CN104826582B - A kind of preparation method of graphene meso-porous titanium dioxide silica aerogel - Google Patents
A kind of preparation method of graphene meso-porous titanium dioxide silica aerogel Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 239000004965 Silica aerogel Substances 0.000 title claims abstract description 36
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 36
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 38
- 239000010439 graphite Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 23
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000000017 hydrogel Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000003643 water by type Substances 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 230000002045 lasting effect Effects 0.000 claims description 7
- 238000012423 maintenance Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 7
- 238000010129 solution processing Methods 0.000 claims description 7
- 238000012546 transfer Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- 241000238370 Sepia Species 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 229910000275 saponite Inorganic materials 0.000 claims description 3
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 3
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 3
- 229960005055 sodium ascorbate Drugs 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 229940001482 sodium sulfite Drugs 0.000 claims description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims 2
- 206010013786 Dry skin Diseases 0.000 claims 1
- SNDJGKIVHKOEHY-UHFFFAOYSA-M S(=S)(=O)(O)O.S[Na] Chemical compound S(=S)(=O)(O)O.S[Na] SNDJGKIVHKOEHY-UHFFFAOYSA-M 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 6
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000010865 sewage Substances 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000004220 aggregation Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 8
- 239000000499 gel Substances 0.000 description 8
- 239000003463 adsorbent Substances 0.000 description 7
- 239000003292 glue Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000013335 mesoporous material Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- -1 rare earth compound Chemical class 0.000 description 3
- 235000019187 sodium-L-ascorbate Nutrition 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-M L-ascorbate Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] CIWBSHSKHKDKBQ-JLAZNSOCSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229940001474 sodium thiosulfate Drugs 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
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- Silicon Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of preparation method of graphene meso-porous titanium dioxide silica aerogel, comprise the following steps：The synthesis of graphite oxide；The preparation of graphene oxide solution；The preparation of graphene silica dioxide gel；The preparation of graphene meso-porous titanium dioxide silica aerogel.This method combines the excellent meso-hole structure feature of mesoporous silicon oxide with the hydrophobicity of graphene, preparing has a kind of new environmentally friendly sorbing material adsorbed compared with high selection to the heavy metal ion and organic pollution in sewage, so do on the one hand because the presence of mesoporous silicon oxide can hinder the aggregation of graphene, so as to keep its high specific surface area；On the other hand because the presence of graphene can be uniformly dispersed mesoporous silicon oxide, so as to keep its stability.Result is that the adsorption capacity of composite is improved, and is easily separated after absorption from solution.The technique of this method is simple, and the aeroge prepared can possess the characteristic of graphene and mesoporous silicon oxide.
Description
Technical field
The present invention relates to mesoporous material and its preparing technical field, specifically, it is related to a kind of graphene-meso-porous titanium dioxide
The preparation method of silica aerogel.
Background technology
There is Metaporous silicon dioxide material chemical property to stablize, specific surface area is big, pore size distribution$ scope is wide and can realize
The advantages of large-scale production, sewage disposal can be used for as adsorbent.But pure silicon dioxide mesoporous material is in itself without activity
Center, adsorbance is not high, the rate of adsorption is slower, limits it in the field extensive use.Therefore Metaporous silicon dioxide material
The concern of research extremely people prepared by functionalization, composite mesopore earth silicon material.
It is mesoporous that Chinese patent CN201010167801.9 provides a kind of carboxylated MCM-41 for Adsorption of Heavy Metals ion
The preparation method of molecular sieve.The patent, using grafting after two steps, is coupled using calcined MCM-41 as carrier with amino silane
Agent and halogenated acid are modified MCM-41.With some transition metal ions mating reaction can occur for its functional group, occur
Effective as selective is adsorbed.
Chinese patent CN201210411154.0 proposes a kind of New Type of Mesoporous material for adsorbing heavy metal ions in wastewater
Preparation method.Using different templates, using different silicon source and rare earth compound as presoma, at 100~150 DEG C,
Crystallization forms sol-gel in 3~8 hours.By removing template agent removing, ordered meso-porous silicon oxide rare earth material is prepared, and be used for
Heavy metal ion adsorbed experiment.
Chinese patent CN201310378526.9 proposes that a kind of graphene oxide of adsorbable water pollutant is magnetic mesoporous
The preparation method of silica composite material.This patent uses hydro-thermal method first, at 180~210 DEG C, reacts 8~72 hours, prepares
Go out the magnetic-particle for subsequent packet silicon.Then by the use of long chain alkane as pore-foaming agent, it is copolymerized, then leads to tetraethyl orthosilicate
Overheating Treatment removes pore-foaming agent, has obtained the magnetic mesoporous silicon oxide particle that surface carries hydroxyl.Finally, lived using carbodiimide
Change graphene oxide, obtain the magnetic mesoporous silica composite material of graphene oxide.Due to surface group, the composite can
To adsorb humic acid and heavy metal ion lead simultaneously.
Chinese patent CN201310309667.5 provides a kind of magnetic mesoporous oxidation for removing Organic Pollutants In Water
Silicon adsorbent and preparation method thereof.First pass through molysite to react in water with alkali, iron hydroxide is made, after centrifugation, add into precipitation
Enter glacial acetic acid, form hydrated ferric oxide colloidal solution；Then non-ionic macromolecule is added into hydrated ferric oxide colloidal solution
Polymer and silicon source presoma, stirring is to being thoroughly mixed, and hydro-thermal reaction 2~48 hours collects the solid product of generation, dries,
It is calcined the magnetic mesoporous silica adsorbent for the Organic Pollutants In Water that is removed.
Chinese patent 201410007948.X proposes the preparation of magnetic mesoporous silicon, preparation method and magnetic mesoporous silicon adsorbent
Method.The patent is using tetraethyl orthosilicate as silicon source, and ferrous sulfate amine is source of iron, and F-127 block copolymers are template, prepare magnetic
Property mesoporous silicon oxide.Oxidation polymerization is occurred into acid condition for the magnetic mesoporous silicon of preparation and Ammonium Persulfate 98.5 and aniline anti-
Should, it is washed out, filters, is dried to obtain magnetic mesoporous silicon adsorbent.
It is surface-functionalized to Metaporous silicon dioxide material progress to improve its adsorptivity from above method；Add
Magnetic iron oxide, is conducive to adsorbent to reclaim.But above method all uses hydro-thermal method when preparing mesoporous material, equipment cost is high；
And the sample prepared is powder body material, there is the problem of recovery is difficult.
Graphene is to pass through sp by the carbon atom of monoatomic layer2The two-dimensional atomic crystal of hydridization formation, with mechanical strength
The advantages of height, big theoretical specific surface area, obvious hydrophobicity, potential high oil-absorbing energy is made it have, containing organic pollution
Application prospect Worth Expecting in sewage disposal.It is due to the piece of graphene although graphene is a kind of preferable adsorbent
Rotating fields easily reassemble to form graphite, reduce and are difficult to separate from solution after specific surface area, and absorption, in practical application
In often it is combined with other sorbing materials.
The content of the invention
It is an object of the invention to overcome defect present in prior art, there is provided a kind of graphene-mesoporous silicon oxide
The preparation method of aeroge, this method has been combined the excellent meso-hole structure feature of mesoporous silicon oxide with the hydrophobicity of graphene
Come, prepare have to the heavy metal ion and organic pollution in sewage it is a kind of new environmentally friendly compared with what high selection was adsorbed
Sorbing material, so do on the one hand because the presence of mesoporous silicon oxide can hinder the aggregation of graphene, so as to keep it
High specific surface area；On the other hand because the presence of graphene can be uniformly dispersed mesoporous silicon oxide, so as to keep it stable
Property.Result is that the adsorption capacity of composite is improved, and is easily separated after absorption from solution.This method technique is simple,
And the aeroge prepared can possess the characteristic of graphene and mesoporous silicon oxide.
Its concrete technical scheme is：
A kind of preparation method of graphene-meso-porous titanium dioxide silica aerogel, comprises the following steps：
Step 1, using improved Hummer ' s methods, using graphite as raw material, prepare graphite oxide：It will be equipped with the concentrated sulfuric acid and dense
The reactor of phosphoric acid is placed in ice-water bath, the volume ratio 2: 1~15: 1 of the concentrated sulfuric acid and concentrated phosphoric acid, is cooled to 0 DEG C, adds 1g graphite
3g KMnO are slowly added in powder, high degree of agitation4, maintenance system temperature no more than 20 DEG C reaction 1h, transfer them to 35~45 DEG C
Water-bath 30min.46mL deionized waters are gradually added, temperature rises to 98 DEG C and continues to react 40min, and mixture is by brown stain
Into glassy yellow, with 140ml deionized waters and the H of mass fraction 30%2O2Solution processing, neutralizes unreacted potassium permanganate, mistake
Filter, with dilute HCl cyclic washings filter cake to filtrate without SO4 2-Afterwards, continue to be washed with deionized to filtrate weakly acidic pH, be drying to obtain
To graphite oxide.
Step 2, preparation graphene oxide solution：Add step 1 and obtain graphite oxide, carry out after ultrasonic disperse, centrifugation point
From unstripped graphite oxide and impurity is removed, until forming the uniform graphene oxide solution of sepia；Obtained oxidation stone
Black alkene is solution-stabilized to be present at least 1~24 hour.
The preparation of step 3, graphene-silica dioxide gel：The oxidation stone that the NaOH aqueous solution, silicon source and step 2 are obtained
Black aqueous solution, is slowly dropped in the cetyl trimethylammonium bromide of lasting stirring (CTAB) aqueous solution, reactant successively
Mol ratio be (0.12~0.25) CTAB: 1 silicon source: 0.6NaOH: 100H2O: χ graphene oxide, reacts 1~12h, and room temperature is old
Change, add after reducing agent, be placed in 1~10h of reaction in 70~100 DEG C of baking ovens, obtain hydrogel, obtained reaction product is carried out
Washing, -70 in vacuum freeze drier~-90 DEG C of 12~24h of drying, do not gone graphene-titanium dioxide of template agent removing
Silica aerogel.
The preparation of step 4, graphene-meso-porous titanium dioxide silica aerogel：The aeroge that step 3 is obtained removes template agent removing ten
Six alkyl trimethyl ammonium bromides, obtain graphene-meso-porous titanium dioxide silica aerogel.
It is preferred that, the supersonic frequency of ultrasonic disperse described in step 2 is 20~60KHz；The rotating speed of the centrifugation is
1000~6000 revs/min.
It is preferred that, the mass ratio of graphene oxide described in step 3 and silicon source is 1: 8~1: 40, wherein, the silicon source choosing
From：Tetraethyl orthosilicate, sodium metasilicate, natural montmorillonite, saponite.
It is preferred that, the mass ratio of reducing agent described in step 3 and graphene oxide is 5: 1~200: 1.Wherein, it is described to go back
Former agent is selected from：Ascorbic acid, sodium ascorbate, sodium sulfite, sodium thiosulfate.
It is preferred that, the method that template agent removing is removed described in step 4 is roasting method, and aeroge is placed in Muffle furnace and calcined,
400~700 DEG C are warming up to, is heated up 15 DEG C per 10min, and keeps 1~6h at such a temperature, room temperature is naturally cooled to.
It is preferred that, the method that template agent removing is removed described in step 4 is solvent extraction, and graphene-dioxy is obtained in step 3
After SiClx hydrogel, with EtOH/CH3COONa is extractant, removes cetyl trimethylammonium bromide；Template agent removing will be removed
Hydrogel is washed, -70 in vacuum freeze drier~-90 DEG C of 12~24h of drying, and obtain aeroge.
Compared with prior art, beneficial effects of the present invention are：
1. making silicon source using different raw materials, reducing agent can have multiple choices so that prepare material variation.
2. preparation method have technique it is simple, with low cost, can large-scale production the characteristics of.
3. Metaporous silicon dioxide material can be improved to organic solvent and the selective absorbing of macromolecular oily matter, and can
To realize the recovery of organic solvent and the Reusability of sorbing material.
4. graphene-meso-porous titanium dioxide the silica aerogel prepared combines graphene, mesoporous silicon oxide and aeroge
Feature, be expected to catalyst carrier, adsorb with separating, high temperature insulating protection in terms of be widely used.
Brief description of the drawings
Fig. 1 is the digital photograph of graphene-meso-porous titanium dioxide silica aerogel in embodiment 1；
Fig. 2 is the XRD of graphene-meso-porous titanium dioxide silica aerogel in embodiment 1；
Fig. 3 schemes for the TEM of pure graphene aerogel；
Fig. 4 is the TEM figures of graphene-meso-porous titanium dioxide silica aerogel in embodiment 1；
Fig. 5 is contact picture of the graphene-meso-porous titanium dioxide silica aerogel with water droplet in embodiment 1.
Embodiment
Technical scheme is described in more detail with specific embodiment below in conjunction with the accompanying drawings.
A kind of preparation of graphene-meso-porous titanium dioxide silica aerogel is carried out according to the following steps：
First, using improved Hummer ' s methods, using graphite as raw material, graphite oxide is prepared：It will be equipped with the concentrated sulfuric acid and dense phosphorus
The reactor of sour (volume ratio 2: 1~15: 1) is placed in ice-water bath, is cooled to 0 DEG C.Add slow in 1g graphite powders, high degree of agitation
Add 3g KMnO4, no more than 20 DEG C reaction 1h of maintenance system temperature.Transfer them to 35~45 DEG C of water-bath 30min.By
Step adds 46mL deionized waters, and temperature rises to 98 DEG C and continues to react 40min, and mixture is by brown stain into glassy yellow.Use 140ml
The H of deionized water and mass fraction 30%2O2Solution processing, neutralizes unreacted potassium permanganate, with dilute HCl cyclic washings filter cake
To filtrate without SO4 2-Afterwards, continue to be washed with deionized to filtrate weakly acidic pH, drying to obtain graphite oxide.
2nd, graphene oxide solution is prepared：Add step one and obtain graphite oxide, carry out after ultrasonic disperse, be centrifuged off
Unstripped graphite oxide and impurity, until forming the uniform graphene oxide solution of sepia；Obtained graphene oxide is molten
Liquid is stabilized at least 1~24 hour；
The supersonic frequency of the ultrasonic disperse is 20~60KHz；The rotating speed of the centrifugation be 1000~6000 turns/
Point.
3rd, the preparation of graphene-aerosil：The oxidation stone that the NaOH aqueous solution, silicon source and step 2 are obtained
Black aqueous solution, is slowly dropped in the cetyl trimethylammonium bromide of lasting stirring (CTAB) aqueous solution, reactant successively
Mol ratio be (0.12~0.25) CTAB: 1 silicon source: 0.6NaOH: 100H2O: χ graphene oxide, reacts 1~12h, and room temperature is old
Change, add after reducing agent, be placed in 70~100 DEG C of 1~10h of reaction, obtain hydrogel.Obtained reaction product is washed,
- 70 in vacuum freeze drier~-90 DEG C of 12~24h of drying, do not gone graphene-silica airsetting of template agent removing
Glue.
The graphene oxide and the mass ratio of silicon source are 1: 8~1: 40, wherein, the silicon source is selected from：Tetraethyl orthosilicate,
Sodium metasilicate, natural montmorillonite, saponite.
The mass ratio of the reducing agent and graphene oxide is 5: 1~200: 1.Wherein, the reducing agent is selected from：Vitamin C
Acid, sodium ascorbate, sodium sulfite, sodium thiosulfate.
4th, the preparation of graphene-meso-porous titanium dioxide silica aerogel：The aeroge that step 3 is obtained removes template agent removing 16
Alkyl trimethyl ammonium bromide, can obtain graphene-meso-porous titanium dioxide silica aerogel.
The method one for removing template agent removing is roasting method, and aeroge is placed in Muffle furnace and calcined, 400~700 DEG C are warming up to
(being heated up 15 DEG C per 10min), and 1~6h is kept at such a temperature, naturally cool to room temperature.
The method two for removing template agent removing is solvent extraction, after step 3 obtains graphene-silica hydrogel, with
EtOH/CH3COONa is extractant, removes cetyl trimethylammonium bromide；The hydrogel for removing template agent removing is washed,
- 70 in vacuum freeze drier~-90 DEG C of 12~24h of drying, obtain aeroge.
Embodiment 1
A. the synthesis of graphite oxide
The reactor that will be equipped with the 20.7ml concentrated sulfuric acid and 2.3ml concentrated phosphoric acid is placed in ice-water bath, is cooled to 0 DEG C.Plus
Enter and 3g KMnO are slowly added in 1g graphite powders, high degree of agitation4, no more than 20 DEG C reaction 1h of maintenance system temperature.Transfer them to
35~45 DEG C of water-bath 30min.Be gradually added 46mL deionized waters, temperature rises to 98 DEG C and continues to react 40min, mixture by
Brown stain is into glassy yellow.With 140ml deionized waters and the H of mass fraction 30%2O2Solution processing, neutralizes unreacted Gao Meng
Sour potassium, with dilute HCl cyclic washings filter cake to filtrate without SO4 2-Afterwards, continue to be washed with deionized to filtrate weakly acidic pH, drying is
Obtain graphite oxide.
B. the preparation of graphene oxide solution
Take 200mg graphite oxides to grind, add after 100mL deionized waters, ultrasonically treated 30min, suspension centrifugal treating
Wherein a small amount of impurity is removed, the graphene oxide solution of isotropic stable is obtained.
C. the preparation of graphene-silica dioxide gel
0.01g NaOH, 0.22g CTAB, 3.7g tetraethyl orthosilicate, the distilled water for measuring 6ml are taken, by NaOH, CTAB
Distilled water is dissolved in, the aqueous solution is made into, then the NaOH aqueous solution, tetraethyl orthosilicate, graphene oxide solution are slowly added dropwise successively
Into the lasting stirring CTAB aqueous solution, 1h is stirred, room temperature ageing is added after reducing agent 0.5g sodium ascorbates, is placed in 70 DEG C instead
2h is answered, hydrogel is obtained.Hydrogel is replaced 10 times with ultra-pure water, to remove water-solubility impurity.
The hydrogel of preparation is dried into 24h in vacuum freeze drier, graphene-silica dioxide gel airsetting is obtained
Glue.
D. the preparation of graphene-meso-porous titanium dioxide silica aerogel
Graphene-aerosil is placed in Muffle furnace and calcined, 540 DEG C (being heated up 15 DEG C per 10min) are warming up to,
And 6h is kept at 540 DEG C, naturally cool to room temperature.Template can be removed, graphene-mesoporous silicon oxide airsetting is obtained
Glue.
Embodiment 2
A. the synthesis of graphite oxide
The reactor that will be equipped with the 28.1ml concentrated sulfuric acid and 1.9ml concentrated phosphoric acid is placed in ice-water bath, is cooled to 0 DEG C.Plus
Enter and 3g KMnO are slowly added in 1g graphite powders, high degree of agitation4, no more than 20 DEG C reaction 1h of maintenance system temperature.Transfer them to
35~45 DEG C of water-bath 30min.Be gradually added 46mL deionized waters, temperature rises to 98 DEG C and continues to react 40min, mixture by
Brown stain is into glassy yellow.With 140ml deionized waters and the H of mass fraction 30%2O2Solution processing, neutralizes unreacted Gao Meng
Sour potassium, with dilute HCl cyclic washings filter cake to filtrate without SO4 2-Afterwards, continue to be washed with deionized to filtrate weakly acidic pH, drying is
Obtain graphite oxide.
B. the preparation of graphene oxide solution
Take 100mg graphite oxides to grind, add after 100mL deionized waters, ultrasonically treated 30min, suspension centrifugal treating
Wherein a small amount of impurity is removed, the graphene oxide solution of isotropic stable is obtained.
C. the preparation of graphene-aerosil
0.01g NaOH, 0.22g CTAB, 3.7g tetraethyl orthosilicate, the distilled water for measuring 6ml are taken, by NaOH, CTAB
Distilled water is dissolved in, the aqueous solution is made into, then the NaOH aqueous solution, tetraethyl orthosilicate, graphene oxide solution are slowly added dropwise successively
Into the lasting stirring CTAB aqueous solution, 1h is stirred, room temperature ageing is added after reducing agent 0.25g sodium ascorbates, is placed in 70 DEG C instead
2h is answered, hydrogel is obtained.Hydrogel is replaced 10 times with ultra-pure water, to remove water-solubility impurity.
The hydrogel of preparation is dried into 24h in vacuum freeze drier, graphene-aerosil is obtained.
D. the preparation of graphene-meso-porous titanium dioxide silica aerogel
Graphene-aerosil is placed in Muffle furnace and calcined, 540 DEG C (being heated up 15 DEG C per 10min) are warming up to,
And 6h is kept at 540 DEG C, naturally cool to room temperature.Template can be removed, graphene-mesoporous silicon oxide airsetting is obtained
Glue.
Embodiment 3
A. the synthesis of graphite oxide
The reactor that will be equipped with the 20.7ml concentrated sulfuric acid and 2.3ml concentrated phosphoric acid is placed in ice-water bath, is cooled to 0 DEG C.Plus
Enter and 3g KMnO are slowly added in 1g graphite powders, high degree of agitation4, no more than 20 DEG C reaction 1h of maintenance system temperature.Transfer them to
35~45 DEG C of water-bath 30min.Be gradually added 46mL deionized waters, temperature rises to 98 DEG C and continues to react 40min, mixture by
Brown stain is into glassy yellow.With 140ml deionized waters and the H of mass fraction 30%2O2Solution processing, neutralizes unreacted Gao Meng
Sour potassium, with dilute HCl cyclic washings filter cake to filtrate without SO4 2-Afterwards, continue to be washed with deionized to filtrate weakly acidic pH, drying is
Obtain graphite oxide.
B. the preparation of graphene oxide solution
Take 200mg graphite oxides to grind, add after 100mL deionized waters, ultrasonically treated 30min, suspension centrifugal treating
Wherein a small amount of impurity is removed, the graphene oxide solution of isotropic stable is obtained.
C. the preparation of graphene-aerosil
0.01g NaOH, 0.22g CTAB, 3.7g tetraethyl orthosilicate, the distilled water for measuring 6ml are taken, by NaOH, CTAB
Distilled water is dissolved in, the aqueous solution is made into, then the NaOH aqueous solution, tetraethyl orthosilicate, graphene oxide solution are slowly added dropwise successively
Into the lasting stirring CTAB aqueous solution, 1h is stirred, room temperature ageing adds after reducing agent 0.32g sodium sulfites, is placed in 70 DEG C of reactions
2h, obtains hydrogel.Hydrogel is replaced 10 times with ultra-pure water, to remove water-solubility impurity.
The hydrogel of preparation is dried into 24h in vacuum freeze drier, graphene-silica dioxide gel airsetting is obtained
Glue.
D. the preparation of graphene-meso-porous titanium dioxide silica aerogel
Graphene-silica dioxide gel is placed in Muffle furnace and calcined, is warming up to 540 DEG C (being heated up 15 DEG C per 10min), and
6h is kept at 540 DEG C, room temperature is naturally cooled to.Template can be removed, graphene-meso-porous titanium dioxide silica aerogel is obtained.
Embodiment 4
A. the synthesis of graphite oxide
The reactor that will be equipped with the 20.7ml concentrated sulfuric acid and 2.3ml concentrated phosphoric acid is placed in ice-water bath, is cooled to 0 DEG C.Plus
Enter and 3g KMnO are slowly added in 1g graphite powders, high degree of agitation4, no more than 20 DEG C reaction 1h of maintenance system temperature.Transfer them to
35~45 DEG C of water-bath 30min.Be gradually added 46mL deionized waters, temperature rises to 98 DEG C and continues to react 40min, mixture by
Brown stain is into glassy yellow.With 140ml deionized waters and the H of mass fraction 30%2O2Solution processing, neutralizes unreacted Gao Meng
Sour potassium, with dilute HCl cyclic washings filter cake to filtrate without SO4 2-Afterwards, continue to be washed with deionized to filtrate weakly acidic pH, drying is
Obtain graphite oxide.
B. the preparation of graphene oxide solution
Take 200mg graphite oxides to grind, add after 100mL deionized waters, ultrasonically treated 30min, suspension centrifugal treating
Wherein a small amount of impurity is removed, the graphene oxide solution of isotropic stable is obtained.
C. the preparation of graphene-silica dioxide gel
Take 0.01g NaOH, 0.22g CTAB, 0.68g NaSiO3·9H2O, the distilled water for measuring 6ml, by NaOH, CTAB
Distilled water is dissolved in, the aqueous solution is made into, then by the NaOH aqueous solution, NaSiO3·9H2O, graphene oxide solution are slowly added dropwise successively
Into the lasting stirring CTAB aqueous solution, 1h is stirred, room temperature ageing is added after reducing agent 0.5g sodium ascorbates, is placed in 70 DEG C instead
2h is answered, hydrogel is obtained.Hydrogel is replaced 10 times with ultra-pure water, to remove water-solubility impurity.
The hydrogel of preparation is dried into 24h in vacuum freeze drier, graphene-aerosil is obtained.
D. the preparation of graphene-meso-porous titanium dioxide silica aerogel
Graphene-silica dioxide gel is placed in Muffle furnace and calcined, is warming up to 540 DEG C (being heated up 15 DEG C per 10min), and
6h is kept at 540 DEG C, room temperature is naturally cooled to.Template can be removed, graphene-meso-porous titanium dioxide silica aerogel is obtained.
Fig. 1 is the digital photograph of graphene-meso-porous titanium dioxide silica aerogel in embodiment 1；Fig. 2 is graphite in embodiment 1
The XRD of alkene-meso-porous titanium dioxide silica aerogel；Fig. 3 schemes for the TEM of pure graphene aerogel；Fig. 4 be embodiment 1 in graphene-
The TEM figures of meso-porous titanium dioxide silica aerogel.Fig. 5 is the contact angle figure with water droplet of the aeroge prepared under the experiment condition, by
Figure understands that graphene-meso-porous titanium dioxide silica aerogel of preparation has super-hydrophobicity.
Graphene prepared by the present invention-meso-porous titanium dioxide silica aerogel combines graphene, mesoporous silicon oxide and airsetting
The characteristics of glue, be expected to catalyst carrier, adsorb with separating, high temperature insulating protection in terms of be widely used.
The foregoing is only a preferred embodiment of the present invention, be only intended to assistant solution the present invention method and its
Core concept, this specification content should not be construed as limiting the invention.Protection scope of the present invention not limited to this, it is any ripe
Those skilled in the art are known in the technical scope of present disclosure, the letter for the technical scheme that can be become apparent to
Altered or equivalence replacement are each fallen within protection scope of the present invention.
Claims (6)
1. the preparation method of a kind of graphene-meso-porous titanium dioxide silica aerogel, it is characterised in that comprise the following steps：
Step 1, using improved Hummer ' s methods, using graphite as raw material, prepare graphite oxide：It will be equipped with the concentrated sulfuric acid and concentrated phosphoric acid
Reactor be placed in ice-water bath, the volume ratio 2: 1~15: 1 of the concentrated sulfuric acid and concentrated phosphoric acid is cooled to 0 DEG C, adds 1g graphite powders,
3g KMnO are slowly added in high degree of agitation4, maintenance system temperature no more than 20 DEG C reaction 1h, transfer them to 35~45 DEG C of water
Bath reaction 30min, is gradually added 46mL deionized waters, and temperature rises to 98 DEG C and continues to react 40min, mixture by brown stain into
Glassy yellow, with 140ml deionized waters and the H of mass fraction 30%2O2Solution processing, neutralizes unreacted potassium permanganate, filters,
With dilute HCl cyclic washings filter cake to filtrate without SO4 2-Afterwards, continue to be washed with deionized to filtrate weakly acidic pH, drying to obtain oxygen
Graphite；
Step 2, preparation graphene oxide solution：Add step 1 and obtain graphite oxide, carry out after ultrasonic disperse, centrifugation is removed
Unstripped graphite oxide and impurity is removed, until forming the uniform graphene oxide solution of sepia；Obtained graphene oxide
It is solution-stabilized to exist at least 1~24 hour；
The preparation of step 3, graphene-aerosil：The graphite oxide that the NaOH aqueous solution, silicon source and step 2 are obtained
Aqueous solution, is slowly dropped in the cetyl trimethylammonium bromide aqueous solution of lasting stirring successively, the mol ratio of reactant
For 0.12CTAB: 1 silicon source: 0.6NaOH: 100H2O: χ graphene oxide, reacts 1~12h, and room temperature ageing is added after reducing agent,
1~10h of reaction in 70~100 DEG C of baking ovens is placed in, the reducing agent is selected from：Ascorbic acid, sodium ascorbate, sodium sulfite, sulphur
Sodium thiosulfate, obtains hydrogel, and obtained reaction product is washed, -70 in vacuum freeze drier~-90 DEG C of dryings
12~24h, is not removed graphene-aerosil of template agent removing；
The preparation of step 4, graphene-meso-porous titanium dioxide silica aerogel：The aeroge that step 3 is obtained removes template agent removing hexadecane
Base trimethylammonium bromide, obtains graphene-meso-porous titanium dioxide silica aerogel.
2. the preparation method of graphene according to claim 1-meso-porous titanium dioxide silica aerogel, it is characterised in that step 2
Described in ultrasonic disperse supersonic frequency be 20~60KHz；The rotating speed of the centrifugation is 1000~6000 revs/min.
3. the preparation method of graphene according to claim 1-meso-porous titanium dioxide silica aerogel, it is characterised in that preferably
Step 3 described in graphene oxide and the mass ratio of silicon source be 1: 8~1: 40, wherein, the silicon source is selected from：Positive silicic acid second
Ester, sodium metasilicate, natural montmorillonite, saponite.
4. the preparation method of graphene according to claim 1-meso-porous titanium dioxide silica aerogel, it is characterised in that step 3
Described in reducing agent and graphene oxide mass ratio be 5: 1~200: 1.
5. the preparation method of graphene according to claim 1-meso-porous titanium dioxide silica aerogel, it is characterised in that step 4
Described in go template agent removing method be roasting method, by aeroge be placed in Muffle furnace calcine, be warming up to 400~700 DEG C, often
10min heats up 15 DEG C, and keeps 1~6h at such a temperature, naturally cools to room temperature.
6. the preparation method of graphene according to claim 1-meso-porous titanium dioxide silica aerogel, it is characterised in that step 4
Described in go template agent removing method be solvent extraction, after step 3 obtains graphene-silica hydrogel, with EtOH/
CH3COONa is extractant, removes cetyl trimethylammonium bromide；The hydrogel for removing template agent removing is washed, in vacuum
- 70 in freeze drier~-90 DEG C of 12~24h of drying, obtain aeroge.
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