CN104959133A - Titanium dioxide film for photocatalyst and preparation method thereof - Google Patents
Titanium dioxide film for photocatalyst and preparation method thereof Download PDFInfo
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- CN104959133A CN104959133A CN201510135953.3A CN201510135953A CN104959133A CN 104959133 A CN104959133 A CN 104959133A CN 201510135953 A CN201510135953 A CN 201510135953A CN 104959133 A CN104959133 A CN 104959133A
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Abstract
The invention provides a preparation method for a titanium dioxide film used for a photocatalyst. The preparation method comprises the following steps: providing a titanium metal substrate and cleaning dirt attached on the surface of the titanium metal substrate; putting the cleaned titanium metal substrate in a boiling aqueous oxalic acid solution for etching so as to properly roughening the surface of the substrate; putting the etched titanium metal substrate in a hydrothermal tank filled with a mixed solution of water, isopropanol and hydrofluoric acid, sealing the hydrothermal tank and carrying out hydrothermal reaction at 170 to 190 DEG C; and cleaning the titanium metal substrate having undergone hydrothermal reaction with water and roasting the cleaned titanium metal substrate at 300 to 900 DEG C so as to obtain the titanium dioxide film used for the photocatalyst. The invention further provides the titanium dioxide film used for the photocatalyst. The titanium dioxide film has a rectangular crystal face which has a plurality of holes. The titanium dioxide film used for the photocatalyst has long service life, a high {001} crystal face exposure rate and holes; and the preparation method is simple and has low cost.
Description
Technical field
The present invention relates to a kind of photochemical catalyst titanium dioxide film and preparation method thereof.
Background technology
Titanium dioxide is a kind of stable chemical nature, conductor oxidate with low cost, has been widely used in photocatalysis, photovoltaic cell, sensor field.In in the past 20 years, sol-gal process, hydro-thermal method, solvent-thermal method, chemical vapour deposition (CVD), anodizing are all applied to the TiO attempting the different nanostructured of preparation
2material, the titanium dioxide that highlight catalytic active is prepared in research is focus in recent decades.
Research shows Detitanium-ore-type TiO
2{ 001}, { 100}, { 101} surface energy respectively is 0.90 J/m
2, 0.53 J/m
2, 0.44J/m
2, surface energy higher { 001} crystal face has higher photocatalytic activity.But, but the Detitanium-ore-type TiO of preparation usually
2material mainly demonstrates { 101} face.2008, { 001} crystal face exposure was the TiO of 47% to have researcher to synthesize
2nano crystal (Nature, 2008,453:638-641).After this, about the report of 001} crystal face high exposure increases sharply, such as prepare using titanium tetrachloride as titanium source have higher 001} crystal face expose TiO
2nano crystal (Journal of the American Chemical Society, 2009,131,3152), but have higher water-disintegrable due to titanium tetrachloride, and obtained product is easily reunited, the method is not easily produced in a large number.
There is titanium sheet to be base material at present, synthesize the exposure { TiO in 001} face by hydro-thermal reaction on its surface
2nanometer film (Journal of Materials Chemistry, 2011,21 (3): 869-873), solves separation and recovery TiO after water treatment
2the problem of catalyst, but TiO
2nanometer film is combined with titanium sheet and insecurely easily comes off, and { 001} crystal face exposure is lower.2014, having researcher using isopropyl alcohol as pattern controlling agent, take titanium sheet as base material, synthesizes combine firmly TiO at titanium plate surface
2nanometer film (International Journal ofPhotoenergy, 2014,2014).Also such as in Japanese patent application (Unexamined Patent 11-197516 publication), disclose following technology, namely, by carrying out anodized to the surface of the base material containing titanium and making surface form amorphous titanium dioxide, then, effects on surface gives thermograde crystallization process on one side in the thickness of slab direction of base material on one side, thus, obtain { 001} face and surface in alignment the structure exposed in the active crystal face being considered to titanium dioxide.But, can't realize practical thus, still there is room for improvement.Subsequently, there is report, in the mode of low temperature electrostatic absorption, precious metals pd is loaded to TiO
2in nanometer film (Chemical Engineering Journal, 2014,252,337-345), its catalytic performance is improved, but this preparation technology is comparatively complicated.
Summary of the invention
In sum, be necessary to provide a kind of long service life, crystal face has nano-pore structure and have higher the photochemical catalyst titanium dioxide film of 001} crystal face exposure, and preparation method thereof, this preparation method is simple.
A kind of photochemical catalyst titanium dioxide film, have the crystal face of rectangle, the crystal face of described rectangle has multiple hole.
A preparation method for photochemical catalyst titanium dioxide film, comprises the following steps: provide titanium metal substrates, and the dirt being attached to titanium metal substrates surface is removed in cleaning; Titanium metal substrates after cleaning is put into the oxalic acid aqueous solution etching processing of boiling by the suitably alligatoring of its surface; The titanium metal substrates of etching processing is put into immediately the hydro-thermal tank that water, isopropyl alcohol and hydrofluoric acid mixed solution are housed, after sealing at 170 DEG C ~ 190 DEG C hydro-thermal reaction 2h ~ 4h; By the titanium metal substrates obtained through hydro-thermal reaction, after simply rinsing with water, roasting 1h ~ 5h at 300 DEG C ~ 900 DEG C, obtains photochemical catalyst titanium dioxide film.
Catalyst titanium dioxide film provided by the invention and preparation method thereof has following beneficial effect.The first, the preparation method of catalyst titanium dioxide film adopts hydro-thermal method one-step synthesis, and preparation technology is simple, cost is lower, is easy to practical application.The second, titanium dioxide film and the titanium metal substrates strong bonded of generation is made by oxalic acid pretreatment, long service life.Three, by regulating hydrothermal temperature, hydro-thermal time etc., the bore hole size in controlled combinations face.Four, porous surface, { the titanium dioxide film organic pollution capable of being fast degraded of 001} crystal face exposure high (can more than 60% be reached).
Accompanying drawing explanation
The stereoscan photograph of the photochemical catalyst titanium dioxide film that Fig. 1 provides for the embodiment of the present invention 1, wherein (a) is low power stereoscan photograph, and (b) is high power stereoscan photograph.
The stereoscan photograph of the photochemical catalyst titanium dioxide film that Fig. 2 provides for the embodiment of the present invention 2, wherein (a) is low power stereoscan photograph, and (b) is high power stereoscan photograph.
Transmission electron microscope (TEM) photo of the photochemical catalyst titanium dioxide film that Fig. 3 provides for the embodiment of the present invention 2.
X-ray diffraction (XRD) figure of the photochemical catalyst titanium dioxide film that Fig. 4 provides for the embodiment of the present invention 2.
The stereoscan photograph of the photochemical catalyst titanium dioxide film that Fig. 5 provides for the embodiment of the present invention 3, wherein (a) is low power stereoscan photograph, and (b) is high power stereoscan photograph.
The stereoscan photograph of the photochemical catalyst titanium dioxide film that Fig. 6 provides for the embodiment of the present invention 4, wherein (a) is low power stereoscan photograph, and (b) is high power stereoscan photograph.
The stereoscan photograph of the titanium dioxide film that Fig. 7 provides for comparative example 1, wherein (a) is low power stereoscan photograph, and (b) is high power stereoscan photograph.
The stereoscan photograph of the titanium dioxide film that Fig. 8 provides for comparative example 2, wherein (a) is low power stereoscan photograph, and (b) is high power stereoscan photograph.
{ the stereoscan photograph of 001} crystal face of the photochemical catalyst titanium dioxide film that Fig. 9 provides for the embodiment of the present invention 2 and embodiment 5, wherein { the stereoscan photograph of 001} crystal face of (a) the photochemical catalyst titanium dioxide film that is embodiment 2, b () is for figure (a) is by PhotoImpact adjustment contrast and brightness, use the image that image analysis software Image-ProPlus observes, { the stereoscan photograph of 001} crystal face of c photochemical catalyst titanium dioxide film that () is embodiment 5, d () is for figure (c) is by PhotoImpact adjustment contrast and brightness, use the image that image analysis software Image-ProPlus observes.
Figure 10 is that { stereoscan photograph of 001} crystal face and adjust contrast and brightness by PhotoImpact uses the image that image analysis software Image-ProPlus observes to different 6 of the difference of embodiment 2 and embodiment 5.
Figure 11 is the segmentation block diagram of the stereoscan photograph of 5000 times of embodiment 2 and embodiment 5.
Figure 12 is all { histograms of the length on a limit of 001} crystal face in the stereoscan photograph of Figure 11.
6 different { histograms of the diameter of the hole in 001} crystal face on the stereoscan photograph of the titanium dioxide film that Figure 13 provides for embodiment 2.
6 different { histograms of the diameter of the hole in 001} crystal face on the stereoscan photograph of the titanium dioxide film that Figure 14 provides for embodiment 5.
Figure 15 is the properties of catalyst detection device of catalyst titanium dioxide film provided by the invention.
The design sketch for ethoxybenzamide of degrading of the catalyst titanium dioxide film that Figure 16 provides for the embodiment of the present invention 2 and embodiment 5.
Figure 17 be embodiment 2 prepare porous surface, the titanium dioxide film that 001} crystal face exposure is high and comparative example 1 prepare { 001} crystal face exposes atresia Detitanium-ore-type TiO
2the photoelectric respone comparison diagram of film.
Figure 18 be embodiment 2 prepare porous surface, the titanium dioxide film that 001} crystal face exposure is high and comparative example 1 prepare { 001} crystal face exposes atresia Detitanium-ore-type TiO
2film is for the effect contrast figure of ethoxybenzamide of degrading.
Detailed description of the invention
Below in conjunction with detailed description of the invention, technical scheme of the present invention is stated further in detail.For the ease of understanding technical scheme of the present invention, first the present invention introduces the preparation method of photochemical catalyst titanium dioxide film.
Photochemical catalyst titanium dioxide film of the present invention carries out upgrading by hydrothermal synthesis method to the surface of titanium metal substrates, then under oxygen atmosphere, carries out roasting to it and obtain.Concrete steps are as follows:
Step S1 be the putting into ethanol carry out Ultrasonic Cleaning containing titanium metal substrates of titanium by main component, thus removing is attached to the dirt on titanium metal substrates surface;
Step S2, with the oxalic acid aqueous solution seethed with excitement to titanium metal substrates etching processing;
Step S3, the titanium metal substrates of etching processing is put into immediately the hydro-thermal tank that water, isopropyl alcohol and hydrofluoric acid mixed solution are housed and carry out upgrading by hydrothermal synthesis method to titanium metal substrates surface, its reaction equation is such as formula 1;
Ti+6HF→H
2TiF
6+2H
2↑
H
2tiF
6+ 4H
2o → Ti (OH)
4+ 6HF (formula 1)
Step S4, the titanium metal substrates of roasting upgrading in oxygen atmosphere, be titanium dioxide by titanium metal substrates surface conversion, its reaction equation is such as formula 2.
Ti (OH)
4→ TiO
2+ 2H
2o (formula 2)
In described step S2, by titanium metal substrates etching processing, by the suitably alligatoring of its surface, thus when Hydrothermal Synthesis afterwards or further roasting time, promote precipitation or the growth of titanium dioxide crystal.Be 0.5h-3h with the oxalic acid aqueous solution of boiling to the time of titanium metal substrates etching processing in this step.Here the titanium sheet water after etching processing rinses.
In described step S3, it is emphasized that the hydro-thermal tank titanium metal substrates of etching processing put into immediately and water, isopropyl alcohol and hydrofluoric acid mixed solution are housed.In described mixed solution, the concentration of hydrofluoric acid is 0.01mol/L ~ 0.05mol/L, and in described mixed solution, the consumption of hydrofluoric acid depends on the area of described titanium metal substrates, preferably 1.6 × 10
-5mol/cm
2to 8.5 × 10
-5mol/cm
2.In described mixed solution, the volume ratio of water and isopropyl alcohol is 1:1 ~ 1:4.In this step the titanium metal substrates of etching processing is put into be equipped with water, isopropyl alcohol and hydrofluoric acid mixed solution hydro-thermal tank sealing after at 170 DEG C ~ 190 DEG C hydro-thermal reaction 2h ~ 4h.
Here some carries out simultaneously to it is emphasized that step S2 and step S3, the concrete step S2 mesoxalic acid aqueous solution is to the formation mixed solution stage of carrying out step S3 while titanium metal substrates etching processing, put into by the mixed solution that step S3 prepares immediately after titanium metal substrates etching processing being completed in step S2 and clean with water, then carry out hydro-thermal reaction.Wherein, emphasized what refer to immediately is exactly as much as possible namely the titanium metal substrates of etching processing was put in several minutes to several tens minutes the mixed solution that S3 prepares, instead of the titanium metal substrates after etching processing places the mixed solution just put into S3 after tens of hours and prepare.
In described step S4, sintering temperature is 300 DEG C ~ 900 DEG C, preferably 300 DEG C ~ 700 DEG C, and roasting time is 1h ~ 5h.If sintering temperature is below 300 DEG C, be difficult to remove isopropyl alcohol, on the other hand, if sintering temperature is more than 900 DEG C, anatase titanium dioxide becomes rutile-type mutually, causes properties of catalyst to reduce.In addition, the hydrogen fluoride corrosion that Hydrothermal Synthesis uses is high, therefore, the titanium metal substrates of Hydrothermal Synthesis process is needed simply to rinse with water before calcining process, but in the condition that this does not use ultrasonic wave etc. too drastic as far as possible.
Introduce photochemical catalyst titanium dioxide film provided by the invention below further.Photochemical catalyst titanium dioxide film { 001} crystal face has multiple hole.Wherein, described photochemical catalyst titanium dioxide film { 001} crystal face is rectangular.Described rectangle the length on one side of 001} crystal face is 1.05 μm ~ 1.75 μm, further, described rectangle 001} crystal face the mode value of length be 1.35 μm ~ 1.70 μm.Described photochemical catalyst titanium dioxide film { on 001} crystal face, the diameter of described hole is 10nm ~ 80nm.Described photochemical catalyst titanium dioxide film degradable organic pollutant or capable of purifying air under ultraviolet lighting.Photochemical catalyst titanium dioxide film { 001} crystal face has multiple hole, is therefore improved by specific area during photocatalyst.In addition, { existence of multiple hole on 001} crystal face, the inactivation of the photocatalyst activity that inhibit electronics to cause with being again combined of hole.If to photochemical catalyst titanium dioxide film irradiating ultraviolet light, then excite the electronics of valency electricity band, move to conductive strips, thus, generate hole at valency electricity band, generate electronics at conductive strips, respectively at the molecule of adsorption or the material of contact and electronics, and the exchange in hole, that is, there is reduction reaction and oxidation reaction.If electronics is combined again with hole, then can not there is above-mentioned reaction, that is, lose catalytic effect.But, due to photochemical catalyst titanium dioxide film { 001} crystal face has multiple hole and this electronics can be hindered again to be combined with hole, concrete, electronics moves to metal base by above-mentioned multiple hole, and then hinder the inactivation being again combined and then suppressing catalyst activity in electronics and hole, catalyst performance raising.
Embodiment 1
Titanium sheet (Baoji Shengrong Titanium Corporation system, purity 99.5%, 240mm × 100mm × 0.15mm) is carried out Ultrasonic Cleaning in ethanol, the organic matter on removing surface.The oxalic acid aqueous solution pretreatment the 0.5h again titanium sheet after cleaning being put into boiling etches, and rear washed with de-ionized water is also dry.Afterwards, the mixed solution of 200mL pure water and 200mL isopropyl alcohol is provided, add aqueous hydrogen fluoride solution wherein again, make 0.02mol/L hydrogen fluoride mixed solution, the cumulative volume of this mixed solution is 400ml, then titanium sheet and hydrogen fluoride mixed solution are put into the polytetrafluoroethylene (PTFE) reactor that volume is 500ml, described titanium sheet is immersed in hydrogen fluoride mixed solution completely, hydro-thermal reaction 2h at 170 DEG C, after the temperature return in reactor to room temperature, take out titanium sheet, with deionized water rinsing, then Muffle furnace roasting 2h at 600 DEG C is put into, obtain that { 001} crystal face exposure is high, porous, photochemical catalyst titanium dioxide film.
Refer to Fig. 1, the stereoscan photograph of its photochemical catalyst titanium dioxide film provided for embodiment 1, can be clear that { 001} surface areas is comparatively large and there is multiple hole, and { 001} crystal face diagonal line length is about 1300nm.
Embodiment 2
Titanium sheet (Baoji Shengrong Titanium Corporation system, purity 99.5%, 240mm × 100mm × 0.15mm) is carried out Ultrasonic Cleaning in ethanol, the organic matter on removing surface.The oxalic acid aqueous solution pretreatment the 1.5h again titanium sheet after cleaning being put into boiling etches, and rear washed with de-ionized water is also dry.Afterwards, the mixed solution of 125mL pure water and 275mL isopropyl alcohol is provided, add aqueous hydrogen fluoride solution wherein again, make 0.03mol/L hydrogen fluoride mixed solution, the cumulative volume of this mixed solution is 400ml, then titanium sheet and hydrogen fluoride mixed solution are put into the polytetrafluoroethylene (PTFE) reactor that volume is 500ml, described titanium sheet is immersed in hydrogen fluoride mixed solution completely, hydro-thermal reaction 3h at 180 DEG C, after the temperature return in reactor to room temperature, take out titanium sheet, simply rinse by deionized water, roasting 2h at 600 DEG C, obtain { the much higher hole of 001} crystal face exposure, photochemical catalyst titanium dioxide film.
Refer to Fig. 2, the stereoscan photograph of its photochemical catalyst titanium dioxide film provided for embodiment 2.{ 001} surface areas is comparatively large and surface exists multiple hole, and { 001} crystal face diagonal line length is about 1350nm as seen from the figure.
The transmission electron microscope photo of the photochemical catalyst titanium dioxide film that Fig. 3 provides for embodiment 2, plane of crystal and the inner opening that all there is round rectangle can be observed, all there is spacing in its plane of crystal and opening and be 0.192nm and orthogonal lattice fringe, respectively corresponding { 200} and { 020} crystal face proves that the crystal face in the plane of crystal observed and opening is TiO
2001} crystal face, opening be about 2nm ~ 25nm, wide about 2nm ~ 15nm.
The known Detitanium-ore-type TiO of X-ray diffraction (XRD) figure of the photochemical catalyst titanium dioxide film that Fig. 4 provides for embodiment 2, contrast JCPDS21-1272
2for principal crystalline phase, there is a small amount of Rutile Type simultaneously.
Embodiment 3
Titanium sheet (Baoji Shengrong Titanium Corporation system, purity 99.5%, 240mm × 100mm × 0.15mm) is carried out Ultrasonic Cleaning in ethanol, the organic matter on removing surface.The oxalic acid aqueous solution pretreatment the 1.5h again titanium sheet after cleaning being put into boiling etches, and rear washed with de-ionized water is also dry.Afterwards, the mixed solution of 125mL pure water and 275mL isopropyl alcohol is provided, add aqueous hydrogen fluoride solution wherein again, make 0.05mol/L hydrogen fluoride mixed solution, the cumulative volume of this mixed solution is 400ml, then titanium sheet and hydrogen fluoride mixed solution are put into the polytetrafluoroethylene (PTFE) reactor that volume is 500ml, described titanium sheet is immersed in hydrogen fluoride mixed solution completely, hydro-thermal reaction 3h at 180 DEG C, after the temperature return in reactor to room temperature, take out titanium sheet, simply rinse by deionized water, roasting 1h at 700 DEG C, obtain that { 001} crystal face exposure is high, porous (hole is more), photochemical catalyst titanium dioxide film.
Refer to Fig. 5, the stereoscan photograph of its photochemical catalyst titanium dioxide film provided for embodiment 3, as seen from the figure photochemical catalyst titanium dioxide film { there is multiple hole in 001} crystal face, bore hole size is comparatively large, distribution is comparatively even, and { 001} crystal face diagonal line length is about 1000nm.
Embodiment 4
Titanium sheet (Baoji Shengrong Titanium Corporation system, purity 99.5%, 240mm × 100mm × 0.15mm) is carried out Ultrasonic Cleaning in ethanol, the organic matter on removing surface.The oxalic acid aqueous solution pretreatment the 3h again titanium sheet after cleaning being put into boiling etches, and rear washed with de-ionized water is also dry.Afterwards, the mixed solution of 80mL pure water and 320mL isopropyl alcohol is provided, add aqueous hydrogen fluoride solution wherein again, make 0.10mol/L hydrogen fluoride mixed solution, the cumulative volume of this mixed solution is 400ml, then titanium sheet and hydrogen fluoride mixed solution are put into the polytetrafluoroethylene (PTFE) reactor that volume is 500ml, described titanium sheet is immersed in hydrogen fluoride mixed solution completely, hydro-thermal reaction 4h at 190 DEG C, after the temperature return in reactor to room temperature, take out titanium sheet, simply rinse by deionized water, roasting 5h at 300 DEG C, obtain { the much higher hole of 001} crystal face exposure, photochemical catalyst titanium dioxide film.
Refer to Fig. 6, the stereoscan photograph of its photochemical catalyst titanium dioxide film provided for embodiment 4, as seen from the figure photochemical catalyst titanium dioxide film { 001} surface areas is comparatively large and there is tiny hole, and { 001} crystal face diagonal line length is about 1550nm.
Embodiment 5
Titanium sheet (Baoji Shengrong Titanium Corporation system, purity 99.5%, 240mm × 100mm × 0.15mm) is carried out Ultrasonic Cleaning in ethanol, the organic matter on removing surface.The oxalic acid aqueous solution pretreatment the 1.5h again titanium sheet after cleaning being put into boiling etches, and rear washed with de-ionized water is also dry.Afterwards, the mixed solution of 125mL pure water and 275mL isopropyl alcohol is provided, add aqueous hydrogen fluoride solution wherein again, make 0.03mol/L hydrogen fluoride mixed solution, the cumulative volume of this mixed solution is 400ml, then titanium sheet and hydrogen fluoride mixed solution are put into the polytetrafluoroethylene (PTFE) reactor that volume is 500ml, described titanium sheet is immersed in hydrogen fluoride mixed solution completely, hydro-thermal reaction 3h at 180 DEG C, after the temperature return in reactor to room temperature, take out titanium sheet, simply rinse by deionized water, roasting 2h at 600 DEG C, obtain { the much higher hole of 001} crystal face exposure, photochemical catalyst titanium dioxide film.
Comparative example 1
Titanium sheet (Baoji Shengrong Titanium Corporation system, purity 99.5%, 240mm × 100mm × 0.15mm) is carried out Ultrasonic Cleaning in ethanol, the organic matter on removing surface.Afterwards, the mixed solution of 125mL pure water and 275mL isopropyl alcohol is provided, adds aqueous hydrogen fluoride solution wherein again, make 0.025mol/L hydrogen fluoride mixed solution, the cumulative volume of this mixed solution is 400ml, then titanium sheet and hydrogen fluoride mixed solution are put into the polytetrafluoroethylene (PTFE) reactor that volume is 500ml, described titanium sheet is immersed in hydrogen fluoride mixed solution completely, hydro-thermal reaction 3h at 180 DEG C, after the temperature return in reactor to room temperature, take out titanium sheet, with deionized water rinsing, roasting 5h at 500 DEG C, obtains the titanium dioxide film of comparative example 1.
Refer to Fig. 7, it is the TiO obtained by the preparation method of comparative example 1
2the stereoscan photograph of film, can observe TiO
2there is hole hardly in plane of crystal.
Comparative example 2
Titanium sheet (Baoji Shengrong Titanium Corporation system, purity 99.5%, 240mm × 100mm × 0.15mm) is carried out Ultrasonic Cleaning in ethanol, the organic matter on removing surface.Afterwards, the mixed solution of 125mL pure water and 275mL isopropyl alcohol is provided, adds aqueous hydrogen fluoride solution wherein again, make 0.03mol/L hydrogen fluoride mixed solution, the cumulative volume of this mixed solution is 400ml, then titanium sheet and hydrogen fluoride mixed solution are put into the polytetrafluoroethylene (PTFE) reactor that volume is 500ml, described titanium sheet is immersed in hydrogen fluoride mixed solution completely, hydro-thermal reaction 3h at 180 DEG C, after the temperature return in reactor to room temperature, take out titanium sheet, with deionized water rinsing, roasting 2h at 600 DEG C, obtains the titanium dioxide film of comparative example 2.
Refer to Fig. 8, the stereoscan photograph of its titanium dioxide film provided for comparative example 2, { 001} crystal face produces and subsides TiO2 crystal, and surface areas is little, and { 001} crystal face diagonal line length is about 240nm as seen from the figure.
The form of the catalyst titanium dioxide film obtained by preparation method of the present invention in order to further description and performance, carry out graphical analysis and performance test to the main catalyst titanium dioxide film to embodiment 2 and embodiment 5 below.
First, SEM(ESEM is carried out to the catalyst titanium dioxide film of embodiment 2 and embodiment 5) graphical analysis, and then make catalyst titanium dioxide film structural feature more clear.
It is as follows that SEM observes the software that the device and analysis condition that use and graphical analysis use.
[SEM device and analysis condition]
InstructName=SU8000
SerialNumber=HI-0946-0005
DataNumber=SU8020
SignalName=LA100(U)
SEDetSetting=LA-BSE,U,Even,VSE=100
AcceleratingVoltage=3000 Volt
DecelerationVoltage=0 Volt
Magnification=50000
WorkingDistance=2600 um
LensMode=High
Condition=Vacc=3kV Mag=x50.0k WD=2.6mm
[SEM graphical analysis software]
PhotoImpact(COREL Products)
Image-Pro plus(Media Cybernetics Inc.)
The following detailed description of image analysis method: first, observed by SEM and obtain that { image of 001} crystal face, re-uses image editing software PhotoImpact, the contrast of above-mentioned image and brightness are adjusted, thus hole part is shown as black, and other parts are shown as white.Image analysis software Image-ProPlus is used to obtain image as shown in Figure 9 to the image analysis obtained like this, the SEM that wherein (a) is the catalyst titanium dioxide film described in embodiment 2 observes and obtains { the image of 001} crystal face, figure (b) adjusts contrast and brightness for scheming (a) by PhotoImpact, uses the image that image analysis software Image-ProPlus observes; The SEM that figure (c) is the catalyst titanium dioxide film described in embodiment 5 observes and obtains { the image of 001} crystal face, figure (d) adjusts contrast and brightness for scheming (c) by PhotoImpact, uses the image that image analysis software Image-ProPlus observes.Use the engineer's scale in SEM image, carry out the correction of length.Then, { 001} crystal face part uses automatic measurement function (dark part being identified as hole and the function measured) pore quantity measured wherein to measure the average diameter of hole simultaneously in shearing.The mean value obtained with and the diameter of central point is referred at 2 of periphery of 2 degree of scales measurement object of connection things in this so-called average diameter.To different 6 of the difference of embodiment 2 and embodiment 5, { 001} crystal face carries out above-mentioned image procossing, the image obtained as shown in Figure 10, wherein scheme (a1) to the different 6 { images of 001} crystal face of figure (a6) the observable difference of SEM that is the catalyst titanium dioxide film described in embodiment 2, figure (b1) to figure (b6) adjusts contrast and brightness to figure (a6) by PhotoImpact for scheming (a1), uses the image that image analysis software Image-ProPlus observes; 6 { images of 001} crystal face that the observable difference of SEM that figure (c1) is the catalyst titanium dioxide film described in embodiment 5 to figure (c6) is different, figure (d1) to figure (d6) adjusts contrast and brightness to figure (c6) by PhotoImpact for scheming (c1), uses the image that image analysis software Image-ProPlus observes.
To different 6 of the difference of embodiment 2 and embodiment 5, { the above-mentioned image analysis result that 001} crystal face carries out, in table 1, lists { size of 001} crystal face and the quantity of hole of embodiment 2 and the catalyst titanium dioxide film described in embodiment 5 in table 1.
Table 1
Embodiment 2 as shown in table 1 is learnt compared with embodiment 5, embodiment 2 { 001} crystal face is large, and each { pore quantity of 001} crystal face is also many.And each of embodiment 2 { on 001} crystal face, the quantity of described multiple hole reaches 700 ~ 1900.
In order to comparing embodiment in more detail 2 and embodiment 5 { size of 001} crystal face carries out following analysis further.First, the SEM image of 5000 times of embodiment 2 and embodiment 5 is obtained.Then, 4 different regions (Figure 11) are formed to these Image Segmentation Usings, be considered at 4 different area inner measurings that { length on a limit in the face of 001} crystal face to be so-calledly considered at this that { face of 001} crystal face refers to and can present complete rectangle and adjacent at least 2 summits can by the crystal face of clear identification.It is described that { measurement of length on a 001} crystal face limit the results are shown in Table 2.If make histogram by the value of table 2, then become as Figure 12.
Table 2
In addition, refer to Figure 13 and Figure 14,6 that the difference for embodiment 2 and embodiment 5 is different { histogram of the diameter of the hole in 001} crystal face makes according to the analysis result obtained by Image-Pro Plus.
Properties of catalyst assessment is carried out to the catalyst titanium dioxide film of embodiment 2 and embodiment 5 below.
Embodiment 2 is assessed by the following method with the properties of catalyst of the catalyst titanium dioxide film of embodiment 5.Test as shown in figure 15, center is added with ultraviolet lamp (low pressure mercury lamp: 10W, λ max=254nm, 180mm) the inwall of cylinder glass reaction vessel (200mL) be provided with the titanic oxide material (being of a size of the sheet material of 120mm × 10mm) of embodiment 2 or embodiment 5.At this, add the ethoxybenzamide aqueous solution 150mL that concentration is 5mg/L, start the importing of oxygen.Under shading, maintain this state for a moment, obtain the sorption equilibrium state of ethoxybenzamide at catalyst surface.Afterwards, light ultraviolet lamp, at each official hour every sub-sampling 4mL experimental liquid, the concentration of the ethoxybenzamide in solution is measured.The concentration of ethoxybenzamide is by HPLC(high-speed liquid chromatography analytic approach) analyze and determine.HPLC device and analysis condition as follows.
[HPLC analysis condition]
HPLC device name: ShimazuLC-10AD
UV detector:SPD-10AV (measuring wavelength: 230nm)
Cylinder: Kromasil C18 (250mm × 4.6mm)
Mobile phase: water/ethanol=2:1(volume ratio) mixed solution
Flow velocity: 1.5mL/min
The result of the properties of catalyst evaluation test of the catalyst titanium dioxide film of above-described embodiment 2 and embodiment 5 as shown in figure 16.Concentration when C is ethoxybenzamide each solution sampling in figure, C
0concentration when being ethoxybenzamide on-test, C/C
0then represent the resolution ratio of each sample of ethoxybenzamide solution.Figure 16 a is the chart drawing above-mentioned resolution ratio relative to test period.Figure 16 b is the chart of the common logarithm drawing the inverse of above-mentioned resolution ratio relative to test period.When it is straight line, mean that reaction is according to Langmuir-Hinsherwood kinetics, the slope of this straight line is larger, then can be interpreted as reaction speed faster.Learnt by Figure 16, the catalyst titanium dioxide film of embodiment 2, relative to the catalyst titanium dioxide film of embodiment 5, wants fast to the decomposition rate of ethoxybenzamide.
Properties of catalyst assessment is carried out below by the titanium dioxide film of different tests to embodiment 2 and comparative example 1.
Refer to Figure 17, for embodiment 2 prepare porous surface, the titanium dioxide film that 001} crystal face exposure is high and comparative example 1 prepare { 001} crystal face exposes the photoelectric respone comparison diagram of atresia anatase type tio2 film.As can be seen from the figure porous surface, { photo-current intensity of the titanium dioxide film that 001} crystal face exposure is high is obviously better than the titanium dioxide film of comparative example 1, show the titanium dioxide film of porous surface under 254nm ultraviolet lighting electronics and hole more easily separated, namely photocatalysis efficiency improves greatly.
Refer to Figure 18, for embodiment 2 prepare porous surface, the titanium dioxide film that 001} crystal face exposure is high and comparative example 1 prepare { 001} crystal face exposes atresia Detitanium-ore-type TiO
2film is for the Piglet s colibacillosis figure of ethoxybenzamide of degrading, and the ethoxybenzamide solution concentration adopted in this experiment is 2mg/L, and light source used is 254nm uviol lamp.Contrast known, embodiment 2 porous surface, { the high titanium dioxide film of 001} crystal face exposure is to the titanium dioxide film of the degradation efficiency of ethoxybenzamide apparently higher than comparative example 1.
Sum up above-mentioned each middle test and experimental configuration can be learnt, the catalyst titanium dioxide film of embodiment 2 is relative to the catalyst titanium dioxide film of embodiment 5, properties of catalyst is high, this due to embodiment 2 001} crystal face than embodiment 5 { 001} crystal face is comparatively large, and should { bore hole size on 001} crystal face is larger.That is, first, due to photocatalytic activity high { 001} surface areas is large, therefore, thinks and to be improved with the contact probability decomposing object.In addition, as the effect of the size of hole, think equally and improve catalyst and the contact probability decomposing object, but when hole is too small, owing to being difficult to invade in the hole of processed water.That is, in example 2, intracrystalline hole is larger than embodiment 5, and processed water is easy to invade crystals, and catalyst improves with the contact probability decomposing object, thinks and can obtain higher properties of catalyst.In addition, embodiment 5 relative to embodiment 2 { 001} surface areas is little, and hole is little.This be due to the Hydrothermal Synthesis of embodiment 5 after cleaning method be use the more too drastic cleaning method such as ultrasonic wave to cause.That is, owing to suppressing the disengaging of the isopropyl alcohol be taken into as crystal structure, impurity concentration reduces, and therefore, the crystallization speed of titanium dioxide improves, and becomes more small crystal.In addition, hole is departed from by the isopropyl alcohol when roasting and generates, but by Ultrasonic Cleaning, the amount of this isopropyl alcohol reduces, and therefore, thinks that the size of obtained hole also diminishes.
In addition, those skilled in the art also can do other change in spirit of the present invention, and these changes done according to the present invention's spirit, all should be included in the present invention's scope required for protection certainly.
Based on above explanation, knownly at least disclose following technical scheme: remarks 1. 1 kinds of photochemical catalyst titanium dioxide films, it is characterized in that, described photochemical catalyst titanium dioxide film has the crystal face of rectangle, and the crystal face of described rectangle has multiple hole.
The photochemical catalyst titanium dioxide film of remarks 2. according to remarks 1, is characterized in that, the crystal face of the rectangle of described photochemical catalyst titanium dioxide film is { 001} crystal face.
The photochemical catalyst titanium dioxide film of remarks 3. according to remarks 1 or 2, is characterized in that, in described multiple hole, the diameter in cavity of more than 50% is within the scope of 20nm ~ 80nm.
The photochemical catalyst titanium dioxide film of remarks 4. according to remarks 1 to 3 any one, is characterized in that, described rectangle crystal face length be 1.05 μm ~ 1.75 μm.
The photochemical catalyst titanium dioxide film of remarks 5. according to remarks 1 to 4 any one, is characterized in that, described rectangle crystal face the mode value of length be 1.35 μm ~ 1.70 μm.
The photochemical catalyst titanium dioxide film of remarks 6. according to remarks 1 to 5 any one, is characterized in that, on the crystal face of each rectangle, the quantity of described multiple hole is 700 ~ 1900.
The photochemical catalyst titanium dioxide film of remarks 7. according to remarks 1 to 6 any one, is characterized in that, described photochemical catalyst titanium dioxide film is formed in the titanium metal substrates that main component is titanium.
The preparation method of remarks 8. 1 kinds of photochemical catalyst titanium dioxide films, comprises the following steps:
A. provide titanium metal substrates, and the dirt being attached to titanium metal substrates surface is removed in cleaning;
B. the titanium metal substrates after cleaning is put into the oxalic acid aqueous solution etching processing of boiling by the suitably alligatoring of its surface;
C. the titanium metal substrates of etching processing is put into the hydro-thermal tank that water, isopropyl alcohol and hydrofluoric acid mixed solution are housed, after sealing at 170 DEG C ~ 190 DEG C hydro-thermal reaction 2h ~ 4h;
D. the titanium metal substrates will obtained through hydro-thermal reaction by step c, after water cleaning, roasting 1h ~ 5h at 300 DEG C ~ 900 DEG C, obtains photochemical catalyst titanium dioxide film.
The preparation method of the photochemical catalyst titanium dioxide film of remarks 9. according to remarks 8, is characterized in that, is 0.5h ~ 3h with the oxalic acid aqueous solution of boiling to the time of titanium metal substrates etching processing in described step b.
The preparation method of the photochemical catalyst titanium dioxide film of remarks 10. according to remarks 8 or 9, is characterized in that, in the described mixed solution of described step c, the concentration of hydrofluoric acid is 0.01mol/L ~ 0.05mol/L.
The preparation method of the photochemical catalyst titanium dioxide film of remarks 11. according to remarks 8 to 10 any one, is characterized in that, in the described mixed solution of described step c, the volume ratio of water and isopropyl alcohol is 1:1 ~ 1:4.
The preparation method of the photochemical catalyst titanium dioxide film of remarks 12. according to remarks 8 to 11 any one, is characterized in that, in described steps d, sintering temperature is 300 DEG C ~ 700 DEG C.
The preparation method of the photochemical catalyst titanium dioxide film of remarks 13. according to remarks 8 to 12 any one, it is characterized in that, when cleaning the dirt on titanium metal substrates surface in described step a, ultrasonic cleaning removes oil and other organic compound of titanium metal substrates adsorption in ethanol.
Claims (13)
1. a photochemical catalyst titanium dioxide film, is characterized in that, described photochemical catalyst titanium dioxide film has the crystal face of rectangle, and the crystal face of described rectangle has multiple hole.
2. photochemical catalyst titanium dioxide film as claimed in claim 1, it is characterized in that, the crystal face of the rectangle of described photochemical catalyst titanium dioxide film is { 001} crystal face.
3. photochemical catalyst titanium dioxide film as claimed in claim 1, is characterized in that, in described multiple hole, the diameter of hole of more than 50% is within the scope of 20nm ~ 80nm.
4. the photochemical catalyst titanium dioxide film as described in claims 1 to 3 item any one, is characterized in that, described rectangle crystal face length be 1.05 μm ~ 1.75 μm.
5. the photochemical catalyst titanium dioxide film as described in claims 1 to 3 item any one, is characterized in that, described rectangle crystal face the mode value of length be 1.35 μm ~ 1.70 μm.
6. the photochemical catalyst titanium dioxide film as described in claims 1 to 3 item any one, is characterized in that, on the crystal face of each rectangle, the quantity of described multiple hole is 700 ~ 1900.
7. the photochemical catalyst titanium dioxide film as described in claims 1 to 3 item any one, is characterized in that, described photochemical catalyst titanium dioxide film is formed in the titanium metal substrates that main component is titanium.
8. a preparation method for photochemical catalyst titanium dioxide film, comprises the following steps:
A. provide titanium metal substrates, and the dirt being attached to titanium metal substrates surface is removed in cleaning;
B. the titanium metal substrates after cleaning is put into the oxalic acid aqueous solution etching processing of boiling by its surface coarsening;
C. the titanium metal substrates of etching processing is put into the hydro-thermal tank that water, isopropyl alcohol and hydrofluoric acid mixed solution are housed, after sealing at 170 DEG C ~ 190 DEG C hydro-thermal reaction 2h ~ 4h;
D. the titanium metal substrates will obtained through hydro-thermal reaction by step c, after rinsing with water, roasting 1h ~ 5h at 300 DEG C ~ 900 DEG C, obtains photochemical catalyst titanium dioxide film.
9. the preparation method of photochemical catalyst titanium dioxide film as claimed in claim 8, is characterized in that, is 0.5h ~ 3h with the oxalic acid aqueous solution seethed with excitement to the time of titanium metal substrates etching processing in described step b.
10. the preparation method of photochemical catalyst titanium dioxide film as claimed in claim 8 or 9, it is characterized in that, in the described mixed solution of described step c, the concentration of hydrofluoric acid is 0.01mol/L ~ 0.05mol/L.
The preparation method of 11. photochemical catalyst titanium dioxide films as claimed in claim 8 or 9, it is characterized in that, in the described mixed solution of described step c, the volume ratio of water and isopropyl alcohol is 1:1 ~ 1:4.
The preparation method of 12. photochemical catalyst titanium dioxide films as claimed in claim 8 or 9, is characterized in that, in described steps d, sintering temperature is 300 DEG C ~ 700 DEG C.
The preparation method of 13. photochemical catalyst titanium dioxide films as claimed in claim 8 or 9, is characterized in that, when cleaning the dirt on titanium metal substrates surface in described step a, ultrasonic cleaning removes oil and the organic compound of titanium metal substrates adsorption in ethanol.
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| CN108155266A (en) * | 2017-12-14 | 2018-06-12 | 浙江大学 | Ultraviolet light detector and method using the anatase type titanium dioxide nano tube array of exposure { 001 } crystal face as substrate |
| CN109046302A (en) * | 2018-08-27 | 2018-12-21 | 合肥工业大学 | A kind of porous petal-like anatase TiO2Nano-crystal film and preparation method thereof |
| CN110655106A (en) * | 2019-10-08 | 2020-01-07 | 浙江工业大学 | Method for in-situ preparation of high-energy crystal face exposed titanium dioxide film |
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| CN113398910A (en) * | 2021-05-21 | 2021-09-17 | 魏富春 | Antibacterial wastewater treatment agent and preparation method thereof |
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