CN110217779A - Carbon nano-tube modification graphene aerogel and its preparation method and application - Google Patents
Carbon nano-tube modification graphene aerogel and its preparation method and application Download PDFInfo
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- CN110217779A CN110217779A CN201910567150.3A CN201910567150A CN110217779A CN 110217779 A CN110217779 A CN 110217779A CN 201910567150 A CN201910567150 A CN 201910567150A CN 110217779 A CN110217779 A CN 110217779A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 184
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 104
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 70
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 70
- 239000004964 aerogel Substances 0.000 title claims abstract description 52
- 238000012986 modification Methods 0.000 title claims abstract description 46
- 230000004048 modification Effects 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 24
- 239000000017 hydrogel Substances 0.000 claims abstract description 21
- 238000012545 processing Methods 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 230000008014 freezing Effects 0.000 claims abstract description 15
- 238000007710 freezing Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims abstract description 4
- 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 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 10
- -1 potassium iodide compound Chemical class 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Inorganic materials [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- 239000004088 foaming agent Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 3
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 3
- 235000007715 potassium iodide Nutrition 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- 150000001412 amines Chemical group 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims 1
- 229930003268 Vitamin C Natural products 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 235000019154 vitamin C Nutrition 0.000 claims 1
- 239000011718 vitamin C Substances 0.000 claims 1
- 230000002209 hydrophobic effect Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 description 16
- 239000003921 oil Substances 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000002048 multi walled nanotube Substances 0.000 description 8
- 235000010323 ascorbic acid Nutrition 0.000 description 7
- 229960005070 ascorbic acid Drugs 0.000 description 7
- 239000011668 ascorbic acid Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 150000004996 alkyl benzenes Chemical class 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
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- 238000007906 compression Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- 241001346815 Spongia officinalis Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/06—Multi-walled nanotubes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/32—Specific surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/34—Length
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of carbon nano-tube modification graphene aerogels and its preparation method and application.The preparation method includes: that the carbon nanotube of amino-functionalization, surfactant, graphene oxide and reducing agent are dispersed in water to form homogeneous mixed dispersion liquid by (1)；(2) mixed dispersion liquid is stirred and is foamed, obtain mix-froth liquid；(3) mix-froth liquid is subjected at 60~100 DEG C 2~12h of reaction, is cooled to 15~35 DEG C, obtain carbon nano-tube modification graphene hydrogel；(4) by carbon nano-tube modification graphene hydrogel at -10~-60 DEG C freezing processing, then carry out constant pressure and dry processing, obtain carbon nano-tube modification graphene aerogel.Carbon nano-tube modification graphene aerogel of the invention has good elasticity, mechanical performance and hydrophobic performance.
Description
Technical field
The present invention relates to a kind of carbon nano-tube modification graphene aerogels and its preparation method and application.
Background technique
With the fast development of petrochemical industry, occurs Oil spills thing in oil exploitation, refining, transportational process
Therefore used in chemical industry and organic solvent discharging, this is all inevitable, and serious dirt can be all caused to environment
Dye.Therefore, scientists from all over the world develop various adsorbents and are used for water-oil separating.Conventional adsorbent for oils and organic solvent has
Zeolite, flyash, active carbon, oil-absorbing resin, commercial sponge etc..That there are adsorption efficiencies is low for these adsorbents, and recycling rate is poor,
Complex process, not environmentally the disadvantages of.
Graphene aerogel is due to its superelevation voidage, high resilience, excellent both thermally and chemically stability and super thin
It is aqueous that there is very high adsorptivity to oils and organic solvent.But the mechanical performance and three-dimensional framework of pure graphene aerogel
Anti-fatigue performance it is poor, be easy to be broken；Applicability is lower in actual water-oil separating and the absorption of organic solvent, limits
Its industrial applications.
Beijing University of Chemical Technology's Materials Academy has developed that a kind of " it is multiple that cabbage shape, graded porous structure graphene/carbon receive pipe
The efficient absorption that aeroge (GCPCA) is used for organic solvent is closed, the multi-walled carbon nanotube of poly-dopamine functionalization is innovative
It is introduced into graphene aerogel structure with graphene/carbon nano-tube aerogel composite that preparation structure is stable.It is demonstrate,proved through test
Bright, obtained graphene aerogel is up to 501 times of aeroge sole mass to the adsorbance of organic solvent chloroform.But
The process the high requirements on the equipment, energy consumption is big, is unfavorable for industrialized production, the aeroge mechanical performance and elasticity of acquisition have
Wait improve.CN105129772B disclose it is a kind of prepare aminated carbon nano tube-graphene aerogel method, by by graphite
Carbon nanotube CNTS powder is added in alkene GO solution, ethylenediamine then is added and ammonium hydroxide is reacted, is freezed again after reaction
It is dry, aminated carbon nano tube-graphene aerogel is obtained, the amido modified surface of graphene oxide of the preparation method, to propose
The graphene aerogel that height generates is to the absorption property of gas formaldehyde, but it is bad in water-oil separating field application effect.
CN107686107A discloses a kind of elastic hydrophobic carbon nanotube-graphene alkene composite aerogel, and graphene oxide, carboxyl carbon are received
Mitron, reducing agent and mixed with polymers form homogeneous aqueous solution, restore by high-temperature heating and drying generates carbon nanotube-graphite
Alkene aeroge.This method complex process, it is at high cost；And in order to enhance its mechanical strength, need to add crosslinking agent, this is just reduced
Its hydrophobic performance.
It is low that a kind of preparation cost is researched and developed as a result, and oil-water separation is good, and the repeatable graphene-based suction being recycled
Enclosure material is very necessary.
Summary of the invention
In view of this, it is an object of the present invention to provide a kind of preparation sides of carbon nano-tube modification graphene aerogel
Method, can low cost prepare carbon nano-tube modification graphene aerogel.
It is another object of the present invention to provide a kind of carbon nano-tube modification graphene aerogel, bullets with higher
Property and mechanical strength, higher absorption property, opposite conventional graphite alkene aeroge preparation cost it is low.
It is yet a further object of the present invention to provide a kind of carbon nano-tube modification graphene aerogels in water-oil separating field
In application.
The present invention adopts the following technical scheme that realization above-mentioned purpose.
On the one hand, the present invention provides a kind of preparation method of carbon nano-tube modification graphene aerogel, includes the following steps:
(1) carbon nanotube of amino-functionalization, surfactant, graphene oxide and reducing agent are dispersed in water to be formed
Mix dispersion liquid；
(2) mixed dispersion liquid is stirred and is foamed, obtain mix-froth liquid；
(3) mix-froth liquid is subjected at 60~100 DEG C 2~12h of reaction, is cooled to 15~35 DEG C, obtain carbon nanometer
Pipe modified graphene hydrogel；
(4) by carbon nano-tube modification graphene hydrogel at -10~-60 DEG C freezing processing, then carry out constant pressure and dry
Processing, obtains carbon nano-tube modification graphene aerogel.
Preparation method according to the present invention, it is preferable that in step (1), the reducing agent be selected from ascorbic acid, ethylenediamine,
One of sodium tetraborate, oxalic acid and potassium iodide compound are a variety of.
Preparation method according to the present invention, it is preferable that in step (1), it is 20~80mg/ml that the foaming agent, which is selected from concentration,
C10~C20 alkyl benzene sulphonate saline solution.
Preparation method according to the present invention, it is preferable that in step (1), the carbon nanotube caliber 3 of the amino-functionalization~
15nm, 10~15 μm of pipe range, 200~400m2/g of specific surface area.
Preparation method according to the present invention, it is preferable that in step (1), in the mixed dispersion liquid, graphene oxide it is dense
Degree is 2~10mg/ml, and the mass ratio of graphene oxide and reducing agent is 1:2~5, and the carbon of graphene oxide and amino-functionalization is received
The mass ratio of mitron is 2~15:1.
Preparation method according to the present invention, it is preferable that further include changing carbon nanotube after freezing processing in step (4)
Property graphene aerogel is 450~1000 DEG C of annealings the step of.
Preparation method according to the present invention, it is preferable that further include changing carbon nanotube before freezing processing in step (4)
Property graphene hydrogel concentration be 1~20vol% ethanol water in carry out washing by soaking the step of.
The present invention also provides a kind of carbon nano-tube modification graphene aerogels that above-mentioned preparation method is prepared.
The present invention provides a kind of application of above-mentioned carbon nano-tube modification graphene aerogel in water-oil separating field again
Carbon nano-tube modification graphene aerogel of the invention has higher mechanical strength and elasticity, is in compressive strength
Under conditions of 5.2MPa and compressive deformation are 50% or more, Repeated Compression 50 times, it is intact to be still able to maintain form.Carbon of the invention
Nanotube modified graphene aeroge has 6~8mg/cm3Density and 99.1% or more porosity, absorption property is good.
Preparation process of the invention is simple, without secondary pollution, substantially reduces preparation cost.
Detailed description of the invention
Fig. 1 is the pictorial diagram of sample shooting prepared by embodiment 2.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below, but protection scope of the present invention is not limited to
This.
The preparation step > of < carbon nano-tube modification graphene aerogel
The preparation step of carbon nano-tube modification graphene aerogel of the invention includes: the preparation of (1) mixed dispersion liquid；
(2) preparation of mix-froth liquid；(3) preparation of carbon nano-tube modification graphene hydrogel；(4) constant pressure and dry；It carries out below detailed
Thin description.
In step (1), water is dispersed by the carbon nanotube of amino-functionalization, surfactant, graphene oxide and reducing agent
It is middle to form homogeneous mixed dispersion liquid.The multi-walled carbon nanotube of amino-functionalization can dispersion more evenly, prevent carbon nanotube it
Between the amine functional group mutually reuniting, and introduce, can also form covalent bond between graphene sheet layer, enhance graphene airsetting
The mechanical strength of glue.Graphene oxide can be using the graphene oxide of improved Hummers method preparation, but is not limited to improved
The graphene oxide of Hummers method preparation.The graphene oxide of the methods of liquid phase method, Mechanical Method, electrochemical oxidation process preparation is equal
Preparation method for use in the present invention.In order to disperse each component more fully in water, processing 2 can be carried out with ultrasonic disperse
~8h, preferably 3~7h, more preferably 4~6h.The piece diameter of graphene oxide can be 5~40 μm；Preferably, graphite oxide
The piece diameter of alkene is 10~35 μm；It is highly preferred that the piece diameter of graphene oxide is 20~45 μm.Using the oxidation of sheet above gauge structure
Graphene can make the graphene aerogel prepared have lower density and porosity, and improve its hydrophobic performance.
In the present invention, the carbon nanotube of amino-functionalization can be obtained using conventional method.For example, carbon nanotube is led to
It crosses ethylenediamine or propane diamine plasma carries out functionalization and obtains the carbon nanotube of amino-functionalization.It can use
Functionalization method disclosed in CN105256530A obtains.The carbon nanotube caliber of amino-functionalization can be 6~10nm,
Pipe range can be 12~14 μm.The carbon nanotube of amino-functionalization can also be purchased from Shenzhen's figure spirit evolution Science and Technology Ltd..Amine
The carbon nanotube of functionalization can be multi-walled carbon nanotube or single-walled carbon nanotube, preferably multi-walled carbon nanotube.It in this way can be with
The hydrophobicity for reducing cost and aeroge is more preferable.
In the present invention, reducing agent is in ascorbic acid, ethylenediamine, sodium tetraborate, oxalic acid and potassium iodide compound
It is one or more；Preferably, reducing agent is selected from ascorbic acid, ethylenediamine, oxalic acid compound one of mixture with potassium iodide or
It is a variety of；It is highly preferred that reducing agent is selected from one or both of ascorbic acid, ethylenediamine mixture.Using above-mentioned graphite oxide
The type of the quality of alkene and reducing agent when reducing agent, can promote the reduction of graphene oxide, preferably improve graphene gas
The hydrophobic performance of gel.
In the present invention, foaming agent can be C10~C20 alkyl benzene sulphonate saline solution, preferably C12~C18 alkyl
Benzene sulfonate aqueous solution, more preferably C12~C14 alkyl benzene sulphonate saline solution.Guaranteeing not influence using above-mentioned foaming agent
Under the premise of graphene aerogel is hydrophobic, mixed liquor uniform in foaming can be made, pore size is moderate.It is according to the present invention certain
Embodiment, foaming agent are selected from C12~C14 alkyl benzene sulphonate sodium-salt aqueous solution, C12~C14 alkyl benzene sulphonate ammonium salt aqueous solution
Or one of C12~C14 alkyl benzene sulphonate alcohol salt aqueous solution or a variety of.A specific embodiment party according to the present invention
Formula, foaming agent are sodium dodecyl benzene sulfonate aqueous solution.In step (1), the concentration of foaming agent can be 20~80mg/ml,
Preferably 30~70mg/ml, more preferably 40~60mg/ml.
In the present invention, the carbon nanotube caliber of the amino-functionalization can be 3~15nm, preferably 5~12nm, it is more excellent
It is selected as 6~10nm；10~15 μm of pipe range, preferably 12~15 μm, more preferably 12~14 μm；200~400m of specific surface area2/
G, preferably 250~300m2/ g, more preferably 250~270m2/g.The carbon nanotube of amino-functionalization using the above structure can be with
Further increase the mechanical strength and elasticity of graphene aerogel.
In mixed dispersion liquid of the invention, the concentration of graphene oxide can be 2~10mg/ml, preferably 2~
10mg/ml, more preferably 2~10mg/ml；The mass ratio of graphene oxide and reducing agent can be 1:2~5, preferably 1:2~
5, more preferably 1:2~5；The mass ratio of the carbon nanotube of graphene oxide and amino-functionalization can be 2~15:1, preferably 2
~15:1, more preferably 2~15:1.Each component uses above-mentioned concentration proportioning, can take into account the graphene aerogel for improving and generating
Mechanical strength, elasticity and absorption property.
In step (2), mixed dispersion liquid is stirred and is foamed, mix-froth liquid is obtained.Foaming process can be under stiring
It carries out.Stirring rate can be 10000~50000rpm, it is preferable that stirring rate is 10000~20000rpm, it is highly preferred that
Stirring rate is 10000~15000rpm.Mixing time can be 1~60min, it is preferable that mixing time is 10~30min,
It is highly preferred that mixing time can be 10~20min.Using above-mentioned stirring condition, faster and better can foam, formation
More evenly, porosity is higher for foaming body hole.
In step (3), mix-froth liquid is reacted, is cooled to 15~35 DEG C, obtains carbon nano-tube modification graphite
Alkene hydrogel.In certain embodiments, mixed liquor is reacted to 2~12h at 60~100 DEG C, is subsequently cooled to 15~35 DEG C,
Obtain graphene hydrogel.This reaction temperature can be with 60~100 DEG C, preferably 70~85 DEG C, more preferably 75~80 DEG C.Reaction
Time can be 2~12h, preferably 4~10h, more preferably 6~8h.Using above-mentioned reducing condition, graphene water can be promoted
The reduction of gel keeps the hydrophobic performance of the graphene hydrogel generated higher.
In step (4), carbon nano-tube modification graphene hydrogel is subjected to freezing processing, is then carried out at constant pressure and dry
Reason, obtains carbon nano-tube modification graphene aerogel.The temperature of freezing processing can be -10~-60 DEG C, preferably -10~-60
DEG C, more preferably -10~-60 DEG C, using above-mentioned freezing processing temperature, it can preferably control the hole ruler of graphene aerogel
It is very little, enhance its elasticity and mechanical strength；The temperature of constant pressure and dry processing can be 15~80 DEG C, preferably 35~75 DEG C, more excellent
It is selected as 50~70 DEG C.Under the premise of not influencing graphene aerogel performance, rate of drying is improved.
It can also include by carbon nano-tube modification graphene hydrogel ethanol water washing by soaking before freezing processing
The step of.The concentration of ethanol water is 1~20vol%；Preferably, the concentration of ethanol water is 1~10vol%；It is more excellent
Selection of land, the concentration of ethanol water are 1~5vol%.Soaking time is no less than 10h；Preferably, soaking time is 20~36h；
It is highly preferred that soaking time is 24~36h.Using above-mentioned washing by soaking step, the impurity in graphene hydrogel can remove,
Avoid influencing the absorption property of the graphene aerogel generated.
After freezing processing, can also include by carbon nano-tube modification graphene aerogel at 450~1000 DEG C of annealing
The step of reason.According to some embodiments of the present invention, 450~1000 DEG C are heated to the rate of heat addition of 10~20 DEG C/min,
Keep 0.5~5h；Cooled down again with the rate of temperature fall of 10~20 DEG C/min.Preferably, added with the rate of heat addition of 12~18 DEG C/min
Heat keeps 1~3h to 450~1000 DEG C, then is cooled down with the rate of temperature fall of 12~18 DEG C/min.It is highly preferred that with 13~15 DEG C/
The rate of heat addition of min is heated to 450~1000 DEG C, keeps 1~2h, then cool down with the rate of temperature fall of 13~15 DEG C/min.Using
Above-mentioned annealing treating process, can greatly improve the hydrophobicity of graphite oxide aerogel, and not influence graphene aerogel
Absorption property and resilience.
< carbon nano-tube modification graphene aerogel and apply >
Carbon nano-tube modification graphene aerogel of the invention, is prepared using above-mentioned preparation method, no longer superfluous here
It states.Carbon nano-tube modification graphene aerogel of the invention is combined to graphene aerogel using the carbon nanotube of amino-functionalization
In, carbon nanotube enhances the frame strength of graphene aerogel, to improve its elasticity and mechanical strength；Pass through lehr attendant
Skill eliminates hydrophilic radical, improves its hydrophobic performance；It is at low cost to be advantageously implemented large-scale production, have in water-oil separating field huge
Big application prospect.
Carbon nano-tube modification graphene aerogel of the invention is used for water-oil separating field.Due to its good elasticity, machine
Tool performance and oil absorbency, hardly water suction is, it can be achieved that water-oil separating.
Raw material used in embodiment and comparative example is described below:
Graphene oxide: being purchased from Changzhou No.6 Element Material Technology Co., Ltd., and piece diameter is 20~25 μm.
The multi-walled carbon nanotube of amino-functionalization: it is purchased from Shenzhen's figure spirit evolution Science and Technology Ltd..
Embodiment 1
(1) by the multi-walled carbon nanotube 30mg of amino-functionalization, neopelex 400mg, graphene oxide 400mg
It is added in 60ml water with ascorbic acid 1200mg, ultrasonic disperse 5h obtains mixed dispersion liquid.
(2) mixed dispersion liquid is stirred to foaming under 10000rpm revolving speed, obtains mix-froth liquid.
(3) reduction reaction 9h will be carried out at 80 DEG C of mix-froth liquid, be cooled to 25 DEG C, obtain carbon nano-tube modification graphene
Hydrogel.
(4) carbon nano-tube modification graphene hydrogel is subjected to washing by soaking in the ethanol water that concentration is 1vol%
For 24 hours, it then takes out and is placed in freezing processing 12h at -45 DEG C, then be warming up to 25 DEG C, then be placed in 65 DEG C and be dried for 24 hours, finally exist
It is made annealing treatment at 500 DEG C, obtains carbon nano-tube modification graphene aerogel sample.Annealing specifically: with 15 DEG C/
The rate of heat addition of min is heated to 500 DEG C, keeps 1h, then cool down with the rate of temperature fall of 15 DEG C/min.
Embodiment 2
(1) by the multi-walled carbon nanotube 30mg of amino-functionalization, neopelex 1000mg, graphene oxide
400mg and ascorbic acid 1200mg is added in 60ml water, and ultrasonic disperse 5h obtains mixed dispersion liquid.
(2) mixed dispersion liquid is stirred to foaming under 10000rpm revolving speed, obtains mix-froth liquid.
(3) reduction reaction 9h will be carried out at 80 DEG C of mix-froth liquid, be cooled to 25 DEG C, obtain carbon nano-tube modification graphene
Hydrogel.
(4) carbon nano-tube modification graphene hydrogel is subjected to washing by soaking in the ethanol water that concentration is 1vol%
For 24 hours, it then takes out and is placed in freezing processing 12h at -45 DEG C, then be warming up to 25 DEG C, then be placed in 65 DEG C and be dried for 24 hours, finally exist
It is made annealing treatment at 500 DEG C, obtains carbon nano-tube modification graphene aerogel sample.Annealing specifically: with 15 DEG C/
The rate of heat addition of min is heated to 500 DEG C, keeps 1h, then cool down with the rate of temperature fall of 15 DEG C/min.
Embodiment 3
(1) by the multi-walled carbon nanotube 30mg of amino-functionalization, neopelex 1000mg, graphene oxide
300mg and ascorbic acid 1200mg is added in 60ml water, and ultrasonic disperse 5h obtains mixed dispersion liquid.
(2) mixed dispersion liquid is stirred to foaming under 10000rpm revolving speed, obtains mix-froth liquid.
(3) reduction reaction 9h will be carried out at 80 DEG C of mix-froth liquid, be cooled to 25 DEG C, obtain carbon nano-tube modification graphene
Hydrogel.
(4) carbon nano-tube modification graphene hydrogel is subjected to washing by soaking in the ethanol water that concentration is 1vol%
For 24 hours, it then takes out and is placed in freezing processing 12h at -45 DEG C, then be warming up to 25 DEG C, then be placed in 65 DEG C and be dried for 24 hours, finally exist
It is made annealing treatment at 500 DEG C, obtains carbon nano-tube modification graphene aerogel sample.Annealing specifically: with 15 DEG C/
The rate of heat addition of min is heated to 500 DEG C, keeps 1h, then cool down with the rate of temperature fall of 15 DEG C/min.
Experimental example
Recovery capability test: sample is placed under certain pressure and pushes generation deformation, then removes pressure detecting sample shape
Become recovery capability.
Fig. 1 is the pictorial diagram of sample shooting prepared by embodiment 2, and as seen from the figure, sample structure is complete, not scaling-off
Phenomenon.
It is tested by recovery capability, when sample application pressure prepared by implementation of compression example 1~3 is 4~5.2MPa, compressed shape
Become 50% or more, still keeps good form compression rebound 50 times.After tested Examples 1 to 3 preparation sample rate be 6~
8mg/cm3, mean porosities 99.1%.
The sample of Examples 1 to 3 preparation and comparative example 1~2 are subjected to contact angle test, test result is shown in Table 1.As a result it shows
Show, the sample of Examples 1 to 3 preparation has good hydrophobic performance.
Table 1
| Test sample | Hydrophobic angle (°) |
| Embodiment 1 | 148 |
| Embodiment 2 | 153 |
| Embodiment 3 | 151 |
Present invention is not limited to the embodiments described above, without departing from the essence of the present invention, this field skill
Any deformation, improvement, the replacement that art personnel are contemplated that each fall within the scope of the present invention.
Claims (10)
1. a kind of preparation method of carbon nano-tube modification graphene aerogel, which comprises the steps of:
(1) carbon nanotube of amino-functionalization, surfactant, graphene oxide and reducing agent are dispersed in water to form homogeneous mix
Close dispersion liquid；
(2) mixed dispersion liquid is stirred and is foamed, obtain mix-froth liquid；
(3) mix-froth liquid is subjected at 60~100 DEG C 2~12h of reaction, is cooled to 15~35 DEG C, obtained carbon nanotube and change
Property graphene hydrogel；
(4) by carbon nano-tube modification graphene hydrogel at -10~-60 DEG C freezing processing, then carry out constant pressure and dry processing,
Obtain carbon nano-tube modification graphene aerogel.
2. preparation method according to claim 1, which is characterized in that the piece diameter of the graphene oxide is 5~40 μm.
3. preparation method according to claim 1, which is characterized in that in step (1), the reducing agent is selected from Vitamin C
One of acid, ethylenediamine, sodium tetraborate, oxalic acid and potassium iodide compound are a variety of.
4. preparation method according to claim 1, which is characterized in that in step (1), it is 20 that the foaming agent, which is selected from concentration,
C10~C20 alkyl benzene sulphonate saline solution of~80mg/ml.
5. preparation method according to claim 1, which is characterized in that in step (1), the carbon nanotube of the amino-functionalization
Caliber be 3~15nm, pipe range be 10~15 μm, specific surface area be 200~400m2/g。
6. preparation method according to claim 1, which is characterized in that in step (1), in the mixed dispersion liquid, oxidation
The concentration of graphene is 2~10mg/ml, and the mass ratio of graphene oxide and reducing agent is 1:2~5, graphene oxide and amine function
The mass ratio of the carbon nanotube of energyization is 2~15:1.
7. described in any item preparation methods according to claim 1~6, which is characterized in that in step (4), after freezing processing,
Further include the steps that making annealing treatment carbon nano-tube modification graphene aerogel at 450~1000 DEG C.
8. preparation method according to claim 7, which is characterized in that in step (4), before freezing processing, further include by
Carbon nano-tube modification graphene hydrogel carries out the step of washing by soaking in the ethanol water that concentration is 1~20vol%.
9. the carbon nano-tube modification graphene aerogel that described in any item preparation methods are prepared according to claim 1~8.
10. application of the carbon nano-tube modification graphene aerogel according to claim 9 in water-oil separating field.
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