CN105664935B - A kind of three-dimensional ordered mesoporous Au TiO2/IO‑SiO2Film visible-light photocatalyst and preparation method - Google Patents
A kind of three-dimensional ordered mesoporous Au TiO2/IO‑SiO2Film visible-light photocatalyst and preparation method Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 51
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 38
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 38
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 38
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 38
- 239000004793 Polystyrene Substances 0.000 claims abstract description 28
- 229920002223 polystyrene Polymers 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 239000004005 microsphere Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011022 opal Substances 0.000 claims abstract description 11
- 238000010276 construction Methods 0.000 claims abstract description 4
- 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 42
- 239000000243 solution Substances 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 235000019441 ethanol Nutrition 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 239000010931 gold Substances 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000003223 protective agent Substances 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
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000005357 flat glass Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical class [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
- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 0.000 claims description 3
- 239000003643 water by type Substances 0.000 claims description 3
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 239000011806 microball 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
- 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 2
- 238000004821 distillation Methods 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 239000004038 photonic crystal Substances 0.000 abstract description 4
- 238000006722 reduction reaction Methods 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000012279 sodium borohydride Substances 0.000 abstract description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 238000010010 raising Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000004098 Tetracycline Substances 0.000 description 5
- 229960002180 tetracycline Drugs 0.000 description 5
- 229930101283 tetracycline Natural products 0.000 description 5
- 235000019364 tetracycline Nutrition 0.000 description 5
- 150000003522 tetracyclines Chemical class 0.000 description 5
- YCIHPQHVWDULOY-FMZCEJRJSA-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;hydrochloride Chemical compound Cl.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 YCIHPQHVWDULOY-FMZCEJRJSA-N 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 238000011160 research Methods 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
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- BRSVJNYNWNMJKC-UHFFFAOYSA-N [Cl].[Au] Chemical compound [Cl].[Au] BRSVJNYNWNMJKC-UHFFFAOYSA-N 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
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 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
- 238000002242 deionisation method Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- -1 uniform stirring 1h Substances 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
Abstract
A kind of three-dimensional ordered mesoporous Au TiO2/IO‑SiO2Film visible-light photocatalyst and preparation method, belong to field of titanium dioxide photocatalysis.The polystyrene microsphere of different-grain diameter is prepared using surfactant- free emulsion polymerization, in this, as template, the method assembled altogether by polystyrene microsphere and silica precursor liquid, synthesizes the high quality silica inverse opal film template of different pore size.Utilize NaBH4As reducing agent, by chemical reduction method, Au nano particles are deposited in titanium dioxide precursor liquid, is then injected into silica counter opal template, the three-dimensional ordered mesoporous Au TiO of noble metal loading can finally be made2/IO‑SiO2Film.The structure can strengthen the absorption to light due to the special construction of photonic crystal, and after depositing Au, because Au fermi level is low compared with the fermi level of titanium dioxide, be advantageous to the separation of electron hole.This 2 points of raisings for being all advantageous to photocatalysis efficiency.
Description
Technical field
The present invention relates to three-dimensional ordered mesoporous Au-TiO2/IO-SiO2Visible-light photocatalyst prepares and its application field.
The catalyst that this method is prepared especially suitable for degradating organic dye under radiation of visible light (such as:Quadracycline), and be catalyzed
Degradation effect is good.
Background technology
As the development of global economy and industrialized schedule speed are accelerated, the demand of the energy of the mankind also rolls up.
Although achieving many achievements in terms of development, the excessive exploitation to the energy utilizes the balance for having destroyed the Nature,
Cause energy crisis.And on the other hand, industrialize bring waste water and gas pollution allow the earth can't bear the heavy load, environmental problem into
In order to which Earthian should most be concerned about the first order issue for being also most badly in need of solving.So one as protection and Environment control is main
Approach, cleaning is found, reproducible, the environment amenable energy becomes a current most important research topic.1972
Year, Fujishima and Honda have found that under the irradiation of light titanium dioxide can make water decomposition produce hydrogen.From this, titanium dioxide
Everybody visual field is entered with photocatalysis.Compared to other semi-conducting materials such as WO3, ZnS, CdS etc., TiO2Due to inexpensive nothing
It is poison, stable chemical performance, corrosion-resistant and there is very high activity.In a word, in the research of photocatalytic semiconductor material, TiO2It is
Most there is a kind of catalysis material of application prospect.Moreover, outside photocatalysis field, TiO2 effect is also a lot, such as the sun
Energy battery, prepare air-sensitive or moisture sensor, prepare antifouling self-cleaning material, for biological composite coating etc..
Although TiO2Have many advantages, such as, but TiO2Also there is the limitation of its own.Wide variety of TiO2For rutile titania
Ore deposit, its energy gap are 3.2ev, can only utilize the ultraviolet light in sunshine less than 5%, this causes utilizations of the TiO2 to solar energy
Efficiency is very low.Therefore, how TiO is made2It fully can effectively become the study hotspot of photocatalysis field using solar energy.
In the method that document is reported at present, physical method can be utilized first, photonic crystal is made in titanium dioxide
Structure, that is, the opal structural of micro-sphere array.Because photonic crystal has multiple scattering effect and slow photon effect, can have
Effect strengthens the scattering of light, increases light path, improves absorptivity of the titanic oxide material to light.Furthermore it is also possible to use chemical method
Titanic oxide material is modified, such as nonmetallic or transition metal ions doping, the deposition of noble metal, with other semiconductors
Material it is compound etc..These methods can reduce the energy gap of titanium dioxide well, reduce inside titanic oxide material
Electronics and the recombination rate in hole, it is set also to be excited with photocatalysis performance under visible light.At present in noble metal loading
In research, the most noble metals used are platinum, and gold and silver are also widely used certainly.Rupa utilizes sol-gel process
Synthesis of titanium dioxide, and deposited gold, silver respectively to depositing noble metal on titanium dioxide surface using Photodeposition and platinum is laggard
Find that all pure titanic oxide material of the titanium dioxide that deposited three kinds of noble metals will get well after photocatalysis performance of having gone test, and it is right
Optically catalytic TiO 2 performance boost maximum is gold, next to that it is silver-colored, it is finally platinum.
Three-dimensional order photonic crystal is introduced into mesoporous material by the present invention, with SiO2Counter opal and surfactant P123
For template, it is combined using sol-gel and chemical reduction method, prepares three-dimensional order Au-TiO2/IO-SiO2Film visible ray light
Catalyst.
The content 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 in IO-SiO2Loaded on the borehole structure of circular hole reticulated film
There is Au-TiO2Particle, Au-TiO2Particle is referred in TiO2Particle surface is loaded with Au, while IO-SiO2Circular hole reticulated film
It is layer structure.
Described circular hole is mesoporous.
High-performance Au-TiO2/IO-SiO2The preparation method of film visible-light photocatalyst, it is characterised in that including following
Step:
(1) surfactant- free emulsion polymerization synthesis monodisperse polystyrene microsphere (PS) is utilized:Deionization is added in the reactor
Water and ethanol, and inertia protection gas is passed through, stirring, then heat, after temperature is increased to 65 DEG C~80 DEG C and stabilization, add
Distilled styrene, persulfate aqueous solution is added after half an hour, stop heating after stirring 24h, treat that emulsion is cooled to room temperature
Afterwards, stirring is stopped, glass fiber filter removes large granular impurity.Followed by ethanol and the multiple eccentric cleaning of deionized water, obtain
To 180nm~500nm monodisperse polystyrene microsphere;
It is above-mentioned that 137ml ethanol, 7ml~10ml styrene, the 0.18g of 10ml water dissolving are preferably corresponded to per 53ml deionized waters
~0.5g potassium peroxydisulfates;
(2) construction from part prepares silica counter opal (IO-SiO altogether2):Silica precursor liquid is prepared first, will just
Silester, 0.1M hydrochloric acid, absolute ethyl alcohol are well mixed to obtain tetraethyl orthosilicate precursor liquid;Then step (1) is obtained poly-
Phenylethylene micro ball solution is configured to the polystyrene aqueous solution, ultrasonic disperse;Before tetraethyl orthosilicate is added in polystyrene solution
Liquid is driven, simultaneously ultrasonic disperse is mixed, gained mixed liquor is mounted in sample bottle, the sheet glass cleaned with piranha solution is vertical
Insert in sample bottle, grown 2~3 days in 55 DEG C of insulating box;Finally obtained composite film material is carried out in Muffle furnace
Calcining, polystyrene microsphere template is removed, can obtain silica counter opal i.e. IO-SiO2Template;
Wherein tetraethyl orthosilicate, 0.1M hydrochloric acid, the mass ratio of absolute ethyl alcohol are 1:1:(1~3), preferably 1:1:1.5;Polyphenyl
The percentage by volume of the ethene aqueous solution is 0.125%~0.3%, preferably 0.125%;By the polystyrene microsphere aqueous solution:Positive silicon
The volume ratio of acetoacetic ester precursor liquid is 20:The mixing of (0.15~0.3) ratio and ultrasonic disperse, preferably 20:0.15 ratio is mixed
Merge ultrasonic disperse.
(3) sol-gel process prepares Au-TiO2Precursor liquid:Isopropyl titanate is added dropwise in concentrated hydrochloric acid, uniformly stirred
A period of time (such as 1h) is mixed, obtains solution A;A certain amount of P123 is added in ethanol solution, then adds certain ratio
The HAuCl of example4·4H2Then O and appropriate PVP adds the NaBH of excessive Fresh as protective agent4Solution reduction chlorine gold
Acid, obtain solution B;Uniform stirring at least 1h after solution A and solution B are mixed;
(4) by obtained Au-TiO2Precursor liquid is added dropwise in IO-SiO2It is aged 1~2 day in template;, will after the completion of to be aged
Film, which is put into Muffle furnace, calcines organics removal, 1 DEG C/min of heating rate;The three-dimensional of anatase is can obtain after the completion of calcining
Order mesoporous Au-TiO2/IO-SiO2Film photocatalyst.Preferably 400 DEG C calcining 4h of above-mentioned calcining.
SiO is prepared in step (2)2Counter opal assembles legal system altogether from polystyrene microsphere and silica precursor liquid
It is standby.
According to the method for claim 1, it is characterised in that prepare SiO in step (2)2The growth temperature that counter opal is selected
Spend for 55 DEG C~65 DEG C.
In step (3), NaBH4It is protective agent for reducing agent and PVP.Au and TiO2Mass ratio for (0.2wt%~
1wt%), preferably 0.6wt%.The mol ratio of Au and PVP dosages is about 1:(1~1.5), preferably 1:1.
Three-dimensional ordered mesoporous Au-TiO prepared by the present invention2/IO-SiO2It is real that film photocatalyst is applied to photocatalytic degradation
Test, be light source with visible ray, quadracycline carries out photocatalytic degradation processing as target degradation product, and research shows, the catalysis
Agent is shown as compared with catalytic activity and good stability.
The three-dimensional ordered mesoporous Au-TiO prepared using the present invention2/IO-SiO2Film photocatalyst, utilize appropriate particle size
The polystyrene microsphere of size is template, the catalyst being prepared.On the one hand, due to slow photon effect in photon crystal structure
Influence, the absorptivity to light can be strengthened.On the other hand, when Au is supported on TiO2When upper, electronics and hole were advantageously reduced
Recombination rate, so as to increase substantially the photocatalysis performance of titanium dioxide.
Brief description of the drawings
Fig. 1 is silica 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 photocatalytic degradation curve.
Embodiment
The method of the present invention is further described below in conjunction with example.These examples have further described and demonstrated this
Embodiment in invention scope.The purpose that the example provided is merely to illustrate, any restriction is not formed to the present invention, not carried on the back
From under conditions of spirit and scope of the invention various changes can be carried out to it.
Embodiment 1
Three-dimensional ordered mesoporous Au-TiO2/IO-SiO2The preparation method of catalyst, step are as follows:
(1) using surfactant- free emulsion polymerization synthesis monodisperse polystyrene microsphere (PS):137ml absolute ethyl alcohols and 53ml are gone
Ionized water is added in four-hole boiling flask, and argon gas is passed through into device and is delayed as protection gas, stir speed (S.S.) 300rmp/min, oil bath
Slow heating.When temperature stabilization is at 71 DEG C in device, the 10ml styrene after being evaporated under reduced pressure is added, then adds 0.18g
The potassium peroxydisulfate in 10ml deionized waters is dissolved in as initiator.Reaction stops heating after 24 hours, after cooling and uses glass fibers
Dimension film carries out suction filtration and goes the removal of impurity and bulky grain, you can obtains the polystyrene suspension of uniform particle diameter, particle diameter is about 370nm.
(2) construction from part prepares SiO altogether2Counter opal (IO-SiO2):By polystyrene microsphere turbid liquid, first with ethanol and go
Ionized water is respectively washed three times, is then configured to the polystyrene microsphere aqueous solution that volume fraction is 0.125%.Before silica
Tetraethyl orthosilicate is pressed in the preparation for driving liquid:0.1MHCl:Absolute ethyl alcohol=1:1:1.5 mass ratio mixes 1h.Then according to
After adding the ratio ultrasonic disperse of 1.5ml silica precursor liquids in the 100ml polystyrene microsphere aqueous solution, load sample bottle
In, the sheet glass cleaned with piranha solution is inserted perpendicularly into bottle, is placed on 55 DEG C of growths 2 in vibrationless insulating box
~3 days.Obtained laminated film is placed on 450 DEG C of calcining 5h in Muffle furnace, you can obtains the IO-SiO of large area, non-gap2。
(3) sol-gel process prepares Au-TiO2Precursor liquid:2.84g isopropyl titanates are added dropwise to 2.4g dense salt
In acid, uniform stirring 1h, solution A is obtained.1.16g P123 are added in 4g ethanol solutions, then add 0.0033g
HAuCl4·4H2O and appropriate PVP are as protective agent.With the NaBH of Fresh4Solution reduction.Solution A and solution B are mixed
After stir 1h.
(4) by obtained Au-TiO2Precursor liquid is added dropwise in IO-SiO2It is aged 1~2 day in template., will after the completion of to be aged
Film is put into calcining 4h organics removals, 1 DEG C/min of heating rate in 400 DEG C of Muffle furnaces.Rutile titania is can obtain after the completion of calcining
The three-dimensional ordered mesoporous Au-TiO of ore deposit2/IO-SiO2Film photocatalyst.
(5) 300mm is taken2The film catalyst of above-mentioned preparation carries out the experiment of visible light photocatalytic degradation quadracycline, salt
The concentration of sour tetracycline is 25mgL-1, it is seen that the degradation rate of quadracycline is 71.5% after light irradiation 2h.
Embodiment 2
Three-dimensional ordered mesoporous Au-TiO2/IO-SiO2The preparation method of catalyst, step are a difference in that with embodiment 1:
HAuCl used4·4H2O quality is 0.0067g, it is seen that the degradation rate of hydrochloric acid element tetracycline is reached after light irradiation 2h
85.4%.0.0134g, it is seen that 79.4% is reached to the degradation rate of hydrochloric acid element tetracycline after light irradiation 2h.
Embodiment 3
Three-dimensional ordered mesoporous Au-TiO2/IO-SiO2The preparation method of catalyst, step are a difference in that with embodiment 1:
HAuCl used4·4H2O quality is 0.01g, it is seen that reaches 92% to the degradation rate of hydrochloric acid element tetracycline after light irradiation 2h.
Embodiment 4
Three-dimensional ordered mesoporous Au-TiO2/IO-SiO2The preparation method of catalyst, step are a difference in that with embodiment 1:
HAuCl used4·4H2O quality is 0.0134g, it is seen that the degradation rate of hydrochloric acid element tetracycline is reached after light irradiation 2h
79.4%.
Embodiment 5
Three-dimensional ordered mesoporous Au-TiO2/IO-SiO2The preparation method of catalyst, step with embodiment 1, except that
Ethanol content in step 3) is 8g.
Embodiment 6
Three-dimensional ordered mesoporous Au-TiO2/IO-SiO2The preparation method of catalyst, step with embodiment 1, except that
Ethanol content in step 3) is 12g.
Embodiment 7
Three-dimensional ordered mesoporous Au-TiO2/IO-SiO2The preparation method of catalyst, step with embodiment 1, except that
Au-TiO in step 4)2Precursor liquid is injected into the IO-SiO being prepared with 300nm PS templates2In.
Embodiment 8
Three-dimensional ordered mesoporous Au-TiO2/IO-SiO2The preparation method of catalyst, step with embodiment 1, except that
Au-TiO in step 4)2Precursor liquid is injected into the IO-SiO being prepared with 450nm PS templates2In.
Claims (7)
- A kind of 1. 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 in IO-SiO2Au-TiO is loaded with the borehole structure of circular hole reticulated film2 Particle, Au-TiO2Particle is referred in TiO2Particle surface is loaded with Au, while IO-SiO2Circular hole reticulated film is layer structure 's.
- 2. according to a kind of high-performance Au-TiO described in claim 12/IO-SiO2Film visible-light photocatalyst, its feature exist In circular hole is mesoporous.
- 3. prepare high-performance Au-TiO2/IO-SiO2The method of film visible-light photocatalyst, it is characterised in that including following step Suddenly:(1) surfactant- free emulsion polymerization synthesis monodisperse polystyrene microsphere (PS) is utilized:In the reactor add deionized water and Ethanol, and inertia protection gas is passed through, stirring, then heat, after temperature is increased to 65 DEG C~80 DEG C and stabilization, add distillation The styrene crossed, persulfate aqueous solution is added after half an hour, stop heating after stirring 24h, after emulsion is cooled to room temperature, stop Only stir, glass fiber filter removes large granular impurity;Followed by ethanol and the multiple eccentric cleaning of deionized water, obtain 180nm~500nm monodisperse polystyrene microsphere;(2) construction from part prepares silica counter opal (IO-SiO altogether2):Silica precursor liquid is prepared first, by positive silicic acid second Ester, 0.1M hydrochloric acid, absolute ethyl alcohol are well mixed to obtain tetraethyl orthosilicate precursor liquid;Then polystyrene step (1) obtained Microballoon is configured to the polystyrene aqueous solution, ultrasonic disperse;Tetraethyl orthosilicate precursor liquid will be added in polystyrene solution, mixing is simultaneously Ultrasonic disperse, gained mixed liquor is mounted in sample bottle, the sheet glass cleaned with piranha solution is inserted perpendicularly into sample bottle In, grown 2~3 days in 55 DEG C of insulating box;Finally obtained composite film material is calcined in Muffle furnace, removed poly- Phenylethylene micro ball template, it can obtain silica counter opal i.e. IO-SiO2Template;(3) sol-gel process prepares Au-TiO2Precursor liquid:Isopropyl titanate is added dropwise in concentrated hydrochloric acid, uniform stirring one The section time, obtain solution A;A certain amount of P123 is added in ethanol solution, then added a certain proportion of HAuCl4·4H2Then O and appropriate PVP adds the NaBH of excessive Fresh as protective agent4Solution reduction gold chloride, is obtained To solution B;Uniform stirring 1h after solution A and solution B are mixed;(4) by obtained Au-TiO2Precursor liquid is added dropwise in IO-SiO2It is aged 1~2 day in template;After the completion of to be aged, by film It is put into Muffle furnace and calcines organics removal, 1 DEG C/min of heating rate;The three-dimensional order of anatase is can obtain after the completion of calcining Mesoporous Au-TiO2/IO-SiO2Film photocatalyst;Above-mentioned 400 DEG C of calcining 4h of calcining.
- 4. according to the method for claim 3, it is characterised in that in step (1) per 53mL deionized waters correspond to 137mL ethanol, 7mL~10mL styrene, 0.18g~0.5g potassium peroxydisulfates of 10mL water dissolving.
- 5. according to the method for claim 3, it is characterised in that tetraethyl orthosilicate in step (2), 0.1M hydrochloric acid, absolute ethyl alcohol Mass ratio is 1:1:(1~3);The percentage by volume of the polystyrene aqueous solution is 0.125%~0.3%;By polystyrene microsphere The aqueous solution:The volume ratio of tetraethyl orthosilicate precursor liquid is 20:The ratio mixing of (0.15~0.3) and ultrasonic disperse.
- 6. according to the method for claim 5, it is characterised in that tetraethyl orthosilicate in step (2), 0.1M hydrochloric acid, absolute ethyl alcohol Mass ratio is 1:1:1.5;The percentage by volume of the polystyrene aqueous solution is 0.125%;450 DEG C are calcined 5 hours.
- 7. according to the method for claim 3, it is characterised in that Au and TiO2Mass ratio be 0.2wt%~1wt%, Au and PVP The mol ratio of dosage is 1:(1~1.5).
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