CN106622201A - Preparation method and application of graphene and titanium dioxide photo-catalysis nano-crystals - Google Patents
Preparation method and application of graphene and titanium dioxide photo-catalysis nano-crystals Download PDFInfo
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- CN106622201A CN106622201A CN201611219022.2A CN201611219022A CN106622201A CN 106622201 A CN106622201 A CN 106622201A CN 201611219022 A CN201611219022 A CN 201611219022A CN 106622201 A CN106622201 A CN 106622201A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 171
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 153
- 239000004408 titanium dioxide Substances 0.000 title abstract description 57
- 230000001699 photocatalysis Effects 0.000 title abstract description 9
- 238000007146 photocatalysis Methods 0.000 title abstract description 7
- 239000002159 nanocrystal Substances 0.000 title abstract 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 174
- 238000003756 stirring Methods 0.000 claims abstract description 38
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011261 inert gas Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 10
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 10
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims description 61
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 238000000703 high-speed centrifugation Methods 0.000 claims description 24
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 18
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- 239000012467 final product Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 2
- -1 Graphite Alkene Chemical class 0.000 claims 2
- 230000007935 neutral effect Effects 0.000 claims 1
- 230000006911 nucleation Effects 0.000 abstract description 23
- 238000010899 nucleation Methods 0.000 abstract description 23
- 239000007791 liquid phase Substances 0.000 abstract description 6
- 238000001354 calcination Methods 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 229910003471 inorganic composite material Inorganic materials 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 238000007664 blowing Methods 0.000 abstract 1
- 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 abstract 1
- 238000007865 diluting Methods 0.000 abstract 1
- 235000010215 titanium dioxide Nutrition 0.000 description 62
- 229960005196 titanium dioxide Drugs 0.000 description 59
- 235000019441 ethanol Nutrition 0.000 description 53
- 239000000243 solution Substances 0.000 description 53
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 21
- 239000010936 titanium Substances 0.000 description 21
- 229910052719 titanium Inorganic materials 0.000 description 21
- 239000000463 material Substances 0.000 description 18
- 239000002131 composite material Substances 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 12
- 238000006068 polycondensation reaction Methods 0.000 description 11
- 150000001336 alkenes Chemical class 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 230000005622 photoelectricity Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000001629 suppression Effects 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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Abstract
The invention discloses a preparation method and application of graphene and titanium dioxide photo-catalysis nano-crystals and belongs to the technical field of inorganic composite materials. The preparation method comprises the following steps: putting graphite powder and sodium nitrate into a flask; adding concentrated sulfuric acid and slowly adding potassium permanganate into the flask; stirring in an ice-bath environment and slowly dropwise adding hydrogen peroxide into the flask; washing with hydrochloric acid under a high-speed centrifuging condition to obtain a graphene oxide ethanol solution; after diluting, slowly adding tetrabutyl titanate, and slowly dropwise adding stronger ammonia water; putting a separated product into an air blowing drying box and drying; putting a dried product into a tubular furnace and inert gas atmosphere, and calcining; cooling to obtain the graphene/titanium dioxide photo-catalysis nano-crystals. The growth of titanium dioxide nano-crystals on graphene can be accurately regulated and controlled and a homogeneous nucleation phenomenon of titanium dioxide in a liquid phase is avoided; a preparation process is moderate and easy to observe, a high-pressure reaction environment is not needed and the safety and reliability of operation are improved.
Description
Technical field
The present invention relates to inorganic composite materials technical field, more particularly to a kind of Graphene optically catalytic TiO 2 nanometer
Brilliant preparation method and application.
Background technology
Graphene is a kind of stable two-dimension plane structure functional material, with very excellent electric conductivity, translucency with
And larger specific surface area, thus its outstanding light, electrical property and catalytic performance can be shown.At present, Graphene has been obtained
Extensive concern is arrived.By the way that Graphene is combined with semiconductor nano material, the composite of excellent performance can be prepared.When
When obtained material is irradiated by excitation source, light induced electron can be transferred in Graphene from semiconductor grain, effectively suppression
Light induced electron processed and hole it is compound, improve the life-span in light induced electron and hole, so as to improve photocatalysis efficiency, significantly improve light
The performance of catalysis material.This composite has potentially in fields such as solar energy, electrode material of lithium battery and sewage disposals
Using.
Titanium dioxide is a kind of nontoxic semi-conducting material, because it has fabulous photoelectric conversion capacity, excellent steady
The excellent specific property such as qualitative and cheap and easy to get so as in photovoltaic solar cell, light-catalyzed reaction, photocatalytic degradation, sewage disposal
Have a wide range of applications Deng field, but due to its forbidden band it is wider the characteristics of, have the shortcomings that degrading activity is slower.So people
Extensive study on the modification is carried out to titanium dioxide optical catalyst, the deposition, semiconductor including catalyst surface noble metal
The compound of photochemical catalyst, the ion doping of photochemical catalyst, photosensitizer and form central hole structure etc..
In recent years, Graphene/semiconductor nanometer composite material achieved numerous studies in fields such as physics, chemistry, materials
Achievement, the particularly preparation of Graphene/titanic oxide nano compound material and application have obtained the high intensity research of scholars.Two
The excellent specific property of Graphene can be well inherited after titanium oxide is compound with Graphene, while greatly extending anti-in photocatalysis
Should in electron-hole recombination time so that Graphene/titanic oxide nano compound material possesses more excellent performance and wider array of
Using.Such as the depollution of environment (catalytic degradation, sterilization), energy reserves (photolysis water hydrogen, reduction CO2 organic-fuels etc.), lead
Battery, capacitor material etc..At present, the preparation method of Graphene mainly has micromechanics stripping method, chemical vapour deposition technique, change
Reduced graphene oxide serving method and solvent-thermal method etc. are learned, and the preparation method of Graphene and composite titania material is mainly water
Hot method, solvent-thermal method and thermal reduction etc., such as：
Publication No. CN 105964236A, publication date is that the Chinese patent literature of on 09 28th, 2016 discloses one kind
The preparation method of graphene/titanium dioxide photocatalyst, the Graphene/titanic oxide nano compound material by single-layer graphene and
Titanium dioxide nanoparticle is constituted, and the titanium dioxide nanoparticle is dispersed in graphenic surface, and the titanium dioxide granule is
Anatase crystal.The patent document, is by the way that presoma Butyl Phthalate is scattered in into a certain proportion of ethanol/glacial acetic acid solution
In, then to its a certain amount of graphene oxide solution of addition, Graphene/titanium dioxide is obtained by hydro-thermal method and Muffle furnace calcining
Photochemical catalyst.
Publication No. CN 103337611A, publication date is that the Chinese patent literature on October 02nd, 2013 discloses a kind of stone
The preparation method of black alkene and composite titania material, it is characterised in that comprise the following steps：1) by the forerunner containing titanium ion
Body is dissolved in absolute ethyl alcohol, is configured to solution, adds graphene oxide solution, and titanium ion inhales on the surface of oxidized Graphene
It is attached and hydrolyze, generate amorphous titanium hydroxide nanometer microparticle；The graphene oxide for obtaining and titanium hydroxide are combined
Material is deposited, is dried, and obtains final product graphene oxide and amorphous titanium peroxide composite；2) in closed high-pressure hydrothermal reaction kettle
Addition aqueous solution, by step 1) graphene oxide that obtains and amorphous titanium peroxide composite be placed in aqueous solution top,
The reduction of graphene oxide and the crystallization of amorphous titanium peroxide are carried out, Graphene and composite titania material is obtained final product.The patent
Document, is that the presoma containing titanium ion is dissolved in absolute ethyl alcohol, is configured to solution, adds graphene oxide solution, is sunk
It is long-pending, dry, then Graphene and composite titania material are obtained by hydro-thermal method.
Publication No. CN 105561963A, publication date is that the Chinese patent literature of on 05 11st, 2016 discloses one kind
The preparation method of nano titanium oxide/graphene oxide composite material, it is characterised in that comprise the following steps：By graphite oxide
Alkene solid dissolving in deionized water and absolute ethyl alcohol, ultrasonically treated 30-90min；Nano titanium oxide is subsequently adding, 1- is stirred
3h so as to be well mixed and obtain suspension；Then suspension is reacted into 1-3h in 100-120 DEG C；Finally by filter and air-dry
Regeneration obtains nano titanium oxide/graphene oxide composite material.The patent document, is that graphene oxide is dissolved in into water and second
In the mixed solution of alcohol, then nano titanium oxide is added thereto to, by stirring and thermal response, Graphene/titanium dioxide is obtained
Optic catalytic composite material.
Publication No. CN 104084186A, publication date is that the Chinese patent literature on October 08th, 2014 discloses one kind
Graphene/optically catalytic TiO 2 composite, it is characterised in that Graphene/optically catalytic TiO 2 composite is by three-dimensional
Graphene skeleton and titanium dioxide nanoparticle are constituted, and the Graphene has macroporous structure, and the titanium dioxide is mesoporous two
Titanium oxide, macropore and it is mesoporous be interconnected, the titanium dioxide nanoparticle is scattered on graphene nanometer sheet, the nanometer two
Titan oxide particles are filled in the macropore of the Graphene, and the titanium dioxide is pure anatase crystal.The patent document, will
Titania nanoparticles mix with graphene oxide ethanol solution obtained in Jing sol-gel processes, and ammonia is added after ultrasonic disperse
Water, is combined by hydro-thermal method and thermal reduction and prepares Graphene/optically catalytic TiO 2 composite.
Prior art with above-mentioned patent document as representative, is carried out by hydro-thermal method, and it has many defects,
Such as：Titanium dioxide nanocrystalline located growth on graphene film cannot accurately be regulated and controled, it is impossible to avoid titanium dioxide in the liquid phase
Homogeneous nucleation phenomenon；Hydro-thermal method is carried out using water heating kettle, and required experiment condition is more harsh, it usually needs high compression ring
Border, and the reaction time is long, generally 6-12 hours, the security reliability of preparation manipulation is relatively low；Hydro-thermal method is typically closed
Reacted in container, whole course of reaction cannot be observed, not intuitively.
The content of the invention
Defect in order to overcome above-mentioned prior art of the invention, there is provided a kind of Graphene optically catalytic TiO 2 is nanocrystalline
Preparation method and application, the present invention can accurately regulate and control growth of the titanium dioxide nanocrystalline on Graphene, it is to avoid titanium dioxide
Homogeneous nucleation phenomenon in the liquid phase, whole preparation process is gently easily observed, it is not necessary to reaction under high pressure environment, improves operation peace
Full reliability.
The present invention is achieved through the following technical solutions：
The nanocrystalline preparation method of a kind of Graphene optically catalytic TiO 2, it is characterised in that comprise the following steps：
A, graphite powder and sodium nitrate are placed in flask, add the concentrated sulfuric acid, divided with ultrasonic disperse 10-30 after flask is sealed
Clock, then flask is placed in into stirring in ice bath environment；
B, potassium permanganate is slowly added in flask, 8-15 hours is stirred in ice bath environment, then be slowly added dropwise ultra-pure water,
Flask is placed in water-bath again, by temperature adjustment to 50 DEG C and stirring reaction 8-15 hour, water-bath pot temperature is adjusted to into 35 DEG C,
Continue to react 12 hours；
C, hydrogen peroxide is slowly dropped in flask, continues to react 3 hours at a temperature of 35 DEG C of water-baths, then existed with hydrochloric acid
Wash under the conditions of high speed centrifugation, then washed to pH of mixed in flask in neutrality with pure water and ethanol continuation, then divided with ultrasound
Dissipate 3 hours, obtain graphene oxide ethanol solution；
D, graphene oxide ethanol solution is diluted after, butyl titanate is slowly added to it with vigorous stirring, with super
Sound disperses 30 minutes, then is slowly added dropwise concentrated ammonia liquor, stirs 24 hours after dripping, then is centrifuged at a high speed；
E, by the product after being centrifuged at a high speed be placed in air dry oven be dried, finally will be dried after products therefrom in pipe
Calcine 2 hours in formula stove and atmosphere of inert gases, it is nanocrystalline that natural cooling obtains final product Graphene/optically catalytic TiO 2.
In step a, the temperature of ice bath environment is 1-5 DEG C, and mixing time is 20-40 minutes.
In step c, the concentration of hydrochloric acid is 5%, and high speed centrifugation rotating speed is 6000r/min, and washing times are 10 times.
In step d, graphene oxide ethanol solution is diluted using ethanol solution, dilutes rear oxidation Graphene
The concentration of ethanol solution is 0.05mg/ml.
In step d, the concentration of concentrated ammonia liquor is 0.1%.
In step e, the temperature of air dry oven is 60 degrees Celsius, and drying time is 12 hours.
Graphene/optically catalytic TiO 2 is nanocrystalline, it is adaptable to the photocatalytic degradation of organic dyestuff.
Graphene/optically catalytic TiO 2 is nanocrystalline, it is adaptable to produce conductive battery.
Beneficial effects of the present invention are mainly manifested in following aspect：
First, the present invention, graphite powder and sodium nitrate " be placed in flask, add the concentrated sulfuric acid, with ultrasound point after flask is sealed
Scattered 10-30 minutes, then flask is placed in into stirring in ice bath environment；Potassium permanganate is slowly added in flask, in ice bath environment
Stirring 8-15 hours, then ultra-pure water is slowly added dropwise, then flask is placed in water-bath, by temperature adjustment to 50 DEG C and stirring reaction
8-15 hours, by water-bath pot temperature 35 DEG C are adjusted to, and continue to react 12 hours；Hydrogen peroxide is slowly dropped in flask, at 35 DEG C
Continue to react 3 hours at a temperature of water-bath, then washed under the conditions of high speed centrifugation with hydrochloric acid, then continue to wash with pure water and ethanol
PH of mixed is washed into flask in neutrality, then with ultrasonic disperse 3 hours, graphene oxide ethanol solution is obtained；By graphite oxide
After the dilution of alkene ethanol solution, with vigorous stirring butyl titanate is slowly added to it, with ultrasonic disperse 30 minutes, then is slowly dripped
Plus concentrated ammonia liquor, stir 24 hours after dripping, then be centrifuged at a high speed；Product after being centrifuged at a high speed is placed in into forced air drying
It is dried in case, products therefrom is calcined 2 hours in tube furnace and atmosphere of inert gases after being finally dried, and natural cooling obtains final product stone
Black alkene/optically catalytic TiO 2 is nanocrystalline ".By accuracy controlling graphene oxide ethanol solution, butyl titanate and ammoniacal liquor
Concentration, can be such that amorphous titania nano-particle is optionally grown on graphene oxide.Graphene/titanium-dioxide photo
Graphene in catalytic nanometer crystalline substance is a kind of two-dimentional material with carbon element, and heating in air atmosphere to burn, and with the shape of carbon dioxide
Formula is scattered and disappeared, thus is continuously passed through inert gas in heating, to ensure oxygen-free environment, is prevented from Graphene burning；Using pipe
The high-temperature calcination of formula stove as amorphous titania crystalline forming and the thermal reduction step of graphene oxide, and by calcination time control
System both can guarantee that Graphene/optically catalytic TiO 2 was nanocrystalline with excellent photoelectricity performance at 2 hours, and it is can guarantee that again
With good catalytic performance.Because if heating duration is too short graphene oxide can be caused fully to be reduced, graphite is made
The nanocrystalline resistance of alkene/optically catalytic TiO 2 is larger, hinders transmission of the electronics in interlayer, affects Graphene/titanium dioxide
The brilliant photoelectricity performance of photocatalytic nanometer；If heating and thermal insulation overlong time, the Graphene/titanium-dioxide photo for generating can be caused to urge
Change is nanocrystalline to reunite, and particle diameter increase, specific surface area is reduced, and affects its catalytic performance." whole preparation method, more existing skill
For art, preparation process is gentle, it is not necessary to reaction under high pressure environment, improves safe operation reliability；Equipment needed thereby is simple and easy to get,
It is simple to operate, it is easy to observe；Growth of the titanium dioxide nanocrystalline on Graphene can accurately be regulated and controled, it is to avoid titanium dioxide is in liquid
Homogeneous nucleation phenomenon in phase." according to transmission electron microscopy figure, it can be seen that the Graphene/titanium-dioxide photo obtained by preparation is urged
Changing nanocrystalline is made up of independent tulle bedded substance, and form is much like with Graphene, while in Graphene/titanium dioxide
Around titanium photocatalytic nanometer crystalline substance and exposed Graphene is found no or free titanium dioxide granule occurs, so as to illustrate
The present invention can avoid titanium dioxide homogeneous nucleation phenomenon in the liquid phase；Simultaneously, it can be seen that the titanium dioxide for being formed is very
It is evenly distributed on Graphene, so as to illustrate that the present invention can life of the accuracy controlling titanium dioxide nanocrystalline on Graphene
It is long；By further scanning, it is found that the titanium dioxide nanocrystalline distribution being grown on Graphene is very intensive compact, so as to table
Understand that the Graphene/optically catalytic TiO 2 obtained by the present invention is nanocrystalline with excellent photocatalysis performance.
2nd, the present invention, in step a, the temperature of ice bath environment is 1-5 DEG C, and mixing time is 20-40 minutes, in ice bath ring
Reacted in border, the environment of a low temperature can be createed, slowed down reaction rate, reaction is at the uniform velocity carried out, made whole oxidation
Process equably occurs, so as to ensure that obtained graphene oxide solution has preferably dispersiveness and single layer structure.
3rd, the present invention, in step c, the concentration of hydrochloric acid is 5%, and high speed centrifugation rotating speed is 6000r/min, and washing times are
10 times, graphene oxide has amphipathic, and the amphipathic of graphene oxide comes from its hydrophilic edge and on surface
Hydrophobic group.Such as ionic surfactant molecules, its it is amphipathic may be because of the ionization of edge-COOH group
Degree, or dispersion liquid pH value and be varied from.Higher pH value may result in the electric charge at edge to be increased, thus increases thin slice
Hydrophily.Conversely, relatively low pH value then reduces the electric charge at edge, cause to disperse bad in water.Therefore, adopt certain concentration for
5% hydrochloric acid, and with 6000r/min high speed centrifugations, fast and effectively can separate graphene oxide.
4th, the present invention, in step d, is diluted using ethanol solution to graphene oxide ethanol solution, dilutes rear oxidation
The concentration of Graphene ethanol solution be 0.05mg/ml, due to graphene oxide can in alcoholic environment almost it is completely peeled off with
Dispersion, and its surface is fully come out.Thus, after butyl titanate is added, the amorphous titania for being formed
Particle is precisely located growth under the attraction of graphene oxide functional group.By carrying out to graphene oxide ethanol solution
Dilution, is obtained the graphene oxide ethanol solution of super low concentration, in using it for subsequent reactions, ensure that graphene oxide exists
More uniformly disperse in ethanol；And in the environment of low concentration, slow down whole course of reaction, the amorphous titanium dioxide for being formed
Titanium particle is more uniformly grown on graphene oxide.
5th, the present invention, in step d, the concentration of concentrated ammonia liquor is 0.1%, and when a small amount of ammoniacal liquor is added, (ammoniacal liquor content is less than
0.05%), the hydrolysis of butyl titanate and polycondensation speed are relatively low, and the oligomer concentrations of the titanium of generation are also very low.Now, due to titanium
Oligomer concentrations value less than the critical concentration of heterogeneous nucleation, therefore there is no titanium dioxide nano granule on the surface of graphene oxide
Son is formed.The appropriate concentration (ammoniacal liquor content is 0.1%) for increasing ammoniacal liquor, the hydrolysis of butyl titanate and polycondensation speed accelerate, and enter
And the oligomer of more titaniums can be produced.When the oligomer concentrations value of titanium reaches the critical concentration of heterogeneous nucleation, titanium dioxide
Occur in the heterogeneous nucleation of surface of graphene oxide.Although forming nano titania core can consume the oligomer of some titaniums,
However, with the carrying out of hydrolytic process, the concentration of oligomer is still above the supersaturation concentration of system, therefore the oligomer of titanium can
Grow to form big titanium dioxide network structure to continue the polycondensation around nano titania core, As time goes on, most
End form uniformly titanium dioxide shell.(ammoniacal liquor content is more than 1.0%), butyl titanate conversely, when ammonia concn is higher
Hydrolysis and polycondensation speed will greatly speed up.Now, the oligomer of substantial amounts of titanium will be produced at short notice so that dioxy
Change titanium shell fast-growth, thickness is also consequently increased rapidly.Then, when titanium dioxide shell thickness is reached the limit values (maximum)
When, due to the restriction of dimensional effect and material diffusion, the oligomer of titanium is no longer in the polycondensation of core-shell structure nanometer particle surface
Growth.With the carrying out of hydrolytic process, the oligomer of titanium can gradually increase, when the oligomer concentrations value of titanium reaches homogeneous nucleation
During critical concentration, free titanium dioxide nano-particle will be generated.If the concentration of catalyst is too high in system, butyl titanate
Hydrolysis and polycondensation speed will be very fast, within the extremely short time, substantial amounts of oligomer can be produced.Now, heterogeneous nucleation with
Homogeneous nucleation process can occur simultaneously, form the nano-particle of big aggregation.Therefore, the ammonia concn for being added by accuracy controlling
Carry out indirect control kinetics, can make titanium dioxide preferentially in surface of graphene oxide heterogeneous nucleation and growth, and can
The generation of its homogeneous nucleation in the solution is effectively avoided, the Graphene/optically catalytic TiO 2 homogeneous so as to prepare dispersion
It is nanocrystalline.
6th, the present invention, in step e, the temperature of air dry oven is 60 degrees Celsius, and drying time is 12 hours, at this
Under part, the nanocrystalline agglomeration of Graphene/optically catalytic TiO 2 in dry run can be well avoided to produce.
Description of the drawings
Fig. 1 is the nanocrystalline projection electron-microscope scanning figure of Graphene/optically catalytic TiO 2 of the present invention；
Fig. 2 is that the nanocrystalline crystal pitch of Graphene/optically catalytic TiO 2 of the present invention characterizes picture；
Fig. 3 for difference of the present invention mix it is more nanocrystalline than Graphene/optically catalytic TiO 2 with General Physics composite graphite alkene-
P25 catalysis materials are under visible light to the degradation curve comparison diagram of rhodamine 6G；
Fig. 4 is that Graphene/optically catalytic TiO 2 of the present invention is nanocrystalline useless to rhodamine 6G simulation under visible light conditions
The degradation process spectral scan curve map of water.
Specific embodiment
Embodiment 1
A kind of nanocrystalline preparation method of Graphene optically catalytic TiO 2, comprises the following steps：
A, 2g graphite powders and 1.2g sodium nitrate are placed in single-necked flask, add the 76ml concentrated sulfuric acids, used after flask is sealed
Ultrasonic disperse 10 minutes, then flask is placed in into stirring in ice bath environment；
B, 8.8g potassium permanganate is slowly added in flask, is stirred 8 hours in ice bath environment, then be slowly added dropwise 72ml to surpass
Pure water, then flask is placed in water-bath, by temperature adjustment to 50 DEG C and stirring reaction 8 hours, by water-bath pot temperature 35 is adjusted to
DEG C, continue to react 12 hours；
C, 22ml hydrogen peroxide is slowly dropped in flask, continues to react 3 hours at a temperature of 35 DEG C of water-baths, then use salt
Acid is washed under the conditions of high speed centrifugation, then continues to wash to pH of mixed in flask in neutrality with pure water and ethanol, then with surpassing
Sound disperses 3 hours, obtains graphene oxide ethanol solution；
D, will graphene oxide ethanol solution dilute after measure 100ml, be slowly added to 0.75ml to it with vigorous stirring
Butyl titanate, with ultrasonic disperse 30 minutes, then is slowly added dropwise concentrated ammonia liquor, stirs 24 hours after dripping, then high speed centrifugation point
From；
E, by the product after being centrifuged at a high speed be placed in air dry oven be dried, finally will be dried after products therefrom in pipe
Calcine 2 hours in formula stove and atmosphere of inert gases, it is nanocrystalline that natural cooling obtains final product Graphene/optically catalytic TiO 2.
By accuracy controlling graphene oxide ethanol solution, butyl titanate and ammonia concn, amorphous two can be made
Titanium oxide nanoparticles are optionally grown on graphene oxide.Graphite during Graphene/optically catalytic TiO 2 is nanocrystalline
Alkene is a kind of two-dimentional material with carbon element, and heating in air atmosphere to burn, and is scattered and disappeared in the form of carbon dioxide, thus in heating
Inert gas is continuously passed through, to ensure oxygen-free environment, Graphene burning is prevented from；Using tube furnace high-temperature calcination as without fixed
Shape titanium dioxide crystal is molded the thermal reduction step with graphene oxide, and calcination time was controlled at 2 hours, both can guarantee that stone
Black alkene/optically catalytic TiO 2 is nanocrystalline with excellent photoelectricity performance, can guarantee that it has good catalytic performance again.Cause
If heating duration is too short graphene oxide to be caused fully to be reduced, Graphene/optically catalytic TiO 2 nanometer is made
Brilliant resistance is larger, hinders transmission of the electronics in interlayer, the photoelectricity for affecting Graphene/optically catalytic TiO 2 nanocrystalline
Energy；If heating and thermal insulation overlong time, can cause generate Graphene/optically catalytic TiO 2 it is nanocrystalline reunite, particle diameter
Increase, specific surface area is reduced, and affects its catalytic performance." whole preparation method, for prior art, preparation process is gentle, no
Reaction under high pressure environment is needed, safe operation reliability is improve；Equipment needed thereby is simple and easy to get, simple to operate, it is easy to observe；Can essence
Really regulate and control growth of the titanium dioxide nanocrystalline on Graphene, it is to avoid titanium dioxide homogeneous nucleation phenomenon in the liquid phase." root
According to transmission electron microscopy figure, it can be seen that it is by independent tulle that Graphene/optically catalytic TiO 2 obtained by preparation is nanocrystalline
What bedded substance was constituted, form is much like with Graphene, while around Graphene/optically catalytic TiO 2 is nanocrystalline simultaneously
Find no exposed Graphene or free titanium dioxide granule occurs, so as to illustrate that the present invention can avoid titanium dioxide from existing
Homogeneous nucleation phenomenon in liquid phase；Simultaneously, it can be seen that the titanium dioxide for being formed is distributed on Graphene visibly homogeneously, from
And illustrate that the present invention can growth of the accuracy controlling titanium dioxide nanocrystalline on Graphene；By further scanning, find
The titanium dioxide nanocrystalline distribution being grown on Graphene is very intensive compact, so as to indicate the graphite obtained by the present invention
Alkene/optically catalytic TiO 2 is nanocrystalline with excellent photocatalysis performance.
Embodiment 2
A kind of nanocrystalline preparation method of Graphene optically catalytic TiO 2, comprises the following steps：
A, 2g graphite powders and 1.2g sodium nitrate are placed in single-necked flask, add the 76ml concentrated sulfuric acids, used after flask is sealed
Ultrasonic disperse 15 minutes, then flask is placed in into stirring in ice bath environment；
B, 8.8g potassium permanganate is slowly added in flask, is stirred 9 hours in ice bath environment, then be slowly added dropwise 72ml to surpass
Pure water, then flask is placed in water-bath, by temperature adjustment to 50 DEG C and stirring reaction 9 hours, by water-bath pot temperature 35 is adjusted to
DEG C, continue to react 12 hours；
C, 22ml hydrogen peroxide is slowly dropped in flask, continues to react 3 hours at a temperature of 35 DEG C of water-baths, then use salt
Acid is washed under the conditions of high speed centrifugation, then continues to wash to pH of mixed in flask in neutrality with pure water and ethanol, then with surpassing
Sound disperses 3 hours, obtains graphene oxide ethanol solution；
D, will graphene oxide ethanol solution dilute after measure 100ml, be slowly added to 0.75ml to it with vigorous stirring
Butyl titanate, with ultrasonic disperse 30 minutes, then is slowly added dropwise concentrated ammonia liquor, stirs 24 hours after dripping, then high speed centrifugation point
From；
E, by the product after being centrifuged at a high speed be placed in air dry oven be dried, finally will be dried after products therefrom in pipe
Calcine 2 hours in formula stove and atmosphere of inert gases, it is nanocrystalline that natural cooling obtains final product Graphene/optically catalytic TiO 2.
In step a, the temperature of ice bath environment is 1 DEG C, and mixing time is 20 minutes.
In step a, the temperature of ice bath environment is 1 DEG C, and mixing time is 20 minutes, is reacted in ice bath environment, energy
The environment of a low temperature is enough createed, slows down reaction rate, reaction is at the uniform velocity carried out, whole oxidizing process is equably occurred,
So as to ensure that obtained graphene oxide solution has preferably dispersiveness and single layer structure.
Embodiment 3
A kind of nanocrystalline preparation method of Graphene optically catalytic TiO 2, comprises the following steps：
A, 2g graphite powders and 1.2g sodium nitrate are placed in single-necked flask, add the 76ml concentrated sulfuric acids, used after flask is sealed
Ultrasonic disperse 20 minutes, then flask is placed in into stirring in ice bath environment；
B, 8.8g potassium permanganate is slowly added in flask, is stirred 11 hours in ice bath environment, then be slowly added dropwise 72ml
Ultra-pure water, then flask is placed in water-bath, by temperature adjustment to 50 DEG C and stirring reaction 11 hours, water-bath pot temperature is adjusted to
35 DEG C, continue to react 12 hours；
C, 22ml hydrogen peroxide is slowly dropped in flask, continues to react 3 hours at a temperature of 35 DEG C of water-baths, then use salt
Acid is washed under the conditions of high speed centrifugation, then continues to wash to pH of mixed in flask in neutrality with pure water and ethanol, then with surpassing
Sound disperses 3 hours, obtains graphene oxide ethanol solution；
D, will graphene oxide ethanol solution dilute after measure 100ml, be slowly added to 0.75ml to it with vigorous stirring
Butyl titanate, with ultrasonic disperse 30 minutes, then is slowly added dropwise concentrated ammonia liquor, stirs 24 hours after dripping, then high speed centrifugation point
From；
E, by the product after being centrifuged at a high speed be placed in air dry oven be dried, finally will be dried after products therefrom in pipe
Calcine 2 hours in formula stove and atmosphere of inert gases, it is nanocrystalline that natural cooling obtains final product Graphene/optically catalytic TiO 2.
In step a, the temperature of ice bath environment is 2 DEG C, and mixing time is 30 minutes.
In step c, the concentration of hydrochloric acid is 5%, and high speed centrifugation rotating speed is 6000r/min, and washing times are 10 times.
In step c, the concentration of hydrochloric acid is 5%, and high speed centrifugation rotating speed is 6000r/min, and washing times are 10 times, aoxidize stone
Black alkene has amphipathic, and the amphipathic of graphene oxide comes from its hydrophilic edge and the hydrophobicity base on surface
Group.Such as ionic surfactant molecules, its it is amphipathic may because of the degree of ionization of edge-COOH group, or point
The pH value of dispersion liquid and be varied from.Higher pH value may result in the electric charge at edge to be increased, thus increases the hydrophily of thin slice.
Conversely, relatively low pH value then reduces the electric charge at edge, cause to disperse bad in water.Therefore, adopt certain concentration for 5% salt
Acid, and with 6000r/min high speed centrifugations, fast and effectively can separate graphene oxide.
Embodiment 4
A kind of nanocrystalline preparation method of Graphene optically catalytic TiO 2, comprises the following steps：
A, 2g graphite powders and 1.2g sodium nitrate are placed in single-necked flask, add the 76ml concentrated sulfuric acids, used after flask is sealed
Ultrasonic disperse 25 minutes, then flask is placed in into stirring in ice bath environment；
B, 8.8g potassium permanganate is slowly added in flask, is stirred 13 hours in ice bath environment, then be slowly added dropwise 72ml
Ultra-pure water, then flask is placed in water-bath, by temperature adjustment to 50 DEG C and stirring reaction 13 hours, water-bath pot temperature is adjusted to
35 DEG C, continue to react 12 hours；
C, 22ml hydrogen peroxide is slowly dropped in flask, continues to react 3 hours at a temperature of 35 DEG C of water-baths, then use salt
Acid is washed under the conditions of high speed centrifugation, then continues to wash to pH of mixed in flask in neutrality with pure water and ethanol, then with surpassing
Sound disperses 3 hours, obtains graphene oxide ethanol solution；
D, will graphene oxide ethanol solution dilute after measure 100ml, be slowly added to 0.75ml to it with vigorous stirring
Butyl titanate, with ultrasonic disperse 30 minutes, then is slowly added dropwise concentrated ammonia liquor, stirs 24 hours after dripping, then high speed centrifugation point
From；
E, by the product after being centrifuged at a high speed be placed in air dry oven be dried, finally will be dried after products therefrom in pipe
Calcine 2 hours in formula stove and atmosphere of inert gases, it is nanocrystalline that natural cooling obtains final product Graphene/optically catalytic TiO 2.
In step a, the temperature of ice bath environment is 3 DEG C, and mixing time is 35 minutes.
In step c, the concentration of hydrochloric acid is 5%, and high speed centrifugation rotating speed is 6000r/min, and washing times are 10 times.
In step d, graphene oxide ethanol solution is diluted using ethanol solution, dilutes rear oxidation Graphene
The concentration of ethanol solution is 0.05mg/ml.
In step d, graphene oxide ethanol solution is diluted using ethanol solution, dilutes rear oxidation Graphene ethanol
The concentration of solution be 0.05mg/ml, due to graphene oxide can in alcoholic environment almost it is completely peeled off with dispersion, and by its
Fully come out on surface.Thus, after butyl titanate is added, the amorphous titania particle for being formed is in oxidation stone
Under the attraction of black alkene functional group, growth is precisely located.By being diluted to graphene oxide ethanol solution, it is obtained ultralow
The graphene oxide ethanol solution of concentration, in using it for subsequent reactions, ensure that graphene oxide is more equal in ethanol
Even dispersion；And in the environment of low concentration, slowing down whole course of reaction, the amorphous titania particle for being formed is more equal
It is grown in evenly on graphene oxide.
Embodiment 5
A kind of nanocrystalline preparation method of Graphene optically catalytic TiO 2, comprises the following steps：
A, 2g graphite powders and 1.2g sodium nitrate are placed in single-necked flask, add the 76ml concentrated sulfuric acids, used after flask is sealed
Ultrasonic disperse 30 minutes, then flask is placed in into stirring in ice bath environment；
B, 8.8g potassium permanganate is slowly added in flask, is stirred 15 hours in ice bath environment, then be slowly added dropwise 72ml
Ultra-pure water, then flask is placed in water-bath, by temperature adjustment to 50 DEG C and stirring reaction 15 hours, water-bath pot temperature is adjusted to
35 DEG C, continue to react 12 hours；
C, 22ml hydrogen peroxide is slowly dropped in flask, continues to react 3 hours at a temperature of 35 DEG C of water-baths, then use salt
Acid is washed under the conditions of high speed centrifugation, then continues to wash to pH of mixed in flask in neutrality with pure water and ethanol, then with surpassing
Sound disperses 3 hours, obtains graphene oxide ethanol solution；
D, will graphene oxide ethanol solution dilute after measure 100ml, be slowly added to 0.75ml to it with vigorous stirring
Butyl titanate, with ultrasonic disperse 30 minutes, then is slowly added dropwise concentrated ammonia liquor, stirs 24 hours after dripping, then high speed centrifugation point
From；
E, by the product after being centrifuged at a high speed be placed in air dry oven be dried, finally will be dried after products therefrom in pipe
Calcine 2 hours in formula stove and atmosphere of inert gases, it is nanocrystalline that natural cooling obtains final product Graphene/optically catalytic TiO 2.
In step a, the temperature of ice bath environment is 4 DEG C, and mixing time is 35 minutes.
In step c, the concentration of hydrochloric acid is 5%, and high speed centrifugation rotating speed is 6000r/min, and washing times are 10 times.
In step d, graphene oxide ethanol solution is diluted using ethanol solution, dilutes rear oxidation Graphene
The concentration of ethanol solution is 0.05mg/ml.
In step d, the concentration of concentrated ammonia liquor is 0.1%.
In step d, the concentration of concentrated ammonia liquor is 0.1%, (ammoniacal liquor content is less than 0.05%), metatitanic acid when a small amount of ammoniacal liquor is added
Four fourth ester hydrolysis and polycondensation speed are relatively low, and the oligomer concentrations of the titanium of generation are also very low.Now, due to the oligomer concentrations of titanium
Value is less than the critical concentration of heterogeneous nucleation, therefore does not have titanium dioxide nano-particle to be formed on the surface of graphene oxide.Suitably
Increase the concentration (ammoniacal liquor content is 0.1%) of ammoniacal liquor, the hydrolysis of butyl titanate and polycondensation speed accelerate, and then can produce more
Titanium oligomer.When the oligomer concentrations value of titanium reaches the critical concentration of heterogeneous nucleation, titanium dioxide is in graphene oxide
The heterogeneous nucleation on surface occurs.Although forming nano titania core can consume the oligomer of some titaniums, however, with hydrolysis
The carrying out of process, the concentration of oligomer is still above the supersaturation concentration of system, therefore the oligomer of titanium can continue in dioxy
Change polycondensation around titanium nanometer core to grow to form big titanium dioxide network structure, As time goes on, ultimately form equably
Titanium dioxide shell.Conversely, (ammoniacal liquor content is more than 1.0%), the hydrolysis and polycondensation of butyl titanate when ammonia concn is higher
Speed will greatly speed up.Now, the oligomer of substantial amounts of titanium will be produced at short notice so that titanium dioxide shell is quick
Growth, thickness is also consequently increased rapidly.Then, when titanium dioxide shell thickness reaches the limit values (maximum), due to size
The restriction of effect and material diffusion, the oligomer of titanium no longer grows in the polycondensation of core-shell structure nanometer particle surface.With water
The carrying out of solution preocess, the oligomer of titanium can gradually increase, when the oligomer concentrations value of titanium reaches the critical concentration of homogeneous nucleation,
Free titanium dioxide nano-particle will be generated.If the concentration of catalyst is too high in system, the hydrolysis and contracting of butyl titanate
Poly- speed will be very fast, within the extremely short time, can produce substantial amounts of oligomer.Now, heterogeneous nucleation and homogeneous nucleation mistake
Journey can occur simultaneously, form the nano-particle of big aggregation.Therefore, by the ammonia concn of accuracy controlling addition come indirect control
Kinetics, can make titanium dioxide preferentially in surface of graphene oxide heterogeneous nucleation and growth, and can effectively avoid
The generation of its homogeneous nucleation in the solution, it is nanocrystalline so as to prepare the homogeneous Graphene/optically catalytic TiO 2 of dispersion.
Embodiment 6
A kind of nanocrystalline preparation method of Graphene optically catalytic TiO 2, comprises the following steps：
A, 2g graphite powders and 1.2g sodium nitrate are placed in single-necked flask, add the 76ml concentrated sulfuric acids, used after flask is sealed
Ultrasonic disperse 30 minutes, then flask is placed in into stirring in ice bath environment；
B, 8.8g potassium permanganate is slowly added in flask, is stirred 15 hours in ice bath environment, then be slowly added dropwise 72ml
Ultra-pure water, then flask is placed in water-bath, by temperature adjustment to 50 DEG C and stirring reaction 15 hours, water-bath pot temperature is adjusted to
35 DEG C, continue to react 12 hours；
C, 22ml hydrogen peroxide is slowly dropped in flask, continues to react 3 hours at a temperature of 35 DEG C of water-baths, then use salt
Acid is washed under the conditions of high speed centrifugation, then continues to wash to pH of mixed in flask in neutrality with pure water and ethanol, then with surpassing
Sound disperses 3 hours, obtains graphene oxide ethanol solution；
D, will graphene oxide ethanol solution dilute after measure 100ml, be slowly added to 0.75ml to it with vigorous stirring
Butyl titanate, with ultrasonic disperse 30 minutes, then is slowly added dropwise concentrated ammonia liquor, stirs 24 hours after dripping, then high speed centrifugation point
From；
E, by the product after being centrifuged at a high speed be placed in air dry oven be dried, finally will be dried after products therefrom in pipe
Calcine 2 hours in formula stove and atmosphere of inert gases, it is nanocrystalline that natural cooling obtains final product Graphene/optically catalytic TiO 2.
In step a, the temperature of ice bath environment is 5 DEG C, and mixing time is 40 minutes.
In step c, the concentration of hydrochloric acid is 5%, and high speed centrifugation rotating speed is 6000r/min, and washing times are 10 times.
In step d, graphene oxide ethanol solution is diluted using ethanol solution, dilutes rear oxidation Graphene
The concentration of ethanol solution is 0.05mg/ml.
In step d, the concentration of concentrated ammonia liquor is 0.1%.
In step e, the temperature of air dry oven is 60 degrees Celsius, and drying time is 12 hours.
In step e, the temperature of air dry oven is 60 degrees Celsius, and drying time is 12 hours, under this condition, can be very
The nanocrystalline agglomeration of Graphene/optically catalytic TiO 2 in dry run is avoided to produce well.
Claims (8)
1. the nanocrystalline preparation method of a kind of Graphene optically catalytic TiO 2, it is characterised in that comprise the following steps：
A, graphite powder and sodium nitrate are placed in flask, add the concentrated sulfuric acid, ultrasonic disperse 10-30 minutes are used after flask is sealed,
Flask is placed in ice bath environment is again stirred；
B, potassium permanganate is slowly added in flask, 8-15 hours are stirred in ice bath environment, then be slowly added dropwise ultra-pure water, then will
Flask is placed in water-bath, by temperature adjustment to 50 DEG C and stirring reaction 8-15 hour, water-bath pot temperature is adjusted to into 35 DEG C, is continued
Reaction 12 hours；
C, hydrogen peroxide is slowly dropped in flask, continues to react 3 hours at a temperature of 35 DEG C of water-baths, then with hydrochloric acid at a high speed
Wash under centrifugal condition, then continue to wash to pH of mixed in flask in neutral then little with ultrasonic disperse 3 with pure water and ethanol
When, obtain graphene oxide ethanol solution；
D, by graphene oxide ethanol solution dilute after, be slowly added to butyl titanate to it with vigorous stirring, with ultrasound point
Dissipate 30 minutes, then be slowly added dropwise concentrated ammonia liquor, stir 24 hours after dripping, then be centrifuged at a high speed；
E, by the product after being centrifuged at a high speed be placed in air dry oven be dried, finally will be dried after products therefrom in tube furnace
Calcine 2 hours with atmosphere of inert gases, it is nanocrystalline that natural cooling obtains final product Graphene/optically catalytic TiO 2.
2. the nanocrystalline preparation method of a kind of Graphene optically catalytic TiO 2 according to claim 1, it is characterised in that：
In step a, the temperature of ice bath environment is 1-5 DEG C, and mixing time is 20-40 minutes.
3. the nanocrystalline preparation method of a kind of Graphene optically catalytic TiO 2 according to claim 1, it is characterised in that：
In step c, the concentration of hydrochloric acid is 5%, and high speed centrifugation rotating speed is 6000r/min, and washing times are 10 times.
4. the nanocrystalline preparation method of a kind of Graphene optically catalytic TiO 2 according to claim 1, it is characterised in that：
In step d, graphene oxide ethanol solution is diluted using ethanol solution, dilutes rear oxidation Graphene ethanol solution
Concentration be 0.05mg/ml.
5. a kind of nanocrystalline preparation method of Graphene optically catalytic TiO 2 according to claim 1 or 4, its feature exists
In：In step d, the concentration of concentrated ammonia liquor is 0.1%.
6. the nanocrystalline preparation method of a kind of Graphene optically catalytic TiO 2 according to claim 1, it is characterised in that：
In step e, the temperature of air dry oven is 60 degrees Celsius, and drying time is 12 hours.
7. the nanocrystalline application of a kind of Graphene optically catalytic TiO 2 according to claim 1, it is characterised in that：Graphite
Alkene/optically catalytic TiO 2 is nanocrystalline, it is adaptable to the photocatalytic degradation of organic dyestuff.
8. the nanocrystalline application of a kind of Graphene optically catalytic TiO 2 according to claim 1, it is characterised in that：Graphite
Alkene/optically catalytic TiO 2 is nanocrystalline, it is adaptable to produce conductive battery.
Priority Applications (1)
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| CN107199029A (en) * | 2017-06-08 | 2017-09-26 | 攀枝花学院 | The preparation method of high efficiency photocatalysis nanometer titanium dioxide/graphene composite |
| CN107886710A (en) * | 2017-10-29 | 2018-04-06 | 山东鲁控电力设备有限公司 | Pedestrian crossing zone's coloured light indicates system and method |
| CN107950570A (en) * | 2017-11-21 | 2018-04-24 | 新化县中润化学科技有限公司 | A kind of preparation method of graphene/titanium dioxide/nano silver composite material |
| CN109277096A (en) * | 2018-11-01 | 2019-01-29 | 长沙矿冶研究院有限责任公司 | Carbon nanotube loaded nanometer Ti4O7Composite material and preparation method and application |
| CN109536013A (en) * | 2018-12-28 | 2019-03-29 | 中国船舶重工集团公司第十二研究所 | A kind of preparation method of the hydrophobic nonpolluting coating of graphene in-situ preparation of graft modification |
| CN109569568A (en) * | 2018-11-14 | 2019-04-05 | 中国矿业大学 | A kind of core-shell structure BiO2-x@TiO2Heterojunction photocatalysis material and the preparation method and application thereof |
| CN110040776A (en) * | 2019-04-25 | 2019-07-23 | 兰州理工大学 | A kind of preparation method and application of titania nanotube-graphene oxide |
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| CN113880520A (en) * | 2021-10-18 | 2022-01-04 | 界首市宝业瑞祥建筑工业化有限公司 | Repair material for micro-cracks on surface of prefabricated part |
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| CN107886710A (en) * | 2017-10-29 | 2018-04-06 | 山东鲁控电力设备有限公司 | Pedestrian crossing zone's coloured light indicates system and method |
| CN107950570A (en) * | 2017-11-21 | 2018-04-24 | 新化县中润化学科技有限公司 | A kind of preparation method of graphene/titanium dioxide/nano silver composite material |
| CN109277096A (en) * | 2018-11-01 | 2019-01-29 | 长沙矿冶研究院有限责任公司 | Carbon nanotube loaded nanometer Ti4O7Composite material and preparation method and application |
| CN109569568A (en) * | 2018-11-14 | 2019-04-05 | 中国矿业大学 | A kind of core-shell structure BiO2-x@TiO2Heterojunction photocatalysis material and the preparation method and application thereof |
| CN109536013A (en) * | 2018-12-28 | 2019-03-29 | 中国船舶重工集团公司第十二研究所 | A kind of preparation method of the hydrophobic nonpolluting coating of graphene in-situ preparation of graft modification |
| CN110040776A (en) * | 2019-04-25 | 2019-07-23 | 兰州理工大学 | A kind of preparation method and application of titania nanotube-graphene oxide |
| CN110040776B (en) * | 2019-04-25 | 2022-04-26 | 兰州理工大学 | Preparation method and application of titanium dioxide nanotube-graphene oxide |
| CN113354104A (en) * | 2021-07-01 | 2021-09-07 | 云南华谱量子材料有限公司 | Ecological system suitable for deepwater environment restoration and construction method thereof |
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| CN114790062A (en) * | 2022-01-24 | 2022-07-26 | 成都理工大学 | Volatile organic waste gas separation device |
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