CN106111053A - A kind of short-bore road ordered meso-porous silicon oxide sulfur-indium-zinc composite photo-catalyst and its preparation method and application - Google Patents
A kind of short-bore road ordered meso-porous silicon oxide sulfur-indium-zinc composite photo-catalyst and its preparation method and application Download PDFInfo
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- CN106111053A CN106111053A CN201610457702.1A CN201610457702A CN106111053A CN 106111053 A CN106111053 A CN 106111053A CN 201610457702 A CN201610457702 A CN 201610457702A CN 106111053 A CN106111053 A CN 106111053A
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- indium
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- porous silicon
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- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 39
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 33
- ZEZRVPYWBUSZSG-UHFFFAOYSA-N [Zn].[In].[S].[Si]=O Chemical compound [Zn].[In].[S].[Si]=O ZEZRVPYWBUSZSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- -1 hydroxyl radical free radical Chemical class 0.000 claims abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- 150000002471 indium Chemical class 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims abstract description 5
- 150000003751 zinc Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910001868 water Inorganic materials 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 4
- 229920000428 triblock copolymer Polymers 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 235000013877 carbamide Nutrition 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 3
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 3
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 125000003367 polycyclic group Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000003463 adsorbent Substances 0.000 abstract description 5
- 239000005416 organic matter Substances 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 229910006213 ZrOCl2 Inorganic materials 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 9
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LUDNDMXNVSDPNT-UHFFFAOYSA-N [Zn].[In].[S].[Si] Chemical compound [Zn].[In].[S].[Si] LUDNDMXNVSDPNT-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
The invention discloses a kind of short-bore road ordered meso-porous silicon oxide sulfur-indium-zinc composite photo-catalyst and its preparation method and application.Described short-bore road ordered meso-porous silicon oxide sulfur-indium-zinc composite photo-catalyst is by tetraethyl orthosilicate, ZrOCl2, zinc salt, indium salts and reducing agent mixing after, in the presence of surfactants, through collosol and gel hydro-thermal alcohol ultrasonic successively process and sucking filtration clean and dry after prepare.It is integrated with photochemical catalytic oxidation that this photocatalyst achieves absorption; volatile organic matter (VOCs) had stronger absorption property and photocatalytic activity; make the hydroxyl radical free radical that catalyst surface produces the most just can degradable material adsorbed and was enriched with effectively VOCs; thus significantly strengthen reaction rate and the efficiency of photocatalytic degradation VOCs; wide environmental conservation application potential can be had as the adsorbent of organic pollution or photocatalyst at field of Environment Protection.
Description
Technical field
The invention belongs to absorbent-type catalysis material technical field, more particularly, to a kind of order mesoporous oxidation in short-bore road
Silicon-sulfur-indium-zinc composite photo-catalyst and its preparation method and application.
Background technology
Volatile organic matter (Volatile organic compounds, VOCs) brings substantial amounts of environment to us and asks
Topic, has the most seriously threatened the life security of the mankind simultaneously.Owing to photocatalysis oxidation technique can irradiate and catalyst at light
In the presence of, VOCs is finally oxidized to CO2And H2O, and paid close attention to widely.At present, some conductor photocatalysis reported
Agent only with in sunlight ultraviolet light (ultraviolet light only accounts for about the 5% of sunlight gross energy and excites and lower just show activity, this
Significantly limit their actual application.Thus, substantial amounts of scientific research personnel start to be devoted to research and develop have visible light-responded
Photocatalyst, and synthesized substantial amounts of visible light activity catalyst, but its catalytic efficiency ultraviolet light response to be less than
Catalyst, and serious photoetch can be caused due to ultraviolet light under sunlight, thus cause these to report
Visible light catalyst is the most unstable.Therefore, in order to realize the actual application of sunlight catalytic agent, then light requirement catalyst should improve
Catalysis activity during visible ray, has stability again under sunlight.
In order to preferably adsorb volatile organic matter, generally using ordered mesoporous material, it is to utilize self-assembling method to obtain
To the important material with orderly pore passage structure of a class, such as ordered meso-porous silicon oxides such as SBA-15.This kind of material has and compares table
Area and pore volume is big, pore-size distribution is narrow and the most adjustable in 2-50nm yardstick, pore passage structure is regular, controlled, and surface is prone to
The series of characteristics such as modification and Heat stability is good.But, tradition ordered mesopore carbon is bar-shaped or fibrous, and duct is longer, and
Granule often in assembling shape, is unfavorable for VOCs diffusion in duct and transmission so that VOCs is slow, no in catalyst surface diffusion
The avtive spot of catalyst can be rapidly reached, thus limit its catalysis activity, there is also the regeneration of adsorbent in-situ simultaneously
A difficult problem, causes rear disposal and the secondary pollution problem of adsorbent.Therefore, the most effectively adsorb volatile organic matter and improve right
Its photocatalysis efficiency, prepares and has stable, efficient sunlight catalytic agent under sunlight, it is possible to strengthen catalyst to light
While absorbing and utilizing, the stability improving catalyst further is technical problem urgently to be resolved hurrily.
So far, have no the preparation about short-bore road ordered meso-porous silicon oxide-sulfur-indium-zinc composite photo-catalyst and
Correlational study in terms of VOCs degraded and report.
Summary of the invention
The technical problem to be solved is lacking of the diffusion overcoming VOCs in prior art in duct and transmission
Fall into and not enough, it is provided that a kind of short-bore road ordered meso-porous silicon oxide-sulfur-indium-zinc with stronger absorption property and photocatalytic activity
The preparation method of composite photo-catalyst, it is possible to solve the problem that reactant can quickly spread at catalyst surface, be rapidly reached
The avtive spot of catalyst, is significantly increased its catalysis activity.
It is an object of the invention to provide the preparation side of a kind of short-bore road ordered meso-porous silicon oxide-sulfur-indium-zinc composite photo-catalyst
Method.
It is a further object of the present invention to provide short-bore road ordered meso-porous silicon oxide-sulfur-indium-zinc that said method prepares multiple
Close photocatalyst.
Another object of the present invention is to provide answering of above-mentioned short-bore road ordered meso-porous silicon oxide-sulfur-indium-zinc composite photo-catalyst
With.
Above-mentioned purpose of the present invention is achieved by the following technical programs:
The preparation method of a kind of short-bore road ordered meso-porous silicon oxide-sulfur-indium-zinc composite photo-catalyst, comprises the steps:
S1. 0.1～10g surfactant is joined water and the concentrated hydrochloric acid solution that 6～100mL volume ratios are 1～10:1
In, at 30～90 DEG C, stir 0.5～24h, obtain mixed solution A；
S2. by 0.1～10mL tetraethyl orthosilicate, 50～500mgZrOCl2, 20～200mg zinc salt, 60～400mg indium salts
Add in step S1 gained mixed solution A successively with 30～300mg reducing agents, at 30～90 DEG C, stir 2～72h, obtain
Mixed solution B；
S3. step S2 gained mixed solution B is loaded in 25～200mL polytetrafluoroethyltank tank, hydro-thermal at 60～250 DEG C
Reaction 2～72h, after being cooled to room temperature, collects precipitate, with 50～2000mL water flushing precipitate, by precipitate 50～
Dry 1～36h at 180 DEG C, obtain short-bore road ordered meso-porous silicon oxide；
S4. short-bore road ordered meso-porous silicon oxide step S3 prepared mixes with the ratio of 0.1～10mg/mL with alcohol, super
Sonication 0.5～60min, reclaims particles in solution thing by sucking filtration, rinses with 50～2000mL alcohol, then at 50～180 DEG C
Lower drying 1～36h, obtains short-bore road ordered meso-porous silicon oxide-sulfur-indium-zinc composite photo-catalyst.
Preferably, surfactant described in step S1 is poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) three block
Copolymer, Polyethylene Glycol or cetyl trimethylammonium bromide.
Preferably, zinc salt described in step S2 is zinc chloride, zinc nitrate or zinc sulfate.
Preferably, indium salts described in step S2 is indium chloride, indium nitrate or indium sulfate.
Preferably, reducing agent described in step S2 is thiourea, carbamide or thioacetamide.
Preferably, alcohol described in step S4 is ethanol or methanol.
Preferably, water described in step S1 and S3 is deionized water.
It addition, short-bore road ordered meso-porous silicon oxide-sulfur-indium-zinc composite photo-catalyst of preparing of said method and at ring
Guarantor field is as the application in the selective absorbent of VOCs or photocatalyst, also within protection scope of the present invention.
The present invention is combined with short-bore road ordered mesoporous carbon material as catalyst using sulfur-indium-zinc, prepares a kind of new
Type adsorbs-optic catalytic composite material efficiently.Can effectively adsorb volatile organic matter under sunlight, catalysis can be strengthened again
Agent, to the absorption of light and utilization, improves the stability of catalyst further.This is owing to sulfur-indium-zinc has narrower band-gap energy
(2.34-2.48eV), visible ray can be effectively absorbed, and then produce more photo-generate electron-hole pair, improve its photocatalytic
Energy.And short-bore road mesoporous material is shorter because of its duct, it is easy to VOCs mass transfer in duct and diffusion.By order mesoporous for short-bore road
The adsorption and enrichment effect of VOCs is combined by silicon oxide with the photocatalysis of sulfur-indium-zinc photocatalyst, makes VOCs at catalyst sulfur
Indium zinc surface can quickly spread, and is rapidly reached the avtive spot of catalyst, improves the absorption to VOCs.Short-bore road has simultaneously
The addition of sequence mesoporous silicon can improve the transfer rate of light induced electron, makes light induced electron be delivered to mesoporous silicon from sulfur-indium-zinc, this
Sample can suppress its photoetch to sulfur-indium-zinc, improves the stability of catalyst, thus significantly improves photocatalysis performance.Cause
This, short-bore road ordered meso-porous silicon oxide-sulfur-indium-zinc composite photo-catalyst is possible not only to improve the sulfur-indium-zinc suction to volatile organic compounds
Attached enrichment, moreover it is possible to improve sunlight stability and the photocatalysis performance of catalyst further, it is achieved thereby that absorption and photocatalysis
The integration of oxidation VOCs.
Compared with prior art, the method have the advantages that
The present invention is by the light of the adsorption and enrichment effect to VOCs of the short-bore road ordered meso-porous silicon oxide with sulfur-indium-zinc photocatalyst
Catalysis mineralization combines, and prepares a kind of new and effective absorption-photocatalysis integrated material, i.e. short-bore road is order mesoporous
Silicon oxide-sulfur-indium-zinc composite photo-catalyst, it is possible to solve the problem that VOCs can quickly spread at catalyst surface, be rapidly reached
The active position of catalyst, is significantly increased its catalysis activity.
Gas phase dimethylbenzene is showed by short-bore road ordered meso-porous silicon oxide-sulfur-indium-zinc composite photo-catalyst that the present invention prepares
Go out good absorption and photocatalytic activity, there is adsorption time short, the advantage that degradation rate is high.Wherein, the adsorption rate of xylol
In 40min, reach 36.6%, the degradation rate of gas phase dimethylbenzene has also been up to 96.9%, it is achieved thereby that inhale in 60min
Attached integrated with photochemical catalytic oxidation VOCs.
It addition, the hydroxyl radical free radical that produces of catalyst surface the most just can degradable material adsorbs and was enriched with effectively
VOCs, is greatly enhanced reaction rate and the efficiency of photocatalysis degradation organic contaminant, solves adsorbent in-situ more simultaneously
A raw difficult problem, it is to avoid the rear disposal of adsorbent and secondary pollution problem.
Accompanying drawing explanation
Fig. 1 is short-bore road ordered meso-porous silicon oxide-sulfur-indium-zinc composite photo-catalyst adsorption dynamics adsorption kinetics to gas phase dimethylbenzene
Curve and kinetics of photocatalytic degradation curve.
Detailed description of the invention
Further illustrate present disclosure below in conjunction with Figure of description and specific embodiment, but should not be construed as this
The restriction of invention.If not specializing, the conventional hands that technological means used in embodiment is well known to those skilled in the art
Section.Unless stated otherwise, the present invention uses reagent, method and apparatus are the art conventional reagent, method and apparatus.
Embodiment 1
1. preparation:
S1. 0.1g Polyethylene Glycol is joined in the water and concentrated hydrochloric acid solution that 6mL volume ratio is 10:1, stir at 90 DEG C
24h, obtains settled solution；
S2. by 10mL tetraethyl orthosilicate, 50mgZrOCl2, 20mg zinc chloride, 60mg indium chloride and 30mg thiourea delay successively
Slowly add step S1 gained settled solution to, at 30 DEG C, stir 2h, obtain white opacity solution；
S3. step S2 gained white opacity solution is loaded in 25mL polytetrafluoroethyltank tank, hydro-thermal reaction at 60 DEG C
72h, after cooling in polytetrafluoroethyltank tank, collects precipitate, rinses precipitate with 50mL water, by the precipitate after washing 50
Dry 36h at DEG C, obtain short-bore road ordered meso-porous silicon oxide；
S4. the short-bore road ordered meso-porous silicon oxide of S3 gained is mixed with the ratio of 0.1mg/mL with methanol, supersound process
0.5min, reclaims particles in solution thing by sucking filtration, rinses with 50mL methanol, then dries 1h at 50 DEG C, obtains short-bore road
Ordered meso-porous silicon oxide-sulfur-indium-zinc composite photo-catalyst.
2. performance test:
Fig. 1 is short-bore road ordered meso-porous silicon oxide-sulfur-indium-zinc composite photo-catalyst adsorption dynamics adsorption kinetics to gas phase dimethylbenzene
Curve and kinetics of photocatalytic degradation curve.As seen from Figure 1, this photocatalyst has good absorption and photocatalysis is lived
Property, the adsorption rate of xylol has reached 36.6% in 40min, and the degradation rate of xylol can reach in 60min
96.9%.Test result indicate that, short-bore road ordered meso-porous silicon oxide-sulfur-indium-zinc composite photo-catalyst prepared by the present invention is a kind of
There is high absorption and the new material of photocatalytic activity.Embodiment 2
S1. 10g poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer is joined 100mL volume ratio
For in the water of 1:1 and concentrated hydrochloric acid solution, at 30 DEG C, stir 24h, obtain settled solution；
S2. by 0.1mL tetraethyl orthosilicate, 500mgZrOCl2, 200mg zinc nitrate, 400mg indium nitrate and 30mg carbamide depends on
Secondary it is added slowly to step S1 gained settled solution, at 90 DEG C, stirs 72h, obtain white opacity solution；
S3. step S2 gained white opacity solution is loaded in 200mL polytetrafluoroethyltank tank, hydro-thermal reaction at 250 DEG C
2h, after cooling in polytetrafluoroethyltank tank, collects precipitate, rinses precipitate with 2000mL water, is existed by the precipitate after washing
Dry 1h at 180 DEG C, obtain short-bore road ordered meso-porous silicon oxide；
S4. the short-bore road ordered meso-porous silicon oxide of step S3 gained is mixed with the ratio of 10mg/mL with ethanol, ultrasonic place
Reason 60min, reclaims particles in solution thing by sucking filtration, uses 2000mL alcohol flushing, then dries 36h at 180 DEG C, obtain short
Duct ordered meso-porous silicon oxide-sulfur-indium-zinc composite photo-catalyst.
Embodiment 3
S1. 5g cetyl trimethylammonium bromide is joined in the water and concentrated hydrochloric acid solution that 80mL volume ratio is 5:1,
Stir 6h at 50 DEG C, obtain settled solution；
S2. by 2mL tetraethyl orthosilicate, 100mgZrOCl2, 150mg zinc sulfate, 200mg indium sulfate and 190mg thioacetyl
Amine is added slowly to step S1 gained settled solution successively, stirs 12h, obtain white opacity solution at 50 DEG C；
S3. step S2 gained white opacity solution is loaded in 100mL polytetrafluoroethyltank tank, hydro-thermal reaction at 120 DEG C
18h, after cooling in polytetrafluoroethyltank tank, collects precipitate, rinses precipitate with 1000mL water, is existed by the precipitate after washing
Dry 8h at 100 DEG C, obtain short-bore road ordered meso-porous silicon oxide；
S4. the short-bore road ordered meso-porous silicon oxide of step S3 gained is mixed with the ratio of 0.5mg/mL with ethanol, ultrasonic
Process 30min, reclaim particles in solution thing by sucking filtration, use 1000mL alcohol flushing, at 100 DEG C, then dry 8h, to obtain final product
Short-bore road ordered meso-porous silicon oxide-sulfur-indium-zinc composite photo-catalyst.
Embodiment 4
S1. 6g poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer is joined 100mL volume ratio
For in the water of 9:1 and concentrated hydrochloric acid solution, at 45 DEG C, stir 3h, obtain settled solution；
S2. by 5.6mL tetraethyl orthosilicate, 152mgZrOCl2, 143mg zinc chloride, 300mg indium nitrate and 34mg sulfur is for second
Amide is added slowly to step S1 gained settled solution successively, stirs 24h, obtain white opacity solution at 45 DEG C；
S3. step S2 gained white opacity solution is loaded in 100mL polytetrafluoroethyltank tank, hydro-thermal reaction at 90 DEG C
24h, after cooling in polytetrafluoroethyltank tank, collects precipitate, with 500mL deionized water rinsing precipitate, by precipitate 60
Dry 12h at DEG C, obtain short-bore road ordered meso-porous silicon oxide；
S4. the short-bore road ordered meso-porous silicon oxide of step S3 gained is mixed with the ratio of 2mg/mL with methanol, ultrasonic place
Reason 5min, reclaims particles in solution thing by sucking filtration, rinses with 500mL methanol, then dries 12h at 60 DEG C, obtains short-bore
Road ordered meso-porous silicon oxide-sulfur-indium-zinc composite photo-catalyst.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (8)
1. the preparation method of short-bore road ordered meso-porous silicon oxide-sulfur-indium-zinc composite photo-catalyst, it is characterised in that include as
Lower step:
S1. 0.1～10g surfactant is joined in the water and concentrated hydrochloric acid solution that 6～100mL volume ratios are 1～10:1,
Stir 0.5～24h at 30～90 DEG C, obtain mixed solution A；
S2. by 0.1～10mL tetraethyl orthosilicate, 50～500mgZrOCl2, 20～200mg zinc salt, 60～400mg indium salts and 30～
300mg reducing agent adds step S1 gained mixed solution A successively to, stirs 2～72h, obtain mixed solution at 30～90 DEG C
B；
S3. step S2 gained mixed solution B is loaded in 25～200mL polytetrafluoroethyltank tank, hydro-thermal reaction at 60～250 DEG C
2～72h, after being cooled to room temperature, collect precipitate, rinse precipitate with 50～2000mL water, by precipitate at 50～180 DEG C
Lower drying 1～36h, obtains short-bore road ordered meso-porous silicon oxide；
S4. short-bore road ordered meso-porous silicon oxide step S3 prepared mixes with the ratio of 0.1～10mg/mL with alcohol, ultrasonic place
Reason 0.5～60min, reclaims particles in solution thing by sucking filtration, rinses with 50～2000mL alcohol, then dries at 50～180 DEG C
Dry 1～36h, obtain short-bore road ordered meso-porous silicon oxide-sulfur-indium-zinc composite photo-catalyst.
Preparation method the most according to claim 1, it is characterised in that surfactant described in step S1 is polycyclic oxygen second
Alkane-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer, Polyethylene Glycol or cetyl trimethylammonium bromide.
Preparation method the most according to claim 1, it is characterised in that zinc salt described in step S2 is zinc chloride, zinc nitrate
Or zinc sulfate；Described indium salts is indium chloride, indium nitrate or indium sulfate；Described reducing agent is thiourea, carbamide or thioacetamide.
Preparation method the most according to claim 1, it is characterised in that alcohol described in step S4 is ethanol or methanol.
Preparation method the most according to claim 1, it is characterised in that water described in step S1 and S3 is deionized water.
6. short-bore road ordered meso-porous silicon oxide-sulfur-indium-zinc complex light that a kind is prepared by method described in any one of Claims 1 to 5
Catalyst.
7. the short-bore road ordered meso-porous silicon oxide-sulfur-indium-zinc composite photo-catalyst described in claim 6 is waved in field of Environment Protection degraded
Send out the application in Organic substance.
Apply the most according to claim 7, it is characterised in that described volatile organic compounds is dimethylbenzene.
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