogen peroxide (H
2O
2) and Fe
2+Fenton reagent (the H of Gou Chenging together
2O
2+ Fe
2+) be exactly a kind of in the photooxidation technology.Esplugas.S (Water Res.2002,36 (4), 1034) group studies show that at high-level oxidation technology such as O
3, O
3/ H
2O
2, UV, UV/O
3, UV/H
2O
2, O
3/ UV/H
2O
2In the process of degradation of phenol such as electrochemical process, Fenton reagent is the fastest.Except wastewater treatment, it also can be used for the purifying of waste residue, precipitation, soil, the dehydration of biologically active mud etc., also can be used for the chemical industry preparation.But, H
2O
2Cost an arm and a leg, and because in course of reaction, intermediate product can take place finally to cause H from consumption reaction with hydroxyl free radical
2O
2Utilization rate is not high, needs to replenish fast, makes the very fast raising of use cost.
The multiphase photocatalysis technology is a kind of process that light is changed into chemical energy.Wherein, TiO
2Be a kind of photochemical catalyst of studying at most, it can only be worked under UV light, though people adopted doping, compound, transplant method such as metal and make it absorb the optical wavelength red shift, but final effect is not clearly.Cuprous (the Cu of semiconductor oxide
2O) direct energy gap is about 2.0eV, can produce electronics and hole under the radiation of visible light fully, aspect hydrogen manufacturing, superconduction, solar cell and the electrode material important application is being arranged.It also is used to visible light degradable organic pollutant (Appl.Cata.A:Gen.2006,299,292).Report is arranged with Cu
+Be deposited on zeolite surface and under radiation of visible light, NOx be decomposed into N
2And O
2(Appl.Surf.Sci.2001,174,177).At Cu
2We find in the multiphase photocatalysis research of O: as semi-conducting material, and Cu
2The very big difference of the photocatalysis principle of O and the existence of titanium dioxide, Cu
2The conduction band current potential of O is very negative, causes exciting the conduction band electron of generation to have very strong reduction characteristic, and the dioxygen oxidation that will be adsorbed on the surface in the presence of visible light is H
2O
2, with Fe
2+Just constituted Fenton reagent (Appl.Cata.A:Gen.2006,299,292) together.
Yet the semiconductor of low energy gap is used for photochemical catalyst and has not high, the easy compound problem [Chem.Rev.1998,171,175] of light activated carrier transport efficient.Simultaneously, Cu
2O is long-time to be contacted with water and is accelerated oxidation easily and loses photocatalytic activity.One of way that addresses this problem is exactly with Cu
2O and other semiconductor or conductor carry out compound [Appl.Cata.B-Environ.2004,52,287].In order to satisfy the practical application needs, the research of heterophase Fenton reagent or film is being subjected to people and is paying close attention to widely simultaneously.
Summary of the invention
The present invention selects titanium dioxide (TiO for use
2) come and Cu
2O carries out compound, because TiO
2The conduction band current potential compare Cu
2O just, and TiO
2Be easy to obtain electronics and form stable titanous.With Cu
2O and TiO
2Be combined with each other by chemical method, and it is fixed on substrate surface with inorganic bond, formed heterophase Fenton thin film after the curing with very strong visible light catalysis activity, not only chemical stability is good to form the nano composite material of this film, and this film has a lot of functions, is with a wide range of applications.
Principle of the present invention is:
The embodiment of conductor photocatalysis activity is finished by light activated free electron and hole acting in conjunction, and electronics is effectively separated with the hole, is the important channel of improving photo-quantum efficiency thereby reduce to each other compound.Fig. 1 has shown TiO
2And Cu
2O semiconductor composite photocatalysis mechanism, the left side are and standard hydrogen electrode electromotive force comparison diagram.TiO
2Conduction band be about-0.2V, band gap is 3.2eV, and Cu
2O is one of at present known semiconductor with the highest conduction band, for-1.4V, band gap is 2.0eV.Under radiation of visible light, electronics is from Cu
2The valence band of O transits to conduction band.When two kinds of semiconductor junctions fashionable because TiO
2Conduction band compare Cu
2The conduction band of O is just a lot, and the optical excitation electronics will be from Cu
2The conduction band of O is transferred to TiO
2Conduction band, cause electronics at TiO
2Accumulate in the crystal, form titanous (Ti
3+) the electronics center, this is confirmed in composite XPS test.Accumulate in TiO
2Electronics on the conduction band passes to TiO
2The O of surface absorption
2, form O
2-Perhaps O
2 2-Ion, these ions again with H
+In conjunction with, form H
2O
2And the hole is at Cu
2Accumulate in the O crystal, form center of positive charge (at last by with the photocatalytic degradation product of organic dyestuff or effective compound consumption of hole scavenger), thereby electron-hole pair is effectively separated, so just strengthened the photocatalysis efficiency of composite.Simultaneously to TiO
2, the hole itself that its optical excitation (ultraviolet light part) produces has very strong oxidisability, and these a spot of holes still can be brought into play its advantage and be come the oxidation organic pollution.Therefore, the H in this compound system
2O
2Output should be very high, and this heterophase Fenton thin film should have very strong oxidisability.
The scheme that realizes the object of the invention is:
With nano-TiO
2As inducing Cu
2The nucleus of O crystallization prepares TiO with chemical methodes such as electrochemistry, chemical deposition, hydro-thermal methods
2/ Cu
2The O nano composite material.By control reaction condition such as TiO
2Conditions such as addition, reaction temperature, reaction time, reactant concentration can obtain the TiO of different catalytic performances
2/ Cu
2The O nano composite material.A certain amount of above-mentioned composite and a certain amount of inorganic coating adhesive are mixed, be coated in to clean and make TiO on the substrate surface
2/ Cu
2The O composite membrane.Composite membrane is at room temperature placed a period of time, treats just to obtain the heterophase Fenton thin film material after adhesive solidifies fully.This heterophase Fenton thin film material in sterilization, kill aspects such as algae, killing cancer cell and degradable organic pollutant good effect all arranged, at architecture indoor sterilization, degradation of organic substances cleaning coating, building is outdoor all has broad application prospects from aspects such as clean coating, metal nonpolluting coating, the sterilization coating of public place, the special sterilization coating of hospital, daily chemical products.
A kind of function nano TiO of the present invention
2/ Cu
2O heterophase Fenton composite film material is characterized in that it is by TiO
2/ Cu
2O nano composite material and inorganic coating adhesive are formed, wherein TiO
2/ Cu
2O nano composite material and inorganic coating adhesive mass ratio are 1: 1～1: 500; TiO
2/ Cu
2TiO in the O nano composite material
2With Cu
2The mass ratio of O is 1: 0.01～1: 100; Wherein, described inorganic coating adhesive is selected from KP1 coating, lithium silicate coating, sodium silicate coating or sodium KP1 coating, preferably from lithium silicate coating.
Prepare the method for above-mentioned functions nano TiO 2/Cu2O heterophase Fenton composite film material, its preparation process is:
Wherein, described chemical method comprises electrochemical process, chemical deposition and hydro-thermal method; Described copper source is selected from metallic copper, Schweinfurt green, copper chloride or copper sulphate; Described inorganic coating adhesive is selected from KP1 coating, lithium silicate coating, sodium silicate coating or sodium KP1 coating; Described substrate is selected from glass, pottery, building wall, plastics, metal, rubber, composite plate, wood floors, fiber, cloth or paper.
The present invention prepares above-mentioned TiO
2/ Cu
2The electrochemical process of O nano composite material, preparation process comprises:
The present invention prepares above-mentioned TiO
2/ Cu
2The chemical deposition of O nano composite material, preparation process comprises:
With the product centrifugation, and use the ethanol centrifuge washing respectively 3～5 times after step 3, reaction are finished, promptly obtain TiO 60 ℃ of following vacuum drying
2/ Cu
2The O nano composite material.
The present invention prepares above-mentioned TiO
2/ Cu
2The hydro-thermal method of O nano composite material (or solvent heat), preparation process comprises:
With the product centrifugation, and use ethanol, distilled water centrifuge washing for several times respectively after step 3, reaction are finished, promptly obtain TiO 60 ℃ of following vacuum drying
2/ Cu
2The O nano composite material.
The method for preparing above-mentioned heterophase Fenton thin film material is characterized in that needed nano-TiO
2/ Cu
2Before the O Composite Preparation, nanoscale TiO
2(self-control or commodity) should be through fully grinding.
Preparation above-mentioned functions nano-TiO
2/ Cu
2The method of O heterophase Fenton composite film material is characterized in that TiO
2/ Cu
2After O nano composite material and inorganic coating adhesive mixed, the coating processes that is coated in technology on the substrate and coating was consistent.
Preparation above-mentioned functions nano-TiO
2/ Cu
2The method of O heterophase Fenton composite film material is characterized in that be 1-30 days needed hardening time under the heterophase Fenton thin film material normal temperature of gained.
The function nano TiO that obtains by method for preparing
2/ Cu
2O heterophase Fenton composite film material visible light (or sunshine) irradiation down can sterilization, kill algae, killing cancer cell and degradable organic pollutant, can be used in architecture indoor sterilization, degradation of organic substances cleaning coating, building outdoor from aspects such as clean coating, metal nonpolluting coating, the special sterilization coating of hospital and daily chemical products.
Description of drawings
Fig. 1. the interface electronics shifts schematic diagram
Fig. 2. nano-TiO
2/ Cu
2O heterophase Fenton composite film material is to the photocatalytic degradation rate of methylene blue
Fig. 3. nano-TiO
2/ Cu
2O heterophase Fenton composite film material is to the photocatalytic degradation rate of reactive brilliant red
The dissimilar nanometers of Fig. 4 are killed algae cloth is entreated liquid cell density change in concentration to Microcystis aeruginosa influence
Fig. 5 nanometer is killed the influence (go up surface curve fiber comparative group for no Fenton laminated film, following surface curve be nanometer kill algae measuring fiber group) of algae cloth to frustule concentration in the water body
Fig. 6 is coated with on the ring-disc electrode of nano film material graph of a relation (a) nano-TiO between the voltage and current
2/ Cu
2O composite, (b) TiO
2, (c) ZnO, (d) Cu
2O (micron particles)
The specific embodiment:
Prepare TiO with electrochemical process
2/ Cu
2The O nano composite material finally obtains function nano TiO
2/ Cu
2The process of O heterophase Fenton composite film material:
In cathode pool, adding the nano-TiO of 2g before the electrolysis through mechanical lapping
2(P25 contains the TiO of the rutile-type of 80% anatase and 20%
2, Dessuga Co) and electrolyte is 0.1 mol NaOH aqueous slkali, titanium is as negative electrode; 1M NaCl salting liquid in the anode pond, adding, copper coin is as anode, and making copper reduction with electrolysis is Cu
2O.The control size of current is 0.5A during electrolysis, and temperature is about 80 ℃, and the reaction time is 20 minutes, should continue to stir in electrolytic process.With the electrolysate centrifugation, and, can obtain TiO 60 ℃ of following vacuum drying respectively with ethanol, distilled water washing 3 times
2/ Cu
2O (mass ratio is 1: 1) nano composite material.With the above-mentioned TiO of the 1g that makes
2/ Cu
2O nano composite material and 10ml lithium silicate (Li
2SiO
3, contain 20% SiO
2, new material factory of Central China Normal University) mix, be sprayed on the sheet glass (75mm * 26mm * 1mm) make TiO on the surface that cleaned under the 130kPa air pressure with air compressor
2/ Cu
2O heterophase Fenton composite film material.Laminated film is at room temperature placed and is treated about 6 days just can use after coating solidifies fully.
This laminated film sheet glass is placed in the organic pollution solution, uses H
2SO
4About the pH value to 4 of regulator solution, add the FeSO of 0.08g/L respectively
4With the EDTA of 0.10g/L, with the irradiation of 300w halogen tungsten lamp and bubbling air, i.e. degrading organic pollutant.The results are shown in Figure 2, Fig. 3.
Fig. 2 is heterophase Fenton composite film material 6 hours photocatalytic degradation rates to the 0.1g/L methylene blue under these conditions, and it can reach 91%, and the composite membrane of unit are is 0.40g/ hour to the degradation rate of methylene blue.
Fig. 3 is this composite membrane 8 hours photocatalytic degradation rates to the 0.1g/L reactive brilliant red under these conditions, and it can reach 46%, and the composite membrane of unit are is 0.15g/ hour to the degradation rate of methylene blue.
TiO with above-mentioned preparation
2/ Cu
2O nano composite material and lithium silicate mix by 1: 10 mass ratio, with air compressor it is sprayed to table that area is 100mm * 100mm glass and, obtain the heterophase Fenton composite film material after the curing, this laminated film organic pollutions such as indoor formaldehyde that are used to degrade, respond well.Concrete experimental result is as shown in table 1.Condition is under the white flag light irradiation of 100W, and (lamp is 10cm from the sample distance, produces the decomposition rate that formaldehyde determination instrument (Model4160-2) is measured formaldehyde with the U.S..
Table 1 nano-TiO
2/ Cu
2The result of formaldehyde in the O heterophase Fenton composite film material degraded air
| Time (minute) | 0 | 10 | 20 | 30 | 40 | 50 | 60 |
| Concentration of formaldehyde (mg/m 2) | 1.34 | 1.08 | 0.80 | 0.80 | 0.52 | 0.36 | 0.31 |
Will be with the TiO of above-mentioned electrochemical production
2/ Cu
2O (mass ratio is 1: 3) nano composite material and lithium silicate apply on culture dish (φ 80) surface by above-mentioned process conditions, various bacteriums are put in the culture dish of heterophase Fenton composite film material.Under indoor civil day light modulation, viral bacteriophage MB was whole inactivations in one minute, was instant; Escherichia coli, golden yellow staphylococcus, Friedlander, serratia marcescens etc. also there is similar killing action.Table 2 and table 3 are nano-TiOs
2/ Cu
2Result's (used bacterial species has: golden yellow staphylococcus, Friedlander, serratia marcescens, Escherichia coli) of O (mass ratio is 1: 3) heterophase Fenton coating kill bacteria, light intensity is 10501X.
Table 2 nano-TiO
2/ Cu
2The effect of O (1: 3) heterophase Fenton coating sterilization (sterilization circle width)
Table 3 nano-TiO
2/ Cu
2O (1: 3) heterophase Fenton coating is present in the virally inactivated effect in the paint and the comparison of Nippon
(remain viral unit: individual)
Prepare TiO with chemical deposition
2/ Cu
2The O nano composite material finally obtains nano-TiO
2/ Cu
2The process of O heterophase Fenton composite film material:
In 200ml diethylene glycol (DEG) solvent, add the nano-TiO of 4g through mechanical lapping
2(P25 contains the TiO of the rutile-type of 80% anatase and 20%
2, Dessuga Co) and the Schweinfurt green of 0.1M, and stir and make TiO
2In system, be uniformly dispersed.About rising temperature to 180 ℃, the reaction time is 3 hours, should continue to stir in course of reaction.With the product centrifugation, and use the ethanol centrifuge washing respectively 3 times after reaction is finished, can obtain TiO 60 ℃ of following vacuum drying
2/ Cu
2The O nano composite material.With above-mentioned composite of the 2g that makes and 15ml lithium silicate (Li
2SiO
3, contain 20% SiO
2, new material factory of Central China Normal University) mix, evenly be coated in glass fabric (300mm * 300mm) make TiO on the surface
2/ Cu
2O heterophase Fenton composite film material.Laminated film is at room temperature placed about 10 days and is treated to solidify fully.
Laboratory result shows this nano-TiO
2/ Cu
2O heterophase Fenton composite film material fiber has killing effect preferably to the important algae Microcystis aeruginosa of forming wawter bloom, the result as shown in Figure 4, its cell density descends fast.In July, 2004, Wu Lihu some zone in Wuxi produced wawter bloom, and the wawter bloom algae is mainly Microcystis aeruginosa.For the checking nanometer is killed the algae killing effect of algae cloth, carried out the small-sized algae test of killing at this.The result because various particles are more in the water sample, be difficult to the number of accurate counting Microcystis aeruginosa cell, so the variation of frustule is represented with Chla as shown in Figure 5.The algae killing effect that kills algae cloth from the variation of Chla as can be seen is fairly obvious.With contrast (no nano-TiO
2/ Cu
2The fiber of O heterophase Fenton composite film material) compare, water body chlorophyll content sharply descends 76% within 1 day, and downward trend afterwards is mild, and this phenomenon is similar to laboratory test results.
Prepare TiO with hydro-thermal (or solvent heat) method
2/ Cu
2The O nano composite material finally obtains nano-TiO
2/ Cu
2The process of O heterophase Fenton composite film material:
Reaction adds the nano-TiO of 3g through mechanical lapping before in 80ml ethanol-water mixed solvent (ethanol and water volume ratio are 1: 3) lining
2(P25 contains the TiO of the rutile-type of 80% anatase and 20%
2, Dessuga Co) and the copper sulphate of 0.05M, adjust pH to 7～9, the ultrasonic TiO that makes
2In system, be uniformly dispersed.Mixed solution is transferred to water heating kettle, put in the Muffle furnace, rising temperature to 180～200 ℃, the reaction time is 18 hours.With the product centrifugation, and use ethanol, distilled water centrifuge washing 3 times respectively after reaction is finished, can obtain TiO 60 ℃ of following vacuum drying
2/ Cu
2The O nano composite material.With the above-mentioned TiO of the 3g that makes
2/ Cu
2O nano composite material and 15ml lithium silicate (Li
2SiO
3, contain 20% SiO
2, new material factory of Central China Normal University) mix, evenly be coated on electrode or the various substrate surface and make TiO
2/ Cu
2O heterophase Fenton composite film material.Laminated film is at room temperature placed about 10 days and is treated to solidify fully.
We use the ring-disc electrode method to compare surface-coated has the electrode of various semiconductor film materials to separate out the situation of hydrogen peroxide (other semiconductive thin films on electrode coating procedure and composite of the present invention consistent) under radiation of visible light.As can be seen from Figure 6, the amount difference of the hydrogen peroxide that different semiconductor film material optical excitation produce, descending order is: nano-TiO
2/ Cu
2The O composite＞＞Cu
2O (micron particles)＞ZnO＞TiO
2(P-25).Be coated with nano-TiO
2/ Cu
2The electrode peak current of O composite has reached 40mA/cm
2, be the H that N=0.43 calculates by collection efficiency
2O
2Productive rate reaches 3.5mMhr
-1Cm
-2(500W Xe light irradiation), high like this H
2O
2Productive rate makes this nano-TiO
2/ Cu
2The application of O heterophase Fenton thin film material under visible light becomes possibility.
What table 4 showed is the nano-TiO of above-mentioned preparation
2/ Cu
2The experimental result of degradable organic pollutant, formaldehyde, kill bacteria, algae and cancer cell under the O heterophase Fenton thin film material visible-light.As seen this nano-TiO
2/ Cu
2The O heterophase Fenton thin film has very powerful, has boundless application prospect.
Nano-TiO on the different substrates of table 4
2/ Cu
2Function under O heterophase Fenton thin film material visible-light excites
The substrate of sample 1 is a sheet glass, and the substrate of sample 2-4 is a glass, and the substrate of sample 5 is a filter paper, and the substrate of sample 6 is glass fibres.
Claims (8)
1. function nano TiO
2/ Cu
2O heterophase Fenton composite film material is characterized in that it is by TiO
2/ Cu
2O nano composite material and inorganic coating adhesive are formed, wherein TiO
2/ Cu
2O nano composite material and inorganic coating adhesive mass ratio are 1: 1～1: 500; TiO
2/ Cu
2TiO in the O nano composite material
2With Cu
2The mass ratio of O is 1: 0.01～1: 100; Wherein, described inorganic coating adhesive is selected from KP1 coating, lithium silicate coating, sodium silicate coating or sodium KP1 coating.
2. function nano TiO as claimed in claim 1
2/ Cu
2O heterophase Fenton composite film material is characterized in that, described inorganic coating adhesive is selected lithium silicate coating for use.
3. function nano TiO
2/ Cu
2The preparation method of O heterophase Fenton composite film material is characterized in that, preparation method's step is:
Step 1, with nano-TiO
2As inducing Cu
2The nucleus of O crystallization is pressed TiO
2With Cu
2The mass ratio of O is to get TiO in 1: 0.01～1: 100
2With the copper source, prepare TiO with chemical method
2/ Cu
2The O nano composite material;
Step 2, step 1 is made TiO
2/ Cu
2O nano composite material and inorganic coating adhesive are to mix in 1: 1～1: 500 by mass ratio, are coated on the substrate surface that cleaned and make TiO
2/ Cu
2The O composite membrane;
Step 3, the TiO that step 2 is made
2/ Cu
2The O composite membrane is at room temperature placed, and treats just to obtain function nano TiO after adhesive solidifies fully
2/ Cu
2O heterophase Fenton thin film material;
Wherein, described chemical method comprises electrochemical process, chemical deposition and hydro-thermal method; Described copper source is selected from metallic copper, Schweinfurt green, copper chloride or copper sulphate; Described inorganic coating adhesive is selected from KP1 coating, lithium silicate coating, sodium silicate coating or sodium KP1 coating; Described substrate is selected from glass, pottery, building wall, plastics, metal, rubber, composite plate, wood floors, fiber, cloth or paper.
4. function nano TiO as claimed in claim 3
2/ Cu
2The preparation method of O heterophase Fenton composite film material is characterized in that, described preparation TiO
2/ Cu
2The chemical method of O nano composite material is an electrochemical process, and preparation process comprises:
Step 1, in the electrolysis cathode pond, add 1 * 10
-5～50 mol NaOH aqueous slkalis are minus plate with titanium or nickel; In 1000 milliliters of anode ponds, add nano-TiO through mechanical lapping
21 * 10
-3～50 grams, and stir,, make the metallic copper dissolving and form Cu as anode with metallic copper with electrolysis
2O;
Step 2, electrolysis: the control size of current is 0.01～3A/cm
2, temperature is at 40～90 ℃, and the reaction time is 1～60 minute, should continue to stir in electrolytic process;
Step 3, with the electrolysate centrifugation, and, promptly obtain TiO 60 ℃ of following vacuum drying respectively with ethanol, distilled water washing 3～5 times
2/ Cu
2The O nano composite material.
5. function nano TiO as claimed in claim 3
2/ Cu
2The preparation method of O heterophase Fenton composite film material is characterized in that, described preparation TiO
2/ Cu
2The chemical method of O nano composite material is a chemical deposition, and preparation process comprises:
Step 1, in the diethylene glycol (DEG) solvent, add nano-TiO through mechanical lapping
2And Schweinfurt green, and stirring makes TiO
2Be uniformly dispersed in system, being made into copper ion concentration is 1 * 10
-3～1 * 10
2Mol, TiO
2With the mass ratio of Schweinfurt green be 1: 0.01～1: 100 mixed solution;
Step 2, the mixed solution rising temperature to 150～190 ℃ that step 1 is obtained, the reaction time is 3～10 hours, should continue to stir in course of reaction;
With the product centrifugation, and use the ethanol centrifuge washing respectively 3～5 times after step 3, reaction are finished, promptly obtain TiO 60 ℃ of following vacuum drying
2/ Cu
2The O nano composite material.
6. function nano TiO as claimed in claim 3
2/ Cu
2The preparation method of O heterophase Fenton composite film material is characterized in that, described preparation TiO
2/ Cu
2The chemical method of O nano composite material is a hydro-thermal method, and preparation process comprises:
Step 1, be to add nano-TiO in 1: 0.001～1: 1000 in the mixed solvent through mechanical lapping in pure water, straight alcohol or ethanol and water volume ratio
2And copper sulphate (or Schweinfurt green, copper chloride), being made into copper ion concentration is 1 * 10
-6～1 * 10
3Mol, TiO
2With the mass ratio of Schweinfurt green be 1: 0.01～1: 100 mixed solution, adjust pH to 7～9, the ultrasonic TiO that makes
2In system, be uniformly dispersed;
Step 2, mixed solution is transferred to water heating kettle, put in the Muffle furnace, rising temperature to 150～200 ℃, the reaction time is 8～30 hours;
With the product centrifugation, and use ethanol, distilled water centrifuge washing for several times respectively after step 3, reaction are finished, promptly obtain TiO 60 ℃ of following vacuum drying
2/ Cu
2The O nano composite material.
7. function nano TiO as claimed in claim 3
2/ Cu
2The preparation method of O heterophase Fenton composite film material is characterized in that, TiO in the step 2
2/ Cu
2After O nano composite material and inorganic coating adhesive mixed, the coating processes that is coated in technology on the substrate and coating was consistent.
8. the described function nano TiO of claim 1
2/ Cu
2The application of O heterophase Fenton composite film material is characterized in that, is used for architecture indoor sterilization, degradation of organic substances cleaning coating, building is outdoor from clean coating, metal nonpolluting coating, the special sterilization coating of hospital and daily chemical product.
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| CN102155078A (en) * | 2010-12-28 | 2011-08-17 | 德州学院 | Nanometer solar fabric photovoltaic surface skin |
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