CN109134923A - Ultra-dispersed porous graphene/nano TiO2Method for preparing composite material - Google Patents
Ultra-dispersed porous graphene/nano TiO2Method for preparing composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 16
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 16
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005457 ice water Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 8
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 8
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- -1 acyl ketone compounds Chemical class 0.000 claims description 14
- 230000001376 precipitating effect Effects 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 150000007524 organic acids Chemical class 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 150000003608 titanium Chemical class 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- GTTYPHLDORACJW-UHFFFAOYSA-N nitric acid;sodium Chemical compound [Na].O[N+]([O-])=O GTTYPHLDORACJW-UHFFFAOYSA-N 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 238000003756 stirring Methods 0.000 abstract description 6
- 238000000967 suction filtration Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 2
- 238000010923 batch production Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000003822 epoxy resin Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- 239000011229 interlayer Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000001934 delay Effects 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- VIRPUNZTLGQDDV-UHFFFAOYSA-N chloro propanoate Chemical compound CCC(=O)OCl VIRPUNZTLGQDDV-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a super-dispersed porous graphene/nano TiO2The preparation method of the composite material comprises the following steps: in an ice-water bath, adding a mixture obtained by mixing graphite powder and sodium nitrate into concentrated sulfuric acid, stirring and mixing, and adding potassium permanganate; then removing the reaction system from the ice-water bath, heating to 33 ℃, and preserving heat for 30-30 min; adding hydrogen peroxide solution, carrying out suction filtration after 2-hour reaction, adding the obtained graphene oxide into a mixed solution of ethanol and water, and then adding TiO2And carrying out ultrasonic reaction on the precursor and a sodium borohydride solution for 12-24 h, and then carrying out suction filtration to obtain the composite material. The method has simple process and low cost, and can be used for batch production.
Description
Technical field
The present invention relates to technical field of composite materials, and in particular to a kind of ultra-dispersed type porous graphene/nano-TiO2It is multiple
The preparation method of condensation material.
Background technique
Graphene is a kind of presently found most thin, most hard, the strongest novel nano-material of electrical and thermal conductivity performance, and stone
More oxide group is contained on black alkene surface, and preferable composite effect can be reached with polymer.Using graphene as novel
After lubricating type material mixes epoxy resin, the coefficient of friction of epoxy resin can be reduced, effectively improves its intensity, toughness, wear-resisting
Property and corrosion resistance.However since the effect of interlayer Van der Waals force causes graphene to be easy to reunite or even stack, thus lose
Advantage possessed by extra specific surface area and two-dimensional structure.Therefore a kind of packing material, the removing situation of graphene itself are used as
It is the key factor for determining material property.In the polymerization process of epoxy resin, the reunion situation of graphene is also to influence its property
The main reason for energy.
However, the graphene that mostly prepared by producer or laboratory at present still has ten layers or more of graphite-structure, synthesis
Graphene by Van der Waals force or dangling bond effect influenced it is easy to reunite at graphite flake.Such " graphite flake " can not actually claim
Make graphene, does not also have the excellent physical and chemical performance that " real graphene " is possessed.If graphene can be made during the preparation process
Realize good removing, and the ultra-dispersed graphene of in-situ preparation single layer in the polymerization process of epoxy resin, graphene can be with
Strong interaction occurs for the interface of epoxy resin, effectively improves the multinomial physical and chemical performance of epoxy resin, reaches in industry
Use standard.
Therefore, graphene modified epoxy of good performance in order to obtain, need to develop it is a kind of it is simple and easy, low at
This, the preparation method of ultra-dispersed graphene that can be mass-produced, to realize graphene being uniformly distributed in the epoxy, and
Guarantee that strong interface interaction occurs between graphene and epoxy molecule.
In consideration of it, the present invention is specifically proposed.
Summary of the invention
The purpose of the present invention is to provide a kind of ultra-dispersed type porous graphene/nano-TiOs2The preparation side of composite material
Method.
To achieve the above object, technical scheme is as follows:
The present invention relates to a kind of ultra-dispersed type porous graphene/nano-TiOs2The preparation method of composite material, the method
The following steps are included:
(1) graphite powder is mixed with sodium nitrate, obtains mixture；
(2) in ice-water bath, the mixture that step (1) obtains is added into the concentrated sulfuric acid, permanganic acid is added after being stirred
Potassium；
(3) reaction system that step (2) obtains is removed from ice-water bath, and is warming up to 33 DEG C, keep the temperature 30~30min；
(4) hydrogen peroxide solution is added in the reaction system obtained to step (3), and reaction is filtered after 2 hours, precipitating is washed
Wash, dry after obtain graphene oxide；
(3) graphene oxide is added in the mixed solution of ethyl alcohol and water, TiO is then added2Presoma and boron
Sodium hydride solution, ultrasonic reaction 12~filtered afterwards for 24 hours will obtain the composite material after washing of precipitate, drying.
Preferably, in step (1) and step (2), graphite powder, sodium nitrate, the concentrated sulfuric acid, potassium permanganate additional proportion be (1
~2g): (1~2g): (20~23ml): (2~3g).
Preferably, in step (4), the concentration of hydrogen peroxide solution is 30 mass %.
Preferably, in step (3), in the mixed solution of ethyl alcohol and water, the volume ratio of ethyl alcohol and water is 1:2.
Preferably, in step (3), after the graphene oxide is added in the mixed solution of ethyl alcohol and water, NaOH is used
The pH value of mixed solution is transferred to 7 by aqueous solution, and TiO is then added2Presoma and sodium borohydride solution.
Preferably, in step (3), the TiO2Presoma is prepared using following methods: by titanium salt and acyl ketone
Conjunction object, which is dissolved in alcohol, obtains solution A, and organic acid is dissolved in alcohol and obtains solution B, A, B solution are mixed to abundant precipitating
Afterwards, it is aged 20~30h, obtains the TiO2Presoma.
Preferably, in step (3), the titanium salt is titanium tetrachloride, and the acyl ketone compounds are acetylacetone,2,4-pentanedione, described to have
Machine acid is selected from least one of formic acid, acetic acid, ethanedioic acid.
Preferably, in step (3), the volume ratio of the alcohol and organic acid is (2~3): (1~2), acyl ketone compounds with
The mass ratio of titanium salt is 1:(8~10).
Preferably, in step (3), the mass ratio of sodium borohydride and graphene oxide is 1:(3~10).
Preferably, in the composite material, nano-TiO2Mass ratio with graphene is (0.3~1): 10.
Beneficial effects of the present invention:
It is at high cost for graphene, easy to reunite, in the epoxy difficult dispersion the problems such as, the present invention provides a kind of oversubscription
Dissipate type porous graphene/nano-TiO2The preparation method of composite material.This method carries out layer to graphene using organic deposition method
Between remove, specifically by organic deposition prepare metastable state TiO2Then presoma is had with the preparation method of graphene
Machine combines, and makes nano-TiO2The in-situ preparation between graphene layer blocks to effectively carry out splitting to graphene
The interlayer of graphene is compound, and stable ultra-dispersed type graphene/nanometer TiO is prepared2Composite material.This method technique letter
It is single, low in cost, can be produced in batches.
Detailed description of the invention
Fig. 1-1, Fig. 1-2 and Fig. 1-3 are the graphene/nanometer TiO that embodiment 1 obtains2Composite material is in different times magnifications
Transmission electron microscope (TEM) photo under several.
Fig. 2 is the graphene/nanometer TiO that comparative example 1 obtains2The TEM photo of composite material.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Detailed description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiment belongs to the range that the present invention is protected.
The present embodiments relate to a kind of ultra-dispersed type porous graphene/nano-TiOs2The preparation method of composite material, should
Method the following steps are included:
(1) graphite powder is mixed with sodium nitrate, obtains mixture.
(2) in ice-water bath, it is slowly added to the mixture that step (1) obtains into the concentrated sulfuric acid, slowly adds after being stirred
Enter potassium permanganate, is slowly stirred 20min after being preferably added to potassium permanganate.
In one embodiment of the invention, in step (1) and step (2), graphite powder, sodium nitrate, the concentrated sulfuric acid, permanganic acid
The additional proportion of potassium is (1~2g): (1~2g): (20~23ml): (2~3g).
(3) reaction system that step (2) obtains is removed from ice-water bath, and is warming up to 33 DEG C, keep the temperature 30~30min,
The process can carry out under oil bath or water bath condition.
(4) hydrogen peroxide solution that mass concentration is 30% is added in the reaction system obtained to step (3), after reaction 2 hours,
System bubble-free generates at this time.Reaction solution is filtered using miillpore filter, will filter obtained precipitating deionized water into
Row repeatedly washing, until sulfate radical-free detects.Graphene oxide is obtained after precipitating is dried in vacuo.
(3) according to 1g:(8~10ml) solid-liquid ratio, graphene oxide obtained above is added to the mixed of ethyl alcohol and water
It closes in solution, tests the pH value of mixed solution, if pH value is less than 7, the pH value of mixed solution is transferred to 7 using NaOH aqueous solution.
Then TiO is slowly added into mixed solution2Presoma and sodium borohydride solution, ultrasonic reaction 12~filtered afterwards for 24 hours will
Ultra-dispersed type porous graphene/nano-TiO is obtained after washing of precipitate, drying2Composite material.
In one embodiment of the invention, in the mixed solution of ethyl alcohol and water, the volume ratio of ethyl alcohol and water is 1:2.
It is studied by many years, a kind of method that can be prepared on a large scale at normal temperature nano-oxide of applicant's independent research
(such as TiO2、SiO2、ZrO2Deng), and it is named as " organic deposition method ", this method can homogeneously be sunk in organic solvent
Product, generates a large amount of high energy metastable state nano-oxide presomas, and then under given conditions, one step of forerunner's physical efficiency decomposes and from group
Dress is monodisperse type nano-oxide cluster.According to response characteristic, can make nano-oxide presoma between graphene layer from
Nano-oxide cluster is assembled into effectively carry out splitting to graphene to form ultra-dispersed graphene.
In one embodiment of the invention, TiO2Presoma is prepared using following methods: alcohol is as solvent, acyl ketone
Class compound is as buffer, and titanium salt is as source metal, and organic acid is as precipitating reagent.Titanium salt and acyl ketone compounds are dissolved in alcohol
In obtain solution A, organic acid is dissolved in alcohol and obtains solution B, by A, B solution be mixed, make to be uniformly distributed in system
Organic acid and alcohol reaction generates hydrone, and it is anti-that hydrolysis directly occurs with the metal salt being uniformly distributed in solvent using the hydrone
It answers, is stirred continuously until reaction generates white opacity precipitating.It sufficiently is aged 20~30h after precipitating, obtains TiO2Presoma.
In one embodiment of the invention, titanium salt is titanium tetrachloride, and acyl ketone compounds are acetylacetone,2,4-pentanedione, organic acid choosing
From at least one of formic acid, acetic acid, ethanedioic acid.
In one embodiment of the invention, the volume ratio of alcohol and organic acid is (2~3): (1~2), acyl ketone compounds
Mass ratio with titanium salt is 1:(8~10).In above-mentioned reaction, the additive amount of organic acid is more, reacts faster, generates precipitating
Time is shorter.The additional amount of pure and mild acyl ketone compounds is more, and titanium salt dissolubility is better, reacts more abundant.But it is added excessively
Pure and mild organic acid can reduce the concentration of reaction system, so that subsequent suction filtration energy consumption increases, it is therefore desirable to by above-mentioned organic reagent
Fixing fabric structure is in a certain range.
In step (3), sodium borohydride is used as the reducing agent of graphene oxide.In one embodiment of the present of invention
In, the mass ratio of sodium borohydride and graphene oxide is 1:(3~10).Sodium borohydride dosage is very few, goes back to graphene oxide
It is former insufficient, it still can residual oxygen graphene in product.Sodium borohydride dosage is excessive, can introduce excessive sodium ion and boron hydrogen radical
Ion equally increases the impurity content in product.
It in one embodiment of the invention, can be by TiO2Presoma is added in sodium borohydride solution, then slowly
It is added dropwise in the mixed liquor of graphene oxide.Due to TiO2Presoma in organic solvent can a step decompose and self assembly be single point
Dissipate type nano-TiO2Cluster, above-mentioned organic solvent is water-miscible or evenly dispersed in water, therefore in graphene oxide quilt
During reduction removing, TiO2Presoma decomposes in one step of interlayer meeting of graphene and is self-assembled into a large amount of nano-TiOs2Cluster,
These nano-TiOs2Cluster is fine and close " interlayer " in the formation between layers of graphene, has effectively carried out interlayer stripping to graphene
From having blocked the interlayer of graphene compound, to prepare stable ultra-dispersed type graphene.
In the composite material finally obtained, nano-TiO2Mass ratio with graphene is (0.3~1): 10.That is nano-TiO2
Quality account for the 3%~10% of graphene quality.
Embodiment 1
Prepare ultra-dispersed type porous graphene/nano-TiO2Composite material, comprising the following steps:
(1) 1g graphite powder is mixed with 1g sodium nitrate, obtains mixture.
(2) in ice-water bath, it is slowly added to the mixture that step (1) obtains into the 20ml concentrated sulfuric acid, delays after being stirred
It is slow that 2g potassium permanganate is added, continue to stir 20min.
(3) reaction system that step (2) obtains is removed from ice-water bath, be placed in water-bath and be warming up to 33 DEG C, heat preservation
30min。
(4) hydrogen peroxide solution that mass concentration is 30% is added in the reaction system obtained to step (3), after reaction 2 hours,
System bubble-free generates at this time.Reaction solution is filtered using miillpore filter, will filter obtained precipitating deionized water into
Row repeatedly washing, until sulfate radical-free detects.Graphene oxide is obtained after precipitating is dried in vacuo.
(3) according to the solid-liquid ratio of 1g:8ml, graphene oxide obtained above is added to 1 volume ethanol and 2 volume of water
Mixed solution in, the pH value of mixed solution is tested, if pH value is less than 7, using NaOH aqueous solution by the pH value tune of mixed solution
To 7.Then TiO is slowly added into mixed solution2The matter of presoma and sodium borohydride solution, sodium borohydride and graphene oxide
Amount is than being 1:10.It is filtered after ultrasonic reaction 12h, ultra-dispersed type porous graphene/nanometer will be obtained after washing of precipitate, drying
TiO2Composite material.
Wherein, TiO2Presoma is prepared using following methods:
10.98ml titanium tetrachloride and 0.149g acetylacetone,2,4-pentanedione are dissolved in 13ml dehydrated alcohol and obtain solution A, by 20ml first
Acid, which is dissolved in 13ml dehydrated alcohol, obtains solution B, and A, B solution are mixed, and is stirred continuously until reaction generates white opacity precipitating.
After being aged for 24 hours at room temperature, TiO is obtained2Presoma.
Embodiment 2
Prepare ultra-dispersed type porous graphene/nano-TiO2Composite material, comprising the following steps:
(1) 1.3g graphite powder is mixed with 1.3g sodium nitrate, obtains mixture.
(2) in ice-water bath, it is slowly added to the mixture that step (1) obtains into the 23ml concentrated sulfuric acid, delays after being stirred
It is slow that 3g potassium permanganate is added, continue to stir 20min.
(3) reaction system that step (2) obtains is removed from ice-water bath, be placed in water-bath and be warming up to 33 DEG C, heat preservation
40min。
(4) hydrogen peroxide solution that mass concentration is 30% is added in the reaction system obtained to step (3), after reaction 2 hours,
System bubble-free generates at this time.Reaction solution is filtered using miillpore filter, will filter obtained precipitating deionized water into
Row repeatedly washing, until sulfate radical-free detects.Graphene oxide is obtained after precipitating is dried in vacuo.
(3) according to the solid-liquid ratio of 1g:10ml, graphene oxide obtained above is added to 1 volume ethanol and 2 volume of water
Mixed solution in, the pH value of mixed solution is tested, if pH value is less than 7, using NaOH aqueous solution by the pH value tune of mixed solution
To 7.Then TiO is slowly added into mixed solution2The matter of presoma and sodium borohydride solution, sodium borohydride and graphene oxide
Amount is than being 1:8.It is filtered after ultrasonic reaction 12h, ultra-dispersed type porous graphene/nanometer will be obtained after washing of precipitate, drying
TiO2Composite material.
Wherein, TiO2Presoma is prepared using following methods:
10.98ml titanium tetrachloride and 0.0743g acetylacetone,2,4-pentanedione are dissolved in 30ml dehydrated alcohol and obtain solution A, by 20ml
Acetic acid, which is dissolved in 30ml dehydrated alcohol, obtains solution B, and A, B solution are mixed, and is stirred continuously until reaction generates white opacity and sinks
It forms sediment.After being aged for 24 hours at room temperature, TiO is obtained2Presoma.
Comparative example 1
In step (3), the commercially available nanoscale TiO of 3g is slowly added into mixed solution2, other operating procedures are the same as embodiment 1.
Comparative example 2
Step does not add TiO in (3)2, other operating procedures are the same as embodiment 1.
Test case
Transmissioning electric mirror test
The graphene/nanometer TiO that embodiment 1 and comparative example 1 are obtained2Composite material carries out transmission electron microscope (TEM) test,
The result is shown in Figure 1-1,1-2,1-3 and Fig. 2.Wherein Fig. 1-1, Fig. 1-2 and Fig. 1-3 are the obtained composite material of embodiment 1 not
With the electromicroscopic photograph under amplification factor, Fig. 2 is electromicroscopic photograph of the obtained composite material of comparative example 1 under different amplification.
It can be seen from the figure that the graphene matter that embodiment 1 obtains is thin and penetrating, it can be determined that be single layer, and visible nano-TiO2?
Graphene surface is uniformly distributed.The graphene stacking that comparative example 1 obtains is more serious, and due to opaque, nano-TiO2Almost
It is invisible.
In conjunction with electromicroscopic photograph as can be seen that nano-TiO is added2It is not only that the property of its nanoparticle is utilized.By
It joined TiO in graphene preparation process in the present invention2Presoma, during graphene oxide is reduced removing, TiO2
Presoma decomposes in one step of interlayer meeting of graphene and is self-assembled into a large amount of nano-TiOs2Cluster, these nano-TiOs2Cluster is in stone
The formation between layers of black alkene is fine and close " interlayer ", has effectively carried out splitting to graphene, has blocked the layer of graphene
Between it is compound, therefore can obtain removing more sufficiently, lamellar spacing is lower, performance is more stable ultra-dispersed type graphene.
It is prepared for ethylene oxide
Ultra-dispersed type porous graphene/nano-TiO that embodiment and comparative example are prepared2Composite material is as epoxy
The additive of resin, the specific steps are as follows:
(1) by the ultra-dispersed type porous graphene/nano-TiO of 0.1g2Composite material is dispersed with stirring in 28.02g epoxy chloropropionate
In alkane, then 22g bisphenol-A and above-mentioned epoxychloropropane are sequentially added in the 230ml four-necked bottle equipped with blender and thermometer,
Heating water bath is warming up to 73 DEG C, and stirring is completely dissolved bisphenol-A.
(2) reaction system is cooled to 70 DEG C, the sodium hydroxide solution that 40ml mass concentration is 20% is added dropwise, is added dropwise
The reaction was continued at 73-80 DEG C afterwards 1.3-2h, solution is in milk yellow at this time, stops heating and is simultaneously down to room temperature.
(3) benzene 60ml is added into reaction system, separatory funnel is moved into after stirring, sub-cloud water layer is divided after standing, then use
It is multiple to distill water washing, whether is in neutrality with pH test paper detection washing water, uses AgNO3Solution checks for chloride ion, then will
Organic layer separates.
(4) upper layer benzole soln is poured into vacuum distillation apparatus, first benzene is removed in distillation under 73 DEG C of normal pressures, after benzene removal,
All volatile matters are removed in vacuum distillation apparatus, pour out resin while hot, are saved.
To the above-mentioned epoxy resin being prepared, GB/T1040.2-2006 carries out tensile strength test according to national standards,
It the results are shown in Table 1.
Table 1
| Embodiment/comparative example | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 |
| Tensile strength test results | 38.3MPa | 39.6MPa | 34.9MPa | 30.3MPa |
It can be seen that the ultra-dispersed type porous stone that Examples 1 and 2 are prepared using the present invention from above-mentioned test result
Black alkene/nano-TiO2Additive of the composite material as epoxy resin, tensile strength are significantly better than comparative example 1 and 2.Explanation is adopted
Epoxide resin is modified with the composite material, its mechanical performance can be obviously improved.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. a kind of ultra-dispersed type porous graphene/nano-TiO2The preparation method of composite material, which is characterized in that the method packet
Include following steps:
(1) graphite powder is mixed with sodium nitrate, obtains mixture；
(2) in ice-water bath, the mixture that step (1) obtains is added into the concentrated sulfuric acid, potassium permanganate is added after being stirred；
(3) reaction system that step (2) obtains is removed from ice-water bath, and is warming up to 35 DEG C, keep the temperature 30~50min；
(4) hydrogen peroxide solution is added in the reaction system that obtains to step (3), and reaction is filtered after 2 hours, by washing of precipitate,
Graphene oxide is obtained after drying；
(5) graphene oxide is added in the mixed solution of ethyl alcohol and water, TiO is then added2Presoma and sodium borohydride
Solution, ultrasonic reaction 12~filtered afterwards for 24 hours will obtain the composite material after washing of precipitate, drying.
2. preparation method according to claim 1, which is characterized in that in step (1) and step (2), graphite powder, nitric acid
Sodium, the concentrated sulfuric acid, potassium permanganate additional proportion be (1~2g): (1~2g): (20~25ml): (2~3g).
3. preparation method according to claim 1, which is characterized in that in step (4), the concentration of hydrogen peroxide solution is 30 matter
Measure %.
4. preparation method according to claim 1, which is characterized in that in step (5), in the mixed solution of ethyl alcohol and water,
The volume ratio of ethyl alcohol and water is 1:2.
5. preparation method according to claim 1, which is characterized in that in step (5), the graphene oxide is added to
After in the mixed solution of ethyl alcohol and water, the pH value of mixed solution is transferred to 7 with NaOH aqueous solution, TiO is then added2Presoma and
Sodium borohydride solution.
6. preparation method according to claim 1, which is characterized in that in step (5), the TiO2Presoma is using following
Method is prepared: titanium salt and acyl ketone compounds is dissolved in alcohol and obtains solution A, organic acid is dissolved in alcohol and obtains solution B,
After A, B solution are mixed to sufficiently precipitating, it is aged 20~30h, obtains the TiO2Presoma.
7. preparation method according to claim 6, which is characterized in that in step (5), the titanium salt is titanium tetrachloride, institute
Stating acyl ketone compounds is acetylacetone,2,4-pentanedione, and the organic acid is selected from least one of formic acid, acetic acid, ethanedioic acid.
8. preparation method according to claim 6, which is characterized in that in step (5), the volume ratio of the alcohol and organic acid
It is 1:(8~10 for (2~5): the mass ratio of (1~2), acyl ketone compounds and titanium salt).
9. preparation method according to claim 1, which is characterized in that in step (5), sodium borohydride and graphene oxide
Mass ratio is 1:(5~10).
10. preparation method according to claim 1, which is characterized in that in the composite material, nano-TiO2With graphene
Mass ratio be (0.5~1): 10.
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