CN107115855A - Controllable graphene composite titanium dioxide mesoporous single crystals mixture of a kind of charge migration and preparation method thereof - Google Patents
Controllable graphene composite titanium dioxide mesoporous single crystals mixture of a kind of charge migration and preparation method thereof Download PDFInfo
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- CN107115855A CN107115855A CN201710271466.9A CN201710271466A CN107115855A CN 107115855 A CN107115855 A CN 107115855A CN 201710271466 A CN201710271466 A CN 201710271466A CN 107115855 A CN107115855 A CN 107115855A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 218
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 156
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 99
- 239000013078 crystal Substances 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 238000013508 migration Methods 0.000 title claims abstract description 15
- 230000005012 migration Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 25
- 210000004271 bone marrow stromal cell Anatomy 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000007787 solid Substances 0.000 claims abstract description 42
- 238000012946 outsourcing Methods 0.000 claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 claims abstract description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 5
- 235000010215 titanium dioxide Nutrition 0.000 claims description 96
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 62
- 239000008188 pellet Substances 0.000 claims description 52
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 52
- 239000007788 liquid Substances 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 24
- 238000000703 high-speed centrifugation Methods 0.000 claims description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 20
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 20
- 239000011258 core-shell material Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 230000005587 bubbling Effects 0.000 claims description 16
- 239000003292 glue Substances 0.000 claims description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 13
- 150000001336 alkenes Chemical class 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000005530 etching Methods 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 239000004575 stone Substances 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 238000011010 flushing procedure Methods 0.000 claims description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000011324 bead Substances 0.000 claims description 4
- 238000006303 photolysis reaction Methods 0.000 claims description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000003344 environmental pollutant Substances 0.000 claims description 3
- 231100000719 pollutant Toxicity 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims 2
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- 238000007539 photo-oxidation reaction Methods 0.000 abstract description 8
- 230000009467 reduction Effects 0.000 abstract description 7
- 238000006722 reduction reaction Methods 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 230000002468 redox effect Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000007540 photo-reduction reaction Methods 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 229910052681 coesite Inorganic materials 0.000 description 10
- 229910052906 cristobalite Inorganic materials 0.000 description 10
- 229910052682 stishovite Inorganic materials 0.000 description 10
- 229910052905 tridymite Inorganic materials 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 4
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 4
- 239000008236 heating water Substances 0.000 description 4
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000009827 uniform distribution Methods 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/39—
-
- B01J35/647—
-
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
- C02F2101/345—Phenols
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention relates to material, a kind of controllable graphene composite titanium dioxide mesoporous single crystals mixture of charge migration is mixed by graphene composite mesopore titanium dioxide single crystalline and graphene outsourcing mesoporous titanium dioxide monocrystalline.Graphene composite mesopore titanium dioxide single crystalline outer surface of the present invention is oxide side, and Pyrogentisinic Acid is demonstrated by the effect of good photooxidative degradation, but the poor effect of photocatalytic water.On the contrary, the reduction face of graphene outsourcing mesoporous titanium dioxide monocrystalline has good photo-reduction water to prepare H2Performance, but the poor effect in photooxidation phenol.It is interesting that by solid fluorescence, immediate current and testing impedance, show that GR MSCs and MSCs GR have similar band gap and chemical property, but they also have antipodal surface and photocatalysis performance.GR MSCs are good at photooxidation and MSCs@GR effects in the reduction of light system are more preferable.Obtain with the controllable mesoporous titanium dioxide monocrystalline of redox property.
Description
Technical field
The present invention relates to Material Field, and in particular to nano material.
Background technology
Medium pore of titania monocrystalline (TiO2- MSCs) there is larger surface area, perfect monocrystalline, active face and electron transfer
Rate.Monocrystalline and nanocrystal TiO2Compare, MSCs substantially has higher electric conductivity and electron mobility.However, TiO2-
MSCs is in terms of light degradation organic pollution and photocatalytic water not as the efficiency high in imagination.TiO2Although-MSCs can provide me
Desired size surface, large-scale electrical communication and structural integrity, but for the mesoporous single crystals of micron-scale,
In TiO2The high recombination rate of the electron hole on inside-MSCs and surface determines their relatively low photocatalytic activities.
The content of the invention
It is an object of the present invention to provide a kind of controllable graphene composite titanium dioxide mesoporous single crystals mixing of charge migration
Thing, to solve the above problems.
The present invention also aims to there is provided the preparation method of graphene composite titanium dioxide mesoporous single crystals mixture, with
Solve the above problems.
It is an object of the present invention to provide the controlling party of graphene composite titanium dioxide mesoporous single crystals mixture charge migration
Method, to solve the above problems.
Technical problem solved by the invention can be realized using following technical scheme：
The controllable graphene composite titanium dioxide mesoporous single crystals mixture of a kind of charge migration, it is characterised in that by graphite
Alkene composite mesopore titanium dioxide single crystalline and graphene outsourcing mesoporous titanium dioxide monocrystalline are mixed.
Graphene is used as the modifying agent of catalyst so that electronics and hole are entered as a preferable electronics capturing agent
Row separation.Graphene is always used as preparing the holder of heterojunction semiconductor, and graphene has outstanding electronic conductivity energy.This
Patent graphene composite mesopore titanium dioxide single crystalline outer surface is oxide side, and Pyrogentisinic Acid is demonstrated by the effect of good photooxidative degradation
Really, but the poor effect of photocatalytic water.On the contrary, there is good light in the reduction face of graphene outsourcing mesoporous titanium dioxide monocrystalline also
Raw water prepares H2Performance, but the poor effect in photooxidation phenol.It is interesting that passing through solid fluorescence, immediate current and resistance
Anti- test, shows that GR-MSCs and MSCs GR have similar band gap and chemical property, but they also have antipodal
Surface and photocatalysis performance.GR-MSCs is good at photooxidation and MSCs@GR effects in the reduction of light system are more preferable.Had
The controllable mesoporous titanium dioxide monocrystalline of redox property.
The preparation method of graphene composite titanium dioxide mesoporous single crystals mixture, it is characterised in that comprise the following steps：
1) graphene is implanted in MSCs by forming Ti-O-C keys, and the graphene composite mesopore two of sandwich structure is made
Aoxidize ti single crystal；
2) graphene is wrapped in the surface of meso-porous titanium dioxide ti single crystal by ultrasonic bubbling method, prepares the stone of core shell structure
Black alkene outsourcing mesoporous titanium dioxide monocrystalline；
3) graphene composite mesopore titanium dioxide single crystalline is mixed with graphene outsourcing mesoporous titanium dioxide monocrystalline, stone is made
Black alkene composite titanium dioxide mesoporous single crystals mixture.
Step 1) in, 30nm-60nm silicon oxide pellets that can be to embed graphene preferably embed graphite as template
The 50nm silicon oxide pellets templates of alkene, the 50nm silicon oxide pellets templates of embedded graphene prepare sandwich by hydro-thermal method
The graphene composite mesopore titanium dioxide single crystalline of structure.
Step 2) in, can be using 30nm-60nm silicon oxide pellets as template, preferred 50nm silicon oxide pellets mould
Plate, meso-porous titanium dioxide ti single crystal is prepared by hydro-thermal method, recycles ultrasonic Bubbling method that graphene is wrapped in into mesoporous TiO 2
The surface of monocrystalline, is prepared for the compound of core shell structure, graphene outsourcing mesoporous titanium dioxide monocrystalline.
The 50nm silicon oxide pellets can pass throughMethod is synthesized.Can be specifically to prepare mixed liquor A：By second
Alcoholic solution, water, ammoniacal liquor are 349.2 by volume：28.8：4 mixing, are made mixed liquor A；Prepare mixed liquid B：By positive silicic acid second
Ester, ethanol solution by volume 18：182 mixing, are made mixed liquid B；Mixed liquor A and mixed liquid B are mixed, used by ethanol solution
Amount 349.2：182 ratio mixing, is made mixed liquor C；By mixed liquor C, magnetic agitation obtains suspension, i.e. silicon ball at room temperature
Glue.
It is preferred that, the ammonia spirit of 167.2mL ethanol solution, 28.8mL water and 4mL is mixed, mixed solution exists
1min is stirred at room temperature.Meanwhile, 18.0mL tetraethyl orthosilicate (TEOS) is blended in 182.0mL ethanol solution at room temperature
In.TEOS solution is added in above-mentioned mixed solution.Magnetic agitation 12h obtains silicon ball glue to precursor liquid at room temperature.
The preparation method of the 50nm silicon oxide pellets templates of embedded graphene：
By silicon ball glue and 1.0mg/mL graphene oxide solution by volume 200：40 mixing, by mixture ultrasonic wave
Afterwards, colloidal liquid is obtained；Colloidal liquid obtains navy blue solids through high speed centrifugation；By navy blue solids vacuum drying
Afterwards, burnt with vacuum tube furnace, obtain silicon oxide pellets template；
By silicon oxide pellets template in TiCl4Soak, then with deionized water rinsing, after flushing, first carry out in solution
Vacuum drying, is then burnt with vacuum tube furnace, obtains the 50nm silicon oxide pellets templates of embedded graphene.
It is preferred that, 200.0mL silicon ball glue and 40.0mL graphene oxide solution (1.0mg/mL) are mixed, will be mixed
After thing ultrasound 12h, khaki homogeneous colloidal liquid is obtained.Colloidal liquid obtains deep by high speed centrifugation (12500R/min)
The solid of blueness.The solid of acquisition is dried in vacuo 12h under the conditions of 60 DEG C, then with vacuum tube furnace, and 2h is burnt under the conditions of 500 DEG C
Obtain graphene silicon oxide pellets template.It is GR-SiO by the silicon oxide pellets template representation after graphene modified2.Take
7.0g silicon oxide pellets template, i.e. GR-SiO2, it is immersed in 30mL TiCl4In solution (0.05M), in 70 DEG C of conditions
Lower processing 1h, it is then multiple with deionized water rinsing.Solid is dried in vacuo 12h under the conditions of 60 DEG C.Dried template exists
In vacuum tube furnace 2h is burnt under the conditions of 500 DEG C.The 50nm silicon oxide pellets template representation of embedded graphene is GR-Ti-SiO2。
Step 1) in, the method that hydro-thermal method prepares the graphene composite mesopore titanium dioxide single crystalline of sandwich structure is：
First, by water, HCl, solution of tetrabutyl titanate, hydrofluoric acid, the 50nm silicon oxide pellets templates of graphene are embedded
Mixing；Then, mixed solution is placed in polytetrafluoroethylene (PTFE) stainless steel autoclave, 12h is handled under the conditions of 453K, consolidate
Body；Then, by NaOH solution by the SiO on solid2Template is etched away, after etching, and high speed centrifugation obtains graphene and is combined
Meso-porous titanium dioxide ti single crystal.
It is preferred that, at room temperature, 14.0mL water and 14.0mL HCl are mixed.The butyl titanate for sequentially adding 0.4mL is molten
The hydrofluoric acid (HF) of liquid (TBOT) and 20 μ L, and 10min is stirred respectively.0.4g GR-Ti-SiO is added in the solution2Mould
Plate, is then placed in polytetrafluoroethylene (PTFE) stainless steel autoclave, 12h is handled under the conditions of 453K.The solid of acquisition passes through NaOH
Solution (2M), 80 DEG C of condition heating water bath 1h etch away SiO2Template.After etching, high speed centrifugation obtains product, is expressed as
GR-MSCs.Product can be washed repeatedly with water and ethanol, 12h then be dried at 60 DEG C, to improve cleanliness factor.
The preparation method of 50nm silicon oxide pellets templates：
By silicon ball glue and 1.0mg/mL graphene oxide solution by volume 200：40 mixing, by mixture ultrasonic wave
Afterwards, colloidal liquid is obtained；Colloidal liquid obtains light blue translucent solids through high speed centrifugation；Will be light blue translucent solid
After body thing vacuum drying, burnt with vacuum tube furnace, obtain silicon oxide pellets template；
By silicon oxide pellets template in TiCl4Soak, then with deionized water rinsing, after flushing, first carry out in solution
Vacuum drying, is then burnt with vacuum tube furnace, obtains the 50nm silicon oxide pellets templates of embedded graphene.
It is preferred that, 200.0mL silicon ball glue and 40.0mL graphene oxide solution (1.0mg/mL) are mixed, will be mixed
After thing ultrasound 12h, khaki homogeneous colloidal liquid is obtained.Colloidal liquid obtains shallow by high speed centrifugation (12500r.p.m)
The solid of Blue-Color Semitransparent.The solid of acquisition is dried in vacuo 12h under the conditions of 60 DEG C, then with vacuum tube furnace, 500 DEG C of conditions
Lower burning 2h obtains sol-gel.It is SiO by the template representation after graphene modified2.7.0g sol-gel is immersed in 30mL
TiCl4In solution (0.05M), 1h is handled under the conditions of 70 DEG C, it is then multiple with deionized water rinsing.By solid in 60 DEG C of bars
12h is dried in vacuo under part.Dried template burns 2h in vacuum tube furnace under the conditions of 500 DEG C.It is expressed as Ti-SiO2。
The preparation method of meso-porous titanium dioxide ti single crystal is：By water, HCl, solution of tetrabutyl titanate, hydrofluoric acid, 50nm dioxies
SiClx bead template is mixed；Then, mixed solution is placed in polytetrafluoroethylene (PTFE) stainless steel autoclave, located under the conditions of 453K
12h is managed, solid is obtained；Then, by NaOH solution by the SiO on solid2Template is etched away, after etching, and high speed centrifugation is obtained
Obtain meso-porous titanium dioxide ti single crystal.
It is preferred that, at room temperature, 14.0mL water and 14.0mL HCl are mixed.Sequentially add 0.4mL butyl titanate
(TBOT) and 20.0 μ L hydrofluoric acid (HF), and stir 10min respectively.0.4g Ti-SiO is added in the solution2Template, so
After be placed in polytetrafluoroethylene (PTFE) stainless steel autoclave, 12h is handled under the conditions of 453K.The solid of acquisition passes through NaOH solution
(0.5M), 40 DEG C of condition heating water bath 1h etch away SiO2Template.After etching, high speed centrifugation obtains product, with water and second
Alcohol washing is multiple, and 12h is then dried at 60 DEG C, TiO is expressed as2 MSCs。
The method that graphene is wrapped in the surface of meso-porous titanium dioxide ti single crystal by ultrasonic Bubbling method, by mesoporous TiO 2 list
Brilliant, graphene oxide is placed in water, then by ultrasonic bubbling in ultrasonic wave direction solution for a period of time after, be centrifuged,
Obtain graphene outsourcing mesoporous titanium dioxide monocrystalline.
It is preferred that, by 0.1g blank TiO2MSCs is placed in 50mL water, and 10mL graphite oxide is added in above-mentioned solution
Alkene (1.0mg/mL).Mixed solution is continued 1h and disperseed by ultrasound and bubbling.Product is collected by centrifugation, so
It is freeze-dried afterwards.The graphene of core shell structure is modified MSCs and is expressed as MSCs@GR.
The control method of graphene composite titanium dioxide mesoporous single crystals mixture charge migration, it is characterised in that control stone
Black alkene is present in the diverse location of mesoporous single crystals, so as to control the migration path and enrichment positions of light induced electron.By controlling electricity
Lotus migrates, and can promote the separation of electron hole, improves photocatalytic activity, obtains oxidized surface and goes back controllable mesoporous of original surface
Monocrystalline, and its application in degrade colourless pollutant phenol and photolysis water hydrogen.
Graphene is implanted in MSCs by forming Ti-O-C keys, and the graphene composite mesopore dioxy of sandwich structure is made
Change the graphene in ti single crystal, sandwich structure as electronics capturing agent, realize electronics inside meso-porous titanium dioxide ti single crystal
Directional transmissions, while hole is concentrated to (110) surface of meso-porous titanium dioxide ti single crystal, so as to reduce electronics and hole
Combined efficiency；
In addition, graphene is wrapped in the surface of meso-porous titanium dioxide ti single crystal by ultrasonic bubbling method, core shell structure is prepared
Graphene outsourcing mesoporous titanium dioxide monocrystalline, electronics can be attracted to shell by Ti-C keys, prevented by surface parcel graphene
Electronics and hole are in the compound of surface；
So as to realize that graphene is present in the control of the diverse location of mesoporous single crystals.
The advantage of the present invention is embodied in：
1) the preparation method building-up process that the present invention is provided is simple, simple operation, and yield is high, and environmental pollution is few.
2) composite photo-catalyst prepared by the present invention, light induced electron and hole can be efficiently separated, and can increase substantially light
Catalytic efficiency.
3) sandwich structure and the graphene dioxide composite ti single crystal of core shell structure that prepared by the present invention are in simulated solar
Degradation of Phenol and reductive water hydrogen producing are distinguished under light has higher activity.
Brief description of the drawings
Fig. 1 is the field emission scanning electron microscope figure for the moieties mentioned in the present invention；
The solid powder fluorescence spectrogram that Fig. 2 excites for the moieties mentioned in the present invention at 350nm；
Fig. 3 is TiO2The photocatalytic activity of MSCs, GR-MSCs and MSCs GR degradation of phenol under identical illumination condition
Curve map.
Embodiment
In order that the technical means, the inventive features, the objects and the advantages of the present invention are easy to understand, tie below
Conjunction, which is specifically illustrating, is expanded on further the present invention.
The controllable graphene composite titanium dioxide mesoporous single crystals mixture of a kind of charge migration, it is characterised in that by graphite
Alkene composite mesopore titanium dioxide single crystalline and graphene outsourcing mesoporous titanium dioxide monocrystalline are mixed.
Graphene is used as the modifying agent of catalyst so that electronics and hole are entered as a preferable electronics capturing agent
Row separation.Graphene is always used as preparing the holder of heterojunction semiconductor, and graphene has outstanding electronic conductivity energy.This
Patent graphene composite mesopore titanium dioxide single crystalline outer surface is oxide side, and Pyrogentisinic Acid is demonstrated by the effect of good photooxidative degradation
Really, but the poor effect of photocatalytic water.On the contrary, there is good light in the reduction face of graphene outsourcing mesoporous titanium dioxide monocrystalline also
Raw water prepares H2Performance, but the poor effect in photooxidation phenol.It is interesting that passing through solid fluorescence, immediate current and resistance
Anti- test, shows that GR-MSCs and MSCs GR have similar band gap and chemical property, but they also have antipodal
Surface and photocatalysis performance.GR-MSCs is good at photooxidation and MSCs@GR effects in the reduction of light system are more preferable.Had
The controllable mesoporous titanium dioxide monocrystalline of redox property.
The preparation method of graphene composite titanium dioxide mesoporous single crystals mixture, it is characterised in that comprise the following steps：
1) graphene is implanted in MSCs by forming Ti-O-C keys, and the graphene composite mesopore two of sandwich structure is made
Aoxidize ti single crystal；
2) graphene is wrapped in the surface of meso-porous titanium dioxide ti single crystal by ultrasonic bubbling method, prepares the stone of core shell structure
Black alkene outsourcing mesoporous titanium dioxide monocrystalline；
3) graphene composite mesopore titanium dioxide single crystalline is mixed with graphene outsourcing mesoporous titanium dioxide monocrystalline, stone is made
Black alkene composite titanium dioxide mesoporous single crystals mixture.
Step 1) in, 30nm-60nm silicon oxide pellets that can be to embed graphene preferably embed graphite as template
The 50nm silicon oxide pellets templates of alkene, the 50nm silicon oxide pellets templates of embedded graphene prepare sandwich by hydro-thermal method
The graphene composite mesopore titanium dioxide single crystalline of structure.
Step 2) in, can be using 30nm-60nm silicon oxide pellets as template, preferred 50nm silicon oxide pellets mould
Plate, meso-porous titanium dioxide ti single crystal is prepared by hydro-thermal method, recycles ultrasonic Bubbling method that graphene is wrapped in into mesoporous TiO 2
The surface of monocrystalline, is prepared for the compound of core shell structure, graphene outsourcing mesoporous titanium dioxide monocrystalline.
The 50nm silicon oxide pellets can pass throughMethod is synthesized.Can be specifically to prepare mixed liquor A：By second
Alcoholic solution, water, ammoniacal liquor are 349.2 by volume：28.8：4 mixing, are made mixed liquor A；Prepare mixed liquid B：By positive silicic acid second
Ester, ethanol solution by volume 18：182 mixing, are made mixed liquid B；Mixed liquor A and mixed liquid B are mixed, used by ethanol solution
Amount 349.2：182 ratio mixing, is made mixed liquor C；By mixed liquor C, magnetic agitation obtains suspension, i.e. silicon ball at room temperature
Glue.
It is preferred that, the ammonia spirit of 167.2mL ethanol solution, 28.8mL water and 4mL is mixed, mixed solution exists
1min is stirred at room temperature.Meanwhile, 18.0mL tetraethyl orthosilicate (TEOS) is blended in 182.0mL ethanol solution at room temperature
In.TEOS solution is added in above-mentioned mixed solution.Magnetic agitation 12h obtains silicon ball glue to precursor liquid at room temperature.
The preparation method of the 50nm silicon oxide pellets templates of embedded graphene：
By silicon ball glue and 1.0mg/mL graphene oxide solution by volume 200：40 mixing, by mixture ultrasonic wave
Afterwards, colloidal liquid is obtained；Colloidal liquid obtains navy blue solids through high speed centrifugation；By navy blue solids vacuum drying
Afterwards, burnt with vacuum tube furnace, obtain silicon oxide pellets template；
By silicon oxide pellets template in TiCl4Soak, then with deionized water rinsing, after flushing, first carry out in solution
Vacuum drying, is then burnt with vacuum tube furnace, obtains the 50nm silicon oxide pellets templates of embedded graphene.
It is preferred that, 200.0mL silicon ball glue and 40.0mL graphene oxide solution (1.0mg/mL) are mixed, will be mixed
After thing ultrasound 12h, khaki homogeneous colloidal liquid is obtained.Colloidal liquid obtains deep by high speed centrifugation (12500R/min)
The solid of blueness.The solid of acquisition is dried in vacuo 12h under the conditions of 60 DEG C, then with vacuum tube furnace, and 2h is burnt under the conditions of 500 DEG C
Obtain graphene silicon oxide pellets template.It is GR-SiO by the silicon oxide pellets template representation after graphene modified2.Take
7.0g silicon oxide pellets template, i.e. GR-SiO2, it is immersed in 30mL TiCl4In solution (0.05M), in 70 DEG C of conditions
Lower processing 1h, it is then multiple with deionized water rinsing.Solid is dried in vacuo 12h under the conditions of 60 DEG C.Dried template exists
In vacuum tube furnace 2h is burnt under the conditions of 500 DEG C.The 50nm silicon oxide pellets template representation of embedded graphene is GR-Ti-SiO2。
In step 1, the method that hydro-thermal method prepares the graphene composite mesopore titanium dioxide single crystalline of sandwich structure is：
First, by water, HCl, solution of tetrabutyl titanate, hydrofluoric acid, the 50nm silicon oxide pellets templates of embedded graphene
Mixing；Then, mixed solution is placed in polytetrafluoroethylene (PTFE) stainless steel autoclave, 12h is handled under the conditions of 453K, consolidate
Body；Then, by NaOH solution by the SiO on solid2Template is etched away, after etching, and high speed centrifugation obtains graphene and is combined
Meso-porous titanium dioxide ti single crystal.
It is preferred that, at room temperature, 14.0mL water and 14.0mL HCl are mixed.The butyl titanate for sequentially adding 0.4mL is molten
The hydrofluoric acid (HF) of liquid (TBOT) and 20 μ L, and 10min is stirred respectively.0.4g GR-Ti-SiO is added in the solution2Mould
Plate, is then placed in polytetrafluoroethylene (PTFE) stainless steel autoclave, 12h is handled under the conditions of 453K.The solid of acquisition passes through NaOH
Solution (2M), 80 DEG C of condition heating water bath 1h etch away SiO2Template.After etching, high speed centrifugation obtains product, is expressed as
GR-MSCs.Product can be washed repeatedly with water and ethanol, 12h then be dried at 60 DEG C, to improve cleanliness factor.
The preparation method of 50nm silicon oxide pellets templates：
By silicon ball glue and 1.0mg/mL graphene oxide solution by volume 200：40 mixing, by mixture ultrasonic wave
Afterwards, colloidal liquid is obtained；Colloidal liquid obtains light blue translucent solids through high speed centrifugation；Will be light blue translucent solid
After body thing vacuum drying, burnt with vacuum tube furnace, obtain silicon oxide pellets template；
By silicon oxide pellets template in TiCl4Soak, then with deionized water rinsing, after flushing, first carry out in solution
Vacuum drying, is then burnt with vacuum tube furnace, obtains the 50nm silicon oxide pellets templates of embedded graphene.
It is preferred that, 200.0mL silicon ball glue and 40.0mL graphene oxide solution (1.0mg/mL) are mixed, will be mixed
After thing ultrasound 12h, khaki homogeneous colloidal liquid is obtained.Colloidal liquid obtains shallow by high speed centrifugation (12500r.p.m)
The solid of Blue-Color Semitransparent.The solid of acquisition is dried in vacuo 12h under the conditions of 60 DEG C, then with vacuum tube furnace, 500 DEG C of conditions
Lower burning 2h obtains sol-gel.It is SiO by the template representation after graphene modified2.7.0g sol-gel is immersed in 30mL
TiCl4In solution (0.05M), 1h is handled under the conditions of 70 DEG C, it is then multiple with deionized water rinsing.By solid in 60 DEG C of bars
12h is dried in vacuo under part.Dried template burns 2h in vacuum tube furnace under the conditions of 500 DEG C.It is expressed as Ti-SiO2。
The preparation method of meso-porous titanium dioxide ti single crystal is：By water, HCl, solution of tetrabutyl titanate, hydrofluoric acid, 50nm dioxies
SiClx bead template is mixed；Then, mixed solution is placed in polytetrafluoroethylene (PTFE) stainless steel autoclave, located under the conditions of 453K
12h is managed, solid is obtained；Then, by NaOH solution by the SiO on solid2Template is etched away, after etching, and high speed centrifugation is obtained
Obtain meso-porous titanium dioxide ti single crystal.
It is preferred that, at room temperature, 14.0mL water and 14.0mL HCl are mixed.Sequentially add 0.4mL butyl titanate
(TBOT) and 20.0 μ L hydrofluoric acid (HF), and stir 10min respectively.0.4g Ti-SiO is added in the solution2Template, so
After be placed in polytetrafluoroethylene (PTFE) stainless steel autoclave, 12h is handled under the conditions of 453K.The solid of acquisition passes through NaOH solution
(0.5M), 40 DEG C of condition heating water bath 1h etch away SiO2Template.After etching, high speed centrifugation obtains product, with water and second
Alcohol washing is multiple, and 12h is then dried at 60 DEG C, TiO is expressed as2 MSCs。
The method that graphene is wrapped in the surface of meso-porous titanium dioxide ti single crystal by ultrasonic Bubbling method, by mesoporous TiO 2 list
Brilliant, graphene oxide is placed in water, then by ultrasonic bubbling in ultrasonic wave direction solution for a period of time after, be centrifuged,
Obtain graphene outsourcing mesoporous titanium dioxide monocrystalline.
It is preferred that, by 0.1g blank TiO2MSCs is placed in 50mL water, and 10mL graphite oxide is added in above-mentioned solution
Alkene (1.0mg/mL).Mixed solution is continued 1h and disperseed by ultrasound and bubbling.Product is collected by centrifugation, so
It is freeze-dried afterwards.The graphene of core shell structure is modified MSCs and is expressed as MSCs@GR.
The control method of graphene composite titanium dioxide mesoporous single crystals mixture charge migration, it is characterised in that control stone
Black alkene is present in the diverse location of mesoporous single crystals, so as to control the migration path and enrichment positions of light induced electron.By controlling electricity
Lotus migrates, and can promote the separation of electron hole, improves photocatalytic activity, obtains oxidized surface and goes back controllable mesoporous of original surface
Monocrystalline, and its application in degrade colourless pollutant phenol and photolysis water hydrogen.
Graphene is implanted in MSCs by forming Ti-O-C keys, and the graphene composite mesopore dioxy of sandwich structure is made
Change the graphene in ti single crystal, sandwich structure as electronics capturing agent, realize electronics inside meso-porous titanium dioxide ti single crystal
Directional transmissions, while hole is concentrated to (110) surface of meso-porous titanium dioxide ti single crystal, so as to reduce electronics and hole
Combined efficiency；
In addition, graphene is wrapped in the surface of meso-porous titanium dioxide ti single crystal by ultrasonic bubbling method, core shell structure is prepared
Graphene outsourcing mesoporous titanium dioxide monocrystalline, electronics can be attracted to shell by Ti-C keys, prevented by surface parcel graphene
Electronics and hole are in the compound of surface；
So as to realize that graphene is present in the control of the diverse location of mesoporous single crystals.
The advantage of the present invention is embodied in：
1) the preparation method building-up process that the present invention is provided is simple, simple operation, and yield is high, and environmental pollution is few.
2) composite photo-catalyst prepared by the present invention, light induced electron and hole can be efficiently separated, and can increase substantially light
Catalytic efficiency.
3) sandwich structure and the graphene dioxide composite ti single crystal of core shell structure that prepared by the present invention are in simulated solar
Degradation of Phenol and reductive water hydrogen producing are distinguished under light has higher activity.
The active investigation method for the photocatalytic degradation simulating pollution thing that the present invention is provided is as follows：
100mL quartz light pipe is taken, photochemical catalyst (0.5g) is weighed, 50mL phenol solution (10mg/l) is added.Mixing
Thing stirs 60min in the dark, and this is to reach absorption-parsing balance.With the 300W for having AM1.5 air quality wave filters
Xe lamps take out analysis sample from mixture, centrifuge immediately after, pass through 0.22 μ as solar source, given time interval
M millipore filter is filtered to remove photochemical catalyst, and filtrate is carried out by CTO-10ASVP high speed liquid chromatographies instrument
Analysis.
The active investigation method for the photo catalytic reduction aquatic products hydrogen that the present invention is provided is as follows：
Photocatalysis prepares H2Experiment carried out in a sealed circulatory system.0.10g sample is suspended in
(1mL H is included in 40mL 25% methanol aqueous solution2PtCl6, 1g/L) and carry out magnetic agitation.Then above-mentioned solution is in 300W
120min is irradiated under Xe lamps (there are the air quality wave filters of AM 1.5), this has resulted in Pt nano materials in catalyst table
The load in face.After system exhaust, light-catalyzed reaction is proceeded by, and product passes through gas-chromatography (Techcomp GC-
7890II) analyzed, apparatus preparation has thermal conductivity detector (TCD) (TCD).
Fig. 1 is that shown in case study on implementation 1-5 field emission scanning electron microscopes, figure a is mesoporous titanium dioxide monocrystalline (TiO2MSCs),
It is that graphene embeds mesoporous titanium dioxide monocrystalline (GR-MSCs) to scheme d, and figure g is graphene outsourcing mesoporous titanium dioxide monocrystalline
(MSCs@GR).For the TiO of different graphene modifieds2MSCs FESEM spectrograms, pure TiO2MSCs has one perfectly
Cube shaped monocrystalline, the appearance exposure of monocrystalline has (110) crystal face and orderly meso-hole structure (Fig. 1-a).Electricity is scanned from Flied emission
Mirror (FESEM) figure can be drawn, be embedded into TiO in graphene2After MSCs, MSCs size is reduced to from 500-700nm
400-600nm, this is due to that the introducing of graphene in lattice can suppress TiO2The growth (Fig. 1 d, g) of monocrystalline.Large-sized stratiform
The disappearance of graphene indicates most graphene and had been embedded in MSCs.With there is the pure of smooth surface
TiO2MSCs compares, and GR-MSCs edge is a bit coarse because the GR-MSCs of sandwich structure its exposure outside
The graphene in portion has some folds.Figure g is the MSCs@GR of core shell structure FESEM spectrograms, and it shows that graphene is wrapped in
TiO2MSCs surface.The graphene of big layer makes MSCs have a small amount of aggregation, is gathered on graphene platelet
TiO2Micro- single crystalline uniform distribution.The graphene that the FESEM spectrograms of MSCs@GR amplifications indicate thin layer is wrapped in MSC surface, production
Core shell structure is given birth to.Shown in transmission electron microscope, figure b, c are mesoporous titanium dioxide monocrystalline (TiO2MSCs), figure e, f is three
Mingzhi's structure graphite alkene embeds mesoporous titanium dioxide monocrystalline (GR-MSCs), and figure h, i are core shell structure graphene outsourcing titanium dioxide
Mesoporous single crystals (MSCs@GR).It is corresponding structural model wherein to embed figure c, f, i.As seen from the figure, the TiO of blank2 MSCs
There is an equally distributed meso-hole structure, hole size is about 40nm.Further with regards to micropore, there are similar duct, size here
In 10-20nm, spread in whole framework, tridimensional network (Fig. 1-b) is formd by whole framework, we can understand
The border for seeing MSCs be relative smooth (Fig. 1-c).When graphene is embedded into TiO in growth seed crystal process2In MSCs
During portion, MSC size can reduce (Fig. 1-e), while its border becomes somewhat coarse, this is due to exposed to sandwich
(Fig. 1-f) caused by the graphene of structural outer.Different with GR-MSCs, the MSCs@GR of core shell structure are shown as in TiO2
MSCs outer surface be uniformly wrapped in thin layer graphene (Fig. 1-h, i).By scheming structural model shown in c, f, i, we can
So that the TiO of graphene modified is more clearly understood2MSCs structure.
Fig. 2 be the sample prepared by case study on implementation 1-5 excited at 350nm solid powder fluorescence (PL) spectrogram (Fig. 2-
A), electrolyte is 0.5M Na2SO4The aqueous solution, light source for 300W Xe lamp simulated solar irradiations be irradiated under the conditions of, it is different
The response diagram (Fig. 2-b) of the instantaneous photoelectric current of catalyst, and the electrochemical impedance (EIS) of catalyst change spectrogram (2.0mM
K3[Fe(CN)6] and 0.5M KCl mixed solution) (Fig. 2-c).
According to the TiO of the graphene modified to different shape2MSC structural analysis, either GR-MSCs are either
MSCs GR suffer from perfect electric transmission efficiency, and this is attributed to the graphene inserted in MSC, and graphene has very good
Electrical conductivity.The TiO of all graphene modifieds of the PL as shown by data of solid catalyst2MSC and blank TiO2MSC is compared
Compared with PL signals suffer from significantly reducing (Fig. 2-a), and the PL signal instruction catalyst GR-MSCs and MSCs@GR of reduction have relatively low
Electron-hole recombination rate.Either graphene is covered in TiO2MSC surfaces are embedded in TiO2Inside MSC, it is all to light
The directional transmissions of raw electronics are highly beneficial, and can cause the probability of recombination in electronics and hole reduces.Mesoporous single crystals are less to compare surface
Product can limit the influence (GR-MSCs that particle size is produced in chemical property：32.05m2/g；MSCs@GR：37.98m2/
g).In addition, instantaneous photocurrent response, and EIS measurement results illustrate generation and the transmission effect of GR-MSCs and MSCs@GR electronics
Rate and the conductibility of electronics are very close, they are more preferable all than blank (Fig. 2-b, c).GR-MSCs current density and MSCs@
GR similar density, and compare TiO2MSC higher (Fig. 2-b).GR-MSCs impedance and MSCs GR are also very close, and
Than the TiO of blank2MSC and P25 lower (Fig. 2-c).What is interesting is blank TiO2 MSC impedance ratio business P25 is lower.This is
Because monocrystalline exposes some high surface energy amount picture (110) faces, its transmission to electronics is highly beneficial.GR-MSCs and MSCs@GR
Outstanding Electronic Performance means that they have outstanding photocatalysis performance.
Fig. 3 is case study on implementation 1, and sample TiO is obtained prepared by 32MSCs, GR-MSCs and MSCs@GR are in identical illumination
Under the conditions of degradation of phenol photocatalytic activity curve, figure b be TiO2The work of MSCs, GR-MSCs and MSCs@GR photolysis water hydrogen gas
Linearity curve.Although GR-MSCs and MSCs GR have the separation of close electric transmission efficiency and electron hole, have
Complete opposite photocatalytic activity.The GR-MSCs of sandwich structure Pyrogentisinic Acid's photooxidation have higher catalytic activity, but
Photochemical catalyzing prepare hydrogen catalytic activity it is relatively low (Fig. 3-a, b).On the contrary, the MSCs@GR of core shell structure are urged in light
Change decomposition water and prepare hydrogen with higher catalytic activity, but photooxidation phenol catalytic activity is relatively low.Under the conditions of lucifuge, institute
There is the absorption of catalyst Pyrogentisinic Acid all relatively low.GR-MSCs shows the highest photodegradation rate of Pyrogentisinic Acid under sunshine irradiation,
Meanwhile, MSCs@GR are demonstrated by best photochemical catalyzing performance in all catalyst.In summary, graphene is controlled
Position in meso-porous titanium dioxide ti single crystal can realize TiO2The selectivity performance of MSCs photocatalytic redox.Sanming City
Controlling the GR-MSCs of structure can have and only excellent photo-oxidative energy, and the GR-MSCs of core shell structure has and only outstanding
Photo-reduction performance, we have been successfully prepared the TiO in selective light redox face2Monocrystalline.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, for example originally
Invention can also be provided with scrim layer while provided with column, can also only set one layer of scrim layer etc., and these change and changed
Enter all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by appended claims and its equivalent
Define.
Claims (10)
1. the controllable graphene composite titanium dioxide mesoporous single crystals mixture of a kind of charge migration, it is characterised in that by graphene
Composite mesopore titanium dioxide single crystalline and graphene outsourcing mesoporous titanium dioxide monocrystalline are mixed.
2. the preparation method of graphene composite titanium dioxide mesoporous single crystals mixture, it is characterised in that comprise the following steps：
1) graphene is implanted in MSCs by forming Ti-O-C keys, and the graphene composite mesopore titanium dioxide of sandwich structure is made
Ti single crystal；
2) graphene is wrapped in the surface of meso-porous titanium dioxide ti single crystal by ultrasonic bubbling method, prepares the graphene of core shell structure
Outsourcing mesoporous titanium dioxide monocrystalline；
3) graphene composite mesopore titanium dioxide single crystalline is mixed with graphene outsourcing mesoporous titanium dioxide monocrystalline, graphene is made
Composite titanium dioxide mesoporous single crystals mixture.
3. the preparation method of graphene composite titanium dioxide mesoporous single crystals mixture according to claim 2, its feature exists
In：
Step 1) in, to embed the 50nm silicon oxide pellets templates of graphene, embed the 50nm silicon oxide pellets of graphene
Template prepares the graphene composite mesopore titanium dioxide single crystalline of sandwich structure by hydro-thermal method；
Step 2) in, with 50nm silicon oxide pellets templates, meso-porous titanium dioxide ti single crystal is prepared by hydro-thermal method, ultrasound is recycled
Graphene is wrapped in the surface of meso-porous titanium dioxide ti single crystal by Bubbling method, is prepared for the compound of core shell structure, graphene outsourcing
Mesoporous titanium dioxide monocrystalline.
4. the preparation method of graphene composite titanium dioxide mesoporous single crystals mixture according to claim 3, its feature exists
In：For making the 50nm silicon oxide pellets template of embedded graphene or the 50nm titanium dioxides of 50nm silicon oxide pellets templates
Silicon bead is made by following methods：First, mixed liquor A is prepared：It is 349.2 by volume by ethanol solution, water, ammoniacal liquor：
28.8：4 mixing, are made mixed liquor A；Secondly, mixed liquid B is prepared：By tetraethyl orthosilicate, ethanol solution by volume 18：182 mix
Close, mixed liquid B is made；Then, mixed liquor A and mixed liquid B are mixed, by ethanol solution consumption 349.2：182 ratio mixing,
Mixed liquor C is made；By mixed liquor C, magnetic agitation obtains suspension, i.e. silicon ball glue at room temperature, namely contains 50nm titanium dioxides
The glue of silicon bead.
5. the preparation method of graphene composite titanium dioxide mesoporous single crystals mixture according to claim 4, its feature exists
In：The preparation method of the 50nm silicon oxide pellets templates of embedded graphene：
By silicon ball glue and 1.0mg/mL graphene oxide solution by volume 200：40 mixing, after mixture ultrasonic wave,
Obtain colloidal liquid；Colloidal liquid obtains navy blue solids through high speed centrifugation；After navy blue solids vacuum drying,
Burnt with vacuum tube furnace, obtain silicon oxide pellets template；
By silicon oxide pellets template in TiCl4Soaked in solution, then with deionized water rinsing, after flushing, first carry out vacuum and do
It is dry, then burnt with vacuum tube furnace, obtain the 50nm silicon oxide pellets templates of embedded graphene.
6. the preparation method of graphene composite titanium dioxide mesoporous single crystals mixture according to claim 5, its feature exists
In：Step 1) in, the method that hydro-thermal method prepares the graphene composite mesopore titanium dioxide single crystalline of sandwich structure is：
First, by water, HCl, solution of tetrabutyl titanate, hydrofluoric acid, the 50nm silicon oxide pellets template of embedded graphene mixes
Close；Then, mixed solution is placed in polytetrafluoroethylene (PTFE) stainless steel autoclave, 12h is handled under the conditions of 453K, consolidate
Body；Then, by NaOH solution by the SiO on solid2Template is etched away, after etching, and high speed centrifugation obtains graphene and is combined
Meso-porous titanium dioxide ti single crystal.
7. the preparation method of graphene composite titanium dioxide mesoporous single crystals mixture according to claim 4, its feature exists
In：The preparation method of 50nm silicon oxide pellets templates：
By silicon ball glue and 1.0mg/mL graphene oxide solution by volume 200：40 mixing, after mixture ultrasonic wave,
Obtain colloidal liquid；Colloidal liquid obtains light blue translucent solids through high speed centrifugation；By light blue translucent solid
After thing vacuum drying, burnt with vacuum tube furnace, obtain silicon oxide pellets template；
By silicon oxide pellets template in TiCl4Soaked in solution, then with deionized water rinsing, after flushing, first carry out vacuum and do
It is dry, then burnt with vacuum tube furnace, obtain the 50nm silicon oxide pellets templates of embedded graphene.
8. the preparation method of graphene composite titanium dioxide mesoporous single crystals mixture according to claim 7, its feature exists
In：The preparation method of meso-porous titanium dioxide ti single crystal is：Water, HCl, solution of tetrabutyl titanate, hydrofluoric acid, 50nm silica is small
Ball template is mixed；Then, mixed solution is placed in polytetrafluoroethylene (PTFE) stainless steel autoclave, 12h is handled under the conditions of 453K,
Obtain solid；Then, by NaOH solution by the SiO on solid2Template is etched away, after etching, and high speed centrifugation obtains mesoporous
Titanium dioxide single crystalline.
9. the preparation method of graphene composite titanium dioxide mesoporous single crystals mixture according to claim 8, its feature exists
In：The method that graphene is wrapped in the surface of meso-porous titanium dioxide ti single crystal by ultrasonic Bubbling method, by meso-porous titanium dioxide ti single crystal, oxygen
Graphite alkene is placed in water, then by ultrasonic bubbling in ultrasonic wave direction solution for a period of time after, be centrifuged, obtain stone
Black alkene outsourcing mesoporous titanium dioxide monocrystalline.
10. the control method of graphene composite titanium dioxide mesoporous single crystals mixture charge migration, it is characterised in that control graphite
Alkene is present in the diverse location of mesoporous single crystals, so as to control the migration path and enrichment positions of light induced electron.By controlling electric charge
Migration, can promote the separation of electron hole, improve photocatalytic activity, obtain oxidized surface and go back the controllable mesoporous list of original surface
Crystalline substance, and its application in degrade colourless pollutant phenol and photolysis water hydrogen.
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