CN105727918A - Method for preparing highly-porous titanium dioxide film photocatalyst - Google Patents
Method for preparing highly-porous titanium dioxide film photocatalyst Download PDFInfo
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- CN105727918A CN105727918A CN201610069356.XA CN201610069356A CN105727918A CN 105727918 A CN105727918 A CN 105727918A CN 201610069356 A CN201610069356 A CN 201610069356A CN 105727918 A CN105727918 A CN 105727918A
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- titanium dioxide
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 55
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 27
- 150000004676 glycans Chemical class 0.000 claims abstract description 23
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 21
- 239000005017 polysaccharide Substances 0.000 claims abstract description 21
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 6
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 4
- 239000000499 gel Substances 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000001913 cellulose Substances 0.000 claims description 10
- 229920002678 cellulose Polymers 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 235000010755 mineral Nutrition 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 229920001817 Agar Polymers 0.000 claims description 2
- 229920001503 Glucan Polymers 0.000 claims description 2
- 239000008272 agar Substances 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 28
- 239000011148 porous material Substances 0.000 abstract description 12
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 abstract description 4
- 235000010980 cellulose Nutrition 0.000 description 9
- 102000004169 proteins and genes Human genes 0.000 description 9
- 108090000623 proteins and genes Proteins 0.000 description 9
- 239000012528 membrane Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002902 bimodal effect Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000004804 polysaccharides Polymers 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/69—Pore distribution bimodal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention relates to a method for preparing a highly-porous titanium dioxide film photocatalyst, and belongs to the technical field of materials.The preparing method includes the steps that balance gel, a BSA solution and an inorganic salt solution are mixed to obtain BSA embedded cellulose gel; then the gel is soaked into a tetraisopropyl titanate alcoholic solution overnight, and tetraisopropyl titanate saturated polysaccharide gel is obtained, rinsed and dried to obtain a porous titanium dioxide film.The titanium dioxide material obtained with the method is of the good double-peak pore structure, and has the high mechanical strength.
Description
Technical field
The invention belongs to field of material technology, in particular to the preparation method of a kind of highly porous titanium dioxide film photocatalyst.It is related specifically to a kind of method utilizing template embedding protein act to prepare titanium dioxide membrane material.
Background technology
Highly porous titanic oxide material has been widely used in various science and industrial circle, e.g., catalyst, sensor, electrode and for the material that separates.At present, the performance of titanic oxide material and its pore structure have very big dependency, and these pore structures include macroscopic pores size, porosity and specific surface area.But, the above-mentioned performance controlling titanium dioxide membrane material is still had any problem, particularly in macropore formation.Titanium dioxide precursor fast sol gel reaction obstacle makes material be difficult to possess desired pore structure.In order to overcome this problem, producing, highly porous titanium dioxide membrane material carries out a lot of trial.
Traditional method obtains bimodal porous titanium dioxide material all in one piece by using a kind of sol-gel technique separating phase.But, owing to there is the mutual relation of a kind of complexity between porosity and the state of sol-gel, the slight change of sol-gel system can frequently result in the change that material hole structure is violent.Seek optimum experimental condition and need the plenty of time, and effect is bad.Therefore, explore another kind of method to be used for preparing expectation hole titanic oxide material and be necessary.
Mould plate technique method can synthesize the titanium dioxide film of required form and micro structure, and the method can meet material demand structurally.In template auxiliary manufacture process, using the mould of required form as template, the form of mould is reversed in the form being transferred to final material.This template contacts with inorganic precursor materials, then material is filled into template.When inorganic precursor materials is filled up completely with, the graded porous structure that template removes generation is similar to primary template.The marked feature of this technology is in that, sol-gel system is less on the impact of loose structure, and formwork structure then determines the loose structure of final material.Therefore, this research focus on select suitable template.Although the method is more complicated in the fabrication process, mould plate technique still relatively traditional material manufacture method have superiority.
In stencil-chosen, the template of polysaccharide structures is widely used on the various inorganic porous materials of production.Polysaccharide structures template universal has benefited from its being widely present under field conditions (factors), it is easy to obtains, has abundant loose structure, and be easily handled.Up to the present, multiple porous silica titanium film has been synthesized using polysaccharide as template.But, there is certain defect in this titanium dioxide film.Such as, sol-gel coating method the porous silica titanium film obtained is prone to be broken into fragment.This is because the framework of template is coated with thin titanium dioxide film, this causes that framework is prone to break.But, the titanic oxide material formed with sol-gel casting method has a mechanical strength of excellence, but its macroporosity of heights impair, because titanium dioxide precursor is filled with the gap of template, and it is condensed into the titanic oxide material of high compaction further.All of shortcoming can be made up of the fiber that thin solid content is relatively low owing to this polysaccharide, and this causes that sol-gel process is not suitable for forming highly porous titanic oxide material.If using the method being formed hole by template, the template using the fibrous structure of the high solids content widened is a kind of effective method overcoming this obstacle.
Being inspired by this, we are at cellulose fiber surface adsorbed proteins, it is thus achieved that a kind of hard template.Owing to obtained template has the fibrous layer that width is big, solid content is high, the template of this novelty is used to be had good structure of double peak holes and high mechanical strength by the titanic oxide material that sol-gel technology manufactures.Porous silica titanium film can as the catalyst of methylene blue.It is known that the titanic oxide material that this is reported first porous is applied in this field, this work will assist in other synthesis with highly porous inorganic material.
Summary of the invention
Present invention aims to the defects such as the titanium dioxide membrane pore structure that the titanium dioxide film that existing sol-gel coating method obtains is easily broken, sol-gel casting method is formed is readily broken, it is provided that a kind of new titanium dioxide porous membrane material synthesis method.Method of the present invention is at the attached protein of cellulose surface, it is thus achieved that a kind of hard template.Owing to obtained template has the fibrous layer that width is big, solid content is high, the titanium dioxide membrane material manufactured by sol-gel technology has good structure of double peak holes and higher mechanical strength.
It is an object of the invention to be achieved through the following technical solutions.
The preparation method of a kind of highly porous titanium dioxide film photocatalyst, it is characterised in that comprise the steps:
(1) crystallite polysaccharide is swollen in distilled water, add the stirring of aqueous slkali low temperature；After dissolving completes, polysaccharide solution is poured in mould and under 10 degrees Celsius, generated gel by mineral acid；Gel mixes with DEAE-hydrochloric acid solution, and is subsequently transferred in aqueous slkali；After 2 hours, rinse with ionizing water, finally with Tris-HCl buffer reequilibrate.
(2) being mixed in flask by balanced gel with BSA solution and inorganic salt solution, sealed by flask, in couveuse, gentle agitation is to adsorption equilibrium, obtains BSA and embeds polysaccharide gel.
(3) BSA is embedded polysaccharide gel dice shape, carries out lyophilization and dry；Cryodesiccated polysaccharide gel is immersed in tetraisopropyl titanate alcoholic solution overnight；By dewatered ethanol, the saturated polysaccharide gel of tetraisopropyl titanate is rinsed, then dry in atmosphere；Finally, by muffler pipe roaster, template titanium dioxide mixing tab is calcined with temperature flowing air, obtain poriferous titanium dioxide net.
In technique scheme, the preparation method of highly porous titanium dioxide film photocatalyst, it is characterised in that described polysaccharide is the one in cellulose, glucosan, agar.
In technique scheme, the preparation method of highly porous titanium dioxide film photocatalyst, it is characterised in that in step (1), aqueous slkali is weight percentage the sodium hydroxide solution of 10%, stirs 6-10 hour under subzero 4 to 10 degrees celsius.
In technique scheme, the preparation method of highly porous titanium dioxide film photocatalyst, it is characterised in that the polysaccharide solution mass percent described in step (1) is 4%-10%, mineral acid is mass concentration is the sulphuric acid of 2%.
In technique scheme, the preparation method of highly porous titanium dioxide film photocatalyst, it is characterised in that gel described in step (1) and DEAE-hydrochloric acid solution mixing condition are 40-80 degree Celsius, and incorporation time is 0-40 minute.
In technique scheme, the preparation method of highly porous titanium dioxide film photocatalyst, it is characterized in that inorganic salt solution described in step (2) can adopt the strong electrolytic solution such as sodium chloride, potassium chloride, the adsorbance of BSA controls by changing the concentration of inorganic salt solution.
In technique scheme, the preparation method of highly porous titanium dioxide film photocatalyst, it is characterised in that in couveuse described in step (2), the temperature of shake is 10-40 degree Celsius, and the time is 8-16 hour.
In technique scheme, the preparation method of highly porous titanium dioxide film photocatalyst, it is characterised in that BSA described in step (3) embeds polysaccharide gel square and is sized to square or the cuboid of 0-4 cubic centimetre；
In technique scheme, the preparation method of highly porous titanium dioxide film photocatalyst, it is characterised in that described in step (3), tetraisopropyl titanate alcoholic solution mass concentration is 10%-40%, and temperature is 10-40 degree Celsius.
In technique scheme, the preparation method of highly porous titanium dioxide film photocatalyst, it is characterised in that described in step (3), the temperature of temperature flowing air is 300-600 degree Celsius, flow is 20-80ml/min.
The present invention compared with prior art, has the advantage that
(1) the present invention adopts protein to be loaded into gel to make final titanium dioxide film be provided simultaneously with the characteristic of macropore and high surface area.
(2) product titanium dioxide film of the present invention has possessed dual pore system, and this makes it can bear the high compaction pressure more than 19 MPas.
(3) the product titanium dioxide film of present invention synthesis possesses desired pore structure, overcomes the problem that conventional method is difficult to obtain expectation pore structure.
(4) the titanium dioxide film of present invention synthesis as the catalyst of methylene blue, can be greatly expanded the application of this material.
Accompanying drawing explanation
Fig. 1 is flow process 1 schematic diagram of the manufacturing process of the invention process example 1 product
Fig. 2 is the scanning electron microscope image of cellulose in the invention process example 1/titanium dioxide hybrid films (A), micropore titanium film (B), cellulose/protein/titanium dioxide hybrid network (C), bimodal porous titanium dioxide film (D)
Fig. 3 is cellulose gel embedding protein (a), titanium dioxide/cellulose hybrid films (b), titanium dioxide/albumen/cellulose hybrid films thermogravimetric analysis under air ambient in the invention process example 1
Fig. 4 be the porous silica titanium film of protein carrying capacity respectively 0 mg/ml, 83 mg/ml, 197 mg/ml in the invention process example 1 X ray diffracting spectrum (all of sample all at 470 DEG C calcine 3 hours, the vertical line of figure bottom is anatase sample, as reference).
Fig. 5 is protein carrying capacity respectively 0 mg/ml (empty circles) of template in the invention process example 1,83 mg/ml (open triangles), 197 mg/ml (open squares), the big pore size distribution differential volume of the hydrargyrum invading each fine pore (vertical axis represent) of porous silica titanium film.
Fig. 6 is the N2 adsorption-desorption isotherm of the porous silica titanium film of template protein load respectively 0 mg/ml (empty circles), 83 mg/ml (open triangles), 197 mg/ml (open squares) in the invention process example 1.Corresponding pore-size distribution Barrett-Joy receives-Halenda(BJH) the isothermal desorption branch of method obtains (P0=101325 handkerchief;DS represents the specific region differentiated by BJH method).
Fig. 7 is that the invention process example 1 Methylene Blue is by CPTN-II photocatalytic degradation of continuous ultraviolet-visible spectrum under irradiation under ultraviolet ray.From top to bottom respectively 0,60,135 and 195 minutes UV-vis spectral illumination time.
Fig. 8 is the concentration change of the invention process example 1 Methylene Blue and different catalyst system irradiation times: do not have titanium dioxide sample (hollow square), micropore titanium film (open circles), porous silica titanium film (open delta) and commercial P25(+).
Fig. 9 is the invention process example 1 Methylene Blue Photodegradation Dynamic at different catalyst system and catalyzings, without titanium dioxide sample (hollow square), micropore titanium film (open circles), porous silica titanium film (open delta) and commercial P25(+).
Detailed description of the invention
Embodiment 1
The microcrystalline Cellulose taking 20g swells in distilled water, is dissolved in the NaOH solution that mass fraction is 10%, gentle agitation 8 hours at-6 DEG C.After dissolving completes, be that 6% cellulose solution pours in mould by mass fraction by mass fraction it is that 2% sulphuric acid regenerates at 10 DEG C.After washing with ion, take 10 grams of cellulose gels and 20 milliliters of 2mol/LDEAE-hydrochloric acid solutions mix 20 minutes at 60 DEG C.And be subsequently transferred in 20mL3.5mol/L sodium hydroxide solution.After 2 hours, DEAE-modified cellulose adsorbent ionizing water is rinsed, with Tris-HCl buffer (20mmol/L, pH are 7.6) reequilibrate, with BSA absorption later.5 grams of equilibrium adsorption agent being transferred to respectively in two 500mL flasks, a flask 1mg/mLBSA solution, another uses the sodium chloride solution of 1mg/mLBSA solution and 60mmol/mL.Flask is sealed, gentle agitation 12 hours in the couveuse of 20 degrees Celsius.When, after adsorption equilibrium, the cellulose gel of embedding BSA is collected as stay in place form.BSA is embedded cellulose gel and is sliced into 0.5X1X1 cubic centimetre size, and dried by lyophilization.Take 2 grams of cryodesiccated templates and be soaked in the TTIP alcoholic solution that 20 DEG C of 100mL mass percentage concentration are 20% overnight.By dewatered ethanol, the saturated template of TTIP is rinsed, to remove the titanium dioxide precursor of residual, then dry in atmosphere.In dry run, moisture a small amount of in air can cause the bunching reaction of titanium dioxide precursor in hydrolysis and template.Finally, by muffler pipe roaster, template titanium dioxide mixing tab is calcined with the moving air of 470 degrees Celsius of 50ml/min, obtain porous silica titanium film.
Claims (9)
1. the preparation method of a highly porous titanium dioxide film photocatalyst, it is characterised in that comprise the steps:
(1) crystallite polysaccharide is swollen in distilled water, add the stirring of aqueous slkali low temperature；After dissolving completes, polysaccharide solution is poured in mould and under 10 degrees Celsius, generated gel by mineral acid；Gel mixes with DEAE-hydrochloric acid solution, and is subsequently transferred in aqueous slkali；
After 2 hours, rinse with ionizing water, finally with Tris-HCl buffer reequilibrate；
(2) being mixed in flask by balanced gel with BSA solution and inorganic salt solution, sealed by flask, in couveuse, gentle agitation is to adsorption equilibrium, obtains the polysaccharide gel of BSA embedding；
(3) BSA is embedded polysaccharide gel dice shape, carries out lyophilization and dry；Cryodesiccated polysaccharide gel is immersed in tetraisopropyl titanate alcoholic solution overnight；With dehydrated alcohol, the saturated polysaccharide gel of tetraisopropyl titanate is rinsed, then dry in atmosphere；Finally, by pipe type calciner, template titanium dioxide mixing tab is calcined with temperature flowing air, obtain porous silica titanium film.
2. the preparation method of highly porous titanium dioxide film photocatalyst according to claim 1, it is characterised in that described polysaccharide is the one in cellulose, glucosan, agar.
3. the preparation method of highly porous titanium dioxide film photocatalyst according to claim 1, it is characterised in that in step (1), aqueous slkali is weight percentage the sodium hydroxide solution of 10%, stirs 6-10 hour under-4-10 degrees celsius.
4. the preparation method of highly porous titanium dioxide film photocatalyst according to claim 1, it is characterised in that the polysaccharide solution mass percent described in step (1) is 4%-10%, and mineral acid is the sulphuric acid of mass concentration 2%.
5. the preparation method of highly porous titanium dioxide film photocatalyst according to claim 1, it is characterised in that gel described in step (1) and DEAE-hydrochloric acid solution mixing temperature are 40-80 degree Celsius, and incorporation time is 10-40 minute.
6. the preparation method of highly porous titanium dioxide film photocatalyst according to claim 1, it is characterized in that inorganic salt solution described in step (2) adopts the strong electrolytic solution such as sodium chloride, potassium chloride, the adsorbance of BSA controls by changing the concentration of inorganic salt solution.
7. the preparation method of highly porous titanium dioxide film photocatalyst according to claim 1, it is characterised in that in couveuse described in step (2), the temperature of shake is 10-40 degree Celsius, and the time is 8-16 hour.
8. the preparation method of highly porous titanium dioxide film photocatalyst according to claim 1, it is characterized in that BSA described in step (3) embeds square or the cuboid that polysaccharide gel square is 0-4 cubic centimetre, tetraisopropyl titanate alcoholic solution mass fraction is 10%-40%, and temperature is 10-40 degree Celsius.
9. the preparation method of highly porous titanium dioxide film photocatalyst according to claim 1, it is characterised in that described in step (3), the temperature of temperature flowing air is 300-600 degree Celsius, and air mass flow is 20-80ml/min.
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|---|---|---|---|---|
| CN1817454A (en) * | 2006-01-18 | 2006-08-16 | 浙江大学 | Production of porous titanium dioxide thin-film |
| CN103785372A (en) * | 2012-10-31 | 2014-05-14 | 关玉芳 | Novel photocatalyst air purification liquid and preparation method thereof |
| CN104990918A (en) * | 2015-07-16 | 2015-10-21 | 重庆大学 | Test paper film based on nanogold and method for detecting lead ion by test paper film |
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|---|---|---|---|---|
| CN1817454A (en) * | 2006-01-18 | 2006-08-16 | 浙江大学 | Production of porous titanium dioxide thin-film |
| CN103785372A (en) * | 2012-10-31 | 2014-05-14 | 关玉芳 | Novel photocatalyst air purification liquid and preparation method thereof |
| CN104990918A (en) * | 2015-07-16 | 2015-10-21 | 重庆大学 | Test paper film based on nanogold and method for detecting lead ion by test paper film |
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