CN110127676A - Hydrophobic silica graphene aerogel and its production method - Google Patents
Hydrophobic silica graphene aerogel and its production method Download PDFInfo
- Publication number
- CN110127676A CN110127676A CN201910567778.3A CN201910567778A CN110127676A CN 110127676 A CN110127676 A CN 110127676A CN 201910567778 A CN201910567778 A CN 201910567778A CN 110127676 A CN110127676 A CN 110127676A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- aerogel
- production method
- graphene
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 118
- 239000004964 aerogel Substances 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 15
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 56
- 239000010439 graphite Substances 0.000 claims abstract description 56
- 238000000137 annealing Methods 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims description 25
- 239000000017 hydrogel Substances 0.000 claims description 25
- 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 24
- 239000006260 foam Substances 0.000 claims description 24
- 150000001336 alkenes Chemical class 0.000 claims description 17
- 238000006722 reduction reaction Methods 0.000 claims description 17
- 238000007710 freezing Methods 0.000 claims description 16
- 230000008014 freezing Effects 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 10
- -1 oxalic acid compound Chemical class 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 239000004088 foaming agent Substances 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 229940071870 hydroiodic acid Drugs 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 2
- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical compound [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 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
- 238000000034 method Methods 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 19
- 235000010323 ascorbic acid Nutrition 0.000 description 11
- 229960005070 ascorbic acid Drugs 0.000 description 11
- 239000011668 ascorbic acid Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 230000003075 superhydrophobic effect Effects 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 206010000269 abscess Diseases 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of hydrophobic silica graphene aerogel and its production methods.Graphite oxide aerogel is carried out to annealing at 450~1000 DEG C and obtains hydrophobic silica graphene aerogel.
Description
Technical field
The present invention relates to a kind of hydrophobic silica graphene aerogel and its production methods.
Background technique
Grapheme material is that one kind has ultra-thin lamellar structure, with good mechanical and thermal stability carbon material.Mesh
The preparation method of preceding graphene mainly has mechanical stripping method, epitaxial growth method, chemical meteorology deposition method and graphene oxide reduction
Method.Graphene oxide reduction method based on chemical reaction realizes economic, quick, large scale preparation graphene.By graphite oxide
Alkene is self-assembled by thermal reduction or electronation to be three-dimensional netted, and graphite oxide aerogel is further dried to obtain.
Graphite oxide aerogel has both the double grading of graphene and aeroge, has efficient adsorptivity to petroleum and organic solvent
It can be with compression resilience, it can be achieved that adsorption-desorption process is repeated, to realize the continuous absorption to petroleum and organic solvent.
CN107311152A discloses a kind of preparation method of graphene, and long-range order graphene oxide liquid crystal is exposed to
It is stood in gas phase crosslinking agent atmosphere, crosslinking agent is made to enter graphene oxide liquid crystal system in a manner of air plllutant, obtaining has liquid
The graphite oxide aerogel of brilliant schlieren texture.This method enhances the skeleton knot of graphite oxide aerogel by introducing crosslinked agent
Structure increases later period cleaning difficulty, and affects the hydrophobicity of graphite oxide aerogel.CN105384165B discloses one
The preparation method of the spongy light graphite alkene aeroge of kind, this method is by being added foaming agent in graphene oxide colloidal solution
It foams, then the foam system after foaming is put into liquid nitrogen and carries out quick-frozen sizing, obtain spongy light graphite alkene gas
Gel, the aeroge resilience that this method obtains is not high, and its hydrophobicity is not high.CN106517160B disclose it is a kind of respectively to
The preparation method of same sex super-elasticity graphene aerogel, this method is using graphene oxide as raw material, with lauryl sodium sulfate water
The abscess that solution stirring generates is template, prepares foaming body, then forms tridimensional network by reducing agent reduction reaction, most
Strengthened afterwards by freezing, heat drying obtains isotropic graphene aerogel.Graphene aerogel is obtained by this method
With high resilience, but its hydrophobicity is not high.
Summary of the invention
In view of this, it is an object of the present invention to provide a kind of production method of hydrophobicity graphene aerogel, energy
Enough steady productions prepare super-hydrophobicity graphene aerogel.
It is another object of the present invention to provide a kind of hydrophobic silica graphene aerogels, have high resilience energy,
And there is superelevation hydrophobic performance.
On the one hand, the present invention provides a kind of production method of hydrophobic silica graphene aerogel, including by graphite oxide
The step of alkene aeroge is made annealing treatment at 450~1000 DEG C.
In accordance with the present production process, it is preferable that prepare graphite oxide aerogel using following steps:
(1) it adds graphene oxide into water and disperses, obtain graphene oxide aqueous dispersions；
(2) reducing agent and foaming agent, stirring to obtain foams are added in graphene oxide aqueous dispersions；
(3) foams are placed in progress 2~12h of reduction reaction at 60~100 DEG C, then cool to room temperature, is aoxidized
Graphene hydrogel；
(4) graphene oxide hydrogel is placed in freezing processing 2 at -45~-10 DEG C~for 24 hours, then takes out and is warming up to room
Temperature, then graphite oxide aerogel is obtained with 30~85 DEG C of dryings under normal pressure.
In accordance with the present production process, it is preferable that in step (1), the piece diameter of the graphene oxide is 2~50 μm,
Lamellar spacing is 1~30nm.
In accordance with the present production process, it is preferable that in step (1), the oxidation stone of the graphene oxide aqueous dispersions
Black alkene concentration is 3~7mg/ml.
In accordance with the present production process, it is preferable that in step (1), oxygen carbon molar ratio is in the graphene oxide
0.15~0.65.
In accordance with the present production process, it is preferable that in step (2), the mass ratio of graphene oxide and reducing agent is 1:2
~5.
In accordance with the present production process, it is preferable that in step (2), the reducing agent be selected from ascorbic acid, ethylenediamine,
Sodium tetraborate, oxalic acid compound one of mixture, hydroiodic acid or a variety of with potassium iodide；The foaming agent be selected from concentration be 20~
The sodium dodecyl benzene sulfonate aqueous solution of 80mg/ml.
In accordance with the present production process, it is preferable that in step (2), stirring rate is 10000~50000rpm, stirring
Time is 1~10min.
In accordance with the present production process, it is preferable that in step (4), by graphene oxide hydrogel before freezing processing
12~the 48h of ethanol water washing by soaking for being 1~10vol% with ethanol content.
On the other hand, the present invention provides the hydrophobic silica graphene aerogel that aforementioned production method obtains.
The present invention eliminates the hydrophilic radical introduced in preparation process, improves its hydrophobicity by the high temperature anneal
Energy.The fields such as petroleum, the organic solvent of hydrophobic silica graphene aerogel of the invention in adsorption treatment on sewage have huge
Big application prospect.It is compared to the graphene aerogel for preparation of not foaming, the graphene oxide airsetting of present invention foaming preparation
The stomata isotropic of glue makes graphene compression resilience all having the same in all directions.
Detailed description of the invention
Fig. 1 is that the hydrophobic silica graphene aerogel sample of embodiment 2 applies the photo of certain pressure deformation about 50%.
Fig. 2 is that the hydrophobic silica graphene aerogel of embodiment 2 removes the photo of deformation recovery after pressure.
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 production method of hydrophobic silica graphene aerogel of the invention includes the preparation step of graphite oxide aerogel
Rapid and annealing process step.It is further explained below.
< annealing process step >
Annealing keeps certain time, then with certain speed cooling for material is heated slowly to certain temperature
A kind of heat treatment process.Not yet have been reported that the production that the high temperature anneal is applied to graphene aerogel.
The preparation method of hydrophobic silica graphene aerogel of the invention include by graphite oxide aerogel 450~
The step of being made annealing treatment at 1000 DEG C.By the high temperature anneal, graphite oxide aerogel is made to generate special molecule
Arrangement eliminates graphite oxide aerogel inner hydrophilic group, to increase the hydrophobicity of graphite oxide aerogel.It is preferred that
Ground is made annealing treatment at 500~1000 DEG C.It is highly preferred that being made annealing treatment at 600~800 DEG C.
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, protected
Hold 0.5~5h；Cooled down again with the rate of temperature fall of 10~20 DEG C/min.Preferably, it is heated with the rate of heat addition of 12~18 DEG C/min
To 450~1000 DEG C, 1~3h is kept, then cool 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 oxide gas
The absorption property and resilience of gel.
Production method of the invention is primarily adapted for use in the graphite oxide aerogel of chemical reduction process preparation, preparation process
In be frequently necessary to introduce reducing agent, crosslinking agent, surfactant and foaming agent etc., this results in the graphene oxide prepared
Contain many hydrophilic radicals inside aeroge, these hydrophilic radicals reduce the hydrophobicity of graphite oxide aerogel.Pass through this
The production method of invention can eliminate the hydrophilic radical of introducing by chemical reaction, and can make graphite oxide aerogel
Molecule rearrangement forms particular molecule arrangement, further increases the hydrophobic performance of graphite oxide aerogel.
The preparation step > of < graphite oxide aerogel
The preparation of graphite oxide aerogel includes: the step of (1) prepares graphene oxide aqueous dispersions；(2) preparation bubble
The step of foam body；(3) the step of preparing graphene oxide hydrogel；(4) constant pressure and dry step.
It in step (1), adds graphene oxide into water and disperses, obtain graphene oxide aqueous dispersions.Of the invention
Graphene oxide also includes graphite oxide.It, can be at ultrasonic disperse in order to disperse graphene oxide more fully in water
Reason.The piece diameter of graphene oxide can be 2~50 μm, and lamellar spacing can be 1~30nm；Preferably, the piece of graphene oxide
Diameter is 2~45 μm, and lamellar spacing is 1~20nm；It is highly preferred that the piece diameter of graphene oxide is 20~45 μm, lamellar spacing 1
~10nm.Using the graphene oxide of sheet above gauge structure, the graphite oxide aerogel prepared can be made to have more preferable
Resilience and hydrophobicity.The graphene oxide concentration of graphene oxide aqueous dispersions can be 3~7mg/ml；Preferably, oxygen
Graphite alkene concentration is 4~7mg/ml；It is highly preferred that graphene oxide concentration is 4~6mg/ml.Using in above-mentioned concentration range
Graphene oxide aqueous dispersions, absorption property and the better graphite oxide aerogel of resilience performance can be formed, further
Improve the hydrophobic performance of graphite oxide aerogel.Oxygen carbon molar ratio is 0.15~0.65 in the graphene oxide；Preferably
0.20~0.50；More preferably 0.35~0.45.The purity of graphene oxide be not less than 95%, it is preferable that purity be 95%~
98%；It is highly preferred that purity is 95%~98%.It, can be with the absorption of graphite oxide aerogel using above-mentioned graphene oxide
Performance and resilience performance.
Graphene oxide of the invention can be using the graphene oxide of improved Hummers method preparation, but is not limited to change
Into Hummers method preparation graphene oxide.The graphite oxide of the methods of liquid phase method, Mechanical Method, electrochemical oxidation process preparation
Alkene is used equally for production method of the invention.
In step (2), reducing agent and foaming agent, stirring to obtain foams are added in graphene oxide aqueous dispersions.
The mass ratio of graphene oxide and reducing agent can be 1:2~5 in graphene oxide aqueous dispersions, preferably 1:2~4, more excellent
It is selected as 1:3~4.Reducing agent compounds mixture selected from ascorbic acid, ethylenediamine, sodium tetraborate, oxalic acid, in hydroiodic acid with potassium iodide
It is one or more；Preferably, reducing agent is selected from ascorbic acid, ethylenediamine, oxalic acid and compounds one of mixture with potassium iodide
Or it is a variety of；Reducing agent is selected from one or both of ascorbic acid, ethylenediamine mixture.Foaming agent is neopelex
Aqueous solution.The neopelex concentration of sodium dodecyl benzene sulfonate aqueous solution can be 20~80mg/ml, it is preferable that
Neopelex concentration is 30~70mg/ml, it is highly preferred that neopelex concentration is 40~60mg/ml.
In step (2), stirring rate can be 5000~30000rpm, it is preferable that stirring rate be 10000rpm~
20000rpm, it is highly preferred that stirring rate is 10000rpm~15000rpm.Mixing time can be 1~10min, it is preferable that
Mixing time is 2~8min, it is highly preferred that mixing time can be 2~5min.It, can faster more using above-mentioned stirring condition
It foams well, more evenly, to make the isotropic of graphite oxide aerogel, resilience is more for the foaming body hole of formation
It is high.
According to embodiment of the present invention, it is added in the graphene oxide aqueous dispersions that concentration is 4~6mg/ml
One or both of ascorbic acid, ethylenediamine mixture adds the neopelex that concentration is 40~60mg/ml
Aqueous solution stirs 2~5min under conditions of stirring rate is 10000rpm~30000rpm, obtains foams.
In step (3), foams are subjected to reduction reaction, are then cooled to room temperature down, obtains graphene oxide water-setting
Glue.Foams of the invention can carry out 2~12h of reduction reaction at 60~100 DEG C；Preferably, it is carried out at 70~90 DEG C
4~10h of reduction reaction；It is highly preferred that carrying out 6~8h of reduction reaction at 80~90 DEG C.Using above-mentioned reducing condition, can make
The hydrophobic performance for restoring the graphene oxide hydrogel generated is higher.
In step (4), graphene oxide hydrogel is subjected to freezing processing, then takes out and is warming up to room temperature, then is carried out often
Press dry dry, acquisition graphite oxide aerogel.Graphene oxide hydrogel of the invention, which can be placed at -45~-10 DEG C, to be freezed
Processing 2~for 24 hours；Preferably, it is placed in 3~18h of freezing processing at -45~-20 DEG C；It is highly preferred that being placed in cold at -45~-35 DEG C
Freeze 10~15h of processing.Using above-mentioned freezing processing technique, graphene oxide hydrogel, and the oxygen formed can be rapidly frozen
The absorption property and resilience of graphite alkene aeroge are higher, further increase its hydrophobic performance.Constant pressure and dry temperature of the invention
Degree can be 30~85 DEG C；Preferably, drying temperature is 45~80 DEG C；It is highly preferred that drying temperature is 50~75 DEG C.Using upper
Drying temperature is stated, under the premise of the graphite oxide aerogel physical and chemical performance for not influencing to generate, further speeds up drying
Rate.
It according to embodiment of the present invention, further include graphene oxide hydrogel washing by soaking step in step (4).
Graphene oxide after washing by soaking is taken out and carries out freezing processing.Washing by soaking step of the invention includes: by graphite oxide
Alkene hydrogel ethanol water washing by soaking then takes out carry out freezing processing.The concentration of ethanol water is 1 in the present invention
~10vol%；Preferably, the concentration of ethanol water is 1~8vol%；It is highly preferred that the concentration of ethanol water be 1~
6vol%.Soaking time can be 12~48h；Preferably, soaking time is 20~36h；It is highly preferred that soaking time be 24~
36h。
< graphite oxide aerogel >
Graphite oxide aerogel of the invention produces to obtain using the above method, and which is not described herein again.Oxygen of the invention
Graphite alkene aeroge is by generating the graphite oxide aerogel with superelevation hydrophobic performance after above-mentioned generation method.To sewage
In the targeted adsorption treatment such as petroleum, organic solvent, and its rate of adsorption is high, and it is continuous that adsorption-desorption may be implemented
Processing.
Raw material used in embodiment and comparative example is described below:
Graphene oxide: Hummers method preparation.
Test method introduced below:
Contact angle test: using contact angle test instrument, by deionized water drop in sample surfaces, forms dropping liquid drop, so
Tester is taken pictures imaging afterwards, directly measures contact angle with protractor.
Recovery capability test: sample is placed under certain pressure and pushes generation deformation, then removes pressure detecting sample shape
Become recovery capability.
Embodiment 1
(1) it adds graphene oxide into water and disperses, obtain the graphene oxide aqueous dispersions that concentration is 4mg/ml；
(2) the above-mentioned graphene oxide aqueous dispersions of 60ml are taken, and 480mg ascorbic acid, ultrasonic disperse are added thereto
10min is sufficiently mixed, and the sodium dodecyl sulfate aqueous solution that 3ml concentration is 50mg/ml is added, under the revolving speed of 10000rmp
5min is stirred, foams are obtained；
(3) foams are placed in progress reduction reaction 6h at 80 DEG C, then under cooled to room temperature, obtain graphite oxide
Alkene hydrogel；
(4) by graphene oxide hydrogel with the ethanol water washing by soaking of 1vol% for 24 hours, then take out and be placed in -45
Freezing processing 12h at DEG C then takes out and is warming up to room temperature, then carries out constant pressure and dry, and drying temperature is 60 DEG C, obtains graphite oxide
Alkene aeroge.
The graphite oxide aerogel of above-mentioned acquisition is made annealing treatment at 500 DEG C, obtains super-hydrophobic graphene gas
Gel sample.Annealing specifically: be heated to 500 DEG C with the rate of heat addition of 15 DEG C/min, keep 1h, then with 15 DEG C/min's
Rate of temperature fall cooling.
Embodiment 2
(1) it adds graphene oxide into water and disperses, obtain the graphene oxide aqueous dispersions that concentration is 5mg/ml；
(2) the above-mentioned graphene oxide aqueous dispersions of 60ml are taken, and 600mg ascorbic acid, ultrasonic disperse are added thereto
10min is sufficiently mixed, and the sodium dodecyl sulfate aqueous solution that 3ml concentration is 50mg/ml is added, under the revolving speed of 10000rmp
5min is stirred, is subsequently poured into the mold of 30 × 30 × 5cm and seals, obtains foams；
(3) foams of sealing are placed in progress reduction reaction 10h at 80 DEG C, then under cooled to room temperature, obtained
Graphene oxide hydrogel；
(4) by graphene oxide hydrogel with the ethanol water washing by soaking of 1vol% for 24 hours, then take out and be placed in -45
Freezing processing 12h at DEG C then takes out and is warming up to room temperature, then carries out constant pressure and dry, and drying temperature is 60 DEG C, obtains graphite oxide
Alkene aeroge.
30 × 30 × 5cm graphite oxide aerogel of above-mentioned acquisition is made annealing treatment at 500 DEG C, is obtained super thin
Aquadag alkene aeroge sample.Annealing specifically: 500 DEG C are heated to the rate of heat addition of 15 DEG C/min, keep 1h, then with
The rate of temperature fall of 15 DEG C/min cools down.
Embodiment 3
(1) it adds graphene oxide into water and disperses, obtain the graphene oxide aqueous dispersions that concentration is 5mg/ml；
(2) the above-mentioned graphene oxide aqueous dispersions of 80ml are taken, and 600mg ascorbic acid, ultrasonic disperse are added thereto
10min is sufficiently mixed, and the sodium dodecyl sulfate aqueous solution that 4ml concentration is 50mg/ml is added, under the revolving speed of 10000rmp
5min is stirred, is subsequently poured into the mold of 30 × 30 × 5cm and seals, obtains foams；
(3) foams are placed in progress reduction reaction 10h at 80 DEG C, then under cooled to room temperature, obtain oxidation stone
Black alkene hydrogel；
(4) by graphene oxide hydrogel with the ethanol water washing by soaking of 1vol% for 24 hours, then take out and be placed in -45
Freezing processing 12h at DEG C then takes out and is warming up to room temperature, then carries out constant pressure and dry, and drying temperature is 60 DEG C, obtains graphite oxide
Alkene aeroge.
The graphite oxide aerogel of above-mentioned acquisition is made annealing treatment at 500 DEG C, obtains super-hydrophobic graphene gas
Gel sample.Annealing specifically: be heated to 500 DEG C with the rate of heat addition of 15 DEG C/min, keep 1h, then with 15 DEG C/min's
Rate of temperature fall cooling.
Embodiment 4
(1) it adds graphene oxide into water and disperses, obtain the graphene oxide aqueous dispersions that concentration is 5mg/ml；
(2) the above-mentioned graphene oxide aqueous dispersions of 8l are taken, and 60g ascorbic acid is added thereto, ultrasonic disperse 10min fills
Divide mixing, adds the sodium dodecyl sulfate aqueous solution that 0.4l concentration is 50mg/ml, stirred under the revolving speed of 10000rmp
5min is subsequently poured into the mold of 30 × 30 × 5cm and seals, and obtains foams；
(3) foams are placed in progress reduction reaction 10h at 80 DEG C, then under cooled to room temperature, obtain oxidation stone
Black alkene hydrogel；
(4) by graphene oxide hydrogel with the ethanol water washing by soaking of 1vol% for 24 hours, then take out and be placed in -45
Freezing processing 12h at DEG C then takes out and is warming up to room temperature, then carries out constant pressure and dry, and drying temperature is 60 DEG C, obtains graphite oxide
Alkene aeroge.
The graphite oxide aerogel of above-mentioned acquisition is made annealing treatment at 500 DEG C, obtains super-hydrophobic graphene gas
Gel sample.Annealing specifically: be heated to 500 DEG C with the rate of heat addition of 15 DEG C/min, keep 1h, then with 15 DEG C/min's
Rate of temperature fall cooling.
Embodiment 5
(1) it adds graphene oxide into water and disperses, obtain the graphene oxide aqueous dispersions that concentration is 5mg/ml；
(2) the above-mentioned graphene oxide aqueous dispersions of 6l are taken, and 60mg ascorbic acid, ultrasonic disperse 10min are added thereto
It is sufficiently mixed, adds the sodium dodecyl sulfate aqueous solution that 0.3l concentration is 50mg/ml, stirred under the revolving speed of 10000rmp
5min is subsequently poured into the mold of 30 × 30 × 5cm and seals, and obtains foams；
(3) foams are placed in progress reduction reaction 10h at 80 DEG C, then under cooled to room temperature, obtain oxidation stone
Black alkene hydrogel；
(4) by graphene oxide hydrogel with the ethanol water washing by soaking of 1vol% for 24 hours, then take out and be placed in -45
Freezing processing 12h at DEG C then takes out and is warming up to room temperature, then carries out constant pressure and dry, and drying temperature is 60 DEG C, obtains graphite oxide
Alkene aeroge.
The graphite oxide aerogel of above-mentioned acquisition is made annealing treatment at 500 DEG C, obtains super-hydrophobic graphene gas
Gel sample.Annealing specifically: be heated to 500 DEG C with the rate of heat addition of 15 DEG C/min, keep 1h, then with 15 DEG C/min's
Rate of temperature fall cooling.
Comparative example 1
(1) it adds graphene oxide into water and disperses, obtain the graphene oxide aqueous dispersions that concentration is 5mg/ml；
(2) the above-mentioned graphene oxide aqueous dispersions of 60ml are taken, and 600mg ascorbic acid, ultrasonic disperse are added thereto
10min is sufficiently mixed, and the sodium dodecyl sulfate aqueous solution that 3ml concentration is 50mg/ml is added, under the revolving speed of 10000rmp
5min is stirred, foams are obtained；
(3) foams are placed in progress reduction reaction 10h at 80 DEG C, then under cooled to room temperature, obtain oxidation stone
Black alkene hydrogel；
(4) by graphene oxide hydrogel with the ethanol water washing by soaking of 1vol% for 24 hours, then take out and be placed in -45
Freezing processing 12h at DEG C then takes out and is warming up to room temperature, then carries out constant pressure and dry, and drying temperature is 60 DEG C, obtains graphite oxide
Alkene aeroge sample.
Fig. 1 is the photo figure that sample prepared by embodiment 2 implements deformation about 50% after certain pressure, and Fig. 2 is to remove pressure
The photo figure that deformation restores afterwards.It is compared by Fig. 1 and Fig. 2 it is found that making its shape to sample application certain pressure prepared by embodiment 2
It alters an agreement 50%, can almost restore after removing pressure to original form, there is high resilience energy.
Contact angle test is done to embodiment 1-5 and comparative example 1 sample prepared, as a result see the table below.The results show that not passing through
The contact angle for crossing the comparative example of annealing is far smaller than the contact angle of embodiment 1-5, illustrates that annealing improves oxygen
The hydrophobic performance of graphite alkene aeroge.
Table 1
| Test sample | Contact angle (°) |
| Embodiment 1 | 152 |
| Embodiment 2 | 153 |
| Embodiment 3 | 155 |
| Embodiment 4 | 154 |
| Embodiment 5 | 153 |
| Comparative example | 138 |
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 production method of hydrophobic silica graphene aerogel, which is characterized in that including by graphite oxide aerogel
The step of being made annealing treatment at 450~1000 DEG C.
2. production method according to claim 1, which is characterized in that prepare graphene oxide airsetting using following steps
Glue:
(1) it adds graphene oxide into water and disperses, obtain graphene oxide aqueous dispersions；
(2) reducing agent and foaming agent, stirring to obtain foams are added in graphene oxide aqueous dispersions；
(3) foams are placed in progress 2~12h of reduction reaction at 60~100 DEG C, then cooled to room temperature, obtain graphite oxide
Alkene hydrogel；
(4) graphene oxide hydrogel is placed in freezing processing 2 at -45~-10 DEG C~for 24 hours, then takes out and is warming up to room temperature, then
Under normal pressure with 30~85 DEG C of dryings, graphite oxide aerogel is obtained.
3. production method according to claim 2, which is characterized in that in step (1), the piece diameter of the graphene oxide is
2~50 μm, lamellar spacing is 1~30nm.
4. production method according to claim 2, which is characterized in that in step (1), the graphene oxide aqueous dispersions
Graphene oxide concentration be 3~7mg/ml.
5. production method according to claim 2, which is characterized in that in step (1), oxygen carbon rubs in the graphene oxide
You are than being 0.15~0.65.
6. production method according to claim 2, which is characterized in that in step (2), the matter of graphene oxide and reducing agent
Amount is than being 1:2~5.
7. production method according to claim 2, which is characterized in that in step (2), the reducing agent is selected from Vitamin C
Acid, ethylenediamine, sodium tetraborate, oxalic acid compound one of mixture, hydroiodic acid or a variety of with potassium iodide；The foaming agent is selected from
Concentration is the sodium dodecyl benzene sulfonate aqueous solution of 20~80mg/ml.
8. production method according to claim 2, which is characterized in that in step (2), stirring rate be 10000~
50000rpm, mixing time are 1~10min.
9. according to the described in any item production methods of claim 2~8, which is characterized in that in step (4), before freezing processing
12~the 48h of ethanol water washing by soaking for being 1~10vol% by graphene oxide hydrogel ethanol content.
10. the hydrophobic silica graphene aerogel that described in any item production methods obtain according to claim 1~9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910567778.3A CN110127676B (en) | 2019-06-27 | 2019-06-27 | Hydrophobic graphene oxide aerogel and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910567778.3A CN110127676B (en) | 2019-06-27 | 2019-06-27 | Hydrophobic graphene oxide aerogel and production method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110127676A true CN110127676A (en) | 2019-08-16 |
| CN110127676B CN110127676B (en) | 2021-01-26 |
Family
ID=67566703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910567778.3A Active CN110127676B (en) | 2019-06-27 | 2019-06-27 | Hydrophobic graphene oxide aerogel and production method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110127676B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112023952A (en) * | 2020-08-25 | 2020-12-04 | 辽宁大学 | Cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material and preparation method and application thereof |
| CN116062739A (en) * | 2023-02-17 | 2023-05-05 | 广东吉美帮新材料有限公司 | Modified graphene aerogel and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601913A (en) * | 2013-11-15 | 2014-02-26 | 复旦大学 | Graphene/polypyrrole hybrid aerogel and preparation method thereof |
| CN104925787A (en) * | 2015-03-19 | 2015-09-23 | 青岛科技大学 | Method for preparing graphene aerogel through constant pressure drying |
| CN106517160A (en) * | 2016-11-22 | 2017-03-22 | 青岛科技大学 | Method for preparing isotropic superelastic graphene aerogel |
| CN107555422A (en) * | 2017-08-18 | 2018-01-09 | 复旦大学 | A kind of 3D printing aeroge based on graphene oxide composite material and preparation method thereof |
-
2019
- 2019-06-27 CN CN201910567778.3A patent/CN110127676B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601913A (en) * | 2013-11-15 | 2014-02-26 | 复旦大学 | Graphene/polypyrrole hybrid aerogel and preparation method thereof |
| CN104925787A (en) * | 2015-03-19 | 2015-09-23 | 青岛科技大学 | Method for preparing graphene aerogel through constant pressure drying |
| CN106517160A (en) * | 2016-11-22 | 2017-03-22 | 青岛科技大学 | Method for preparing isotropic superelastic graphene aerogel |
| CN107555422A (en) * | 2017-08-18 | 2018-01-09 | 复旦大学 | A kind of 3D printing aeroge based on graphene oxide composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吴斌: "石墨烯气凝胶的制备及应用研究", 《中国优秀硕士论文数据库》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112023952A (en) * | 2020-08-25 | 2020-12-04 | 辽宁大学 | Cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material and preparation method and application thereof |
| CN116062739A (en) * | 2023-02-17 | 2023-05-05 | 广东吉美帮新材料有限公司 | Modified graphene aerogel and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110127676B (en) | 2021-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109019590B (en) | Lignin-based hierarchical pore carbon material and preparation method thereof | |
| CN104998589B (en) | A kind of preparation method of efficiently oil suction carbon aerogels material | |
| CN110327851A (en) | Elastic graphite alkene aeroge and its preparation method and application | |
| CN110156432B (en) | Carbon fiber composite graphene aerogel and preparation method and application thereof | |
| CN106517160A (en) | Method for preparing isotropic superelastic graphene aerogel | |
| CN110127676A (en) | Hydrophobic silica graphene aerogel and its production method | |
| CN107552023B (en) | High-adsorption ultralight three-dimensional hierarchical pore structure carbon aerogel material for water treatment and preparation method thereof | |
| CN103910356B (en) | A kind of preparation method of three-dimensional grapheme | |
| CN110255540B (en) | Oleophylic and hydrophobic graphene aerogel and preparation method and application thereof | |
| CN104085881B (en) | A kind of method preparing three-dimensional grapheme | |
| Tsyntsarski et al. | Porosity development during steam activation of carbon foams from chemically modified pitch | |
| CN109133040A (en) | A kind of preparation method of the adjustable graphene aerogel of pore-size | |
| CN105621420A (en) | Method for preparing silicon dioxide aerogel through foaming | |
| CN109876771A (en) | A kind of sponge gourd activity carbon aerogel material, preparation method and application | |
| CN110127675A (en) | The manufacturing method of graphene aerogel | |
| CN110142011A (en) | A kind of preparation method of structurally ordered fluorine nitrogen-doped graphene aeroge | |
| CN110510617A (en) | A kind of constant pressure and dry preparation method of large scale alumina silica aeroge | |
| CN104355313A (en) | Simple and easy preparation method for silicon dioxide hydrophobic porous materials | |
| CN108996486A (en) | A kind of classifying porous charcoal and its preparation method and application | |
| CN110203910A (en) | The preparation method of modified graphene aeroge | |
| CN110217779A (en) | Carbon nano-tube modification graphene aerogel and its preparation method and application | |
| CN115321525B (en) | Preparation method of graphene nano-network with macroporous structure | |
| CN106430147B (en) | A kind of Ultrasound-microwave preparation has the functional mesoporous hollow carbon sphere of open architecture | |
| CN108706583A (en) | A kind of preparation method of nanoporous carbon materials | |
| CN102863645B (en) | Method for preparing high-functionality foamed polymer material by supercritical CO2 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Tong Shanghui Inventor after: Wang Haixia Inventor before: Tong Shanghui |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Hydrophobic graphene oxide aerogel and its production method Granted publication date: 20210126 Pledgee: China Construction Bank Corporation Hefei Binhu New Area sub branch Pledgor: Zhongsu New Technology Co.,Ltd. Registration number: Y2024980016703 |