CN104689855B - Preparation method of supported visible-light response WO3/{001}TiO2 compound photocatalyst - Google Patents
Preparation method of supported visible-light response WO3/{001}TiO2 compound photocatalyst Download PDFInfo
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Abstract
The invention relates to a preparation method of a supported visible-light response WO3/{001}TiO2 compound photocatalyst, which comprises three steps of (1) pretreatment of a supporter, (2) preparation of {001} crystal face exposure anatase TiO2 single crystals, and (3) preparation of the supported compound photocatalyst, the support supported catalyst with TiO2 as a center and coated with a WO3 core-shell structure is prepared, the characteristic that the tungsten trioxide (WO3) is taken as a narrow-gap (2.8eV) n-type semiconductor, and can be excited in a visible light range is fully utilized, the energy level difference between two semiconductor materials is utilized to effectively separate charges, the separating efficiency of a photon-generated carrier and the utilization rate of visible light are improved, the photocatalytic activity is high and unlikely to be lost, the catalytic activity is preserved for a long time, furthermore, the preparation process is simple, the reaction condition is mild, the reaction speed is easy to control, the cost is low, and the method is applicable to industrial promotion and application.
Description
Technical field
The present invention relates to catalysis material studying technological domain is and in particular to a kind of visible light-responded wo of support type3/
{001}tio2The preparation method of composite photo-catalyst.
Background technology
tio2Because oxidability is strong, catalysis activity is high, physico-chemical property is stable and inexpensive, nontoxic the advantages of, be widely used in
Wastewater treatment, air cleaning and the photocatalysis field such as self-cleaning that sterilizes.But nano-catalyst particles are trickle, if straight in the reactor
Connect filling, easily taken away by current, its application in reality produces can be limited.If catalyst activity component is adopted such as gas
The modes such as phase, hydro-thermal or sol-gel process are supported on the carriers such as porous material can solve this to a certain extent
Problem.
Supported catalyst agent carrier, can be divided into mineral-type carrier and organic carrier by its chemical composition.Mineral-type includes glass
Glass class, ceramic-like, metal class and adsorbent class etc.；Organic is mainly high molecular polymer.Mineral-type carrier is in piece mostly
Shape, spherical or bar-shaped, the mostly scattered heap filling of these carriers, are technically difficult to control to.
At present, will have nanometer tio of photocatalytic activity2Research on polymer nanofiber for the particle load causes
The extensive concern of people.Polymer/the tio being obtained by the method2Nano hybridization fiber has larger specific surface area and hole
Gap rate, can guarantee that the permeability of light, is realizing tio2While photocatalyst, photocatalysis efficiency is remarkably improved.hong、
Im, wu, he, Wang Feng et al. are by the method such as electrostatic spinning technique and solution blending, collosol and gel by nanometer tio2Load to poly- third
On the nanofibers such as alkene nitrile (pan), polyvinyl acetate (pvac), Kynoar (pvdf), yong etc., liao etc., han adopt
With sedimentation by tio2It is supported on p3On ht, lynn m etc. uses magnetic sputtering method by tio2It is supported on polyester fiber, obtain receives
Rice hybridized fiber is respectively provided with higher photocatalysis efficiency.
Polymer/tio2The permeability of nano hybridization fiber optic is good, is emerging research tendency in recent years, but Static Spinning
Silk technical matters are more complicated, and magnetic sputtering method is also higher to technical requirements, Common deposition method again it cannot be guaranteed that enough adhesive force, if
Can set about from the easily operated method such as hydro-thermal, deposition, develop load effect more preferable low temperature load technology, then to not being resistant to height
The application of the polymer nanofiber carrier of temperature has great significance.
Content of the invention
It is an object of the invention to provide a kind of reaction is gentle, light penetrability is good, visible light-responded and catalysis activity is high, alive
The visible light-responded wo of the lasting support type of property3/{001}tio2The preparation method of composite photo-catalyst.
In order to realize foregoing invention purpose, the technical solution adopted in the present invention comprises the steps of:
(1) support pretreatment
Light-permeable carrier is soaked 1～3 hour with the sodium hydroxide solution of 0.5mol/l, is repeatedly cleaned with distilled water, dry
Dry standby；
The anatase tio that (2) 001 crystal faces expose2Single crystal preparation
Butyl titanate is dropped to hf and goes for a mixed liquor of 1:5～10 mixed preparing according to mol ratio with dehydrated alcohol
Ionized water is according to mol ratio in the b mixed liquor of the proportions of 1:20～25, making the butyl titanate in a mixed liquor mix with b
The mol ratio of the deionized water in liquid is 1:100～150, drips speed and controls at 2～3 per second, and mix and blend 1～2 hour obtains
tio2Colloidal sol, is aged 24～48h under room temperature；Tio by ageing2Colloidal sol centrifugal sedimentation, with distilled water, absolute ethanol washing, 80～
100 DEG C of drying, grind, you can obtain the anatase tio that 001 crystal face exposes2Powder；
(3) preparation of supported composite photocatalyst
By sodium tungstate, cetyl trimethylammonium bromide and distilled water, according to mass ratio, the ratio for 1:0.0017:10 is mixed
Close, dropwise instill the hcl that concentration is 3mol/l in gained mixed solution, be simultaneously introduced 001 crystal face exposure of step (2)
Anatase tio2Powder, makes sodium tungstate and hcl, tio2The mol ratio of powder is 1:15:1～100, to mixed liquor after stirring and evenly mixing
Light-permeable carrier after middle addition step (1) pre-treatment, stirring and evenly mixing, question response uses distilled water, ethanol cyclic washing completely afterwards,
Dry, obtain the visible light-responded wo of support type3/{001}tio2Composite photo-catalyst.
Above-mentioned light-permeable carrier can be polymer nanofiber carrier or wire mesh carrier；Polymer nanofiber carries
Body can adopt glass fibre or synthetic fibers carrier；Wherein synthetic fibers carrier specifically polyacrylonitrile or polyester or polyamide
Fiber carrier.
Above-mentioned metal gauze can adopt nickel screen or stainless steel cloth.
Above-mentioned steps (2) optimum condition is: butyl titanate and dehydrated alcohol be 1:5～10 mixed preparing according to mol ratio
A mixed liquor drop in the b mixed liquor of hf and deionized water proportions for 1:22 according to mol ratio, make in a mixed liquor
Butyl titanate and b mixed liquor in the mol ratio of deionized water be 1:100～120, drip speed and control at 2～3 per second, mixing
Stirring 1～2 hour, obtains tio2Colloidal sol, is aged 24h under room temperature；Tio by ageing2Colloidal sol centrifugal sedimentation, with distilled water, no
Water-ethanol washs, 90 DEG C of drying, grinds, you can obtain the anatase tio that 001 crystal face exposes2Powder.
The visible light-responded wo of support type provided by the present invention3/{001}tio2The preparation method of composite photo-catalyst is
Using improved sol-gel process, first prepare the anatase tio of { 001 } face exposure at room temperature2, by tio2Powder with
wo3It is deposited on light-permeable carrier, formed with tio2Centered on periphery parcel wo3Nucleocapsid structure carrier load type catalyst,
It takes full advantage of Tungstic anhydride. (wo3) as narrow band gap (2.8ev) n-type semiconductor, can be excited in visible-range
Characteristic, efficiently separates electric charge using the energy level difference between two kinds of semi-conducting materials, improve photo-generated carrier separation efficiency and can
See light utilization efficiency, photocatalytic activity is high and is difficult to lose activity, and keeps catalysis activity for a long time, and preparation process is simple,
Reaction condition is gentle, response speed is easily controllable, and cost is relatively low, is suitable to industrial application.
Brief description
Fig. 1 is with unsupported polyester fibre surface macroscopic view picture after sodium hydroxide solution immersion.
Fig. 2 is to be loaded with tio2Polyester fibre surface macroscopic view picture.
Fig. 3 is to be loaded with wo3/{001}tio2Polyester fibre surface macroscopic view picture.
Fig. 4 is the polyester fibre surface micro-structure diagram soaking without sodium hydroxide solution.
Fig. 5 is the polyester fibre surface micro-structure diagram soaking through sodium hydroxide solution.
Fig. 6 is to be loaded with wo3/{001}tio2Polyester fibre surface micro-structure diagram.
Fig. 7 is the degradation effect comparison diagram of different loaded photocatalyst PARA FORMALDEHYDE PRILLS(91,95)s.
Specific embodiment
With reference to experimental data and embodiment, technical scheme is described in detail, but the present invention not only limits
In following implementation situations.
Embodiment 1
With wo3With tio2Mol ratio be 1:10 as a example, prepare the visible light-responded wo of this support type3/{001}tio2Multiple
The method of closing light catalyst is realized by following steps:
(1) support pretreatment
The polyester fiber carrier of light-permeable is soaked 2 hours with the sodium hydroxide solution of 0.5mol/l, with distilled water repeatedly
Cleaning, dry for standby；
The anatase tio that (2) 001 crystal faces expose2Single crystal preparation
1. measure 30.4ml dehydrated alcohol to be added in 35.2ml butyl titanate, make butyl titanate and dehydrated alcohol according to rubbing
Your ratio is 1:5, mixes, that is, is configured to a mixed liquor；
2. measure 180ml deionized water, add 20.2mlhf, make hf and deionized water be 1:22 according to mol ratio, mix,
Obtain b mixed liquor；
3. a mixed liquor is dropwise dropped in b mixed liquor, drip speed and control at 2 per second, make the metatitanic acid fourth in a mixed liquor
The mol ratio of the deionized water in ester and b mixed liquor is 1:105, and mixed on low speed stirs 1 hour, obtains tio2Colloidal sol, in room temperature
Lower ageing 24 hours；
4. by the tio after ageing2Colloidal sol centrifugal sedimentation, with distilled water, ethanol cyclic washing 3 times, in 90 DEG C of forced air dryings
Dry in case, after grinding, obtain the anatase tio that 001 crystal face exposes2Powder.
(3) preparation of supported composite photocatalyst
Weigh 0.3g sodium tungstate, 0.0005g cetyl trimethylammonium bromide (ctab) is dissolved in 30ml distilled water, makes tungsten
The mass ratio of sour sodium, cetyl trimethylammonium bromide and distilled water is 1:0.0017:10, stirs, dropwise drips thereto
Enter the hcl that 5ml concentration is 3mol/l, be simultaneously introduced the anatase tio that 001 crystal face prepared by 0.8g step (1) exposes2Powder
End, makes sodium tungstate and hcl, tio2The mol ratio of powder is 1:15:10, adds according in the mixed liquor of every 80ml after stirring and evenly mixing
The amount of 1.5g polyester fiber carrier adds polyester fiber carrier, and in constant temperature oscillator, low-speed oscillation uses distillation completely afterwards to reaction
Water, ethanol cyclic washing, dry, obtain the visible light-responded wo of support type3/{001}tio2Composite photo-catalyst.
Embodiment 2
With wo3With tio2Mol ratio be 1:1 as a example, prepare the visible light-responded wo of this support type3/{001}tio2Compound
The method of photocatalyst is realized by following steps:
(1) support pretreatment
The polyester fiber carrier of light-permeable is soaked 1 hour with the sodium hydroxide solution of 0.5mol/l, with distilled water repeatedly
Cleaning, dry for standby；
The anatase tio that (2) 001 crystal faces expose2Single crystal preparation
1. measure 30.4ml dehydrated alcohol to be added in 35.2ml butyl titanate, make butyl titanate and dehydrated alcohol according to rubbing
Your ratio is 1:5, mixes, that is, is configured to a mixed liquor；
2. measure 180ml deionized water, add 20.2mlhf, make hf and deionized water be 1:22 according to mol ratio, mix,
Obtain b mixed liquor；
3. a mixed liquor is dropwise dropped in b mixed liquor, drip speed and control at 3 per second, make the metatitanic acid fourth in a mixed liquor
The mol ratio of the deionized water in ester and b mixed liquor is 1:100, and mixed on low speed stirs 2 hours, obtains tio2Colloidal sol, in room temperature
Lower ageing 48 hours；
4. by the tio after ageing2Colloidal sol centrifugal sedimentation, with distilled water, ethanol cyclic washing 3 times, does in 100 DEG C of air blast
Dry in dry case, after grinding, obtain the anatase tio that 001 crystal face exposes2Powder.
(3) preparation of supported composite photocatalyst
Weigh 3.0g sodium tungstate, 0.005g cetyl trimethylammonium bromide (ctab) is dissolved in 30ml distilled water, stirring,
Dropwise instill the hcl that 50ml concentration is 3mol/l thereto, be simultaneously introduced 001 crystal face prepared by 0.8g step (1) and expose
Anatase tio2Powder, makes sodium tungstate and hcl, tio2The mol ratio of powder is 1:15:1, according to every 80ml's after stirring and evenly mixing
The amount adding 1.5g polyester fiber carrier in mixed liquor adds polyester fiber carrier, and in constant temperature oscillator, low-speed oscillation is to reaction
Use distilled water, ethanol cyclic washing afterwards completely, dry, obtain the visible light-responded wo of support type3/{001}tio2Composite photocatalyst
Agent.
Embodiment 3
With wo3With tio2Mol ratio be 1:100 as a example, prepare the visible light-responded wo of this support type3/{001}tio2Multiple
The method of closing light catalyst is realized by following steps:
(1) support pretreatment
Light-permeable carrier is soaked 1 hour with the sodium hydroxide solution of 0.5mol/l, is repeatedly cleaned with distilled water, dry standby
With；
The anatase tio that (2) 001 crystal faces expose2Single crystal preparation
1. measure 30.4ml dehydrated alcohol to be added in 35.2ml butyl titanate, make butyl titanate and dehydrated alcohol according to rubbing
Your ratio is 1:10, mixes, that is, is configured to a mixed liquor；
2. measure 185ml deionized water, add 20.2mlhf, make hf and deionized water be 1:20 according to mol ratio, mix,
Obtain b mixed liquor；
3. a mixed liquor is dropwise dropped in b mixed liquor, drip speed and control at 2 per second, make the metatitanic acid fourth in a mixed liquor
The mol ratio of the deionized water in ester and b mixed liquor is 1:150, and mixed on low speed stirs 1 hour, obtains tio2Colloidal sol, in room temperature
Lower ageing 36 hours；
4. by the tio after ageing2Colloidal sol centrifugal sedimentation, with distilled water, ethanol cyclic washing 2 times, in 80 DEG C of forced air dryings
Dry in case, after grinding, obtain the anatase tio that 001 crystal face exposes2Powder.
(3) preparation of supported composite photocatalyst
Weigh 0.3g sodium tungstate, 0.0005g cetyl trimethylammonium bromide (ctab) is dissolved in 30ml distilled water, makes tungsten
The mass ratio of sour sodium, cetyl trimethylammonium bromide and distilled water is 1:0.0017:10, stirs, dropwise drips thereto
Enter the hcl that 5ml concentration is 3mol/l, be simultaneously introduced the anatase tio that 001 crystal face prepared by 8g step (1) exposes2Powder
End, makes sodium tungstate and hcl, tio2The mol ratio of powder is 1:15:100, adds according in the mixed liquor of every 80ml after stirring and evenly mixing
The amount entering 1.5g polyester fiber carrier adds polyester fiber carrier, and in constant temperature oscillator, low-speed oscillation is used afterwards completely to reaction and steamed
Distilled water, ethanol cyclic washing, dry, obtain the visible light-responded wo of support type3/{001}tio2Composite photo-catalyst.
Embodiment 4
With wo3With tio2Mol ratio be 1:15 as a example, prepare the visible light-responded wo of this support type3/{001}tio2Multiple
The method of closing light catalyst is realized by following steps:
(1) support pretreatment
Light-permeable carrier is soaked 3 hours with the sodium hydroxide solution of 0.5mol/l, is repeatedly cleaned with distilled water, dry standby
With；
The anatase tio that (2) 001 crystal faces expose2Single crystal preparation
1. measure 48.7ml dehydrated alcohol to be added in 35.2ml butyl titanate, make butyl titanate and dehydrated alcohol according to rubbing
Your ratio is 1:8, mixes, that is, is configured to a mixed liquor；
2. measure 185ml deionized water, add 20.2mlhf, make hf and deionized water be 1:22 according to mol ratio, mix,
Obtain b mixed liquor；
3. a mixed liquor is dropwise dropped in b mixed liquor, drip speed and control at 2 per second, make the metatitanic acid fourth in a mixed liquor
The mol ratio of the deionized water in ester and b mixed liquor is 1:120, and mixed on low speed stirs 1 hour, obtains tio2Colloidal sol, in room temperature
Lower ageing 24 hours；
4. by the tio after ageing2Colloidal sol centrifugal sedimentation, with distilled water, ethanol cyclic washing 3 times, in 90 DEG C of forced air dryings
Dry in case, after grinding, obtain the anatase tio that 001 crystal face exposes2Powder.
(3) preparation of supported composite photocatalyst
Weigh 0.3185ml sodium tungstate, 0.0005g cetyl trimethylammonium bromide (ctab) is dissolved in 30ml distilled water,
Make sodium tungstate, cetyl trimethylammonium bromide and distilled water mass ratio be 1:0.0017:10, stir, thereto by
Instill the hcl that 5ml concentration is 3mol/l, be simultaneously introduced the anatase that 001 crystal face prepared by 1.2g step (1) exposes
tio2Powder, makes sodium tungstate and hcl, tio2The mol ratio of powder is 1:15:15, according to the mixed liquor of every 80ml after stirring and evenly mixing
The amount of middle addition 1.5g polyester fiber carrier adds polyester fiber carrier, and in constant temperature oscillator, low-speed oscillation is to after react completely
With distilled water, ethanol cyclic washing, dry, obtain the visible light-responded wo of support type3/{001}tio2Composite photo-catalyst.
Embodiment 5
With wo3With tio2Mol ratio be 1:50 as a example, prepare the visible light-responded wo of this support type3/{001}tio2Multiple
The method of closing light catalyst is realized by following steps:
(1) support pretreatment
Light-permeable carrier is soaked 3 hours with the sodium hydroxide solution of 0.5mol/l, is repeatedly cleaned with distilled water, dry standby
With；
The anatase tio that (2) 001 crystal faces expose2Single crystal preparation
1. measure 36.5ml dehydrated alcohol to be added in 35.2ml butyl titanate, make butyl titanate and dehydrated alcohol according to rubbing
Your ratio is 1:6, mixes, that is, is configured to a mixed liquor；
2. measure 185ml deionized water, add 20.2mlhf, make hf and deionized water be 1:25 according to mol ratio, mix,
Obtain b mixed liquor；
3. a mixed liquor is dropwise dropped in b mixed liquor, drip speed and control at 2 per second, make the metatitanic acid fourth in a mixed liquor
The mol ratio of the deionized water in ester and b mixed liquor is 1:110, and mixed on low speed stirs 1 hour, obtains tio2Colloidal sol, in room temperature
Lower ageing 28 hours；
4. by the tio after ageing2Colloidal sol centrifugal sedimentation, with distilled water, ethanol cyclic washing 3 times, in 100 DEG C of forced air dryings
Dry in case, after grinding, obtain the anatase tio that 001 crystal face exposes2Powder.
(3) preparation of composite photo-catalyst
Weigh 0.3g sodium tungstate, 0.0005g cetyl trimethylammonium bromide (ctab) is dissolved in 30ml distilled water, makes tungsten
The mass ratio of sour sodium, cetyl trimethylammonium bromide and distilled water is 1:0.0017:10, stirs, dropwise drips thereto
Enter the hcl that 5ml concentration is 3mol/l, be simultaneously introduced the anatase tio that 001 crystal face prepared by 4g step (1) exposes2Powder
End, makes sodium tungstate and hcl, tio2The mol ratio of powder is 1:15:50, adds according in the mixed liquor of every 80ml after stirring and evenly mixing
The amount of 1.5g polyester fiber carrier adds polyester fiber carrier, and in constant temperature oscillator, low-speed oscillation uses distillation completely afterwards to reaction
Water, ethanol cyclic washing, dry, obtain the visible light-responded wo of support type3/{001}tio2Composite photo-catalyst.
Embodiment 6
In the step (3) of above-described embodiment 1～5, by the fiberglass carrier of polyester fiber carrier equivalent or polypropylene
Replacing, other steps are all identical with corresponding embodiment for nitrile or Fypro carrier, its light transmission and load effect with poly-
The effect of ester fiber carrier is close.
Embodiment 7
In the step (3) of above-described embodiment 1～5, polyester fiber carrier is replaced with the nickel screen of equivalent or stainless steel cloth
Change, other steps are all identical with corresponding embodiment, its light transmission and load effect are preferable, the effect phase with polyester fiber carrier
Closely.
In order to verify beneficial effects of the present invention, applicant, by substantial amounts of laboratory research, now passes through following experiment right
It illustrates:
1st, the macroscopic view change before and after polyester fiber load
The polyester fiber of three parts of equivalent is used respectively the sodium hydroxide solution of 0.5mol/l soak 2 hours, by a copy of it
Put into tio2The anatase tio being exposed with 001 crystal face in Detitanium-ore-type2In powder colloidal sol, obtain being loaded with tio2Polyester fine
Dimension；Another obtains being loaded with wo according to the method for embodiment 13/{001}tio2Polyester fiber；Unsupported gathering after soaking
Ester fiber (Fig. 1) as blank, respectively be loaded with tio2Polyester fiber (Fig. 2) and be loaded with wo3/{001}tio2's
Polyester fiber (Fig. 3) is contrasted, and is taken pictures with camera, observes surface color change.
By Fig. 1～3 contrast as can be seen that the polyester fiber color after load there occurs different degrees of change, illustrate poly-
A certain amount of catalyst has been loaded on ester fiber.
2nd, the micro-variations before and after polyester fiber load
It is analyzed in accelerating potential 22kv with the scanning electron microscope of model jsm-5800, observe without hydrogen-oxygen
Change being loaded with of the polyester fiber that sodium solution soaks and the polyester fiber soaking through sodium hydroxide solution and embodiment 1 gained
wo3/{001}tio2Polyester fiber surface, the micro-variations that occurred of polyester fibre surface before and after contrast different disposal, ginseng
See Fig. 4～6.
By Fig. 4～6 contrast as can be seen that the polyester fibre surface without sodium hydroxide solution immersion is smooth, it is unfavorable for light
Catalyst adheres to, and the polyester fibre surface generation through sodium hydroxide solution immersion is uneven, is conducive to photocatalyst to adhere to,
It is loaded with wo3/{001}tio2Polyester fiber substantially it can be seen that being attached with one layer of catalyst in its surface, and adhere to and urge
Integral surface opposed flattened is made after agent.
3rd, loaded catalyst photocatalytic activity test
Be passed through after certain density formaldehyde gases are mixed with dry air and humid air in photocatalytic reaction device with device
In catalyst packed layer carry out light-catalyzed reaction, using air sampler collection formaldehyde enter the forward and backward gas of reaction unit
In formaldehyde, corresponding absorbance is recorded by ultraviolet spectrophotometer, calculates content of formaldehyde, and then obtain the removal of formaldehyde
Rate.
During experimental implementation, -5 DEG C of cryogenic thermostat ethanol bath temperature；Dry air and the equal 0.5l/min of humid air flow, first
Aldehyde flow 30ml/min, total flow about 1l/min, the light source of photocatalytic reaction device adopts 500w xenon lamp to utilize jb420 cut-off filter
The visible ray that mating plate removes ultraviolet light wave band in xenon lamp and obtains, the central shaft of reaction pipeline section is apart from light source 20cm, light work(herein
Rate is up to 1800w/m2；Larger bubbles absorption tube 10ml；With 0.5l/min flow, sample air sampler 10min.
Using the polyester fiber of unsupported catalyst as blank, it is loaded with pure tio more respectively2, pure wo3And tio2/
wo3The degradation effect to indoor formaldehyde for the loaded photocatalyst, result is as shown in Figure 7:
As shown in Figure 7, three kinds of loaded catalyst PARA FORMALDEHYDE PRILLS(91,95)s all have corresponding degradation effect, under visible light, load wo3
The clearance of PARA FORMALDEHYDE PRILLS(91,95) is better than load tio2；Load tio2/wo3Photocatalyst best results, be 0.15mg/ to initial concentration
m3The clearance of formaldehyde reaches as high as 77.9%, and with pure tio2With pure wo3Compare and be less susceptible to lose activity.
In the same manner, with same method to polyacrylonitrile, polyamide, glass fibre, nickel screen and stainless steel cloth as load
The loaded catalyst of body is verified, structure is close with the effect of polyester fiber, all makes catalytic specie have preferable attachment
Property, and PARA FORMALDEHYDE PRILLS(91,95) has preferable degradation effect.
Claims (6)
1. the visible light-responded wo of a kind of support type3/{001}tio2The preparation method of composite photo-catalyst it is characterised in that by with
Lower step composition:
(1) support pretreatment
Light-permeable carrier is soaked 1～3 hour with the sodium hydroxide solution of 0.5mol/l, is repeatedly cleaned with distilled water, dry standby
With；
The anatase tio that (2) 001 crystal faces expose2Single crystal preparation
Butyl titanate and dehydrated alcohol are dropped to hf and deionization according to mol ratio for a mixed liquor of 1:5～10 mixed preparing
Water is according to mol ratio in the b mixed liquor of the proportions of 1:20～25, making in butyl titanate and the b mixed liquor in a mixed liquor
Deionized water mol ratio be 1:100～150, drip speed control at 2～3 per second, mix and blend 1～2 hour, obtain tio2
Colloidal sol, is aged 24～48h under room temperature；Tio by ageing2Colloidal sol centrifugal sedimentation, with distilled water, absolute ethanol washing, 80～100
DEG C dry, grind, you can obtain 001 crystal face expose anatase tio2Powder；
(3) preparation of supported composite photocatalyst
The ratio mixing for 1:0.0017:10 according to mass ratio by sodium tungstate, cetyl trimethylammonium bromide and distilled water, to
Dropwise instill the hcl that concentration is 3mol/l in gained mixed solution, be simultaneously introduced the sharp titanium that 001 crystal face of step (2) exposes
Ore deposit tio2Powder, makes sodium tungstate and hcl, tio2The mol ratio of powder is 1:15:1～100, adds after stirring and evenly mixing in mixed liquor
Enter the light-permeable carrier after step (1) pre-treatment, stirring and evenly mixing, question response uses distilled water, ethanol cyclic washing completely afterwards, dry
Dry, obtain the visible light-responded wo of support type3/{001}tio2Composite photo-catalyst.
2. the visible light-responded wo of support type according to claim 13/{001}tio2The preparation side of composite photo-catalyst
Method it is characterised in that: described light-permeable carrier is polymer nanofiber carrier or wire mesh carrier.
3. the visible light-responded wo of support type according to claim 23/{001}tio2The preparation side of composite photo-catalyst
Method it is characterised in that: described polymer nanofiber carrier is glass fibre or synthetic fibers carrier.
4. the visible light-responded wo of support type according to claim 33/{001}tio2The preparation side of composite photo-catalyst
Method it is characterised in that: described synthetic fibers carrier is polyacrylonitrile or polyester or Fypro carrier.
5. the visible light-responded wo of support type according to claim 23/{001}tio2The preparation side of composite photo-catalyst
Method it is characterised in that: described metal gauze is nickel screen or stainless steel cloth.
6. the visible light-responded wo of support type according to claim 13/{001}tio2The preparation side of composite photo-catalyst
Method it is characterised in that: described step (2) be by butyl titanate and dehydrated alcohol according to mol ratio for 1:5～10 mixed preparing a
Mixed liquor drops in hf and the b mixed liquor of deionized water proportions for 1:22 according to mol ratio, makes the titanium in a mixed liquor
The mol ratio of the deionized water in acid butyl ester and b mixed liquor is 1:100～120, drips speed and controls at 2～3 per second, mix and blend
1～2 hour, obtain tio2Colloidal sol, is aged 24h under room temperature；Tio by ageing2Colloidal sol centrifugal sedimentation, with distilled water, dehydrated alcohol
Washing, 90 DEG C of drying, grind, you can obtain the anatase tio that 001 crystal face exposes2Powder.
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| CN105107550B (en) * | 2015-08-28 | 2017-10-17 | 西安科技大学 | A kind of support type WO3/TiOF2The preparation method of composite visible light catalyst |
| CN105107532B (en) * | 2015-08-28 | 2017-10-10 | 西安科技大学 | A kind of WO3/TiOF2The preparation method of composite visible light catalyst |
| CN108927157B (en) * | 2018-06-27 | 2019-12-31 | 重庆市畜牧科学院 | Cu2O/{001}TiO2Preparation method of composite catalyst and application of composite catalyst to dynamic purification of ammonia gas |
| CN109225202B (en) * | 2018-09-30 | 2021-06-25 | 辽宁大学 | Fixed Z-type TiO2|Ti|WO3Photocatalytic composite membrane and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462769A (en) * | 2009-01-09 | 2009-06-24 | 厦门大学 | Titanium dioxide nanoplate and synthesizing method thereof |
| US20140083494A1 (en) * | 2012-09-21 | 2014-03-27 | Electronics And Telecommunications Research Institute | Method of forming metal oxide nanotube and dye-sensitized solar cell formed thereby |
| CN104275170A (en) * | 2014-09-12 | 2015-01-14 | 西安科技大学 | Normal-temperature preparation method of {001} surface anatase TiO2 monocrystals |
-
2015
- 2015-02-05 CN CN201510061453.XA patent/CN104689855B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462769A (en) * | 2009-01-09 | 2009-06-24 | 厦门大学 | Titanium dioxide nanoplate and synthesizing method thereof |
| US20140083494A1 (en) * | 2012-09-21 | 2014-03-27 | Electronics And Telecommunications Research Institute | Method of forming metal oxide nanotube and dye-sensitized solar cell formed thereby |
| CN104275170A (en) * | 2014-09-12 | 2015-01-14 | 西安科技大学 | Normal-temperature preparation method of {001} surface anatase TiO2 monocrystals |
Non-Patent Citations (3)
| Title |
|---|
| Ultrasound assisted synthesis of TiO2–WO3 heterostructures for the catalytic degradation of Tergitol (NP-9) in water;Sambandam Anandan, Jerry J.Wu;《Ultrasonics Sonochemistru》;20140122;第21卷(第4期);全文 * |
| 二氧化钛纳米片的合成及光催化性能;刘文军等;《广东化工》;20130815;第40卷(第15期);全文 * |
| 纳米TiO2复合材料的制备及应用研究;鞠剑峰;《中国博士学位论文全文数据库 工程科技I辑》;20070115(第1期);3.1.1实验（一）复合材料的制备 * |
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