CN104959133B - Photochemical catalyst titanium dioxide film and preparation method thereof - Google Patents
Photochemical catalyst titanium dioxide film and preparation method thereof Download PDFInfo
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- CN104959133B CN104959133B CN201510135953.3A CN201510135953A CN104959133B CN 104959133 B CN104959133 B CN 104959133B CN 201510135953 A CN201510135953 A CN 201510135953A CN 104959133 B CN104959133 B CN 104959133B
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Abstract
The present invention provides a kind of preparation method of photochemical catalyst titanium dioxide film, comprises the following steps：Titanium metal substrates are provided, and clean the dirt that removal is attached to titanium metal substrates surface；Suitably be roughened on its surface by etching processing during titanium metal substrates after cleaning are put into the oxalic acid aqueous solution of boiling；The titanium metal substrates of etching processing are put into the hydro-thermal tank equipped with water, isopropanol and hydrofluoric acid mixed solution, after sealing at 170 DEG C ~ 190 DEG C hydro-thermal reaction；The titanium metal substrates that will be obtained by hydro-thermal reaction, after being cleaned with water, are calcined at 300 DEG C~900 DEG C, obtain photochemical catalyst titanium dioxide film.The present invention also provides photochemical catalyst titanium dioxide film, and its crystal face with the crystal face of rectangle, the rectangle has multiple holes.Catalyst of the present invention titanium dioxide film long service life, with { 001 } crystal face exposure higher and with hole, its preparation method is simple, 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 light and has urged
The fields such as change, photovoltaic cell, sensor.In past 20 years, sol-gal process, hydro-thermal method, solvent-thermal method, chemical vapor deposition
Product, anodizing are applied to the TiO for attempting preparing different nanostructureds2Material, research prepares highlight catalytic active
Titanium dioxide is focus in recent decades.
Research shows Detitanium-ore-type TiO2{ 001 }, { 100 }, { 101 } surface can respectively be 0.90J/m2、0.53J/
m2、0.44J/m2, { 001 } crystal face that surface can be higher is with photocatalytic activity higher.However, but the usual anatase for preparing
Type TiO2Material mainly shows { 101 } face.2008, there is researcher to synthesize the TiO that { 001 } crystal face exposure is 47%2Receive
Meter Dan Jing (Nature, 2008,453:638-641).Hereafter, the report about { 001 } crystal face exposure high increases sharply, for example
Prepared with the exposed TiO of { 001 } crystal face higher as titanium source using titanium tetrachloride2Nano crystal (Journal of the
American Chemical Society, 2009,131,3152), but because titanium tetrachloride has higher water-disintegrable, and system
The product for obtaining is susceptible to reunite, and the method is difficult a large amount of productions.
There is titanium sheet at present for base material, the TiO in exposure { 001 } face is synthesized on its surface by hydro-thermal reaction2Nanometer film
(Journal of Materials Chemistry,2011,21(3):869-873), separated and recovered after solving water process
TiO2The problem of catalyst, but TiO2Nanometer film combined with titanium sheet and it is insecure easily come off, and { 001 } crystal face exposure is relatively low.
2014, there is researcher using isopropanol as pattern controlling agent, with titanium sheet as base material, synthesize what is be firmly combined with titanium plate surface
TiO2Nanometer film (International Journal ofPhotoenergy, 2014,2014).Also for example in Japan Patent Shen
Please following technology is disclosed in (Unexamined Patent 11-197516 publications), i.e. anode is carried out by the surface to the base material containing titanium
Oxidation processes simultaneously make surface form amorphous titanium dioxide, then, while assigning temperature ladder in the thickness of slab direction of base material to surface
Degree one side crystallization treatment, so that, obtain being considered as { 001 } face and the surface in alignment in the active crystal face of titanium dioxide and revealing
The construction for going out.But, thus can't realize practical, still there is room for improvement.Then, have been reported that and inhaled with low temperature electrostatic
Precious metals pd is loaded to TiO by attached mode2In nanometer film (Chemical Engineering Journal, 2014,252,
337-345), it is improved its catalytic performance, but the preparation technology is complex.
The content of the invention
In sum, it is necessary to which a kind of long service life is provided, there is nano-pore structure on crystal face and with higher
{ 001 } the photochemical catalyst titanium dioxide film of crystal face exposure, and preparation method thereof, the preparation method is simple.
A kind of photochemical catalyst titanium dioxide film, the crystal face with rectangle, the crystal face of the rectangle has multiple holes.
A kind of preparation method of photochemical catalyst titanium dioxide film, comprises the following steps：Titanium metal substrates are provided, and are cleaned
Removal is attached to the dirt on titanium metal substrates surface；Titanium metal substrates after cleaning are put into the oxalic acid aqueous solution of boiling and are etched
Suitably be roughened on its surface by treatment；The titanium metal substrates of etching processing are immediately placed in and are mixed equipped with water, isopropanol and hydrofluoric acid
Close solution hydro-thermal tank in, after sealing at 170 DEG C~190 DEG C hydro-thermal reaction 2h~4h；The titanium that will be obtained by hydro-thermal reaction
Metal base, after simply being rinsed with water, is calcined 1h~5h at 300 DEG C~900 DEG C, obtains photochemical catalyst titanium dioxide film.
Catalyst titanium dioxide film that the present invention is provided and preparation method thereof has the advantages that.Firstth, it is catalyzed
The preparation method of agent titanium dioxide film uses hydro-thermal method one-step synthesis, and preparation process is simple, cost are relatively low, it is easy to actual to answer
With.Secondth, being pre-processed by oxalic acid makes the titanium dioxide film of generation and titanium metal substrates strong bonded, long service life.3rd,
By adjusting hydrothermal temperature, hydro-thermal time etc., the bore hole size of crystal face is can control.4th, porous surface, { 001 } crystal face it is sudden and violent
The titanium dioxide film organic pollution capable of being fast degraded of dew rate (more than 60% can be reached) high.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of the photochemical catalyst titanium dioxide film that the embodiment of the present invention 1 is provided, wherein (a) is
Low power stereoscan photograph, (b) is high power stereoscan photograph.
Fig. 2 is the stereoscan photograph of the photochemical catalyst titanium dioxide film that the embodiment of the present invention 2 is provided, wherein (a) is
Low power stereoscan photograph, (b) is high power stereoscan photograph.
Fig. 3 is transmission electron microscope (TEM) photo for the photochemical catalyst titanium dioxide film that the embodiment of the present invention 2 is provided.
Fig. 4 is X-ray diffraction (XRD) figure for the photochemical catalyst titanium dioxide film that the embodiment of the present invention 2 is provided.
Fig. 5 is the stereoscan photograph of the photochemical catalyst titanium dioxide film that the embodiment of the present invention 3 is provided, wherein (a) is
Low power stereoscan photograph, (b) is high power stereoscan photograph.
Fig. 6 is the stereoscan photograph of the photochemical catalyst titanium dioxide film that the embodiment of the present invention 4 is provided, wherein (a) is
Low power stereoscan photograph, (b) is high power stereoscan photograph.
Fig. 7 is the stereoscan photograph of the titanium dioxide film that comparative example 1 is provided, wherein (a) is low power stereoscan photograph,
B () is high power stereoscan photograph.
Fig. 8 is the stereoscan photograph of the titanium dioxide film that comparative example 2 is provided, wherein (a) is low power stereoscan photograph,
B () is high power stereoscan photograph.
Fig. 9 is sweeping for { 001 } crystal face of the photochemical catalyst titanium dioxide film that the embodiment of the present invention 2 and embodiment 5 are provided
Electromicroscopic photograph is retouched, wherein the stereoscan photograph of (a) for { 001 } crystal face of the photochemical catalyst titanium dioxide film of embodiment 2,
B () is that (a) adjusts contrast and brightness by PhotoImpact, observed using image analysis software Image-ProPlus
Image, (c) is the stereoscan photograph of { 001 } crystal face of the photochemical catalyst titanium dioxide film of embodiment 5, and (d) passes through for (c)
PhotoImpact adjusts contrast and brightness, the image observed using image analysis software Image-ProPlus.
Figure 10 is the stereoscan photograph of respectively different 6 { 001 } crystal face of embodiment 2 and embodiment 5 and passes through
PhotoImpact adjustment contrast and brightness, the image observed using image analysis software Image-ProPlus, wherein
(a1) to (a6) is 6 respectively different stereoscan photographs of { 001 } crystal face of embodiment 2；(b1) to (b6) is 2 points of embodiment
6 not different stereoscan photographs of { 001 } crystal face adjust contrast and brightness by PhotoImpact, use image point
The image that analysis software I mage-ProPlus is observed；(c1) to (c6) is sweeping for 6 respectively different { 001 } crystal faces of embodiment 5
Retouch electromicroscopic photograph；(d1) to (d6) is that the stereoscan photograph of 6 respectively different { 001 } crystal faces of embodiment 5 passes through
PhotoImpact adjusts contrast and brightness, the image observed using image analysis software Image-ProPlus.
Figure 11 is the segmentation block diagram of the stereoscan photograph of 5000 times of embodiment 2 and embodiment 5.
Figure 12 is a histogram for the length on side of all { 001 } crystal faces in the stereoscan photograph of Figure 11.
Different 6 on (a1) of Figure 13 to the stereoscan photograph that (a6) is the titanium dioxide film that embodiment 2 is provided
{ 001 } histogram of the diameter of the hole in crystal face.
Different 6 on (c1) of Figure 14 to the stereoscan photograph that (c6) is the titanium dioxide film that embodiment 5 is provided
{ 001 } histogram of the diameter of the hole in crystal face.
The properties of catalyst detection device of the catalyst titanium dioxide film that Figure 15 is provided for the present invention.
Figure 16 is the catalyst titanium dioxide film that the embodiment of the present invention 2 and embodiment 5 are provided for ethoxybenzamide of degrading
Design sketch, wherein (a) is the chart that above-mentioned resolution ratio is drawn relative to test period；B () is drawn relative to test period
The chart of the common logarithm reciprocal of above-mentioned resolution ratio.
Figure 17 is porous surface, the titanium dioxide film and comparative example 1 that { 001 } crystal face exposure is high prepared by embodiment 2
{ 001 } crystal face for preparing exposes non-porous Detitanium-ore-type TiO2The photoelectric respone comparison diagram of film.
Figure 18 is porous surface, the titanium dioxide film and comparative example 1 that { 001 } crystal face exposure is high prepared by embodiment 2
{ 001 } crystal face for preparing exposes non-porous Detitanium-ore-type TiO2Effect contrast figure of the film for ethoxybenzamide of degrading.
Specific embodiment
Technical scheme is further stated in detail with reference to specific embodiment.For the ease of understanding this hair
Bright technical scheme, the present invention introduces the preparation method of photochemical catalyst titanium dioxide film first.
Photochemical catalyst of the invention is that the surface of titanium metal substrates is modified by hydrothermal synthesis method with titanium dioxide film,
Then it is calcined under oxygen atmosphere and is obtained.Comprise the following steps that:
Step S1, by main component for being put into ethanol containing titanium metal substrates for titanium carries out ultrasonic wave cleaning, so as to remove
It is attached to the dirt on titanium metal substrates surface；
Step S2, with the oxalic acid aqueous solution of boiling to titanium metal substrates etching processing；
Step S3, the titanium metal substrates of etching processing are immediately placed in equipped with water, isopropanol and hydrofluoric acid mixed solution
Titanium metal substrates surface is modified by hydrothermal synthesis method in hydro-thermal tank, its reaction equation such as formula 1；
Ti+6HF→H2TiF6+2H2↑
H2TiF6+4H2O→Ti(OH)4+ 6HF (formula 1)
Step S4, is calcined the titanium metal substrates of modification in oxygen atmosphere, is titanium dioxide by titanium metal substrates surface conversion
Titanium, its reaction equation such as formula 2.
Ti(OH)4→TiO2+2H2O (formula 2)
In the step S2, by titanium metal substrates etching processing, its surface being suitably roughened, so as to after
When during Hydrothermal Synthesiss or being further calcined, promote the precipitation or growth of titanium dioxide crystal.With boiling in the step
Oxalic acid aqueous solution be 0.5h-3h to time of titanium metal substrates etching processing.Here the titanium sheet after etching processing is rinsed with water.
In the step S3, it is emphasized that the titanium metal substrates of etching processing are immediately placed in equipped with water, isopropanol
In the hydro-thermal tank of hydrofluoric acid mixed solution.The concentration of hydrofluoric acid is 0.01mol/L~0.05mol/L in the mixed solution,
The consumption of hydrofluoric acid depends on the area of the titanium metal substrates, preferably 1.6 × 10 in the mixed solution-5mol/cm2
To 8.5 × 10-5mol/cm2.The mixed solution reclaimed water is 1 with the volume ratio of isopropanol:1~1:4.In this step will etching
The titanium metal substrates for the treatment of are put into after the hydro-thermal tank interior sealing equipped with water, isopropanol and hydrofluoric acid mixed solution 170 DEG C~190
Hydro-thermal reaction 2h~4h at DEG C.
Need exist for it is emphasised that step S2 and step S3 some while carrying out, specific step S2 mesoxalic acids
The formation mixed solution stage of step S3 is carried out while the aqueous solution is to titanium metal substrates etching processing, when in step S2 to titanium
Category base material etching processing is completed and is immediately placed in the mixed solution for being prepared by step S3 after being cleaned with water, is then entered
Water-filling thermal response.Wherein, emphasized refer to immediately be exactly as far as possible by the titanium metal substrates of etching processing in several minutes extremely
Is put into the mixed solution that S3 is prepared in dozens of minutes, rather than the titanium metal substrates after etching processing place tens of hours it
Just it is put into afterwards in the mixed solution that S3 is prepared.
In the step S4, sintering temperature is 300 DEG C~900 DEG C, and preferably 300 DEG C~700 DEG C, roasting time is 1h
~5h.If sintering temperature is below 300 DEG C, it is difficult to remove isopropanol, on the other hand, if sintering temperature is more than 900 DEG C,
Anatase titanium dioxide is mutually changed into rutile-type, causes properties of catalyst to reduce.In addition, the hydrogen fluoride that Hydrothermal Synthesiss are used
Corrosivity is high, therefore, the titanium metal substrates that Hydrothermal Synthesiss are treated were needed simply to be rinsed with water before calcining process, but
This does not use the too drastic condition such as ultrasonic wave as far as possible.
The photochemical catalyst titanium dioxide film of present invention offer is provided.Photochemical catalyst titanium dioxide film
{ 001 } crystal face has multiple holes.Wherein, { 001 } crystal face of the photochemical catalyst titanium dioxide film is rectangular.The rectangle
{ 001 } length on one side of crystal face is 1.05 μm~1.75 μm, further, the length on one side of rectangle { 001 } crystal face
Mode value be 1.35 μm~1.70 μm.The diameter of described hole on { 001 } crystal face of the photochemical catalyst titanium dioxide film
It is 10nm~80nm.Photochemical catalyst titanium dioxide film degradable organic pollutant or capable of purifying air under ultraviolet lighting.
{ 001 } crystal face of photochemical catalyst titanium dioxide film has multiple holes, and specific surface area when accordingly acting as photochemical catalyst is obtained
Improve.In addition, on { 001 } crystal face multiple holes presence, it is suppressed that the photocatalysis further in conjunction with caused by electronics and hole
The inactivation of agent activity.If to photochemical catalyst titanium dioxide film irradiating ultraviolet light, exciting the electronics of valency electricity band, move to and lead
Electric band, thus, in valency electricity band generation hole, generates electronics, respectively in the molecule or the material of contact of adsorption in conductive strips
With electronics, and hole exchange, i.e. occur reduction reaction and oxidation reaction.If electronics and hole further in conjunction with,
Above-mentioned reaction will not occur, i.e. lose catalytic effect.But, because { 001 } crystal face of photochemical catalyst titanium dioxide film has
Having multiple holes can hinder the electronics with hole further in conjunction with specifically, electronics moves to Metal Substrate by above-mentioned multiple holes
Material, so hinder electronics and hole further in conjunction with so that suppress the inactivation of catalyst activity, catalyst performance is improved.
Embodiment 1
By titanium sheet (Baoji Shengrong Titanium Corporation systems, purity 99.5%, 240mm × 100mm
× 0.15mm) ultrasonic wave cleaning is carried out in ethanol, remove the organic matter on surface.Titanium sheet after cleaning is put into the grass of boiling again
In aqueous acid pre-process 0.5h perform etching, after cleaned and dried with deionized water.Afterwards, there is provided 200mL pure water and 200mL
The mixed solution of isopropanol, aqueous hydrogen fluoride solution is added thereto to again, be made 0.02mol/L hydrogen fluoride mixed solutions, the mixing
The cumulative volume of solution is 400ml, and it is anti-that titanium sheet and hydrogen fluoride mixed solution then are put into the polytetrafluoroethylene (PTFE) that volume is 500ml
Answer in kettle, the titanium sheet is fully immersed in hydrogen fluoride mixed solution, the hydro-thermal reaction 2h at 170 DEG C, when the temperature in reactor
Degree is returned to after room temperature, takes out titanium sheet, with deionized water rinsing, is then placed in Muffle furnace and is calcined 2h at 600 DEG C, is obtained
{ 001 } crystal face exposure is high, porous, photochemical catalyst titanium dioxide film.
Fig. 1 is referred to, it is the stereoscan photograph of the photochemical catalyst titanium dioxide film that embodiment 1 is provided, wherein (a)
It is low power stereoscan photograph, (b) is high power stereoscan photograph, it may be clearly seen that { 001 } surface areas are larger and deposit
In multiple holes, { 001 } crystal face diagonal line length is about 1300nm.
Embodiment 2
By titanium sheet (Baoji Shengrong Titanium Corporation systems, purity 99.5%, 240mm × 100mm
× 0.15mm) ultrasonic wave cleaning is carried out in ethanol, remove the organic matter on surface.Titanium sheet after cleaning is put into the grass of boiling again
In aqueous acid pre-process 1.5h perform etching, after cleaned and dried with deionized water.Afterwards, there is provided 125mL pure water and 275mL
The mixed solution of isopropanol, aqueous hydrogen fluoride solution is added thereto to again, be made 0.03mol/L hydrogen fluoride mixed solutions, the mixing
The cumulative volume of solution is 400ml, and it is anti-that titanium sheet and hydrogen fluoride mixed solution then are put into the polytetrafluoroethylene (PTFE) that volume is 500ml
Answer in kettle, the titanium sheet is fully immersed in hydrogen fluoride mixed solution, the hydro-thermal reaction 3h at 180 DEG C, when the temperature in reactor
Degree is returned to after room temperature, takes out titanium sheet, is simply rinsed with deionized water, and 2h is calcined at 600 DEG C, obtains { 001 } crystal face sudden and violent
Dew rate porous, photochemical catalyst titanium dioxide film high.
Fig. 2 is referred to, it is the stereoscan photograph of the photochemical catalyst titanium dioxide film that embodiment 2 is provided, wherein (a)
It is low power stereoscan photograph, (b) is high power stereoscan photograph.{ 001 } surface areas are larger and surface is present as seen from the figure
Multiple holes, { 001 } crystal face diagonal line length is about 1350nm.
Fig. 3 is the transmission electron microscope photo of the photochemical catalyst titanium dioxide film that embodiment 2 is provided, it can be observed that crystal table
All there is the opening of round rectangle in face and inside, all there is spacing for 0.192nm in its plane of crystal and opening and be mutually perpendicular to
Lattice fringe, respectively correspond to { 200 } and { 020 } crystal face, it was demonstrated that it was observed that plane of crystal and opening in crystal face be
TiO2{ 001 } crystal face, opening is about 2nm~25nm, about 2nm~15nm wide.
Fig. 4 is X-ray diffraction (XRD) figure for the photochemical catalyst titanium dioxide film that embodiment 2 is provided, and contrasts JCPDS21-
1272 understand Detitanium-ore-type TiO2It is principal crystalline phase, while in the presence of a small amount of Rutile Type.
Embodiment 3
By titanium sheet (Baoji Shengrong Titanium Corporation systems, purity 99.5%, 240mm × 100mm
× 0.15mm) ultrasonic wave cleaning is carried out in ethanol, remove the organic matter on surface.Titanium sheet after cleaning is put into the grass of boiling again
In aqueous acid pre-process 1.5h perform etching, after cleaned and dried with deionized water.Afterwards, there is provided 125mL pure water and 275mL
The mixed solution of isopropanol, aqueous hydrogen fluoride solution is added thereto to again, be made 0.05mol/L hydrogen fluoride mixed solutions, the mixing
The cumulative volume of solution is 400ml, and it is anti-that titanium sheet and hydrogen fluoride mixed solution then are put into the polytetrafluoroethylene (PTFE) that volume is 500ml
Answer in kettle, the titanium sheet is fully immersed in hydrogen fluoride mixed solution, the hydro-thermal reaction 3h at 180 DEG C, when the temperature in reactor
Degree is returned to after room temperature, takes out titanium sheet, is simply rinsed with deionized water, and 1h is calcined at 700 DEG C, obtains { 001 } crystal face sudden and violent
Dew rate (hole is more) high, porous, photochemical catalyst titanium dioxide film.
Fig. 5 is referred to, it is the stereoscan photograph of the photochemical catalyst titanium dioxide film that embodiment 3 is provided, wherein (a)
It is low power stereoscan photograph, (b) is high power stereoscan photograph, as seen from the figure { 001 } of photochemical catalyst titanium dioxide film
There are multiple holes in crystal face, bore hole size is larger, distribution is more uniform, and { 001 } crystal face diagonal line length is about 1000nm.
Embodiment 4
By titanium sheet (Baoji Shengrong Titanium Corporation systems, purity 99.5%, 240mm × 100mm
× 0.15mm) ultrasonic wave cleaning is carried out in ethanol, remove the organic matter on surface.Titanium sheet after cleaning is put into the grass of boiling again
In aqueous acid pre-process 3h perform etching, after cleaned and dried with deionized water.Afterwards, there is provided 80mL pure water is different with 320mL
The mixed solution of propyl alcohol, aqueous hydrogen fluoride solution being added thereto to again, being made 0.10mol/L hydrogen fluoride mixed solutions, the mixing is molten
The cumulative volume of liquid is 400ml, and titanium sheet and hydrogen fluoride mixed solution then are put into the polytetrafluoroethyl-ne alkene reaction that volume is 500ml
In kettle, the titanium sheet is fully immersed in hydrogen fluoride mixed solution, the hydro-thermal reaction 4h at 190 DEG C, when the temperature in reactor
Return to after room temperature, take out titanium sheet, simply rinsed with deionized water, 5h is calcined at 300 DEG C, obtain the exposure of { 001 } crystal face
Rate porous, photochemical catalyst titanium dioxide film high.
Fig. 6 is referred to, it is the stereoscan photograph of the photochemical catalyst titanium dioxide film that embodiment 4 is provided, wherein (a)
It is low power stereoscan photograph, (b) is high power stereoscan photograph, as seen from the figure { 001 } of photochemical catalyst titanium dioxide film
Surface areas are larger and there is tiny hole, and { 001 } crystal face diagonal line length is about 1550nm.
Embodiment 5
By titanium sheet (Baoji Shengrong Titanium Corporation systems, purity 99.5%, 240mm × 100mm
× 0.15mm) ultrasonic wave cleaning is carried out in ethanol, remove the organic matter on surface.Titanium sheet after cleaning is put into the grass of boiling again
In aqueous acid pre-process 1.5h perform etching, after cleaned and dried with deionized water.Afterwards, there is provided 125mL pure water and 275mL
The mixed solution of isopropanol, aqueous hydrogen fluoride solution is added thereto to again, be made 0.03mol/L hydrogen fluoride mixed solutions, the mixing
The cumulative volume of solution is 400ml, and it is anti-that titanium sheet and hydrogen fluoride mixed solution then are put into the polytetrafluoroethylene (PTFE) that volume is 500ml
Answer in kettle, the titanium sheet is fully immersed in hydrogen fluoride mixed solution, the hydro-thermal reaction 3h at 180 DEG C, when the temperature in reactor
Degree is returned to after room temperature, takes out titanium sheet, is simply rinsed with deionized water, and 2h is calcined at 600 DEG C, obtains { 001 } crystal face sudden and violent
Dew rate porous, photochemical catalyst titanium dioxide film high.
Comparative example 1
By titanium sheet (Baoji Shengrong Titanium Corporation systems, purity 99.5%, 240mm × 100mm
× 0.15mm) ultrasonic wave cleaning is carried out in ethanol, remove the organic matter on surface.Afterwards, there is provided 125mL pure water is different with 275mL
The mixed solution of propyl alcohol, aqueous hydrogen fluoride solution being added thereto to again, being made 0.025mol/L hydrogen fluoride mixed solutions, the mixing is molten
The cumulative volume of liquid is 400ml, and titanium sheet and hydrogen fluoride mixed solution then are put into the polytetrafluoroethyl-ne alkene reaction that volume is 500ml
In kettle, the titanium sheet is fully immersed in hydrogen fluoride mixed solution, the hydro-thermal reaction 3h at 180 DEG C, when the temperature in reactor
Return to after room temperature, take out titanium sheet, with deionized water rinsing, 5h is calcined at 500 DEG C, obtain the titanium dioxide of comparative example 1
Film.
Fig. 7 is referred to, it is the TiO obtained by the preparation method of comparative example 12The stereoscan photograph of film, wherein (a)
It is low power stereoscan photograph, (b) is high power stereoscan photograph, it can be observed that TiO2Plane of crystal there's almost no hole
Hole.
Comparative example 2
By titanium sheet (Baoji Shengrong Titanium Corporation systems, purity 99.5%, 240mm × 100mm
× 0.15mm) ultrasonic wave cleaning is carried out in ethanol, remove the organic matter on surface.Afterwards, there is provided 125mL pure water is different with 275mL
The mixed solution of propyl alcohol, aqueous hydrogen fluoride solution being added thereto to again, being made 0.03mol/L hydrogen fluoride mixed solutions, the mixing is molten
The cumulative volume of liquid is 400ml, and titanium sheet and hydrogen fluoride mixed solution then are put into the polytetrafluoroethyl-ne alkene reaction that volume is 500ml
In kettle, the titanium sheet is fully immersed in hydrogen fluoride mixed solution, the hydro-thermal reaction 3h at 180 DEG C, when the temperature in reactor
Return to after room temperature, take out titanium sheet, with deionized water rinsing, 2h is calcined at 600 DEG C, obtain the titanium dioxide of comparative example 2
Film.
Fig. 8 is referred to, it is the stereoscan photograph of the titanium dioxide film that comparative example 2 is provided, wherein (a) is scanned for low power
Electromicroscopic photograph, (b) is high power stereoscan photograph, and TiO2 crystal { 001 } crystal face is produced and collapsed as seen from the figure, and surface areas
Small, { 001 } crystal face diagonal line length is about 240nm.
The form of the catalyst titanium dioxide film obtained by preparation method of the present invention for further description and
Performance, carries out graphical analysis and performance test to the catalyst mainly to embodiment 2 and embodiment 5 with titanium dioxide film below.
First, the catalyst to embodiment 2 and embodiment 5 carries out SEM (ESEM) graphical analysis with titanium dioxide film,
And then become apparent from catalyst titanium dioxide film structural feature.
The software that the used device of SEM observations and analysis condition and graphical analysis are used is as follows.
[SEM devices and analysis condition]
InstructName=SU8000
SerialNumber=HI-0946-0005
DataNumber=SU8020
SignalName=LA100 (U)
SEDetSetting=LA-BSE, U, Even, VSE=100
AcceleratingVoltage=3000Volt
DecelerationVoltage=0Volt
Magnification=50000
WorkingDistance=2600um
LensMode=High
Condition=Vacc=3kV Mag=x50.0k WD=2.6mm
[SEM image analysis software]
PhotoImpact (COREL Products)
Image-Pro plus (Media Cybernetics company systems)
The following detailed description of image analysis method:First, the image for obtaining { 001 } crystal face is observed by SEM, reuses figure
As software for editing PhotoImpact, the contrast of above-mentioned image and brightness are adjusted, so that, hole part is shown as black
Color, other parts are shown as white.The image for so obtaining is analyzed using image analysis software Image-ProPlus
To image as shown in Figure 9, wherein the SEM observations that (a) is the catalyst titanium dioxide film described in embodiment 2 are obtained { 001 }
The image of crystal face, (b) is that (a) is adjusted into contrast and brightness by PhotoImpact, uses image analysis software Image-
The image that ProPlus is observed；C () is that the SEM observations of the catalyst titanium dioxide film described in embodiment 5 obtain { 001 } crystalline substance
The image in face, (d) is that (c) is adjusted into contrast and brightness by PhotoImpact, uses image analysis software Image-
The image that ProPlus is observed.Using the engineer's scale in SEM image, the correction of length is carried out.Then, { 001 } crystal face portion is sheared
Point, measure pore quantity therein using automatic measurement function (dark part is identified as into hole and the function of measuring) and measure simultaneously
The average diameter of hole.Herein so-called average diameter refer to 2 degree of scales measure 2 points of periphery of object of connection thing and in
The average value that the diameter of heart point is obtained.Respectively different 6 { 001 } crystal face of embodiment 2 and embodiment 5 is carried out above-mentioned
Image procossing, the image for obtaining is as shown in Figure 10, wherein (a1) to (a6) is the catalyst titanium dioxide film described in embodiment 2
The image of respectively different 6 { 001 } crystal face that obtains of SEM observations, (b1) to (b6) is to pass through (a1) to (a6)
PhotoImpact adjusts contrast and brightness, the image observed using image analysis software Image-ProPlus；(c1) extremely
(c6) for the SEM of the catalyst titanium dioxide film described in embodiment 5 observes respectively different 6 { 001 } crystal face for obtaining
Image, (d1) to (d6) is that (c1) to (c6) is adjusted into contrast and brightness by PhotoImpact, uses image analysis software
The image that Image-ProPlus is observed.
The above-mentioned image analysis result that respectively different 6 { 001 } crystal face of embodiment 2 and embodiment 5 is carried out is shown in
Table 1, lists the size and hole of { 001 } crystal face of embodiment 2 and the catalyst titanium dioxide film described in embodiment 5 in table 1
The quantity in hole.
Table 1
Embodiment 2 as shown in table 1 relatively learns that { 001 } crystal face of embodiment 2 is big, and each { 001 } compared with Example 5
The pore quantity of crystal face is also more.And the quantity of the multiple hole has reached 700 on each { 001 } crystal face of embodiment 2
~1900.
For comparing embodiment 2 in more detail and the size of { 001 } crystal face of embodiment 5, analysis below is further carried out.
First, 5000 times of embodiment 2 and embodiment 5 of SEM image is obtained.Then, these images are carried out with segmentation and forms 4 not
With region (Figure 11), be considered as the length on side in the face of { 001 } crystal face in 4 different area inner measurings, herein
So-called is considered as that the face of { 001 } crystal face is to refer to that complete rectangle is presented and at least 2 adjacent summits can be clear
The crystal face of clear identification.The measurement of length on one side of { 001 } crystal face the results are shown in Table 2.If being made Nogata with the value of table 2
Figure, then into such as Figure 12.
Table 2
It is embodiment 2 and embodiment 5 in addition, referring to (a1) to (a6) of Figure 13 and (c1) of Figure 14 to (c6)
The histogram of the diameter of the hole in 6 respectively different { 001 } crystal faces, is according to the analysis obtained by Image-Pro Plus
What result was made.
The catalyst to embodiment 2 and embodiment 5 carries out properties of catalyst assessment with titanium dioxide film below.
Embodiment 2 is commented by the following method with the catalyst of embodiment 5 with the properties of catalyst of titanium dioxide film
Estimate.Test is as shown in figure 15, and center is added with ultraviolet lamp (low pressure mercury lamp：10W, λ max=254nm, 180mm) cylindrical shape
The inwall of glass system reaction vessel (200mL) is provided with the titanic oxide material of embodiment 2 or embodiment 5, and (size is 120mm
The sheet material of × 10mm).Here, it is the ethoxybenzamide aqueous solution 150mL of 5mg/L to add concentration, start the importing of oxygen.Under shading
Maintain the state for a moment, obtain sorption equilibrium state of the ethoxybenzamide in catalyst surface.Afterwards, ultraviolet lamp is lighted, at each
The time of regulation measures per sub-sampling 4mL experimental liquids, the concentration to the ethoxybenzamide in solution.The concentration of ethoxybenzamide passes through
HPLC (high-speed liquid chromatography analytic approach) analyses determine.HPLC devices and analysis condition are as follows.
[HPLC analysis conditions]
HPLC device names:ShimazuLC-10AD
UV detector:SPD-10AV (measurement 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 each solution sampling of ethoxybenzamide in figure, C0Concentration when being ethoxybenzamide on-test, C/C0Then table
Show the resolution ratio of each sample of ethoxybenzamide solution.(a) is the chart that above-mentioned resolution ratio is drawn relative to test period in Figure 16.Figure
(b) is the chart of the common logarithm reciprocal that above-mentioned resolution ratio is drawn relative to test period in 16.When it is straight line, meaning
Reaction according to Langmuir-Hinsherwood kinetics, the slope of the straight line is bigger, then can be construed to reaction speed
It is faster.Learnt by Figure 16, the catalyst titanium dioxide film of the catalyst titanium dioxide film relative to embodiment 5 of embodiment 2,
Decomposition rate to ethoxybenzamide is fast.
Properties of catalyst assessment is carried out to the titanium dioxide film of embodiment 2 and comparative example 1 below by different tests.
Refer to Figure 17, be embodiment 2 prepare titanium dioxide film porous surface, that { 001 } crystal face exposure is high with
{ 001 } crystal face prepared by comparative example 1 exposes the photoelectric respone comparison diagram of non-porous anatase type tio2 film.As can be seen from the figure table
The photo-current intensity of the titanium dioxide film that face is porous, { 001 } crystal face exposure is high is significantly stronger than the titanium dioxide of comparative example 1
Film, shows that the titanium dioxide film of the porous surface electronics under 254nm ultraviolet lightings is more easily separated with hole, i.e., photocatalysis efficiency is big
It is big to improve.
Refer to Figure 18, be embodiment 2 prepare titanium dioxide film porous surface, that { 001 } crystal face exposure is high with
{ 001 } crystal face prepared by comparative example 1 exposes non-porous Detitanium-ore-type TiO2Film, should for the Piglet s colibacillosis figure of ethoxybenzamide of degrading
Ethoxybenzamide solution concentration employed in experiment is 2mg/L, and light source used is 254nm uviol lamps.Knowable to contrast, the table of embodiment 2
The titanium dioxide film that face is porous, { 001 } crystal face exposure is high to the degradation efficiency of ethoxybenzamide apparently higher than comparative example 1 dioxy
Change titanium film.
Summarize it is above-mentioned it is each it is middle test and experimental configuration it is known that embodiment 2 catalyst titanium dioxide film relative to
The catalyst titanium dioxide film of embodiment 5, properties of catalyst is high, and this is because { 001 } crystal face of embodiment 2 compares embodiment
5 { 001 } crystal face is larger, and the bore hole size being somebody's turn to do on { 001 } crystal face is bigger.That is, firstly, since photocatalytic activity is high
{ 001 } surface areas are big, it is therefore contemplated that being improved with the contact probability for decomposing object.In addition, as the size of hole
Effect, it also hold that when raising catalyst is too small with the contact probability for decomposing object, but hole, due to being difficult to invade processed
In the hole of water.That is, in example 2, the hole in crystal is bigger than embodiment 5, processed water is easy to invade crystal
Inside, catalyst is improved with the contact probability for decomposing object, it is believed that can obtain properties of catalyst higher.In addition, real
Apply example 5 small relative to { 001 } surface areas of embodiment 2, and hole is small.This is clear after the Hydrothermal Synthesiss due to embodiment 5
Washing method is caused using the relatively more too drastic cleaning method such as ultrasonic wave.That is, due to the isopropyl for suppressing to be taken into as crystal structure
The disengaging of alcohol, impurity concentration reduction, therefore, the crystallization speed of titanium dioxide is improved, as more small crystal.In addition, hole
Hole is departed from and generated by the isopropanol in roasting, but is cleaned and the reduction of the amount of the isopropanol by ultrasonic wave, it is therefore contemplated that institute
The size of the hole for obtaining also diminishes.
In addition, those skilled in the art can also make other changes in spirit of the invention, these are according to present invention essence certainly
The change that god is made, should all be included in scope of the present invention.
Explanation based on more than, it is known that at least disclose following technical scheme：It is attached a kind of 1. photochemical catalyst titanium dioxides
Titanium film, it is characterised in that the crystal face that the photochemical catalyst titanium dioxide film has the crystal face of rectangle, the rectangle has multiple
Hole.
Photochemical catalyst titanium dioxide film of the note 2. according to note 1, it is characterised in that the photochemical catalyst uses two
The crystal face of the rectangle of oxidation titanium film is { 001 } crystal face.
Photochemical catalyst titanium dioxide film of the note 3. according to note 1 or 2, it is characterised in that the multiple hole
In more than 50% empty diameter in the range of 20nm~80nm.
Photochemical catalyst titanium dioxide film of the note 4. according to 1 to 3 any one of note, it is characterised in that institute
The length for stating one side of rectangle crystal face is 1.05 μm~1.75 μm.
Photochemical catalyst titanium dioxide film of the note 5. according to 1 to 4 any one of note, it is characterised in that institute
The mode value for stating the length on one side of rectangle crystal face is 1.35 μm~1.70 μm.
Photochemical catalyst titanium dioxide film of the note 6. according to 1 to 5 any one of note, it is characterised in that every
The quantity of the multiple hole is 700~1900 on the crystal face of one rectangle.
Photochemical catalyst titanium dioxide film of the note 7. according to 1 to 6 any one of note, it is characterised in that institute
It is in the titanium metal substrates of titanium that the photochemical catalyst titanium dioxide film stated is formed in main component.
A kind of 8. preparation methods of photochemical catalyst titanium dioxide film are attached, are comprised the following steps：
A., titanium metal substrates are provided, and clean the dirt that removal is attached to titanium metal substrates surface；
B. etching processing is suitably thick by its surface in the titanium metal substrates after cleaning being put into the oxalic acid aqueous solution of boiling
Change；
C. the titanium metal substrates of etching processing are put into the hydro-thermal tank equipped with water, isopropanol and hydrofluoric acid mixed solution,
After sealing at 170 DEG C~190 DEG C hydro-thermal reaction 2h~4h；
D. the titanium metal substrates that will be obtained by hydro-thermal reaction by step c, after being cleaned with water, at 300 DEG C~900 DEG C
Roasting 1h~5h, obtains photochemical catalyst titanium dioxide film.
The preparation method of photochemical catalyst titanium dioxide film of the note 9. according to note 8, it is characterised in that the step
With the oxalic acid aqueous solution for seething with excitement it is 0.5h~3h to the time of titanium metal substrates etching processing in rapid b.
The preparation method of photochemical catalyst titanium dioxide film of the note 10. according to note 8 or 9, it is characterised in that institute
The concentration for stating hydrofluoric acid in the mixed solution of step c is 0.01mol/L~0.05mol/L.
The preparation method of photochemical catalyst titanium dioxide film of the note 11. according to 8 to 10 any one of note, its
It is characterised by, the mixed solution reclaimed water of the step c is 1 with the volume ratio of isopropanol：1~1：4.
The preparation method of photochemical catalyst titanium dioxide film of the note 12. according to 8 to 11 any one of note, its
It is characterised by, sintering temperature is 300 DEG C~700 DEG C in the step d.
The preparation method of photochemical catalyst titanium dioxide film of the note 13. according to 8 to 12 any one of note, its
It is characterised by, when the dirt on titanium metal substrates surface is cleaned in the step a, is cleaned by ultrasonic removes titanium metal substrates in ethanol
The oil of adsorption and other organic compounds.
Claims (11)
1. a kind of photochemical catalyst titanium dioxide film, it is characterised in that the photochemical catalyst titanium dioxide film has rectangle
Crystal face, the crystal face of the rectangle has multiple holes, in the multiple hole the diameter of more than 50% hole 20nm~
In the range of 80nm.
2. photochemical catalyst titanium dioxide film as claimed in claim 1, it is characterised in that the photochemical catalyst titanium dioxide
The crystal face of the rectangle of film is { 001 } crystal face.
3. photochemical catalyst titanium dioxide film as claimed in claim 1 or 2, it is characterised in that the one of the crystal face of the rectangle
The length on side is 1.05 μm~1.75 μm.
4. photochemical catalyst titanium dioxide film as claimed in claim 1 or 2, it is characterised in that the one of the crystal face of the rectangle
The mode value of the length on side is 1.35 μm~1.70 μm.
5. photochemical catalyst titanium dioxide film as claimed in claim 1 or 2, it is characterised in that institute on the crystal face of each rectangle
The quantity for stating multiple holes is 700~1900.
6. photochemical catalyst titanium dioxide film as claimed in claim 1 or 2, it is characterised in that the photochemical catalyst dioxy
Change titanium film to be formed in the titanium metal substrates that main component is titanium.
7. a kind of photochemical catalyst titanium dioxide film, it is characterised in that the photochemical catalyst titanium dioxide film has rectangle
Crystal face, the crystal face of the rectangle has multiple holes, and the length on one side of the crystal face of the rectangle is 1.05 μm~1.75 μm.
8. photochemical catalyst titanium dioxide film as claimed in claim 7, it is characterised in that the photochemical catalyst titanium dioxide
The crystal face of the rectangle of film is { 001 } crystal face.
9. photochemical catalyst titanium dioxide film as claimed in claim 7 or 8, it is characterised in that the one of the crystal face of the rectangle
The mode value of the length on side is 1.35 μm~1.70 μm.
10. photochemical catalyst titanium dioxide film as claimed in claim 7 or 8, it is characterised in that institute on the crystal face of each rectangle
The quantity for stating multiple holes is 700~1900.
11. photochemical catalyst titanium dioxide films as claimed in claim 7 or 8, it is characterised in that the photochemical catalyst dioxy
Change titanium film to be formed in the titanium metal substrates that main component is titanium.
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