CN107824173A - A kind of titanous auto-dope titania nanoparticles partial reduction stannic oxide/graphene nano piece composite and preparation method thereof - Google Patents
A kind of titanous auto-dope titania nanoparticles partial reduction stannic oxide/graphene nano piece composite and preparation method thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 291
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 89
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 79
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 44
- 230000009467 reduction Effects 0.000 title claims abstract description 40
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 38
- 239000010936 titanium Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 9
- BQFCCCIRTOLPEF-UHFFFAOYSA-N chembl1976978 Chemical compound CC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 BQFCCCIRTOLPEF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 241000790917 Dioxys <bee> Species 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000012163 sequencing technique Methods 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 4
- 239000000975 dye Substances 0.000 abstract description 3
- 238000006303 photolysis reaction Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 30
- 239000000463 material Substances 0.000 description 17
- 238000001228 spectrum Methods 0.000 description 15
- 238000009833 condensation Methods 0.000 description 11
- 230000005494 condensation Effects 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 6
- 230000003321 amplification Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 125000005909 ethyl alcohol group Chemical group 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 238000003199 nucleic acid amplification method Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000001453 impedance spectrum Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 230000005622 photoelectricity Effects 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 241000208340 Araliaceae Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910003081 TiO2−x Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 235000008434 ginseng Nutrition 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 241001466460 Alveolata Species 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005707 optogalvanic effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/396—Distribution of the active metal ingredient
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of titanous auto-dope titania nanoparticles partial reduction stannic oxide/graphene nano piece composite and preparation method thereof, composite is in powdered, its powder particle includes the partial reduction stannic oxide/graphene nano piece as substrate and the titanous auto-dope titania nanoparticles as loaded article, and titanous auto-dope titania nanoparticles uniform deposition is on partial reduction stannic oxide/graphene nano piece.Composite photoelectric properties prepared by the present invention significantly improve, it is provided simultaneously with good chemical stability and reusing, titania nanoparticles loading on stannic oxide/graphene nano piece is realized using one step hydro thermal method while realizes the auto-dope of titanous and the partial reduction of graphene oxide, the titanous doping titanium dioxide nano particle size distribution of acquisition is uniform, method is simple to operate, mild condition, technique are simple, and good future is shown in photocatalytic degradation industry organic dyestuff and photolysis water hydrogen field.
Description
Technical field
The present invention relates to field of compound material, and in particular to a kind of titanous auto-dope titania nanoparticles-part
The preparation method of redox graphene nanosheet composite material and manufactured composite.
Background technology
Environmental pollution and energy crisis are the two large problems that the world faces the puzzlement mankind, with the rapid hair of social economy
Exhibition, largely the industrial and agricultural wastewater containing organic pollution enters water body, because these pollutants have high toxicity, difficult degradation and easy
The features such as accumulation, serious threat is constituted to the ecosystem and human health, the harm of organic pollutants causes the world
The extensive concern of scope, also due to the fossil fuel exhausted, a series of problem of environmental pollution values caused by combustion of fossil fuel
It must pay close attention to, and explore new replacement clean energy resource if Hydrogen Energy is there is an urgent need to, compel with to clean energy resource and green technology
It is essential and asks growing, effective application of solar energy, which has become many Green Chemistry and electric energy etc., has great potential
Application prospect, in order to solve a series of environment and energy problem, heterogeneous photocatalyst obtains numerous researchers and paid attention to, can be with
Radiant light is absorbed, is converted solar energy into electrical energy or chemical energy, so as to be efficiently applied to many places, such as organic pollution
Light degradation, solar energy water decomposes production hydrogen, DSSC and carbon dioxide photo-reduction, in addition, all these applications
All have cost it is low, efficiency high, it is easy to use the characteristics of.
Titanium dioxide as novel semiconductor material（TiO2）It is widely used in photocatalytic degradation, the gas of organic pollution
Body sensor, DSSC, biomaterial and photodissociation aquatic products hydrogen, and its low cost, good mechanical property are raw
Thing compatibility is good, compared with other conductor photocatalysis materials, TiO2It is strong, nontoxic with biological and chemical inertia, oxidability
And the advantages of being not susceptible to photochemical corrosion, it has also become the widest research of photochemical catalyst research, it is but, following two main scarce
Point greatly limit TiO2Extensive use：（1）Due to big band gap（Anatase is 3.2 eV, and rutile is 3.0 eV）, its light
The UV regions for being limited in solar spectrum are absorbed, only account for 3-5% solar energy；（2）The recombination rate of Photoinduced Charge carrier is high.
For problem above, researcher has had attempted to many methods, is shifted with more effectively responding TiO2 from UV
To visible region, and reduce the recombination efficiency of electron hole pair：
For first problem, in order that TiO2Light abstraction width expand to visible region, it is most of all to focus on O or Ti
Site introduces dopant, with TiO2Intermediate gap state is introduced in band gap, however, in TiO2The middle other dopants of introducing may
The thermal instability of composite, and increase Carrier recombination center can be caused, it is near several so as to influence the efficiency of photoelectrocatalysis
Year, by reducing TiO2Obtain auto-dope Ti3+TiO2（TiO2-x）, TiO is reduced so as to reach2The purpose of band-gap energy, has inhaled
Drawn the extensive concern of domestic and international researcher, it is many it has been reported that synthesis TiO2-xMethod have chemical vapor deposition, high energy grain
Application of vacuum or addition reducing agent under son bombardment and high temperature, but the operation of these methods is more complicated, synthesis condition it is harsh and
The facility cost needed is high, can be influenceed in terms of commercial Application by certain；
For Second Problem, it will usually with some similar to noble metal nano particles or the light induced electron receiver of carbon-based material,
Because noble metal is with high costs, be not suitable for large-scale application, therefore, inexpensive carbon-based material, which is likely to become, substitutes your rare gold
Effective substitute of category.Graphene is that be found in recent years a kind of by the tightly packed graphite flake layer formed of carbon atom and has
The two-dimensional material of alveolate texture, its special structure make it have very high specific surface area, excellent heat conductivility, excellent
Electron transport ability and preferable absorption property, it is very suitable for developing high performance composite.TiO2With graphene oxide
(GO) after compound, interface electron transfer rate is accelerated, the compound of light induced electron and hole is restrained effectively, improves to having
The physical and chemical adsorption of machine thing, its photocatalytic activity is enhanced, in recent years, numerous researchers widely uses sol-gel, original
The methods of position growth, hydro-thermal and anaerobic are calcined carrys out compound TiO2With graphene oxide, applied to photocatalytic degradation, hydrolytic hydrogen production,
Solar cell, lithium ion battery and antiseptic etc., in order to improve TiO2With the photocatalysis performance of RGO composites,
Researcher more can enter row metal, nonmetal doping in composite material surface, but the operation of these methods is more complicated, synthesizes bar
Part is harsh and the facility cost of needs is high, can be influenceed in terms of commercial Application by certain.Therefore, one kind is found more to accelerate
Speed, simple, economic method synthesis TiO2 and RGO composites are particularly important.Therefore, in view of the above-mentioned problems, being necessary
It is proposed further solution.
The content of the invention
The purpose of the present invention is：A kind of titanous auto-dope titanium dioxide with excellent visible light catalytic performance is provided
Nano particle-partial reduction stannic oxide/graphene nano piece composite.
To achieve the above object, the technical scheme is that：A kind of titanous auto-dope titania nanoparticles-portion
Divide redox graphene nanosheet composite material, the composite is in powdered, and its powder particle is included as substrate
Partial reduction stannic oxide/graphene nano piece and the titanous auto-dope titania nanoparticles as loaded article, the titanous
Auto-dope titania nanoparticles uniform deposition is on the partial reduction stannic oxide/graphene nano piece.
The present invention also provides another technical scheme：A kind of titanous auto-dope titania nanoparticles-part is also
The preparation method of former stannic oxide/graphene nano piece composite, comprises the following steps：
（1）Graphene oxide powder is scattered in solvent orange 2 A and forms mixed solution A；
（2）Titanium dioxide predecessor is scattered in solvent B and forms mixed solution B；
（3）The mixed solution B is added in the mixed solution A and forms mixed solution C；
（4）To the mixed solution C successively stir process, hydro-thermal process and drying and processing, titanous auto-dope dioxy is obtained
Change titanium nano particle-partial reduction stannic oxide/graphene nano piece composite；
Wherein, the mass ratio of the graphene oxide powder and the titanium dioxide predecessor is 1:5-1:2；
Step（1）And step（2）Without sequencing.
In above-mentioned technical proposal, graphite is transformed into graphene oxide solution by hummer methods, then by graphene oxide
Solution passes sequentially through eccentric cleaning and obtains the graphene oxide powder after freezing.
In above-mentioned technical proposal, the quality of the graphene oxide powder is 0.1g-0.3g, the titanium dioxide predecessor
For butyl titanate, the volume of the butyl titanate is 0.3ml-0.8ml.
In above-mentioned technical proposal, the solvent orange 2 A includes absolute ethyl alcohol and deionized water, absolute ethyl alcohol therein and go from
The volume ratio of sub- water is 200:1-250:1, step（1）In, the graphene oxide powder is dissolved in the absolute ethyl alcohol first
In, the deionized water is added in the solution then formed to the graphene oxide powder and the absolute ethyl alcohol, aoxidizes stone
The mass ratio of black alkene powder and solvent orange 2 A is 1:200-1:50.
In above-mentioned technical proposal, the solvent B is the body of absolute ethyl alcohol, the titanium dioxide predecessor and the solvent B
Product is than being 1:45-1:40.
In above-mentioned technical proposal, step（3）In, will in a manner of being added dropwise while the mixed solution A is stirred continuously
The mixed solution B is added in the mixed solution A.
In above-mentioned technical proposal, step（4）In stir process for ultrasonic agitation 0.5h-1h.
In above-mentioned technical proposal, step（4）In the reaction temperature of hydro-thermal process be 200 DEG C -250 DEG C, the reaction time is
9h-11h。
In above-mentioned technical proposal, step（4）In drying and processing for centrifugation dry.
The beneficial effects of the invention are as follows：
（1）Titanous auto-dope titania nanoparticles-partial reduction stannic oxide/graphene nano piece disclosed by the invention is compound
Material, the auto-dope of titanous makes to introduce intermediate gap state in titanium dioxide band gap, wide so as to solve titanium dioxide band gap
Problem, its light abstraction width is set to expand to visible region, compound with graphene oxide reduce further electronics and hole
Restructuring, so as to improve composite to the photo-catalysis capability of organic dyestuff and for light decompose production hydrogen, with simple dioxy
The composite for changing titanium/graphene is compared, and the titanium dioxide/graphene composite material photoelectric properties for adulterating titanous significantly carry
Height, good chemical stability and reusing are provided simultaneously with, can be by the titanous auto-dope nano titania of invention
Particle-partial reduction stannic oxide/graphene nano piece composite is applied to the side such as photocatalytic pollutant degradation and photodissociation aquatic products hydrogen
Face, possess the superiority such as high, the simple, fast, economical of flow of precision；
（2）Titanous auto-dope titania nanoparticles-partial reduction stannic oxide/graphene nano piece disclosed by the invention is compound
The preparation method of material, load of the titania nanoparticles on stannic oxide/graphene nano piece is realized using one step hydro thermal method
Realize the auto-dope of titanous and the partial reduction of graphene oxide, the titanous doping titanium dioxide nano of acquisition simultaneously
Particle size distribution is uniform, and method is simple to operate, mild condition, technique are simple, in photocatalytic degradation industry organic dyestuff and light
Solution water hydrogen preparation field shows good future.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments described in invention, for those of ordinary skill in the art, on the premise of not paying creative work,
Other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is the SEM figures of composite prepared by the embodiment of the present invention 1；
Fig. 2 a are the TEM figures that composite up-sizing prepared by the embodiment of the present invention 1 is 50nm；
Fig. 2 b are the TEM figures that composite up-sizing prepared by the embodiment of the present invention 1 is 100nm；
Fig. 2 c are the SAED figures of composite prepared by the embodiment of the present invention 1；
Fig. 2 d are the HRTEM figures for the spacing of lattice that composite prepared by the embodiment of the present invention 1 embodies titanium dioxide；
Fig. 3 a are the EDS figures of composite prepared by the embodiment of the present invention 1；
Fig. 3 b are the Elemental redistribution collection of illustrative plates of composite prepared by the embodiment of the present invention 1；
Fig. 4 a are answering for simple titanium dioxide, titanous auto-dope titania nanoparticles and the preparation of the embodiment of the present invention 1
The full spectrograms of XPS of condensation material；
Fig. 4 b are the narrow spectrograms of XPS of Ti elements corresponding to the composite of the preparation of the embodiment of the present invention 1；
Fig. 4 c are the narrow spectrograms of XPS of O elements corresponding to the composite of the preparation of the embodiment of the present invention 1；
Fig. 4 d are the narrow spectrograms of XPS of C element corresponding to the composite of the preparation of the embodiment of the present invention 1；
Fig. 5 a are answering for simple titanium dioxide, titanous auto-dope titania nanoparticles and the preparation of the embodiment of the present invention 1
The XRD spectrum of condensation material；
Fig. 5 b are answering for simple titanium dioxide, titanous auto-dope titania nanoparticles and the preparation of the embodiment of the present invention 1
The amplification XRD spectrum in 101 face regions of condensation material；
Fig. 5 c are the XRD spectrum of graphene oxide；
Fig. 6 a are answering for simple titanium dioxide, titanous auto-dope titania nanoparticles and the preparation of the embodiment of the present invention 1
The Raman collection of illustrative plates of condensation material；
Fig. 6 b are answering for simple titanium dioxide, titanous auto-dope titania nanoparticles and the preparation of the embodiment of the present invention 1
Condensation material is in displacement 150cm-1Locate the amplification Raman collection of illustrative plates at peak；
Fig. 6 c are answering for simple titanium dioxide, titanous auto-dope titania nanoparticles and the preparation of the embodiment of the present invention 1
Amplification Raman collection of illustrative plates of the condensation material at D, G peak；
Fig. 6 d are the infared spectrum of composite prepared by simple titanium dioxide, graphene oxide and the embodiment of the present invention 1；
Fig. 7 a are answering for simple titanium dioxide, titanous auto-dope titania nanoparticles and the preparation of the embodiment of the present invention 1
The ultraviolet-visible light of condensation material diffuses spectrogram；
Fig. 7 b are answering for simple titanium dioxide, titanous auto-dope titania nanoparticles and the preparation of the embodiment of the present invention 1
The photoluminescence spectra of condensation material；
Fig. 7 c are answering for simple titanium dioxide, titanous auto-dope titania nanoparticles and the preparation of the embodiment of the present invention 1
The photocurrent response figure of condensation material；
Fig. 7 d are answering for simple titanium dioxide, titanous auto-dope titania nanoparticles and the preparation of the embodiment of the present invention 1
Impedance spectrum of the condensation material under illumination condition；
Fig. 8 a are answering for simple titanium dioxide, titanous auto-dope titania nanoparticles and the preparation of the embodiment of the present invention 1
The efficiency chart of condensation material degradation of methylene blue under visible light conditions；
Fig. 8 b are the UV absorption wavelength graph of composite prepared by the embodiment of the present invention 1.
Wherein, SEM schemes：Electron scanning imaging figure；TEM schemes：Transmitted electron scanning imaging figure；HRTEM schemes：High-resolution is saturating
The sub- scanning imaging figure of radio；SAED schemes：SEAD figure；EDS schemes：Energy spectrum diagram；XRD spectrum：X ray diffracting spectrum；XPS
Spectrogram：X-ray photoelectron spectroscopic analysis spectrogram.
Embodiment
In order that those skilled in the art more fully understand the technical scheme in the present invention, below in conjunction with of the invention real
The accompanying drawing in example is applied, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described implementation
Example only part of the embodiment of the present invention, rather than whole embodiments.It is common based on the embodiment in the present invention, this area
The every other embodiment that technical staff is obtained under the premise of creative work is not made, should all belong to protection of the present invention
Scope.
In order to facilitate the understanding of the purposes, features and advantages of the present invention, with reference to the accompanying drawings and examples
Further illustrate technical scheme.But the invention is not restricted to listed embodiment, it should also be included in institute of the present invention
It is required that interest field in other any known change.
First, " one embodiment " or " embodiment " referred to herein refers to may be included at least one realization side of the present invention
Special characteristic, structure or characteristic in formula." in one embodiment " that different places occur in this manual not refers both to
Same embodiment, nor the single or selective embodiment mutually exclusive with other embodiment.
Secondly, the present invention is described in detail using structural representation etc., when the embodiment of the present invention is described in detail, for ease of saying
Bright, schematic diagram can disobey general proportion and make partial enlargement, and the schematic diagram is example, and it should not limit the present invention herein
The scope of protection.
Embodiment 1
First, it is below titanous auto-dope titania nanoparticles-partial reduction stannic oxide/graphene nano piece composite
Preparation method：
The graphite oxide for the drying for obtaining dissolving in absolute ethyl alcohol will be freezed after the graphene oxide water solution eccentric cleaning of synthesis
Alkene powder, 0.1g graphene oxide powders are scattered in 20ml absolute ethyl alcohols, then add 0.1ml deionized waters and form mixing
Solution A, 0.3ml titanium dioxide predecessor butyl titanates and 20ml absolute ethyl alcohols are formed into mixed solution B, by mixed solution B
It is slowly dropped in mixed solution A and forms mixed solution C, 1h is stirred by ultrasonic in mixed solution C, then by mixed solution C 220
DEG C reaction temperature under react 10h, afterwards centrifugation drying, obtain titanous auto-dope titania nanoparticles-partial reduction
Stannic oxide/graphene nano piece composite.
Above-mentioned graphene oxide powder is made with the following method：Graphene oxide is synthesized, below 15 DEG C of ice bath, by 2g stones
Ink and 6g potassium permanganate are dissolved in the anhydrous concentrated sulfuric acids of 46mL, are warming up to 35 DEG C and are stirred 2h, are warming up to 80 DEG C of dropwise addition 100ml water,
95 DEG C plus 300ml water are then heated to, anhydrous hydrogen peroxide 1-2ml, treatment conditions are added dropwise：It is lyophilized.
2nd, following is that the titanous auto-dope titania nanoparticles-partial reduction graphene oxide prepared is received
Rice piece composite makees the process of photoelectricity test：
Working electrode, configuration supporting electrolyte are made respectively, prepare, to electrode and reference electrode, 1. to make work by 5mg titanouses
The powder of auto-dope titania nanoparticles-partial reduction stannic oxide/graphene nano piece composite is dissolved in 500uL isopropanols
In, then 50uL 0.5% perfluorosulfonic acid type polymer solution is added dropwise, 1h is ultrasonically treated, composite mixed solution is obtained, takes
The above-mentioned composite mixed solutions of 3uL are added dropwise on glass-carbon electrode, as working electrode；2. configure 0.1 M sodium sulfites to prop up
Hold electrolyte；3. made using platinum filament to electrode；4. calomel electrode makees reference electrode；
The optogalvanic effect of composite is detected using the chronoptentiometry of electrochemical workstation, wherein between having the time of no light
It is divided into 30s.
3rd, following is that the titanous auto-dope titania nanoparticles-partial reduction graphene oxide prepared is received
Rice piece composite makees photocatalytic degradation organic polluting water process：
The composite of simple titanium dioxide, titanous auto-dope titania nanoparticles and preparation is impregnated in just respectively
The methylene blue that beginning concentration is 40 mg/L is polluted in the aqueous solution, is first stirred 12 hours in dark surrounds and is reached adsorption equilibrium shape
After state, then 0-120 min are irradiated under visible light, time interval is 30 min, each time interval, takes corresponding solution test purple
Outer visible light absorption value.
Four：It is the result that the composite of preparation is detected and tested below
（One）Fig. 1 is the SEM figures of the composite prepared, it can be seen that titania nanoparticles uniform deposition is received in graphene
The surface of rice piece；
（Two）Fig. 2 a are the TEM figures that the composite up-sizing prepared is 50nm, and Fig. 2 b are the composite pantograph prepared
The very little TEM for 100nm schemes, and further demonstrates titanous auto-dope titania nanoparticles uniform deposition in graphene nano
The surface of piece, titanous auto-dope titania nanoparticles size is about 6nm；
Fig. 2 c are the SAED figures of the composite prepared, and Fig. 2 d are that the composite prepared embodies the spacing of lattice of titanium dioxide
HRTEM schemes, and TiO2 Detitanium-ore-types (101) crystal face spacing of lattice is 0.35 nm；
（Three）Fig. 3 a are the EDS figures of the composite prepared, and Fig. 3 b are the Elemental redistribution collection of illustrative plates of the composite prepared, show gold
Modification bismuth molybdate nanometer sheet/Nano tube array of titanium dioxide mainly contains tri- kinds of elements of Ti, O, C；
（Four）Fig. 4 a are the composite of simple titanium dioxide, titanous auto-dope titania nanoparticles and preparation
The full spectrograms of XPS, Fig. 4 b are the narrow spectrograms of XPS of Ti elements corresponding to the composite prepared；Fig. 4 c are the composite pair prepared
The narrow spectrograms of XPS for the O elements answered, Fig. 4 d are the narrow spectrograms of XPS of C element corresponding to the composite prepared, and Fig. 4 a can in composing entirely
To be clearly visible the peak of tri- kinds of elements of Ti, O, C, this it appears that titanous from the narrow spectrums of Ti 2p high-resolution XPS
Peak, from the narrow spectrums of the C 1s high-resolution XPS of sample it can be seen that C=O disappears substantially, show the oxygen-containing functional group in GO in hydro-thermal
It is partially reduced in course of reaction, it is seen that hydro-thermal reaction causes trivalent titanium doped and graphene is reduced while carried out；
（Five）Fig. 5 a are the composite of simple titanium dioxide, titanous auto-dope titania nanoparticles and preparation
XRD spectrum, Fig. 5 b exist for the composite of simple titanium dioxide, titanous auto-dope titania nanoparticles and preparation
The amplification XRD spectrum in 101 faces region, Fig. 5 c are the XRD spectrum of graphene oxide, it can be seen that titanous auto-dope titanium dioxide
Nano particle and the composite prepared are offset to the left relative to the XRD peaks of simple titanium dioxide, and this phenomenon is attributed to trivalent
It is titanium doped to there is trivalent in titanium auto-dope titania nanoparticles and the composite sample of preparation；Do not go out in Fig. 5 c figures
, there is the diffraction maximum corresponding to titanium dioxide, this is probably due to ultrasonic disperse in the dilute characteristic diffraction peak of existing graphite oxide
The ordered lamellar structure of graphene oxide is damaged with subsequent hydro-thermal process, forms the graphite oxide of partial reduction
Alkene, and titania is formed on graphene oxide layer surface, hinders the orderly accumulation of graphene oxide synusia, with
Fig. 2 c result matches)
（Six）Fig. 6 a are the drawing of the composite of simple titanium dioxide, titanous auto-dope titania nanoparticles and preparation
Graceful collection of illustrative plates, unmodified titanium dioxide shows typical Detitanium-ore-type Raman spectrum in Fig. 6 a, and auto-dope Ti3+Dioxy
Change titanium crystal and new peak position occur, illustrate to reduce Ti3+Afterwards titania structure change result in it is unordered, so as to excite
The marginal zone of crystal；
Fig. 6 b are the composite of simple titanium dioxide, titanous auto-dope titania nanoparticles and preparation in displacement
150cm-1Locate peak amplification Raman collection of illustrative plates, Fig. 6 c be simple titanium dioxide, titanous auto-dope titania nanoparticles and
The composite of preparation D, G peak amplification Raman collection of illustrative plates, it is evident that titanous auto-dope titania nanoparticles with
And the peak of titanous auto-dope titania nanoparticles-partial reduction stannic oxide/graphene nano piece composite is to high displacement
Direction is offset, and illustrate to have in composite that trivalent is titanium doped, is found out from Fig. 6 c, D peaks are greater than G peaks, and declaratives aoxidize stone
Black alkene reduces to obtain partial reduction graphene oxide, it is seen that hydro-thermal reaction causes trivalent titanium doped and graphene is reduced while entered
OK, the proof meets XPS and XRD interpretation of result simultaneously；
Fig. 6 d be simple titanium dioxide, graphene oxide and the composite of preparation infared spectrum, the piece of graphene oxide
Contain many oxygen-containing functional groups, 3403 cm on layer-1It is-OH stretching vibration absworption peak corresponding to the wide absworption peak for locating to occur,
1728 cm-1Belong to C=O stretching vibration, 1626 cm-1It is the skeletal vibration peak in not oxidized graphite area, it is flexible to shake
Dynamic peak, 1072 cm-1It is the stretching vibration peak of C-O in C-O-C, from titanous auto-dope titania nanoparticles-part
The infrared spectrogram of redox graphene nanosheet composite material compound can be seen that the master of graphene oxide in compound
The vibration peak of oxygen-containing functional group is wanted, such as 1728 cm-1、1390 cm-1、1238 cm-1With 1072 cm-1Intensity have significantly
Weaken, illustrate graphene oxide in water-heat process there occurs a certain degree of reduction, but be reduced to graphite completely
Alkene.479 cm-1The strong absworption peak that place occurs belongs to Ti-O-Ti stretching vibration, illustrates titanium dioxide and graphene oxide
Preferably combined；
（Seven）Fig. 7 a are the purple of the composite of simple titanium dioxide, titanous auto-dope titania nanoparticles and preparation
Outside-visible ray diffuses spectrogram, that reflects the optical property of prepared photochemical catalyst and different bandgap structures, merely
Titanium dioxide only absorbs ultraviolet light, and its basic absorption edge is close to 400 nm, compared with simple titanium dioxide, titanous auto-dope
Titania nanoparticles and titanous auto-dope titania nanoparticles-partial reduction stannic oxide/graphene nano piece composite wood
Material absorption in region between 400 and 800nm further improves；
Fig. 7 b are the photic hair of the composite of simple titanium dioxide, titanous auto-dope titania nanoparticles and preparation
Higher transmitting peak intensity is presented in light spectrum, simple titanium dioxide, and titanous auto-dope titania nanoparticles-part is also
The PL intensity of former stannic oxide/graphene nano piece composite further weakens, and illustrates interface electronics from titanous auto-dope titanium dioxide
The conduction band of titanium is transferred to partial reduction stannic oxide/graphene nano piece surface, the restructuring in electronics and hole is reduced, so as to enhance
The photocatalytic activity of titanous auto-dope titania nanoparticles-partial reduction stannic oxide/graphene nano piece composite；
Fig. 7 c are the photoelectric current of the composite of simple titanium dioxide, titanous auto-dope titania nanoparticles and preparation
Response diagram, using 0.1 M anhydrous sodium sulfate as electrolyte, xenon lamp（400 below nm wavelength is filtered with optical filter）Simulate visible
Light, the distance of light source to beaker is 15 cm, and intensity of illumination is 60 mW/cm2, in the electrode body of CHI660D electrochemical workstations three
System is lower to carry out photoelectricity current test, titanous auto-dope titania nanoparticles and titanous auto-dope nano titania
The density of photocurrent of grain-partial reduction stannic oxide/graphene nano piece composite is respectively 0.0025,0.0046,0.0192,
0.0132 mA/cm2, it is the density of photocurrent of simple titanium dioxide respectively（0.0006 mA/cm2）4 times, 7.7 times, 32 times,
22 times, represent to improve the separation effect of electron hole pair after TiO2 nano-tube arrays modification bismuth molybdate nanometer sheet and gold nano grain
Rate, it can be seen that the density of photocurrent highest when graphene oxide dosage increases to 0.2g, continue to increase graphene oxide amount, light
Current density is on a declining curve；
Fig. 7 d are the composite of simple titanium dioxide, titanous auto-dope titania nanoparticles and preparation in illumination bar
Impedance spectrum under part, using 0.1 M anhydrous sodium sulfate as electrolyte, xenon lamp（400 below nm wavelength is filtered with optical filter）
Simulated visible light, the distance of light source to beaker is 15 cm, and intensity of illumination is 60 mW/cm2, in CHI660D electrochemical workstations
Ac impedance measurement is carried out under three-electrode system.Under illumination condition, simple titanium dioxide, titanous auto-dope titanium dioxide are received
The exchange of rice grain and titanous auto-dope titania nanoparticles-partial reduction stannic oxide/graphene nano piece composite
Impedance spectrum.Compared with simple titanium dioxide, titanous auto-dope titania nanoparticles show less semicircle, table
It is bright that effective photo-generate electron-hole separation is realized on titanous auto-dope titanium dioxide electrodes.In addition, titanous auto-dope
Titania nanoparticles-partial reduction stannic oxide/graphene nano piece composite is shown minimum half in AC impedance spectrum
Circular arc, show after graphene is introduced, electron acceptor occurs faster interfacial charge transfer and causes the effective of electron-hole pair
Separation；
Fig. 8 a are the composite of simple titanium dioxide, titanous auto-dope titania nanoparticles and preparation in visible ray
Under the conditions of degradation of methylene blue efficiency chart, Fig. 8 b be prepare composite UV absorption wavelength graph.
Mixed certainly with the simple titanium dioxide of 500W Xenon light shinings, titanous auto-dope titania nanoparticles and titanous
Miscellaneous titania nanoparticles-partial reduction stannic oxide/graphene nano piece composite degradation of methylene blue under visible light, with
Simple titanium dioxide compares, and titanous auto-dope titanium dioxide significantly improves to the degradation efficiency of methylene blue, while trivalent
Titanium auto-dope titania nanoparticles-light degradation of the partial reduction stannic oxide/graphene nano piece composite to methylene blue exists
Degraded substantially during 120min completely, degradation efficiency reaches 100%.
Embodiment 2
It is the preparation of titanous auto-dope titania nanoparticles-partial reduction stannic oxide/graphene nano piece composite below
Method：The graphene oxide water solution of synthesis is freezed to the oxidation stone for the drying for obtaining dissolving in absolute ethyl alcohol after eccentric cleaning
Black alkene powder, 0.2g graphene oxide powders are scattered in 20ml absolute ethyl alcohols, are added 0.1ml deionized waters and are formed mixing
Solution A, 0.5ml titanium dioxide predecessor butyl titanates and 20ml absolute ethyl alcohols are formed into mixed solution B, by mixed solution B
Mixed solution, which is slowly dropped in mixed solution A, forms mixed solution C, then will mixing after mixed solution C is stirred by ultrasonic into 1h
Solution C reacts 10h under 220 DEG C of reaction temperature, and centrifugation drying, obtains titanous auto-dope nano titania afterwards
Grain-partial reduction stannic oxide/graphene nano piece composite.
Photoelectricity test process and photocatalytic degradation organic polluting water process ginseng to composite manufactured in the present embodiment
Examine embodiment 1.
Embodiment 3
It is the preparation of titanous auto-dope titania nanoparticles-partial reduction stannic oxide/graphene nano piece composite below
Method：The graphene oxide water solution of synthesis is freezed to the oxidation stone for the drying for obtaining dissolving in absolute ethyl alcohol after eccentric cleaning
Black alkene, 0.3g graphene oxide powders are scattered in 20ml absolute ethyl alcohols, it is molten then to add the formation mixing of 0.1ml deionized waters
Liquid A, 0.8ml titanium dioxide predecessor butyl titanates and 20ml absolute ethyl alcohols are formed into mixed solution B, mixed solution B is delayed
Slow be added drop-wise in mixed solution A forms mixed solution C, and mixed solution C is stirred by ultrasonic into 1h, then reacted mixed solution C
Temperature be 220 DEG C under conditions of hydro-thermal reaction 10h, be then centrifuged for drying, obtain titanous auto-dope titania nanoparticles-
Partial reduction stannic oxide/graphene nano piece composite.
Photoelectricity test process and photocatalytic degradation organic polluting water process ginseng to composite manufactured in the present embodiment
Examine embodiment 1.
Certainly the above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow be familiar with technique
People can understand present disclosure and implement according to this, it is not intended to limit the scope of the present invention.It is all according to this hair
The modification that the Spirit Essence of bright main technical schemes is done, it should all be included within the scope of the present invention.
Claims (10)
1. a kind of titanous auto-dope titania nanoparticles-partial reduction stannic oxide/graphene nano piece composite, it is special
Sign is that the composite is in powdered, and its powder particle includes the partial reduction stannic oxide/graphene nano piece as substrate
It is equal with the titanous auto-dope titania nanoparticles as loaded article, the titanous auto-dope titania nanoparticles
It is even to be deposited on the partial reduction stannic oxide/graphene nano piece.
A kind of 2. preparation of titanous auto-dope titania nanoparticles-partial reduction stannic oxide/graphene nano piece composite
Method, it is characterised in that comprise the following steps：
（1）Graphene oxide powder is scattered in solvent orange 2 A and forms mixed solution A；
（2）Titanium dioxide predecessor is scattered in solvent B and forms mixed solution B；
（3）The mixed solution B is added in the mixed solution A and forms mixed solution C；
（4）To the mixed solution C successively stir process, hydro-thermal process and drying and processing, titanous auto-dope dioxy is obtained
Change titanium nano particle-partial reduction stannic oxide/graphene nano piece composite；
Wherein, the mass ratio of the graphene oxide powder and the titanium dioxide predecessor is 1:5-1:2；
Step（1）And step（2）Without sequencing.
3. preparation method according to claim 2, it is characterised in that graphite is transformed into graphite oxide by hummer methods
Alkene solution, then graphene oxide solution is passed sequentially through into eccentric cleaning and obtains the graphene oxide powder after freezing.
4. preparation method according to claim 2, it is characterised in that the quality of the graphene oxide powder is 0.1g-
0.3g, the titanium dioxide predecessor are butyl titanate, and the volume of the butyl titanate is 0.3ml-0.8ml.
5. preparation method according to claim 2, it is characterised in that the solvent orange 2 A includes absolute ethyl alcohol and deionization
The volume ratio of water, absolute ethyl alcohol therein and deionized water is 200:1-250:1, step（1）In, first by the graphite oxide
Alkene powder is dissolved in the absolute ethyl alcohol, is added in the solution then formed to the graphene oxide powder and the absolute ethyl alcohol
Enter the deionized water, the mass ratio of graphene oxide powder and solvent orange 2 A is 1:200-1:50.
6. preparation method according to claim 2, it is characterised in that the solvent B is absolute ethyl alcohol, the titanium dioxide
Predecessor and the solvent B volume ratio are 1:45-1:40.
7. preparation method according to claim 2, it is characterised in that step（3）In, it is being stirred continuously the mixed solution
The mixed solution B is added in the mixed solution A in a manner of being added dropwise while A.
8. preparation method according to claim 2, it is characterised in that step（4）In stir process for ultrasonic agitation
0.5h-1h。
9. preparation method according to claim 2, it is characterised in that step（4）In the reaction temperature of hydro-thermal process be
200 DEG C -250 DEG C, reaction time 9h-11h.
10. preparation method according to claim 2, it is characterised in that step（4）In drying and processing for centrifugation dry.
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| WO2019085532A1 (en) * | 2017-11-01 | 2019-05-09 | 南通纺织丝绸产业技术研究院 | Composite material of trivalent titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheets and preparation method therefor |
| CN111068671A (en) * | 2019-12-19 | 2020-04-28 | 西安近代化学研究所 | High-selectivity amino acid decarboxylation catalyst and preparation method thereof |
| CN114920289A (en) * | 2022-05-12 | 2022-08-19 | 山东大学 | Preparation method of titanium sesquioxide nanowire |
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| CN114920289A (en) * | 2022-05-12 | 2022-08-19 | 山东大学 | Preparation method of titanium sesquioxide nanowire |
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