CN107715856A - A kind of graphene composite material - Google Patents
A kind of graphene composite material Download PDFInfo
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- CN107715856A CN107715856A CN201711042344.9A CN201711042344A CN107715856A CN 107715856 A CN107715856 A CN 107715856A CN 201711042344 A CN201711042344 A CN 201711042344A CN 107715856 A CN107715856 A CN 107715856A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000004793 Polystyrene Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 239000010408 film Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 238000003780 insertion Methods 0.000 claims description 6
- 230000037431 insertion Effects 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000001338 self-assembly Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003643 water by type Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 claims description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000003491 array Methods 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- POXRUQZSBXFWGH-UHFFFAOYSA-L dipotassium dithionate Chemical compound [K+].[K+].[O-]S(=O)(=O)S([O-])(=O)=O POXRUQZSBXFWGH-UHFFFAOYSA-L 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- -1 meanwhile Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to grapheme material and graphene applied technical field, specially a kind of graphene composite material.The preparation of the graphene composite material of the present invention includes the steps such as the preparation of grapheme material, the preparation of TiO2 nanometer cups, the preparation of graphene/TiO2 nanometer cup composites.Graphene prepared by the present invention/TiO2 nanometer cup specific surface areas are big, and the introducing of graphene can be good at preventing the compound again of electronics and hole, effectively improve production hydrogen effect by TiO2 and graphene are compound, greatly improve the utilization rate to sunshine.
Description
Technical field
The present invention relates to grapheme material and graphene applied technical field, specially a kind of graphene composite material.
Background technology
Photocatalysis technology is the basic nanometer technology being born in the 1970s, including titanium dioxide, zinc oxide, oxidation
Because its oxidability is strong, forbidden band is wide for many oxides such as tin, zirconium dioxide, cadmium sulfide, sulfide semiconductor, wherein titanium dioxide
Degree is wider, has good absorption to ultraviolet light, chemical property is stable, nontoxic, and the light for turning into most widely used urges agent nanometer material
Material.TiO2 nano materials are a kind of white inorganic nano materials, have nontoxic, optimal opacity, optimal whiteness and light
Degree, it is considered to be a kind of current best Chinese white of performance in the world, be widely used in coating, plastics, papermaking, off-set oil
The industry such as ink, chemical fibre, rubber, cosmetics, meanwhile, titanium dioxide has preferable ultraviolet masking action, is mixed frequently as sun-screening agent
Enter in textile fabric, sun care preparations is made in being also added into sun-proof creams in ultra-fine titania powder.Because the energy is asked
The getting worse of topic, exploitation novel energy turns into inevitable path, therefore photodissociation aquatic products hydrogen just turns into exploitation novel energy method
In study hotspot.Graphene be by carbon atom it is tightly packed into individual layer two dimension carbonaceous material.Graphene is due to fabulous
Electricity, optics, the performance such as machinery and it is wide concerned.Due to TiO2 energy gap, wavelength in the visible spectrum can only be absorbed
Light less than 380nm excites generation electrons, so relatively low to the utilization rate of visible ray, hydrogen generation efficiency is not high, by
Its area load noble metal, doped metal ion or anion or composite is prepared to improve the utilization rate to visible ray.
Because graphene has good electron transport property, can be good at preventing the compound again of electronics and hole, therefore will
TiO2 produces hydrogen effect with compound effectively improve of graphene.
Asked so providing a kind of graphene/TiO2 composites with improving TiO2 production hydrogen effect as what we to be solved
Topic.
The content of the invention
It is an object of the invention to provide a kind of graphene/TiO2 composites with and preparation method thereof, it is above-mentioned to solve
The problem of in background technology.To achieve the above object, there is provided following technical scheme：
A kind of graphene composite material, its preparation include step：
S1, grapheme material preparation：By the mixed of graphite powder and potassium dithionate, phosphorus pentoxide and the concentrated sulfuric acid in reactor
React in zoarium system, stir 5 hours under 80 DEG C of water bath conditions, to forming solution, cooling, filter, it is dry after pre-oxidized
Graphite；The graphite of pre-oxidation mixes in three-neck flask under conditions of ice-water bath with concentrated sulfuric acid solution, and the height being gradually added into
Potassium manganate, stir 2 hours, after being warming up to 40 DEG C, continue stirring 1 hour, and be 1 according to volume ratio：15 amount adds 30wt%
The mixed solution of hydrogen peroxide and deionized water；Filter, cleaned 1 time with the watery hydrochloric acid and deionized water that mass fraction is 10% respectively,
Centrifugation, graphene oxide is obtained after drying；The graphene oxide powder is pressed 1：1000 mass ratio is added in distilled water, is used
It is 10 that ammoniacal liquor, which adjusts its pH, the ultrasonic 3h in the case where power is 150W, obtains stable graphene oxide suspension, is dripped in suspension
Add hydrazine hydrate, its addition adds 0 .015 milliliters by every milligram of graphene oxide powder, is heated with 80 DEG C of waters bath with thermostatic control
10h, reactant is washed to neutrality, 50 DEG C of drying, that is, obtain thin graphene material under vacuo；
The preparation of S2, TiO2 nanometer cup：It is 0.28mol/L by 50mL ethanol, 15mL deionized waters, 3mL concentration under room temperature condition
The mixed solution that is made into of hydrochloric acid instill dropwise containing 10mL butyl titanates, 60mL ethanol, 5mL acetylacetone,2,4-pentanediones solution in,
Under 50Hz frequencies, ultrasonic vibration 2 hours, TiO2 colloidal sols are made；TiO2 colloidal sols are spin-coated on FTO glass with 5000rpm rotating speed
On, Muffle furnace is then placed in, is sintered 2 hours under the conditions of 500 DEG C, forming anatase type tio2 on FTO glass after sintering receives
Rice crystal film, thickness 30nm；Polystyrene PS small columns are dissolved in volume ratio as 1 using 6% mass ratio:2 water and ethanol
Mixed solution in, and the mixed solution is slowly expelled to microsyringe the surface of water, it is freely disperseed, until with
Individual layer is paved with the whole water surface, then adds the lauryl sodium sulfate aqueous solution that 1ml mass ratioes are 2% and is opened to reduce the surface of water
Power, make the arrangement of individual layer small column compact, finally place 24 hours, make the roundlet column sedimentation to be suspended in water, whole process is all being sealed
Closed loop is completed in border；The TiO2 films sintered are had to the water of PS small columns with 30 degree of angle tilt insertion previous step self assembly
In solution, the PS small columns single thin film of self assembly on the water surface is slowly picked up, then under nitrogen protection, 90 DEG C of drying one are small
When, PS roundlet column templates are made；Again by with PS roundlet column templates TiO2 film normals insertion TiO2 colloidal sols in 30 seconds, finally
Slowly propose and be put into Muffle furnace, sintered 2 hours under the conditions of 500 DEG C, so as to obtain TiO2 nanometer cup arrays；
The preparation of S3, graphene/TiO2 nanometer cup composites：The .2mg graphene materials of 11 .4~34 are added by 50ml distilled water
The proportionate relationship of material, the thin graphene material obtained in step S1 is added in distilled water, it is dilute after ultrasonic disperse 60min
Be interpreted into graphene suspension, nanometer cup array in the TiO2 in step S2 be added in above-mentioned graphene suspension, TiO2 and
Mol ratio with graphene is 1：1, under magnetic stirring, it is 11~12 that ammoniacal liquor is added dropwise into solution and adjusts its pH value, obtains institute
Graphene/TiO2 nanometer cup the precursor solutions needed, the reactor with polytetrafluoroethyllining lining is transferred to by the precursor solution
In, 16~24h is reacted after sealing at 120 DEG C~180 DEG C, product is washed with distilled water to after neutrality to be dried at 60 DEG C, will
Dried powder is put into vacuum drying oven, and 550~650 DEG C of 2~5h of calcining, furnace cooling are raised to 10 DEG C/min programming rate
To room temperature, that is, obtain graphene/TiO2 nanometer cup composites.
Compared with prior art, the beneficial effects of the invention are as follows：Graphene prepared by the present invention/TiO2 nanometer cups compare surface
Product is big, and introducings of graphene can be good at the compound again of prevention electronics and hole, by TiO2 with graphene is compound can be effective
Production hydrogen effect is improved, greatly improves the utilization rate to sunshine.
Embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below in conjunction with the embodiment of the present invention,
Obviously, described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
A kind of graphene composite material, its preparation method are：
S1, grapheme material preparation：By the mixed of graphite powder and potassium dithionate, phosphorus pentoxide and the concentrated sulfuric acid in reactor
React in zoarium system, stir 5 hours under 80 DEG C of water bath conditions, to forming solution, cooling, filter, it is dry after pre-oxidized
Graphite；The graphite of pre-oxidation mixes in three-neck flask under conditions of ice-water bath with concentrated sulfuric acid solution, and the height being gradually added into
Potassium manganate, stir 2 hours, after being warming up to 40 DEG C, continue stirring 1 hour, and be 1 according to volume ratio：15 amount adds 30wt%
The mixed solution of hydrogen peroxide and deionized water；Filter, cleaned 1 time with the watery hydrochloric acid and deionized water that mass fraction is 10% respectively,
Centrifugation, graphene oxide is obtained after drying；The graphene oxide powder is pressed 1：1000 mass ratio is added in distilled water, is used
It is 10 that ammoniacal liquor, which adjusts its pH, the ultrasonic 3h in the case where power is 150W, obtains stable graphene oxide suspension, is dripped in suspension
Add hydrazine hydrate, its addition adds 0 .015 milliliters by every milligram of graphene oxide powder, is heated with 80 DEG C of waters bath with thermostatic control
10h, reactant is washed to neutrality, 50 DEG C of drying, that is, obtain thin graphene material under vacuo；
The preparation of S2, TiO2 nanometer cup：It is 0.28mol/L by 50mL ethanol, 15mL deionized waters, 3mL concentration under room temperature condition
The mixed solution that is made into of hydrochloric acid instill dropwise containing 10mL butyl titanates, 60mL ethanol, 5mL acetylacetone,2,4-pentanediones solution in,
Under 50Hz frequencies, ultrasonic vibration 2 hours, TiO2 colloidal sols are made；TiO2 colloidal sols are spin-coated on FTO glass with 5000rpm rotating speed
On, Muffle furnace is then placed in, is sintered 2 hours under the conditions of 500 DEG C, forming anatase type tio2 on FTO glass after sintering receives
Rice crystal film, thickness 30nm；Polystyrene PS small columns are dissolved in volume ratio as 1 using 6% mass ratio:2 water and ethanol
Mixed solution in, and the mixed solution is slowly expelled to microsyringe the surface of water, it is freely disperseed, until with
Individual layer is paved with the whole water surface, then adds the lauryl sodium sulfate aqueous solution that 1ml mass ratioes are 2% and is opened to reduce the surface of water
Power, make the arrangement of individual layer small column compact, finally place 24 hours, make the roundlet column sedimentation to be suspended in water, whole process is all being sealed
Closed loop is completed in border；The TiO2 films sintered are had to the water of PS small columns with 30 degree of angle tilt insertion previous step self assembly
In solution, the PS small columns single thin film of self assembly on the water surface is slowly picked up, then under nitrogen protection, 90 DEG C of drying one are small
When, PS roundlet column templates are made；Again by with PS roundlet column templates TiO2 film normals insertion TiO2 colloidal sols in 30 seconds, finally
Slowly propose and be put into Muffle furnace, sintered 2 hours under the conditions of 500 DEG C, so as to obtain TiO2 nanometer cup arrays；
The preparation of S3, graphene/TiO2 nanometer cup composites：The .2mg graphene materials of 11 .4~34 are added by 50ml distilled water
The proportionate relationship of material, the thin graphene material obtained in step S1 is added in distilled water, it is dilute after ultrasonic disperse 60min
Be interpreted into graphene suspension, nanometer cup array in the TiO2 in step S2 be added in above-mentioned graphene suspension, TiO2 and
Mol ratio with graphene is 1：1, under magnetic stirring, it is 11~12 that ammoniacal liquor is added dropwise into solution and adjusts its pH value, obtains institute
Graphene/TiO2 nanometer cup the precursor solutions needed, the reactor with polytetrafluoroethyllining lining is transferred to by the precursor solution
In, 16~24h is reacted after sealing at 120 DEG C~180 DEG C, product is washed with distilled water to after neutrality to be dried at 60 DEG C, will
Dried powder is put into vacuum drying oven, and 550~650 DEG C of 2~5h of calcining, furnace cooling are raised to 10 DEG C/min programming rate
To room temperature, that is, obtain graphene/TiO2 nanometer cup composites.
Graphene prepared by the present invention/TiO2 nanometer cup specific surface areas are big, and the introducing of graphene can be good at preventing electricity
Son is compound again with hole, and compound effectively improve of TiO2 and graphene is produced into hydrogen effect, greatly improves the profit to sunshine
With rate.
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art,
It can still modify to the technical scheme described in foregoing embodiments, or which part technical characteristic is carried out etc.
With replacing, within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., this should be included in
Within the protection domain of invention.
Claims (2)
- A kind of 1. graphene composite material, it is characterised in that：The preparation of the graphene composite material includes step：S1, grapheme material preparation：By the mixed of graphite powder and potassium dithionate, phosphorus pentoxide and the concentrated sulfuric acid in reactor React in zoarium system, stir 5 hours under 80 DEG C of water bath conditions, to forming solution, cooling, filter, it is dry after pre-oxidized Graphite；The graphite of pre-oxidation mixes in three-neck flask under conditions of ice-water bath with concentrated sulfuric acid solution, and the height being gradually added into Potassium manganate, stir 2 hours, after being warming up to 40 DEG C, continue stirring 1 hour, and be 1 according to volume ratio：15 amount adds 30wt% The mixed solution of hydrogen peroxide and deionized water；Filter, cleaned 1 time with the watery hydrochloric acid and deionized water that mass fraction is 10% respectively, Centrifugation, graphene oxide is obtained after drying；The graphene oxide powder is pressed 1：1000 mass ratio is added in distilled water, is used It is 10 that ammoniacal liquor, which adjusts its pH, the ultrasonic 3h in the case where power is 150W, obtains stable graphene oxide suspension, is dripped in suspension Add hydrazine hydrate, its addition adds 0 .015 milliliters by every milligram of graphene oxide powder, is heated with 80 DEG C of waters bath with thermostatic control 10h, reactant is washed to neutrality, 50 DEG C of drying, that is, obtain thin graphene material under vacuo；The preparation of S2, TiO2 nanometer cup：It is 0.28mol/L by 50mL ethanol, 15mL deionized waters, 3mL concentration under room temperature condition The mixed solution that is made into of hydrochloric acid instill dropwise containing 10mL butyl titanates, 60mL ethanol, 5mL acetylacetone,2,4-pentanediones solution in, Under 50Hz frequencies, ultrasonic vibration 2 hours, TiO2 colloidal sols are made；TiO2 colloidal sols are spin-coated on FTO glass with 5000rpm rotating speed On, Muffle furnace is then placed in, is sintered 2 hours under the conditions of 500 DEG C, forming anatase type tio2 on FTO glass after sintering receives Rice crystal film, thickness 30nm；Polystyrene PS small columns are dissolved in volume ratio as 1 using 6% mass ratio:2 water and ethanol Mixed solution in, and the mixed solution is slowly expelled to microsyringe the surface of water, it is freely disperseed, until with Individual layer is paved with the whole water surface, then adds the lauryl sodium sulfate aqueous solution that 1ml mass ratioes are 2% and is opened to reduce the surface of water Power, make the arrangement of individual layer small column compact, finally place 24 hours, make the roundlet column sedimentation to be suspended in water, whole process is all being sealed Closed loop is completed in border；The TiO2 films sintered are had to the water of PS small columns with 30 degree of angle tilt insertion previous step self assembly In solution, the PS small columns single thin film of self assembly on the water surface is slowly picked up, then under nitrogen protection, 90 DEG C of drying one are small When, PS roundlet column templates are made；Again by with PS roundlet column templates TiO2 film normals insertion TiO2 colloidal sols in 30 seconds, finally Slowly propose and be put into Muffle furnace, sintered 2 hours under the conditions of 500 DEG C, so as to obtain TiO2 nanometer cup arrays；The preparation of S3, graphene/TiO2 nanometer cup composites：The .2mg graphene materials of 11 .4~34 are added by 50ml distilled water The proportionate relationship of material, the thin graphene material obtained in step S1 is added in distilled water, it is dilute after ultrasonic disperse 60min Be interpreted into graphene suspension, nanometer cup array in the TiO2 in step S2 be added in above-mentioned graphene suspension, TiO2 and Mol ratio with graphene is 1：1, under magnetic stirring, it is 11~12 that ammoniacal liquor is added dropwise into solution and adjusts its pH value, obtains institute Graphene/TiO2 nanometer cup the precursor solutions needed, the reactor with polytetrafluoroethyllining lining is transferred to by the precursor solution In, 16~24h is reacted after sealing at 120 DEG C~180 DEG C, product is washed with distilled water to after neutrality to be dried at 60 DEG C, will Dried powder is put into vacuum drying oven, and 550~650 DEG C of 2~5h of calcining, furnace cooling are raised to 10 DEG C/min programming rate To room temperature, that is, obtain graphene/TiO2 nanometer cup composites.
- A kind of 2. graphene composite material according to claim 1 and preparation method thereof.
Priority Applications (1)
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