CN106076337A - A kind of composite photocatalyst material and preparation method thereof - Google Patents
A kind of composite photocatalyst material and preparation method thereof Download PDFInfo
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- CN106076337A CN106076337A CN201610552849.9A CN201610552849A CN106076337A CN 106076337 A CN106076337 A CN 106076337A CN 201610552849 A CN201610552849 A CN 201610552849A CN 106076337 A CN106076337 A CN 106076337A
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- 239000000463 material Substances 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000005253 cladding Methods 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 33
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 229950000845 politef Drugs 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- 238000002525 ultrasonication Methods 0.000 claims description 2
- 229910001868 water Inorganic materials 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims 1
- 229910021389 graphene Inorganic materials 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 238000005234 chemical deposition Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- NJSVDVPGINTNGX-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethanamine Chemical compound CCC[Si](OC)(OC)OCN NJSVDVPGINTNGX-UHFFFAOYSA-N 0.000 description 9
- 229960004756 ethanol Drugs 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 6
- 229940012189 methyl orange Drugs 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- UCSUOYMTZRJAIH-UHFFFAOYSA-N iron(2+) oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[Fe+2] UCSUOYMTZRJAIH-UHFFFAOYSA-N 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The present invention relates to a kind of composite photocatalyst material and preparation method thereof, belong to field of new.Present invention chemical deposition is by TiO2It is coated on Fe3O4Surface, is combined it with graphene oxide by hydro-thermal method, by regulation and control TiO2The content of presoma, has synthesized and has had different TiO2The Fe of cladding thickness3O4@TiO2By series of experiments ,/GO composite, proves that composite prepared by the present invention possesses preferable Photocatalytic Degradation Property.
Description
Technical field
The present invention relates to a kind of composite photocatalyst material based on titanium dioxide and preparation method thereof, belong to new material neck
Territory.
Technical background
Titanium dioxide (TiO2) material has been widely used in environmental area as the photocatalyst of function admirable.Due to
TiO2Self there is photo-generated carrier to be easily combined, the defect such as in catalytic process quantum yield is low so that based on TiO2Photocatalysis skill
The application of art is restricted.The conductor photocatalysis system with heterojunction structure can be effectively improved the separation of photo-generated carrier,
This be due between two kinds of different materials formed electric field be conducive to light induced electron in the migration at interface, thus inhibit electronics-
Hole is to being combined.Recently there are some researches show, TiO2/ graphene composite material shows the photoelectric properties of excellence, can significantly carry
The separation of high photo-generated carrier.It is another principal element limiting its environmental applications that nano composite material reclaims, magnetic function
The appearance of composite is expected to solve this problem.Therefore titanium dioxide-iron oxides-Graphene (Fe3O4@TiO2/ GO) compound
Material is to TiO2The actual environment application of material is significant.Research is had to point out Fe3O4@TiO2TiO in/GO composite2
Cladding Fe3O4Thickness be the principal element affecting its catalytic performance.TiO2Clad is the thickest, the TiO of cladding2Measure the most, be available for
The photo-generated carrier content produced is the highest, is conducive to improving its catalytic performance.Separately there are some researches show, increase Fe3O4The particle diameter of core has
It is beneficial to improve the separation of photo-generated carrier, thus improves catalytic efficiency.Above two different viewpoints shows Fe3O4@TiO2/ GO is multiple
Condensation material structure is the key factor restricting its catalytic performance.
The present invention utilizes chemical deposition, by regulation and control TiO2The content of presoma butyl titanate (TBOT), synthesizes
A series of have different TiO2The Fe of cladding thickness3O4@TiO2/ GO composite.This material possesses higher photocatalysis characteristic,
Can be used for the fast degradation of dye molecule.
Summary of the invention
The present invention is prepared for a kind of Fe3O4@TiO2/ GO composite photocatalyst material.The present invention modifies first with APTMS
Fe3O4Granule, utilizes chemical precipitation method, by regulation and control TiO2The content of presoma TBOT, has synthesized a series of different TiO2Cladding
The Fe of thickness3O4@TiO2, afterwards by hydro-thermal method, by Fe3O4@TiO2Granule is combined with GO and obtains Fe3O4@TiO2/ GO composite wood
Material.The Fe of present invention synthesis is proved by series of experiments3O4@TiO2/ GO composite has the light degradation effect of excellence.
The particular content of the present invention is illustrated by following description:
(1) synthesis Fe3O4: by 1.350g Iron(III) chloride hexahydrate (FeCl3·6H2O), 3.854g ammonium acetate
(CH3COONH4), 0.4557g sodium citrate (C6H5Na3O7) it is dissolved in 70mL ethylene glycol ((CH2OH)2) in solution, under electric stirring
In 170 DEG C of oil baths, react 1h form dark solution, proceeded in 100mL politef reactor afterwards, keep 200 DEG C
Lower reaction 16h, after being cooled to room temperature, after black solid separates with Magnet and uses ethanol purge 5 times, vacuum drying at 50 DEG C,
Obtain product Fe3O4。
(2) Fe that synthesis APTMS modifies3O4: the Fe that will obtain in 60mg step (1)3O4It is dissolved in 20mL under ultrasonication
In dehydrated alcohol, add 75mL ethanol and 5mL deionized water, after ultrasonic for mixed liquor 20min, be transferred to the there-necked flask of 100mL
In, add 2mL APTMS solution under electric stirring, mixed liquor is reacted at water-bath 60 DEG C 7h, with Magnet separation product and use
After ethanol purge 5 times, obtain the Fe that APTMS modifies3O4。
(3) the different TiO of synthesis2The Fe of thickness3O4@TiO2Material: the Fe that APTMS step (2) obtained modifies3O4Dispersion
In 80mL dehydrated alcohol with nitrile volume ratio is the solution of 3:1, add 0.5mL ammonia (NH3·H2O), by 0.05,0.1,
0.25,0.5,1,2mL TBOT be dissolved in respectively in 2mL dehydrated alcohol, under electric stirring, be added dropwise over what above-mentioned APTMS modified
Fe3O4In dispersion liquid, after reaction 30min, add 15mg cetyl trimethylammonium bromide (CTAB), continue reaction 30min, use
Magnet separation product with after ethanol purge 5 times, vacuum drying at 50 DEG C, obtain product difference TiO2The Fe of cladding thickness3O4@
TiO2。
(4) synthesis Fe3O4@TiO2/ GO material: the graphene oxide (GO) 30mg Hummers method prepared is molten
Ultrasonic 1.5h in 50mL deionized water, the different TiO that will obtain in 40mg step (3)2The Fe of cladding thickness3O4@TiO2Material
Add above-mentioned GO solution, react 30min under electric stirring, mixed liquor is transferred in politef reactor, anti-at 180 DEG C
Answer 18h, after being cooled to room temperature, separate with Magnet and use washes of absolute alcohol 5 times, vacuum drying at 50 DEG C, obtain product Fe3O4@
TiO2/GO。
(5) methyl orange degradation: the Fe that will obtain in 10mg step (4)3O4@TiO2/ GO adds 2mL 2 × 10-5Mol/L's
In methyl orange solution, under the conditions of lucifuge react 30min reach adsorption equilibrium, carry out ultraviolet lighting the most again, every time sampling, use
The concentration of methyl orange in UV spectrophotometer measuring solution, investigates photocatalysis efficiency.
Accompanying drawing explanation
Principal character below by the marginal data present invention.
The different TiO that accompanying drawing 1 is prepared for the present invention2The Fe of cladding thickness3O4@TiO2The scanner uni transmission electron microscope of/GO shines
Sheet, particle diameter distribution DLS curve and EDS power spectrum.Result shows Fe3O4@TiO2Even particulate dispersion is on GO sheet.Along with TBOT's
Content increases to 2mL, Ti constituent content from 0 and increases to 12% from 0.When TBOT content is more than 1mL, substantially reuniting occurs in product.
The Fe that accompanying drawing 2 is prepared for the present invention3O4@TiO2/ GO the material high-resolution-ration transmission electric-lens when TBOT=0.5mL shines
Sheet and Elemental redistribution scanning figure.Result shows Fe3O4@TiO2There is obvious nucleocapsid structure, TiO in/GO material2It is evenly coated at
Fe3O4Outer layer.Fe3O4Material is based on (311) face exposed, and spacing of lattice is 0.25nm；TiO2Material is mainly with exposure
(101) face is main, and spacing of lattice is 0.35nm.
The Fe that accompanying drawing 3 is prepared for the present invention3O4@TiO2/ GO material XRD spectra.Result shows, Fe3O4Material is in a cube knot
Structure (JCPDS 65-3107), TiO2Material is anatase tetragonal system (JCPDS 21-1272), works as TiO2When cladding thickness is less
(TBOT < 0.5mL), part Fe3O4Fe can be oxidized to2O3, along with TiO2The increase of cladding thickness, Fe3O4Oxidation be suppressed,
TiO is described2Layer serves increase Fe3O4The effect of stability
The Fe that accompanying drawing 4 is prepared for the present invention3O4@TiO2The Raman spectrogram of/GO material.Result shows, Fe3O4219,284
And 391cm-1Place has obvious eigen vibration peak, TiO2Having Detitanium-ore-type characteristic peak, GO is at 1340cm-1And 1596cm-1Place
Show obvious D peak and G peak.Fe3O4@TiO2In/GO composite, D peak illustrates GO and Fe with the increase of G p-ratio3O4@
TiO2When granule combines, part GO is reduced to RGO.
The Fe that accompanying drawing 5 is prepared for the present invention3O4@TiO2The infrared spectrum of/GO material.Result shows, GO and Fe3O4@TiO2
After granule combines, GO surface oxygen functional group content reduces, and demonstrates part GO further and is reduced to RGO.
The Fe that accompanying drawing 6 is prepared for the present invention3O4@TiO2/ GO the material B-H loop when TBOT=0.5mL.Result table
Bright, Fe3O4@TiO2The magnetic saturation of/GO material is 28emu/g, illustrates that this composite has and can realize Magneto separate.
The Fe that accompanying drawing 7 is prepared for the present invention3O4@TiO2/ GO the material degradation kinetics curve to methyl orange.Can from figure
To find out, when TBOT addition is 0.5mL, composite prepared by the present invention had the catalytic performance of excellence, at 50 minutes
In, can be with the methyl orange of 80% in degraded solutions.
Inventive embodiments
Embodiment 1Fe3O4@TiO2Prepared by/GO composite: by 1.350g FeCl3·6H2O、3.854g CH3COONH4、
0.4557g C6H5Na3O7It is dissolved in 70mL ethylene glycol solution, after reacting 1h in 170 DEG C of oil baths, proceeds to polytetrafluoroethyl-ne alkene reaction
In still, react 16h at keeping 200 DEG C, with ethanol purge vacuum drying after gained solid Magneto separate, obtain Fe3O4Product.Will
60mg Fe3O4Ultrasonic it is dissolved in 20mL dehydrated alcohol, adds 75mL ethanol and 5mL deionized water ultrasonic 20min, by mixed liquor
It is transferred in 100mL there-necked flask, adds and at 60 DEG C, react 7h after 2mL APTMS solution, Magneto separate product with after ethanol purge
It is dispersed in the nitrile (v/v=3:1) of 80mL ethanol/, obtains the Fe that APTMS modifies3O4.By 0.05,0.1,0.25,0.5,
1, during 2mL TBOT is dissolved in 2mL dehydrated alcohol respectively, and it is separately added into the Fe that APTMS modifies3O4In solution, react 30min
After, add 15mg cetyl trimethylammonium bromide (CTAB), continue reaction 30min.Magneto separate product is the most clear with dehydrated alcohol
Wash final vacuum to dry, obtain that there is different TiO2The Fe of cladding thickness3O4@TiO2Product.By 40mg Fe3O4@TiO2Add GO molten
In liquid, after reaction 30min, it is transferred in politef reactor, at keeping 180 DEG C, reacts 18h.Product is cooled to room temperature,
Magneto separate is also dried with washes of absolute alcohol final vacuum, obtains having different TiO2The Fe of cladding thickness3O4@TiO2/GO。
Embodiment 2Fe3O4@TiO2/ GO the composite photocatalytic degradation to methyl orange: Fe3O4@TiO2/ GO composite
Preparation method is with embodiment 1.10mg had different TiO2The Fe of cladding thickness3O4@TiO2/ GO material is added separately to 2mL 2
×10-5In the methyl orange solution of mol/L, under the conditions of lucifuge, first react 30min reach adsorption equilibrium, start ultraviolet light afterwards
According to, every sampling in 10 minutes.By the concentration of methyl orange in UV spectrophotometer measuring solution, obtain clearance with light application time
Change curve, utilize First-order kinetics equation formula matching degradation curve, obtain the speed constant of photocatalytic degradation, and compare
More different TiO2The cladding thickness impact on photocatalysis efficiency.
Claims (4)
1. composite photocatalyst material and preparation method thereof, it comprises the steps of:
(1) synthesis Fe3O4: by 1.350g Iron(III) chloride hexahydrate (FeCl3·6H2O), 3.854g ammonium acetate (CH3COONH4)、
0.4557g sodium citrate (C6H5Na3O7) it is dissolved in 70mL ethylene glycol ((CH2OH)2) in solution, 170 DEG C of oil baths under electric stirring
Middle reaction 1h forms dark solution, is proceeded in politef reactor afterwards, reacts 16h, be cooled at keeping 200 DEG C
After room temperature, after black solid separates with Magnet and uses washes of absolute alcohol 5 times, vacuum drying at 50 DEG C, obtain product Fe3O4；
(2) Fe that synthesis APTMS modifies3O4: the Fe that will obtain in 60mg step (1)3O4It is dissolved in 20mL anhydrous under ultrasonication
In dehydrated alcohol, add 75mL dehydrated alcohol and 5mL deionized water, after ultrasonic for mixed liquor 20min, be transferred to the three of 100mL
In mouth bottle, add 2mL 3-aminopropyl trimethoxy siloxane (APTMS) solution under electric stirring, by mixed liquor water-bath 60 DEG C
Lower reaction 7h, with Magnet separation product and with after washes of absolute alcohol 5 times, obtains the Fe that APTMS modifies3O4；
(3) the different TiO of synthesis2The Fe of thickness3O4@TiO2: butyl titanate (TBOT) is dissolved in 2mL dehydrated alcohol, electronic
It is added dropwise over Fe under stirring3O4In dispersion liquid, after reaction 30min, add 15mg cetyl trimethylammonium bromide (CTAB), continue
Continuous reaction 30min, with Magnet separation product and with after washes of absolute alcohol 5 times, vacuum drying at 50 DEG C, obtain product difference
TiO2The Fe of cladding thickness3O4@TiO2；
(4) synthesis Fe3O4@TiO2/ GO material: the Fe that will obtain in 40mg step (3)3O4@TiO2Material adds GO solution, electronic
React 30min under stirring, mixed liquor is transferred in politef reactor, at 180 DEG C, react 18h, after being cooled to room temperature,
Separate with Magnet and use washes of absolute alcohol 5 times, vacuum drying at 50 DEG C, obtain product Fe3O4@TiO2/GO。
2. a kind of composite photocatalyst material as claimed in claim 1 and preparation method thereof, in step (3), TiO2Presoma TBOT
Dosage be 0.05,0.1,0.25,0.5,1,2mL.
3. a kind of composite photocatalyst material as claimed in claim 1 and preparation method thereof, in step (3), Fe3O4Dispersion liquid
Compound method is: the Fe modified by APTMS3O4In being scattered in the anhydrous dehydrated alcohol of 80mL and nitrile volume ratio being the solution of 3:1,
Add 0.5mL ammonia (NH3·H2O) mix homogeneously.
4. a kind of composite photocatalyst material as claimed in claim 1 and preparation method thereof, in step (4), the preparation of GO solution
Method is: the GO that 30mg Hummers method prepares is dissolved in ultrasonic 1.5h in 50mL deionized water, obtains GO solution.
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