CN108557876A - High Efficiency Superfine TiO2Nano particle and photocatalytic nanometer coating - Google Patents

High Efficiency Superfine TiO2Nano particle and photocatalytic nanometer coating Download PDF

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CN108557876A
CN108557876A CN201810051619.3A CN201810051619A CN108557876A CN 108557876 A CN108557876 A CN 108557876A CN 201810051619 A CN201810051619 A CN 201810051619A CN 108557876 A CN108557876 A CN 108557876A
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tio
nano particle
added
coating
preparation
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孙再成
高祥
宗绪鹏
姜文帅
栾世梁
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Beijing University of Technology
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Beijing University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
    • C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C09D139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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Abstract

High Efficiency Superfine TiO2Nano particle and photocatalytic nanometer coating, belong to catalysis material technical field.With TiCl3For titanium source, alcohol is solvent, hydro-thermal is carried out in 70 180 DEG C of water heating kettle 3 12 hours, the TiO of acquisition2Nano particle.The TiO2Nano particle has higher specific surface area and higher photocatalytic activity.With the TiO2Nano particle is that main functional component is developed with photocatalytic activity water solubility and oil-soluble nano paint.The coating is easy to be coated in substrate by way of spraying, and the pollutant in water removal and in air is effectively removed under sunlight.It can be used for building, indoor wall, surface of vehicle, the carrier surfaces such as windowpane are as automatic cleaning coating and pollutant elimination, and indoor air purification, open-air purification all has preferable effect, while also having the function of preferable antibiotic and sterilizing.

Description

High Efficiency Superfine TiO2Nano particle and photocatalytic nanometer coating
Technical field
The invention belongs to catalysis material technical fields, and in particular to the system of a kind of optically catalytic TiO 2 coating and its film Preparation Method.
Background technology
Titanium dioxide is widely used in filler, dyestuff, opto-electronic conversion material as a kind of common semi-conducting material The every field such as material, photochemical catalyst, catalyst carrier.With the development of nano material, the TiO of nano-scale2In photocatalysis side The application in face causes more and more researchs.For example using titanium dioxide be photochemical catalyst in purification of water quality, indoor air purification, And air contaminant treatment, automatic cleaning coating etc..This is mainly due to titanium dioxide to have unique spectrochemical property institute band The extensive use come.Titanium dioxide can absorb sunlight as semi-conducting material, generate the electrons and holes of photoproduction, photoproduction Electronics is reacted with oxygen molecule generates superoxide radical, and photohole produces hydroxyl radical free radical, Yi Jiguang with water molecule reaction Raw hole all has very strong oxidability, is referred to as active oxygen radical.These free radicals have very strong energy of oxidation Power, can be with the oxysulfide (SOx) in oxidation air, and nitrogen oxides (NOx), volatile organic compound (VOC) makes these Pollutant, which is further oxided, achievees the purpose that air purification.In addition can go out the trace organic compound dissolved in water in water Object, such as phenyl compound, halogen-containing compound can also utilize the heavy metal in light induced electron reduction aqueous solution, reach water The purpose of matter purification, in addition, the free radical with Strong oxdiative ability generated under illumination also can effectively kill substrate surface absorption Bacterium, play the purpose of sterilization.TiO under light illumination2Surface becomes super hydrophilic surface, therefore when drop is in TiO2Surface Meeting new city water membrane, rather than independent drop can be applied to high level in conjunction with strong oxidation performance as self-cleaning coating The outer surface of building and the surface of windowpane are played the role of self-cleaning.
Light-catalyzed reaction is happened on solid-liquid or gas-solid interface, and catalyst surface and interface has the activity of catalyst important Contribution.Therefore superfine Ti O is prepared2Nano particle will be conducive to improve TiO2Photocatalysis efficiency.This is mainly due to nanosizings can The specific surface area of material is set to increase, surface-active site is increased.TiO2Nano material is also widely researched and developed, such as military Chinese university reports a kind of method (CN 1583888A) of 3-10 nano-titanium dioxides nano-crystalline photocatalysis agent.Patent CN1850333A discloses a kind of mesoporous titanium dioxide photocatalytic material and preparation method thereof.Mesoporous TiO2Impart the material compared with High 100~300m of specific surface area2/g.Patent CN 1384165A disclose a kind of titanium dioxide of photocatalytic transparent hydrophilic coating Titanium nano paint, introducing organosilicon is formed transparent as binder in titania nanoparticles (10-20 nanometers) dispersion liquid Coating.Based binder inhibits the performance of photochemical catalyst to a certain extent.
Current main TiO2Nano particle synthesis one is being pyrolyzed in the presence of organic molecule using titanate esters as raw material or Hydro-thermal obtains the TiO of organic dispersion2Nano particle, however cost is higher, another kind is to hydrolyze to obtain with inorganic titanate hydro-thermal Obtain TiO2Nanostructure, be mostly powder body material be difficult stable dispersion in a solvent.
Invention content
One of the objects of the present invention is to provide a kind of superfine Ti O2The synthetic method of nano particle, the TiO2Nano particle Preparation method is simple and practical, particle size is less than 3.0 nanometers, specific surface area is higher, photocatalysis performance is excellent, can be applied to give up The processing of water and exhaust gas, the purification of room air and anti-biotic material.
Another object of the present invention is to be that main component is prepared for water based paint using this high efficiency photocatalyst, simultaneously By surfactant by TiO2Particle is transferred in organic phase, is prepared for oil paint, which can be by spraying, brushing The modes such as painting, dipping are implemented on base material, which illustrates the performance of good photocatalytically degradating organic dye.
In order to achieve the above objectives, the present invention uses following technical scheme：
A kind of superfine Ti O2The synthetic method of nano particle, by TiCl3Solution is added in ethyl alcohol, is obtained by hydro-thermal reaction White precipitate is obtained, ethyl alcohol washing is then carried out, drying can be obtained ultra-fine nano particle, the TiO obtained2Nano particle Size is less than 3 nanometers.And obtained nanoparticle surface is clean, without organo-functional group, there is higher photocatalysis to live Property, in addition, since particle size is smaller, specific surface area is higher, can reach 300m2/g。
It is anatase phase or rutile phase that its crystal form can be controlled by reaction condition, passes through raw material in the preparation It is added or is added without SnCl4The reaction condition control anatase phase or rutile phase of aqueous solution.Further preferably TiO2 Nano spherical particle or TiO2Nanometer rods.
Preferably, per 1-4 milliliters of 15-20wt%TiCl3Aqueous solution correspondence, which is added in 60 milliliters of ethyl alcohol, is reacted, At room temperature stir 30 minutes, then alcohol thermal response keep the temperature 1-12 hour at 70-180 DEG C, centrifugation, washing, dry acquisition TiO2Ball Shape nano-particle.
Preferably, per 1-4 milliliters of 15-20wt%TiCl3Aqueous solution corresponds to the SnCl of 1-4 milliliters of 0-1M (preferably 0.5M)4Water Solution and 60 milliliters of ethyl alcohol, are stirred at room temperature 30 minutes, and then alcohol thermal response keeps the temperature 1-12 hours at 70-180 DEG C, centrifugation, Washing, drying obtain TiO2Nanometer rods, gained TiO2Nanometer rods have mesoporous.
The method overcome the expensive disadvantages of metatitanic acid organic ester, and do not need complicated washing step and can be obtained The solid powder of titanium dioxide superfine nano particle.
In order to reach second purpose, the present invention uses following technical proposals：
The water based paint preparation method of the solid powder of titanium dioxide superfine nano particle, by previously obtained titanium dioxide The solid powder of superfine nano particle, is added directly into water, and concentration is controlled in 0.1-6g/L, by ultrasonic disperse, TiO2 Powder is very easy to be re-dispersed into water, forms transparent aqueous solution；The dispersion liquid can store half a year or more at room temperature, such as Having prevented precipitation from generating for a long time can shake up or be ultrasonically treated before use.Thus, it is possible to be directly prepared into high degree of dispersion TiO2Aqueous dispersions and water based paint.In order to increase film forming, water-soluble polymer can further be added, can contribute to TiO2The film forming of coating.
Preferably, every 1~60mg TiO2Nano particle is added in 10 milliliters of water ultrasonic disperse 15-30 minutes, is obtained Transparent solution；Water-soluble polymer such as polyvinylpyrrolidone (PVP), polyvinyl alcohol, polyoxyethylene etc. is added, preferably makes to gather Close a concentration of 0.01-5g/L of object.Obtain stable TiO2Aqueous nanoparticle dissipates coating, further preferred water-soluble polymer Addition form be aqueous solution.
The oil paint preparation method of the solid powder of titanium dioxide superfine nano particle, by titanium dioxide superfine nano The solid powder and surfactant of grain are added in organic solvent, and TiO is made2Organic solvent dispersion coating；Implementing to coat It is preceding that a small amount of film forming agent, auxiliary film forming is added.Film forming agent adopted here is organic titanate or is that titanium tetrachloride (uses ethyl alcohol When organic solvent, titanium tetrachloride is added or titanium tetrachloride is added in the form of ethanol solution, titanium tetrachloride in ethanol can shape At metatitanic acid ethyl alcohol ester, there is equivalent efficacy with four fourth fat of metatitanic acid is added), the oil paint of organic system is made.
Preferably, per 1-300mg TiO2Nano particle corresponds to 1-50mg surfactants, and correspondence is added to 100 milliliters Organic solvent for ultrasonic dispersion 15-30 minutes, obtains transparent dispersion liquid.It is corresponding simultaneously that 0.1-10 millis are added before implementing to coat Butyl titanate or corresponding titanium tetrachloride are risen, TiO is formed2The oil paint of nano particle.
Surfactant is selected from the ionic surfactant of phosphate, sulfonic group or amino, further detergent alkylate Sodium sulfonate, cetyl trimethylammonium bromide and nonionic surfactant and block copolymer.
Organic solvent is selected from the common solvents such as alcohol, ketone, phenyl, tetrahydrofuran, chloroform, dimethylformamide.
The water based paint obtained or oil paint are coated in using the method for spraying in matrix, the thickness of floating coat The concentration of coating and the number of spraying determine.
Beneficial effects of the present invention are as follows：
1, the present invention provides a kind of simple, cheap methods to prepare the TiO of anatase2Nano-particle and rutile are brilliant The TiO of phase2Nanometer rods.
2, TiO of the invention2Nano particle can be easy in stable dispersion to water or organic solvent.
3, TiO of the invention2Nano particle can be used for preparing the efficient coating with photocatalysis performance, in sunlight Or purification of the realization to pollutant and air under ultraviolet light.
Description of the drawings
Fig. 1 are that Examples 1 and 2 obtain TiO2The XRD diagram of nano particle, center line 1 are the anatase that embodiment 1 obtains TiO2Nano-particle, line 2 are the TiO for the Rutile Type that embodiment 2 obtains2Nanometer rods.
Fig. 2 is the TiO that embodiment 1 obtains2The transmission electron microscope and size distribution plot of nano-particle.
Fig. 3 is the TiO that embodiment 2 obtains2The transmission electron microscope of nanometer rods and the transmission electron microscope of stick and the diameter of nanometer rods and Length dimension distribution map.
Fig. 4 is the TiO that embodiment 3 obtains2The nitrogen adsorption desorption curve and pore size distribution curve of nanometer rods；(two in figure Line, below be adsorption curve, above be desorption curve)
Fig. 5 is the TiO that embodiment 1 obtains2The TiO that nano-particle (line 2), embodiment 3 obtain2Nanometer rods (line 3) and quotient Product P25TiO2The photocatalytic degradation rhodamine B curve under the illumination of full spectrum of nano particle (line 1).It is rhodamine B to scheme A The change curve of rhodamine B concentration in degradation process, figure B is corresponding degradation reaction rate curve.
Fig. 6 is the water base TiO in embodiment 42The TiO that coating spraying obtains2The ultraviolet-visible of nanometer rods figure layer penetrates light Spectrum.Its center line 1- lines 5 represent successively respectively coating spraying 0,5,10,20,30 times.Fig. 7 is the water base TiO in embodiment 42Coating It is sprayed in circle drawn on blank sheet of paper 30 times, sprays the rhodamine B solution of upper 500ppm on blank sheet of paper again after dry, it is to be dried Afterwards, which is placed in the time that illumination is different under the xenon lamp of 300W.
Fig. 8 is 5 medium oil TiO of embodiment2The TiO that coating spraying obtains2The ultraviolet-visible of nanometer rods figure layer penetrates spectrum. Its center line 1- lines 5 represent successively respectively coating spraying 0,10,20,30,40 times.
Fig. 9 is 5 medium oil TiO of embodiment2Coating sprays on the plastic substrate, and the thickness of coating is determined by the parameter sprayed (0,10,20,30,40 time).Concentration variation (A) and the degradation rate curve of illumination rhodamine B under 300W xenon lamps are shown in figure (B)。
Figure 10 is the oiliness TiO in embodiment 52Coating is sprayed on 10x10cm2Substrate of glass on, spray 40 times, by it It is placed in 30x30x30cm3Closed container in, formaldehyde is placed in container, after the concentration of formaldehyde and smog stabilization after, in 300W Xenon light shining under concentration of formaldehyde variation；Wherein, A is the variation of concentration of formaldehyde, and B is the variation of concentration of formaldehyde percentage.Figure 11 be the oiliness TiO in embodiment 52Coating is sprayed on 10x10cm2Substrate of glass on, spray 40 times, place it in 30x30x30cm3Closed container in, formaldehyde is placed in container, after the concentration of formaldehyde and smog stabilization after, in the xenon of 300W Variation of the light according to lower concentration of formaldehyde.Wherein, A is the variation of PM2.5 concentration, and B is the variation of PM2.5 percentages.
Specific implementation mode
In order to better illustrate the present invention, with reference to preferred embodiments and drawings, the present invention will be further described.It is excellent Select 15-20wt%TiCl3Aqueous solution is：TiCl3It is dissolved in the hydrochloric acid solution of 30wt%, TiCl3A concentration of 15-20wt%.
Embodiment 1
TiO2The preparation method of nano particle：
1. by the TiCl of 2 milliliters of 15-20wt%3Aqueous solution is added in 60 milliliters of ethyl alcohol, and is stirred at room temperature 30 Minute.Then above-mentioned solution is transferred in 100 milliliters of hydrothermal reaction kettle, places it in convection oven and is warming up to 100 DEG C And it is maintained at 100 DEG C 6 hours.Natural cooling.
2. the dispersion liquid obtained in step 1 is put in centrifuge tube, supernatant, acquired solid is removed by centrifugation.
3. 10 milliliters of ethanol solution is added in the solid obtained in step 2, ultrasound, will be unreacted to being completely dispersed TiCl3It removes, is then centrifuged for, obtain solid.
4. the solid obtained in step 3, which is put into drying in 70 DEG C of baking ovens, obtains about TiO2Powder about 200mg.
Dotted line in Fig. 1 is to obtain TiO2The pattern of the XRD of nano particle, it can be seen that the TiO obtained2Nano particle For anatase phase.Fig. 2 is is obtained TiO2The transmission electron microscope picture and size distribution plot of nano particle.It can be seen that being obtained TiO2The size of nano particle is about that the 2-10 nanometers of lattice dimensions that can see in high resolution electron microscopy figure are received for 0.346 Rice, this is Detitanium-ore-type TiO2(101) lattice dimensions.This also demonstrates obtained TiO2Nano particle is anatase.
Embodiment 2
TiO2The preparation method of nanometer rods
1. by the TiCl of 2 milliliters of 15-20%3Aqueous solution and the SnCl4 aqueous solutions of 1 milliliter of 0.5M are added to 60 milliliters of second In alcohol, and it is stirred at room temperature 30 minutes.Then above-mentioned solution is transferred in 100 milliliters of hydrothermal reaction kettle, is placed it in It is warming up to 100 DEG C in convection oven and is maintained at 100 DEG C 6 hours.Natural cooling.
2. the dispersion liquid obtained in step 1 is put in centrifuge tube, supernatant, acquired solid is removed by centrifugation.
3. 10 milliliters of ethanol solution is added in the solid obtained in step 2, ultrasound, will be unreacted to being completely dispersed TiCl3It removes, is then centrifuged for, obtain solid.
It is dried 4. the solid obtained in step 3 is put into 70 DEG C of baking ovens, drying acquisition about TiO in case2Powder is about 210mg。
Solid line in Fig. 1 is to obtain TiO2The pattern of the XRD of nano particle, it can be seen that the TiO obtained2Nano particle For rutile phase.Fig. 3 is is obtained TiO2The transmission electron microscope picture and size distribution plot of nanometer rods.From low power transmission electron microscope picture It can be seen that the TiO obtained2It is in mainly rodlike.A diameter of 1.5 nanometers, about 8 nanometers of stick length.It can in high resolution electron microscopy figure With the lattice dimensions seen for 0.324 nanometer, this is rutile TiO2(111) lattice dimensions.This also demonstrates obtained TiO2 Nano particle is rutile phase.
Embodiment 3
TiO2The preparation method of nanometer rods
1. by the TiCl of 4 milliliters of 15-20%3Aqueous solution and the SnCl4 aqueous solutions of 2 milliliters of 0.5M are added to 60 milliliters of second In alcohol, and it is stirred at room temperature 30 minutes.Then above-mentioned solution is transferred in 100 milliliters of hydrothermal reaction kettle, is placed it in It is warming up to 180 DEG C in convection oven and is maintained at 180 DEG C 6 hours.Natural cooling.
2. the dispersion liquid obtained in step 1 is put in centrifuge tube, supernatant, acquired solid is removed by centrifugation.
3. 10 milliliters of ethanol solution is added in the solid obtained in step 2, ultrasound, will be unreacted to being completely dispersed TiCl3It removes, is then centrifuged for, obtain solid.
It is dried 4. the solid obtained in step 3 is put into 70 DEG C of baking ovens, drying acquisition about TiO in case2Powder is about 300mg。
Fig. 4 is obtained TiO2The N of nanometer rods2Adsorption desorption curve and pore size distribution curve, it can be seen that TiO2Nanometer rods Adsorption desorption curve is typical type IV curves, that is to say, that there are mesoporous.Its aperture is in 3-5 nanometer ranges.Its BET compares table Area is 312m2/ g, it can be seen that the TiO obtained2Nanometer rods have higher specific surface area.Fig. 5 is obtained TiO2Nanometer The design sketch of the photocatalytic degradation rhodamine B of particle and nanometer rods.It can be seen from the figure that, the TiO of anatase2Nano particle has Have and P25TiO2Similar photocatalytic activity.And the TiO of Rutile Type2Nanometer rods then have better photocatalytic activity.TiO2 Nanometer rods degradation rate constant is 2 times of P25.That is TiO2Nanometer rods have better photocatalytic activity.
Embodiment 4
TiO2The preparation method of water-based coating
1. taking 300mg TiO2Nanometer rods are added to ultrasonic disperse 5-10 minutes in 100 milliliters of water, obtain transparent moisture Dispersion liquid.
2. 3 milliliters of 1wt% aqueous povidone solutions are added into above-mentioned dispersion liquid.
3. the solution spraying is obtained TiO on glass slide2Coating is dried under infrared lamp after often spraying 5 times, is then sprayed again again Next layer.The thickness of coating is determined by the parameter of spraying.
Fig. 6 is the TiO that different passes are sprayed on glass slide2The UV-Vis spectrum of nanometer rods.It can be seen that not spraying The transmitance of Tu Shi, sheet glass maintain~90%, and with the increase of coating layer thickness, transmitance continuously decreases, but visible Without absorption peak in light area.It can be seen that the figure layer is only reduction of the transmitance of glass, the color of substrate will not be changed.
Fig. 7 is that 30 times TiO are sprayed on blank sheet of paper2Then nanometer rods spray the rhodamine B of 50ppm, then sieve under light illumination The degradation process of red bright B.Wherein with being TiO at the circle of black line mark2Nanometer rods spraying area.Rhodamine is equal when illumination starts Even is dispersed on blank sheet of paper.After illumination in 30 minutes, there is TiO2The region rhodamine B of nanometer rods is obviously faded, this explanation TiO2Nanometer rods have excellent light degradation property.
Embodiment 5
TiO2The preparation method of oiliness coating
1. taking 300mg TiO2Nanometer rods and 6mg neopelexes are added to ultrasonic disperse in 100 milliliters of ethyl alcohol 10-30 minutes, obtain transparent alcohol dispersion liquid.
2. 1 milliliter of TiCl is added into above-mentioned dispersion liquid4, ageing is stirred at room temperature 1 hour for use.
3. the solution spraying is obtained TiO on glass slide2Coating, after often spraying 5 times, with being dried under infrared lamp, then again Spray next layer.The thickness of coating is determined by the parameter of spraying.
Fig. 8 is the TiO that different passes are sprayed on glass slide2The UV-Vis spectrum of nanometer rods.It can be seen that not spraying The transmitance of Tu Shi, sheet glass maintain~90%, and with the increase of coating layer thickness, transmitance continuously decreases, but visible Without absorption peak in light area.It can be seen that the figure layer is only reduction of the transmitance of glass, the color of substrate will not be changed.
Fig. 9 is by TiO2Nanometer rods coating sprays on the plastic substrate, and coating layer thickness has the parameter of spraying to control, and by the material Material is placed in the rhodamine liquor of 100 milliliters of 5ppm, and the illumination under the xenon lamp of 300W takes 1 milliliter of monitoring within the set time The concentration of its rhodamine B changes.It can be seen that the concentration of rhodamine B continuously decreases, illustrate TiO of the rhodamine B by substrate surface2 Degradation.
Figure 10 and Figure 11 is shown TiO2Nanometer rods coating is sprayed on 10x10cm2Substrate of glass on, be placed in 30x30x30cm3Closed container in, a small amount of formaldehyde or smog are placed in container, the concentration with formaldehyde or PM2.5 reaches steady After fixed, substrate of glass, and the variation of the formaldehyde and PM2.5 concentration in monitoring of containers are irradiated using 300W xenon lamps.It can be seen that holding Formaldehyde and PM2.5 in device all continuously decrease.It is possible thereby to illustrate, which can eliminate PM2.5 and formaldehyde.
Embodiment 6
TiO2The preparation method of oiliness coating
1. taking 300mg TiO2Nanometer rods and 60mg cetyl trimethylammonium bromides are added in 100 milliliters of toluene ultrasonic Dispersion 10-30 minutes, obtains transparent toluene dispersion liquid.
2. 1 milliliter of butyl titanate is added into above-mentioned dispersion liquid, ageing is stirred at room temperature 1 hour for use.
3. the solution spraying is obtained TiO on glass slide2Coating, after often spraying 5 times, with being dried under infrared lamp, then again Spray next layer.The thickness of coating is determined by the parameter of spraying.
The above embodiment of the present invention only examples made by the present invention to clearly illustrate, are not to embodiment of the present invention Restriction.The obvious variation amplified out on the basis of the above description is still in protection scope of the present invention.

Claims (10)

1. a kind of superfine Ti O2The synthetic method of nano particle, which is characterized in that by TiCl3Solution is added in ethyl alcohol, passes through water Thermal response obtains white precipitate, then carries out ethyl alcohol washing, and drying can be obtained ultra-fine nano particle, the TiO obtained2It receives The size of rice grain is less than 3 nanometers.
2. a kind of superfine Ti O described in accordance with the claim 12The synthetic method of nano particle, which is characterized in that its crystal form passes through Reaction condition control is anatase phase or rutile phase, is added or is added without SnCl by raw material in the preparation4It is water-soluble The reaction condition control anatase phase or rutile phase of liquid.
3. a kind of superfine Ti O according to claim 22The synthetic method of nano particle, which is characterized in that per 1-4 milliliters 15-20wt%TiCl3Aqueous solution correspondence is added in 60 milliliters of ethyl alcohol and is reacted, and is stirred at room temperature 30 minutes, then alcohol Thermal response keeps the temperature 1-12 hours at 70-180 DEG C, and centrifugation, washing, drying obtain TiO2Nano spherical particle；
Or per 1-4 milliliters of 15-20wt%TiCl3Aqueous solution corresponds to the SnCl of 1-4 milliliters of 0-1M (being not 0)4Aqueous solution and 60 milliliters Ethyl alcohol, is stirred at room temperature 30 minutes, and then alcohol thermal response keeps the temperature 1-12 hours at 70-180 DEG C, and centrifugation, washing, drying obtain TiO2Nanometer rods, gained TiO2Nanometer rods have mesoporous.
4. the superfine Ti O being prepared according to claim 1-3 any one of them methods2Nano particle.
5. including the superfine Ti O of claim 42The preparation method for coating of nano particle, which is characterized in that coating is water based paint Or oil paint；
Wherein water based paint preparation method：By the superfine Ti O of acquisition2Nano particle is added directly into water, and concentration control exists 0.1-6g/L, by ultrasonic disperse, TiO2Powder is re-dispersed into water, forms transparent aqueous solution；Water-soluble polymeric is added Object；
Or the preparation method of oil paint：By the superfine Ti O of acquisition2Nano particle and surfactant are added to organic solvent, system At TiO2Organic solvent dispersion coating；Film forming agent is added before implementing to coat, film forming agent adopted here is organic titanate Or titanium chloride, obtain the oil paint of organic system.
6. according to the preparation method of claim 5, which is characterized in that water-soluble polymer be selected from polyvinylpyrrolidone (PVP), Polyvinyl alcohol, polyoxyethylene；Organic solvent preferably is selected from alcohol, ketone, phenyl, tetrahydrofuran, chloroform, dimethylformamide common solvents Solvent.
7. according to the preparation method of claim 5, which is characterized in that polymer is a concentration of in water based paint preparation method 0.01-5g/L；In oil paint preparation method：Per 1-300mg TiO2Nano particle corresponds to 1-50mg surfactants, corresponding It is added to 100 milliliters of organic solvent for ultrasonic dispersion 15-30 minutes, obtains transparent dispersion liquid；It is corresponding simultaneously to implement to apply 0.1-10 milliliters of titanate esters or titanium tetrachloride are added before covering, forms TiO2The oil paint of nano particle, it is organic molten using ethyl alcohol When agent, titanium tetrachloride is added or titanium tetrachloride is added in the form of ethanol solution.
8. according to the preparation method of claim 5, which is characterized in that surfactant is selected from neopelex, 16 Alkyl trimethyl ammonium bromide and nonionic surfactant and block copolymer.
9. according to the preparation method of claim 7, it is characterised in that it is preceding to TiO to implement coating2The titanate esters choosing being added in dispersion liquid From tetraethyl titanate, four fourth fat of metatitanic acid, tetraisopropyl titanate.
10. the O containing superfine Ti being prepared according to any one of claim 5-9 methods2The coating of nano particle.
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CN110079187A (en) * 2019-04-08 2019-08-02 沈阳化工大学 A kind of aqueous dual preparation method except methanal paint
CN110143611A (en) * 2019-05-07 2019-08-20 武汉理工大学 Anatase/rutile compound phase TiO2The liquid phase preparation process of photocatalysis and energy storage material
CN110668494A (en) * 2019-10-29 2020-01-10 北京工业大学 High yield of pure anatase TiO2Simple synthesis of nanoparticles
CN113318723A (en) * 2021-06-18 2021-08-31 陕西科技大学 Titanium dioxide photocatalytic material and preparation method and application thereof
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110079187A (en) * 2019-04-08 2019-08-02 沈阳化工大学 A kind of aqueous dual preparation method except methanal paint
CN110143611A (en) * 2019-05-07 2019-08-20 武汉理工大学 Anatase/rutile compound phase TiO2The liquid phase preparation process of photocatalysis and energy storage material
CN110143611B (en) * 2019-05-07 2020-10-30 武汉理工大学 Anatase/rutile composite phase TiO2Liquid phase preparation method of photocatalysis and energy storage material
CN110668494A (en) * 2019-10-29 2020-01-10 北京工业大学 High yield of pure anatase TiO2Simple synthesis of nanoparticles
CN113797927A (en) * 2020-06-12 2021-12-17 赵石永 Sterilization film, preparation method thereof and application thereof in lighting device
CN113318723A (en) * 2021-06-18 2021-08-31 陕西科技大学 Titanium dioxide photocatalytic material and preparation method and application thereof
CN113398913A (en) * 2021-06-18 2021-09-17 陕西科技大学 Tin dioxide/titanium dioxide composite photocatalyst and preparation method and application thereof
CN114011476A (en) * 2021-11-08 2022-02-08 四川大学 Adsorption-catalytic decomposition integrated titanium dioxide and application thereof
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Application publication date: 20180921