CN105664935A - Three dimensional ordered meso-porous Au-TiO2/IO-SiO2 film visible light photocatalyst and preparation method thereof - Google Patents
Three dimensional ordered meso-porous Au-TiO2/IO-SiO2 film visible light photocatalyst and preparation method thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 50
- 229910052681 coesite Inorganic materials 0.000 title claims abstract description 37
- 229910052906 cristobalite Inorganic materials 0.000 title claims abstract description 37
- 229910052682 stishovite Inorganic materials 0.000 title claims abstract description 37
- 229910052905 tridymite Inorganic materials 0.000 title claims abstract description 37
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000004793 Polystyrene Substances 0.000 claims abstract description 32
- 229920002223 polystyrene Polymers 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000004005 microsphere Substances 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000011022 opal Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 10
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 14
- 229960004756 ethanol Drugs 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- 229960001866 silicon dioxide Drugs 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000010276 construction Methods 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 241000252506 Characiformes Species 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 239000005357 flat glass Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 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 description 3
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- -1 stopping stirring Substances 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000004038 photonic crystal Substances 0.000 abstract description 4
- 239000010970 precious metal Substances 0.000 abstract description 4
- 238000006722 reduction reaction Methods 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract description 3
- 230000031700 light absorption Effects 0.000 abstract description 2
- 239000012279 sodium borohydride Substances 0.000 abstract description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract 2
- 238000000926 separation method Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 5
- NWXMGUDVXFXRIG-WESIUVDSSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O NWXMGUDVXFXRIG-WESIUVDSSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
-
- 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
-
- 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
- B01J37/16—Reducing
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a three dimensional ordered meso-porous Au-TiO2/IO-SiO2 film visible light photocatalyst and a preparation method thereof, and belongs to the field of titanium dioxide photocatalysis. The method comprises the following steps: preparing polystyrene microspheres with different particle sizes through a soap-free emulsion polymerization technology, and synthesizing a high quality silica inverse opal film template with different apertures through a polystyrene microsphere and silica precursor liquid co-assembling technology with the polystyrene microspheres as a template; and depositing Au nanoparticles in a titanium dioxide precursor liquid through a chemical reduction technology by using NaBH4 as a reducing agent, and injecting the Au nanoparticles to the silica inverse opal template in order to finally make a precious metal deposited three dimensional ordered meso-porous Au-TiO2/IO-SiO2 film. The special structure of photonic crystals can enhance the light absorption; and the Fermi level of deposited Au is lower than that of titanium dioxide, so electron-cavity separation is facilitated, thereby increase of the photocatalysis efficiency is facilitated.
Description
Technical field
The present invention relates to three-dimensional ordered mesoporous Au-TiO2/IO-SiO2Visible-light photocatalyst preparation and Application Areas thereof. The method is prepared the catalyzer and is specially adapted under radiation of visible light degradating organic dye (as: tetracycline hydrochloride), and catalytic degradation effect is good.
Background technology
Along with the development of global economy and the process speed of industrialization are accelerated, the demand of the energy of the mankind also rolls up. Although achieving a lot of achievement in development, but the excessive exploitation of the energy being utilized the balance having destroyed the Nature, causing energy dilemma. And on the other hand, the waste water and gas that industrialization brings pollutes and allows the earth can't bear the heavy load, environmental problem has become Earthian should be concerned about the first order issue being also badly in need of most solving. So, as a main approach of protection and harnessing environment, searching is cleaned, renewable, and the environment amenable energy becomes a current the most important research topic. 1972, Fujishima and Honda found under the irradiation of light, and titanium dioxide can make water decomposition produce hydrogen. From then on, titanium dioxide and photochemical catalysis enter everybody visual field. Compared to other semiconductor material such as WO3, ZnS, CdS etc., TiO2Due to inexpensive nontoxic, stable chemical performance, corrosion-resistant and there is very high activity. In a word, in the research of photocatalytic semiconductor material, TiO2It it is a kind of catalytic material having application prospect most. Moreover, outside photocatalysis field, the effect of TiO2 also has a lot, as solar cell, preparation air-sensitive or moisture sensor, the antifouling self-cleaning material of preparation, for biological composite coating etc.
Although TiO2There is plurality of advantages, but TiO2Also there is the limitation of himself. The TiO of widespread use2For anatase octahedrite, its energy gap is 3.2ev, can only utilize the UV-light less than 5% in sunlight, and this makes TiO2 that the utilising efficiency of sun power is very low. Therefore, how to make TiO2Sun power can be fully effectively utilized to become the research focus of photocatalysis field.
In the method that current document is reported, first can utilize physical method, titanium dioxide is made the structure of photonic crystal, also be exactly the opal structural of micro-sphere array.There is due to photonic crystal multiple scattering effect and slow photon effect, can effectively strengthen scattering of light, increase light path, it is to increase titanic oxide material is to the specific absorption of light. In addition, it is also possible to make chemically titanic oxide material to be carried out modification, such as doping that is nonmetal or transition metal ion, the deposition of precious metal, with compound of other semiconductor material etc. These methods can reduce the energy gap of titanium dioxide well, reduces the recombination rate in titanic oxide material internal electron and hole so that it is also can be excited under visible light and have photocatalysis performance. At present in the research of noble metal loading, the maximum precious metal used is platinum, and gold and silver are also widely used certainly. Rupa utilizes sol-gel method synthesis of titanium dioxide, and utilize Photodeposition to depositing noble metal on titanium dioxide surface, carry out after deposited gold and silver and platinum respectively after photocatalysis performance is tested, finding that the titanic oxide material that the titanium dioxide that deposited three kinds of precious metals is all pure to be got well, and to optically catalytic TiO 2 performance boost maximum be gold, next is silver, is finally platinum.
Three-dimensional order photonic crystal is introduced in mesoporous material by the present invention, with SiO2Counter opal and tensio-active agent P123 are template, utilize sol-gel and chemical reduction method to combine, prepare three-dimensional order Au-TiO2/IO-SiO2Film visible-light photocatalyst.
Summary of the invention
It is an object of the invention to provide a kind of order mesoporous Au-TiO of high performance three-dimensional2/IO-SiO2Film photocatalyst and preparation method.
High-performance Au-TiO of the present invention2/IO-SiO2Film visible-light photocatalyst, it is characterised in that, described high-performance Au-TiO2/IO-SiO2Film visible-light photocatalyst is at IO-SiO2On the borehole structure of circular hole reticulated film, load has Au-TiO2Particle, Au-TiO2Particle refers at TiO2Particle surface load has Au, simultaneously IO-SiO2Circular hole reticulated film is laminate structure.
Described circular hole is Jie hole.
High-performance Au-TiO2/IO-SiO2The preparation method of film visible-light photocatalyst, it is characterised in that, comprise the following steps:
(1) surfactant-free emulsion polymerization synthesis monodisperse polystyrene microsphere (PS) is utilized: add deionized water and ethanol in the reactor; and lead to and protect gas into inertia; stir, then heat, after temperature is elevated to 65 DEG C～80 DEG C and is stable; add the vinylbenzene distilled; add persulfate aqueous solution after half an hour, stop heating after stirring 24h, be cooled to after room temperature until emulsion; stopping stirring, glass fibre is filtered to remove large granular impurity. Utilize ethanol and deionized water repeatedly eccentric cleaning subsequently, obtain the monodisperse polystyrene microsphere of 180nm～500nm;
0.18g～0.5g Potassium Persulphate of the corresponding 137ml ethanol of above-mentioned preferably every 53ml deionized water, 7ml～10ml vinylbenzene, 10ml water dissolution;
(2) construction from part prepares silicon-dioxide counter opal (IO-SiO altogether2): first prepare silicon-dioxide precursor liquid, tetraethoxy, 0.1M hydrochloric acid, dehydrated alcohol are mixed and obtain tetraethoxy precursor liquid; Then the polystyrene microsphere solution that step (1) obtains is mixed with the polystyrene aqueous solution, ultrasonic disperse; To add tetraethoxy precursor liquid in polystyrene solution, mixing is ultrasonic disperse also, is contained in sample bottle by gained mixed solution, and the sheet glass cleaned with piranha solution vertically inserts in sample bottle, grows 2～3 days in the thermostat container of 55 DEG C; Finally the composite film material obtained is calcined in retort furnace, remove polystyrene microsphere template, silicon-dioxide counter opal and IO-SiO can be obtained2Template;
Wherein the mass ratio of tetraethoxy, 0.1M hydrochloric acid, dehydrated alcohol is 1:1:(1～3), it is preferable that 1:1:1.5; The percent by volume of the polystyrene aqueous solution is 0.125%～0.3%, it is preferable that 0.125%; In the polystyrene microsphere aqueous solution: the volume ratio of tetraethoxy precursor liquid is 20:(0.15～0.3) ratio mixing also ultrasonic disperse, it is preferable to the ratio mixing also ultrasonic disperse of 20:0.15.
(3) sol-gel method prepares Au-TiO2Precursor liquid: dropwise joined in concentrated hydrochloric acid by isopropyl titanate, evenly stirs for some time (such as 1h), obtains solution A; A certain amount of P123 is joined in ethanol solution, then adds a certain proportion of HAuCl4·4H2O and appropriate PVP is as protective material, and then adds the NaBH of excessive Fresh4Solution reduction hydrochloro-auric acid, obtains solution B; At least 1h is evenly stirred after solution A and solution B being mixed;
(4) by obtained Au-TiO2Forerunner's drop is added in IO-SiO2Ageing 1～2 day in template; After ageing completes, film is put into retort furnace and calcines organics removal, temperature rise rate 1 DEG C/min; The three-dimensional ordered mesoporous Au-TiO of anatase octahedrite can be obtained after having calcined2/IO-SiO2Film photocatalyst. Above-mentioned calcining is 400 DEG C of calcining 4h preferably.
Preparation SiO in step (2)2Counter opal selects the construction from part preparation altogether of polystyrene microsphere and silicon-dioxide precursor liquid.
According to the method for claim 1, it is characterised in that, preparation SiO in step (2)2The growth temperature that counter opal is selected is 55 DEG C～65 DEG C.
In step (3), NaBH4For reductive agent and PVP are protective material. Au and TiO2Mass ratio be (0.2wt%～1wt%), it is preferable to 0.6wt%. The mol ratio of Au and PVP consumption is about 1:(1～1.5), it is preferable to 1:1.
Three-dimensional ordered mesoporous Au-TiO prepared by the present invention2/IO-SiO2Film photocatalyst is applied to photocatalytic degradation experiment, is light source with visible ray, and tetracycline hydrochloride carries out photocatalytic degradation process as target degradation product, and research shows, this catalyzer shows as relatively catalytic activity and satisfactory stability.
The present invention is adopted to prepare the three-dimensional ordered mesoporous Au-TiO2/IO-SiO2Film photocatalyst, utilizes the polystyrene microsphere of appropriate particle size size for template, the catalyzer prepared. On the one hand, due to the impact of photon effect slow in photon crystal structure, the specific absorption to light can be strengthened. On the other hand, when Au load is at TiO2Time upper, be conducive to reducing the recombination rate in electronics and hole, thus increase substantially the photocatalysis performance of titanium dioxide.
Accompanying drawing explanation
Fig. 1 is silicon-dioxide counter opal (IO-SiO prepared by embodiment 12) scanning electron microscope (SEM) photograph;
Fig. 2 is Au-TiO prepared by embodiment 22/IO-SiO2Scanning electron microscope (SEM) photograph;
Fig. 3 is Au-TiO prepared by embodiment 32The transmission electron microscope picture of microballoon;
Fig. 4 is three-dimensional ordered mesoporous Au-TiO prepared by embodiment 32/IO-SiO2Film light catalyzed degradation curve.
Embodiment
Below in conjunction with example, the method for the present invention is further described. These examples have further described and demonstrated the embodiment in the scope of the invention. The present invention only for illustrative purposes, is not formed any restriction by the example provided, and it can be carried out various change when not deviating from spirit and scope of the invention.
Embodiment 1
Three-dimensional ordered mesoporous Au-TiO2/IO-SiO2The preparation method of catalyzer, step is as follows:
(1) surfactant-free emulsion polymerization synthesis monodisperse polystyrene microsphere (PS) is adopted: 137ml dehydrated alcohol and 53ml deionized water join in four mouthfuls of flasks; lead in device into argon gas as protection gas; stir speed (S.S.) is 300rmp/min, and oil bath slowly heats up.Until temperature-stable is when 71 DEG C in device, add the 10ml vinylbenzene after underpressure distillation, then add Potassium Persulphate that 0.18g is dissolved in 10ml deionized water as initiator. Reacting and stop heating after 24 hours, cooling is rear and carries out taking out the elimination removal of impurity and macrobead with glass fibre membrane, can obtain the polystyrene suspension liquid of uniform particle diameter, and particle diameter is about 370nm.
(2) construction from part prepares SiO altogether2Counter opal (IO-SiO2): by polystyrene microsphere turbid liquid, first clean three times respectively with ethanol and deionized water, then it is mixed with the polystyrene microsphere aqueous solution that volume fraction is 0.125%. Tetraethoxy is pressed in the preparation of silicon-dioxide precursor liquid: 0.1MHCl: the quality of dehydrated alcohol=1:1:1.5 is than mix and blend 1h. Then according to after the 100ml polystyrene microsphere aqueous solution adds the ratio ultrasonic disperse of 1.5ml silicon-dioxide precursor liquid, load in sample bottle, the sheet glass cleaned with piranha solution is vertically inserted in bottle, be placed in the thermostat container of friction 55 DEG C growth 2～3 days. The laminated film obtained be placed in retort furnace 450 DEG C calcining 5h, the IO-SiO of large area, non-gap can be obtained2。
(3) sol-gel method prepares Au-TiO2Precursor liquid: 2.84g isopropyl titanate is dropwise joined in the concentrated hydrochloric acid of 2.4g, evenly stir 1h, obtain solution A. 1.16gP123 is joined in 4g ethanol solution, then add 0.0033gHAuCl4·4H2O and appropriate PVP is as protective material. With the NaBH of Fresh4Solution reduction. 1h is stirred after solution A and solution B being mixed.
(4) by obtained Au-TiO2Forerunner's drop is added in IO-SiO2Ageing 1～2 day in template. After ageing completes, film is put into 400 DEG C of retort furnaces and calcines 4h organics removal, temperature rise rate 1 DEG C/min. The three-dimensional ordered mesoporous Au-TiO of anatase octahedrite can be obtained after having calcined2/IO-SiO2Film photocatalyst.
(5) 300mm is got2The film catalyst of above-mentioned preparation carries out the experiment of visible light photocatalytic degradation tetracycline hydrochloride, and the concentration of tetracycline hydrochloride is 25mg L-1, it is seen that illumination penetrate 2h after tetracycline hydrochloride degradation rate be 71.5%.
Embodiment 2
Three-dimensional ordered mesoporous Au-TiO2/IO-SiO2The preparation method of catalyzer, step is with embodiment 1, and difference is: HAuCl used4·4H2The quality of O is 0.0067g, it is seen that illumination penetrate 2h after to hydrochloric acid element tsiklomitsin degradation rate reach 85.4%. 0.0134g, it is seen that illumination penetrate 2h after to hydrochloric acid element tsiklomitsin degradation rate reach 79.4%.
Embodiment 3
Three-dimensional ordered mesoporous Au-TiO2/IO-SiO2The preparation method of catalyzer, step is with embodiment 1, and difference is: HAuCl used4·4H2The quality of O is 0.01g, it is seen that illumination penetrate 2h after to hydrochloric acid element tsiklomitsin degradation rate reach 92%.
Embodiment 4
Three-dimensional ordered mesoporous Au-TiO2/IO-SiO2The preparation method of catalyzer, step is with embodiment 1, and difference is: HAuCl used4·4H2The quality of O is 0.0134g, it is seen that illumination penetrate 2h after to hydrochloric acid element tsiklomitsin degradation rate reach 79.4%.
Embodiment 5
Three-dimensional ordered mesoporous Au-TiO2/IO-SiO2The preparation method of catalyzer, step is with embodiment 1, and difference is, step 3) in ethanol content be 8g.
Embodiment 6
Three-dimensional ordered mesoporous Au-TiO2/IO-SiO2The preparation method of catalyzer, step is with embodiment 1, and difference is, step 3) in ethanol content be 12g.
Embodiment 7
Three-dimensional ordered mesoporous Au-TiO2/IO-SiO2The preparation method of catalyzer, step is with embodiment 1, and difference is, step 4) in Au-TiO2Precursor liquid is injected into IO-SiO that the PS Template preparation of 300nm obtains2In.
Embodiment 8
Three-dimensional ordered mesoporous Au-TiO2/IO-SiO2The preparation method of catalyzer, step is with embodiment 1, and difference is, step 4) in Au-TiO2Precursor liquid is injected into IO-SiO that the PS Template preparation of 450nm obtains2In.
Claims (7)
1. a high-performance Au-TiO2/IO-SiO2Film visible-light photocatalyst, it is characterised in that, described high-performance Au-TiO2/IO-SiO2Film visible-light photocatalyst is at IO-SiO2On the borehole structure of circular hole reticulated film, load has Au-TiO2Particle, Au-TiO2Particle refers at TiO2Particle surface load has Au, simultaneously IO-SiO2Circular hole reticulated film is laminate structure.
2. according to a kind of high-performance Au-TiO according to claim 12/IO-SiO2Film visible-light photocatalyst, it is characterised in that, circular hole is Jie hole.
3. prepare high-performance Au-TiO2/IO-SiO2The method of film visible-light photocatalyst, it is characterised in that, comprise the following steps:
(1) surfactant-free emulsion polymerization synthesis monodisperse polystyrene microsphere (PS) is utilized: add deionized water and ethanol in the reactor, and lead to and protect gas into inertia, stir, then heat, after temperature is elevated to 65 DEG C～80 DEG C and is stable, add the vinylbenzene distilled, add persulfate aqueous solution after half an hour, stop heating after stirring 24h, be cooled to after room temperature until emulsion, stopping stirring, glass fibre is filtered to remove large granular impurity; Utilize ethanol and deionized water repeatedly eccentric cleaning subsequently, obtain the monodisperse polystyrene microsphere of 180nm～500nm;
(2) construction from part prepares silicon-dioxide counter opal (IO-SiO altogether2): first prepare silicon-dioxide precursor liquid, tetraethoxy, 0.1M hydrochloric acid, dehydrated alcohol are mixed and obtain tetraethoxy precursor liquid; Then the polystyrene microsphere solution that step (1) obtains is mixed with the polystyrene aqueous solution, ultrasonic disperse; To add tetraethoxy precursor liquid in polystyrene solution, mixing is ultrasonic disperse also, is contained in sample bottle by gained mixed solution, and the sheet glass cleaned with piranha solution vertically inserts in sample bottle, grows 2～3 days in the thermostat container of 55 DEG C; Finally the composite film material obtained is calcined in retort furnace, remove polystyrene microsphere template, silicon-dioxide counter opal and IO-SiO can be obtained2Template;
(3) sol-gel method prepares Au-TiO2Precursor liquid: isopropyl titanate is dropwise joined in concentrated hydrochloric acid, evenly stirs for some time, obtain solution A; A certain amount of P123 is joined in ethanol solution, then adds a certain proportion of HAuCl4·4H2O and appropriate PVP is as protective material, and then adds the NaBH of excessive Fresh4Solution reduction hydrochloro-auric acid, obtains solution B; 1h is evenly stirred after solution A and solution B being mixed;
(4) by obtained Au-TiO2Forerunner's drop is added in IO-SiO2Ageing 1～2 day in template; After ageing completes, film is put into retort furnace and calcines organics removal, temperature rise rate 1 DEG C/min; The three-dimensional ordered mesoporous Au-TiO of anatase octahedrite can be obtained after having calcined2/IO-SiO2Film photocatalyst. Above-mentioned calcining is 400 DEG C of calcining 4h preferably; ;
4. according to the method for claim 3, it is characterised in that, 0.18g～0.5g Potassium Persulphate of the corresponding 137ml ethanol of every 53ml deionized water, 7ml～10ml vinylbenzene, 10ml water dissolution in step (1).
5. according to the method for claim 3, it is characterised in that, in step (2), the mass ratio of tetraethoxy, 0.1M hydrochloric acid, dehydrated alcohol is 1:1:(1～3);The percent by volume of the polystyrene aqueous solution is 0.125%～0.3%; In the polystyrene microsphere aqueous solution: the volume ratio of tetraethoxy precursor liquid is 20:(0.15～0.3) ratio mixing and ultrasonic disperse.
6. according to the method for claim 5, it is characterised in that, in step (2), the mass ratio of tetraethoxy, 0.1M hydrochloric acid, dehydrated alcohol is 1:1:1.5; The percent by volume of the polystyrene aqueous solution is 0.125%; Calcine 5 hours for 450 DEG C.
7. according to the method for claim 3, it is characterised in that, Au and TiO2Mass ratio be that the mol ratio of 0.2wt%～1wt%, Au and PVP consumption is about 1:(1～1.5).
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