CN107281982B - A kind of adjustable graphene of hydrophilic and hydrophobic/clay composite elastic aeroge and preparation method thereof - Google Patents
A kind of adjustable graphene of hydrophilic and hydrophobic/clay composite elastic aeroge and preparation method thereof Download PDFInfo
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Abstract
The invention discloses the adjustable graphene of a kind of hydrophilic and hydrophobic/clay composite elastic aeroges and preparation method thereof.This method is prepared for clay dispersion and graphene oxide dispersion respectively first, then reducing agent is added with graphene oxide dispersion in clay dispersion after mixing and reacted, and obtains graphene/clay composite hydrogel of partial reduction.Graphene/clay composite hydrogel of partial reduction is successively dialysed, is freeze-dried and is heat-treated and has just obtained the graphene/clay composite elastic aeroge.The invention has the advantages of low raw material cost, and preparation process is environmentally protective.Graphene/clay composite aerogel has low density and good resilience, and hydrophilic and hydrophobic can be adjusted by the type or content for changing clay, and clay enhances the intensity of graphene aerogel matrix.
Description
Technical field
The invention belongs to aeroge technical fields, are related to a kind of adjustable graphene of hydrophilic and hydrophobic/clay composite elastic gas
Gel and preparation method thereof.
Background technique
Aeroge be a kind of low-density, macropore volume, high-specific surface area porous solid material, be widely used in environment
The multiple fields such as protection, efficient catalytic, supercapacitor.With the rise of graphene research, researcher can pass through various sides
Two-dimensional graphene piece is assembled into three-dimensional grapheme aeroge by method.Common method is first with improved Hummers method by graphite
At graphene oxide, graphene oxide may be implemented to restore and be assembled under the action of reducing agent or high temperature and pressure for oxidation removing
Three-dimensional grapheme network, then drying can be obtained by graphene aerogel.Due to containing on graphene oxide in reduction process
Oxygen groups substantially reduce, so that graphene aerogel itself has stronger hydrophobicity, have good suction to organic pollutant
Attached performance.In recent years, some researchers are by improving preparation method or suitable reducing agent being selected to prepare elastic graphite alkene
Aeroge, for example, the ultra-light elastic graphene aerogel that Qiu etc. is prepared with multistep processes can press repeatedly under 80% compression ratio
Contracting without occur permanent deformation [L.Qiu, Z.Liu, L.Y.Chang, Y.Z.Wu, D.Li.Nature Communications,
2012,3,1241].This kind of elastic graphite alkene aeroge has certain intensity, after adsorbing and squeezing out organic solvent, again
It is immersed in and remains to be returned to original state in solvent, realize material and the repetition of solvent is absorbed, expanded graphene airsetting
Application of the glue in terms of pollution processing.
However, the stronger hydrophobicity of graphene aerogel itself is unfavorable for its absorption to aqueous stain.Composite hydrophilic
Property substance be expected to adjust the hydrophilic and hydrophobic of graphene aerogel, so that its is met absorption to variety classes solvent in pollutant.Mesh
The preceding report in relation to the adjustable graphene composite aerogel of hydrophilic and hydrophobic is less.The dry amphipathic bacterium of the directly freezeds such as Wang is fine
The mixed dispersion liquid of dimension element and hydrophily graphene oxide, obtained bacteria cellulose/graphene oxide composite aerogel is to having
Solvent and water have good dispersiveness, obtain after being heat-treated to bacteria cellulose/graphene oxide composite aerogel
Bacteria cellulose/graphene composite aerogel then only to organic solvent have good adsorptivity (Yonggui Wang,
Sandeep Yadav,Thorsten Heinlein,Valentino Konjik,HergenBreitzke,
GerdBuntkowsky,J.Schneider, Kai Zhang.RSC Advances, 2014,4,21553-21558), and
Do not refer to composite aerogel to the repetition absorbent properties of solvent in the document.Hydrophilic titanium oxide is loaded to stone by Liu et al.
In black alkene aeroge matrix, the content by adjusting titanium dioxide makes the water contact angle of composite aerogel within the scope of 0~157 degree
Adjustable (Wenjun Liu, JingyuCai, ZhengxinDing, Zhaohui Li.Applied Catalysis B:
Environmental,2015,174–175,421-426).In addition, being adsorbed in this graphene/titanium dioxide composite aerogel
Lipophilic solvent octadecenic acid or water soluble dyestuffs methyl orange be irradiated processing 4~8 hours after can degrade, to realize compound
The recycling of aeroge, but radiation treatment removal solvent is at high cost, and the time is very long.Therefore, preparation has good resilience
And the adjustable graphene composite aerogel of hydrophilic and hydrophobic is meaningful.
Summary of the invention
The purpose of the present invention is to provide a kind of adjustable graphene of hydrophilic and hydrophobic/clay composite elastic aeroge and its systems
Preparation Method.
To achieve the above object, technical scheme is as follows:
A kind of adjustable graphene of hydrophilic and hydrophobic/clay composite elastic aeroge, the aeroge is with graphene aerogel
For matrix, hydrophilic clay is dispersed phase.
Wherein, the hydrophilic clay is attached to the abscess wall surface of graphene aerogel.
Wherein, the density of the aeroge is 2~20mg cm-3, aperture is 10~100 μm, and water static contact angle is 50 °
~120 °.
Wherein, the hydrophilic clay is selected from attapulgite, sodium-based montmorillonite, calcium-base montmorillonite, lithium base montmorillonite, magnesium-based and covers
At least one of de- soil and lithium diatomaceous earth.
Wherein, the density of the aeroge is preferably 2.5~10mg cm-3, more preferably 3.0~6.0mg cm-3。
After reciprocating compression 10 times permanent deformation will not occur for aeroge of the invention under 80% compression ratio.
A kind of preparation method of the adjustable graphene of hydrophilic and hydrophobic/clay composite elastic aeroge, the specific steps are as follows:
(1) in deionized water by hydrophilic clay dispersion, clay dispersion is obtained.
Wherein, after hydrophilic clay dispersion in deionized water, through ultrasonic disperse and centrifugal purification, clay dispersion is obtained.
Wherein, the hydrophilic clay is selected from attapulgite, sodium-based montmorillonite, calcium-base montmorillonite, lithium base montmorillonite, magnesium-based and covers
At least one of de- soil and lithium diatomaceous earth；
It is preferred that the time of ultrasonic disperse is 10~30min；
It is preferred that the rate being centrifuged is 500~3000rpm；
The concentration of the clay dispersion is 4~20mg ml-1。
(2) graphene oxide dispersion is prepared with Hummers method or improved Hummers method.
Wherein, the graphene oxide dispersion can be prepared according to Hummers method or improved Hummers method.
The improved Hummers for example may is that natural graphite, phosphorus pentoxide, potassium peroxydisulfate and the concentrated sulfuric acid according to 2:1:1:
The mass ratio of (3~10) reacts 3~10h at 50~100 DEG C after mixing；It is successively washed and is done after reaction
It is dry, obtain pre-oxidation graphite；Graphite, potassium permanganate and the concentrated sulfuric acid will be pre-oxidized according to 1:(1~5): the mass ratio of (10~30)
0.5~5h is reacted at 20~50 DEG C after mixing, the water dilution of 500~1000ml is then added, terminates reaction；To dilution
In dispersion liquid afterwards be added 10~50ml 30wt% aqueous hydrogen peroxide solution and stir evenly, then washed, dialyse with
And the graphene oxide dispersion is obtained after 30~240min of ultrasound removing at 50~300W.
The concentration of the graphene oxide dispersion is 4~13mg ml-1。
(3) clay dispersion of step (1) is added in the graphene oxide dispersion of step (2) preparation, after stirring
Obtain graphene oxide/clay mixed dispersion liquid.
It is preferred that graphene oxide/clay mixed dispersion liquid solid content is 4~18mg ml-1；
It is preferred that graphene oxide and the mass ratio of hydrophilic clay are 1:4~4:1.
(4) it dissolves reduce agent in graphene oxide made from step (3)/clay mixed dispersion liquid, heating, pre-freeze, solution
Freeze and heat again, obtains graphene/clay composite hydrogel.
Wherein, heating is 5~10min of heating at 70~100 DEG C；Pre-freeze be at -50~-196 DEG C pre-freeze 30~
60min；Again heating be at 70~100 DEG C heating 12~for 24 hours.
Wherein, the reducing agent is selected from ascorbic acid, sodium ascorbate, thioacetic acid, ethylenediamine, p-phenylenediamine and amino
At least one of acid；
It is preferred that the mass ratio of reducing agent and graphene oxide is (2~10): 1.
(5) graphene made from step (4)/clay composite hydrogel is successively dialysed, is freeze-dried and is heat-treated,
Obtain the graphene/clay composite elastic aeroge.
Wherein, specific step is as follows for the dialysis: deionization is added in Xiang Suoshu graphene/clay composite hydrogel
Water, immersion 2~for 24 hours afterwards pour out water repeat 5~10 times.
Wherein, specific step is as follows for the freeze-drying: by the graphene obtained after dialysis/clay composite hydrogel
Dry 10~60min at -50~-75 DEG C is gradually increased to 50 DEG C and drying in 24~72h from -15 DEG C, true when dry
Reciprocal of duty cycle is 0.1~50Pa.
Wherein, specific step is as follows for the heat treatment: will be by dialysing and graphene/clay after freeze-drying process
Composite hydrogel 1~5h of constant pressure and dry at 100~300 DEG C.
The present invention has the positive effect that:
1) present invention is selected and is attached to hydrophilic clay with hydrophobic graphene aerogel matrix surface, is obtained
A kind of graphene/clay composite elastic aeroge that water static contact angle is 50 °~120 ° was obtained, the aeroge has both parent
Water, hydrophobic and elastic etc. performances, have good dispersiveness to organic solvent and water, and the weight to organic solvent or water may be implemented
Relapse receipts.
2) present invention is by changing the type of clay or the hydrophilic and hydrophobic of the adjustable graphene aerogel matrix of content.
3) clay that the present invention selects is hydrophilic simultaneously in the imparting graphene aerogel matrix, also enhances graphite
The intensity of alkene aeroge matrix, obtained graphene/clay composite elastic aeroge have as graphene aerogel matrix
Good resilience performance.
4) clay selected in method of the invention is low in cost, and preparation process is environmentally protective.
Detailed description of the invention
Graphene/attapulgite clay compounded elastic aeroge scanning electron microscope (SEM) in Fig. 1 embodiment of the present invention 1
Figure.
Graphene/attapulgite clay compounded elastic aeroge is 10 times in compression performance test in Fig. 2 embodiment of the present invention 1
Combined pressure contracting-Recovery Process load-deformation curve.
Graphene aerogel 10 bout compressions-Recovery Process in compression performance test in Fig. 3 comparative example 1 of the present invention
Load-deformation curve.
It is connect inside graphene/attapulgite clay compounded elastic aeroge with the water static state on surface in Fig. 4 embodiment of the present invention 1
Feeler tests photo.
Photo is tested with the water static contact angle on surface inside graphene aerogel in Fig. 5 comparative example 1 of the present invention.
Specific embodiment
Below by specific embodiment, the present invention is further illustrated, but the present invention is not limited thereto.
Experimental method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
1 graphene oxide dispersion of preparation example
Graphene oxide dispersion used can be prepared according to improved Hummers method in following embodiments, specifically
Steps are as follows: by natural graphite, phosphorus pentoxide, potassium peroxydisulfate and the concentrated sulfuric acid according to 2:1:1:10 mass ratio after mixing
6h is reacted at 80 DEG C；It is successively washed and is dried after reaction, obtain pre-oxidation graphite；Graphite, Gao Meng will be pre-oxidized
Sour potassium and the concentrated sulfuric acid react 2h according to the mass ratio of 1:5:30 at 35 DEG C after mixing, and after reaction plus 700ml water is dilute
It releases, terminates reaction；30ml is added into the dispersion liquid after dilution, then the aqueous hydrogen peroxide solution of 30wt% is washed, dialysed
And graphene oxide dispersion is obtained after ultrasound removing 120min at 150W；The concentration of the graphene oxide dispersion is
8mg ml-1。
Embodiment 1
Graphene/attapulgite clay compounded elastic aeroge, is made by following methods:
1) 0.5g attapulgite is added in 100g deionized water, is centrifuged 10min under 1000rpm after ultrasonic 20min,
Ultrasound 20min again is taken after the dispersion liquid of upper layer, then 10min is centrifuged at 2000rpm, takes upper layer dispersion liquid, obtaining concentration is 4mg
ml-1Attapulgite dispersion liquid；
2) by 5ml, 4mg ml-1Attapulgite dispersion liquid, 2.5ml deionized water and 2.5ml, 8mg ml-1System
Graphene oxide dispersion made from standby example 1 is uniformly mixed, and 40mg ascorbic acid is then added, stirring and dissolving, obtains at room temperature
Mixed dispersion liquid；
3) mixed dispersion liquid is placed in 90 DEG C of oil baths and heats 7min, be subsequently placed in -75 DEG C and taken out after pre-freeze 30min,
It thaws to be placed in 70 DEG C of oil baths at room temperature and heats 20h, obtain graphene/attapulgite composite hydrogel；
4) graphene/attapulgite composite hydrogel is dialysed 5 days in deionized water, it is then dry at -75 DEG C
60min is gradually heated to 30 DEG C and drying in 48h from -15 DEG C, and vacuum degree when dry is 20Pa；It is finally that freezing is dry
Aeroge after dry is heat-treated 2h in 200 DEG C of baking ovens, obtains graphene/attapulgite clay compounded elastic aeroge and (is denoted as sample
1).The graphene/attapulgite clay compounded elastic aeroge density is 4.5mg cm after tested-3。
The graphene prepared in embodiment 1/attapulgite clay compounded elastic aeroge scanning electron microscope (SEM) figure is such as
Shown in Fig. 1.Can be learnt from Fig. 1 (a): graphene sheet layer in the elastic aeroge of the graphene of preparation/attapulgite clay compounded it
Between be connected with each other and stack and form three-dimensional network structure, aperture is 10~50 μm；Can learn from Fig. 1 (b): rodlike is recessed
Convex stick soil is successfully supported on the abscess wall surface of graphene aerogel.
To the graphene prepared in embodiment 1/attapulgite clay compounded elastic aeroge with 0.2mm s-1Compression speed pressure
It contracts 80% deformation, then with the reply of phase same rate, is repeated 10 times, test results are shown in figure 2.The every second compression of composite elastic aeroge
External force is removed afterwards to remain to be returned to original state, and there is good resilience performance；Graphene/attapulgite clay compounded elastic airsetting
Compressive strength of the glue under 80% compression ratio when the first second compression is 0.01MPa.
Water static contact angle test is carried out to the graphene prepared in embodiment 1/attapulgite clay compounded elastic aeroge.Such as
Shown in Fig. 4, the water static contact angle inside composite elastic aeroge is 79 degree, and the water static contact angle on surface is 58 degree.
The graphene prepared in embodiment 1/attapulgite clay compounded elastic aeroge can adsorb the water (Luo Dan in pentane
Bright B dyeing).As it can be seen that before absorption, the water of rhodamine B dyeing is a red water droplet in pentane solution bottom for experiment；After absorption,
Red water droplet in pentane disappears, and shows that the aeroge has adsorbed the water in the pentane.
Comparative example 1
Graphene aerogel is made by following methods:
1) by 2.5ml, 8mg ml-1Preparation example 1 graphene oxide dispersion and 7.5ml deionized water mixing it is equal
It is even, 40mg ascorbic acid is then added, at room temperature stirring and dissolving；
2) it will be placed in 90 DEG C of oil baths dissolved with the graphene oxide dispersion of ascorbic acid and heat 8min, be subsequently placed in -75
It is taken out after pre-freeze 30min in DEG C, thaws to be placed in 70 DEG C of oil baths at room temperature and heat 20h, obtain graphene hydrogel；
3) graphene hydrogel is dialysed 5 days in deionized water, then the dry 60min at -75 DEG C, in 48h
30 DEG C and drying are gradually heated to from -15 DEG C, vacuum degree when dry is 20Pa；Finally the aeroge after freeze-drying is existed
It is heat-treated 2h in 200 DEG C of baking ovens, obtains graphene aerogel (being denoted as sample 2).The graphene aerogel density is after tested
1.8mg cm-3。
As shown in figure 5, the water static contact angle inside the graphene aerogel prepared in comparative example 1 is 136 degree, surface
Water static contact angle is 121 degree.Compare known to Fig. 4 and Fig. 5: Compound Punch stick soil makes graphene aerogel intrinsic silicon and surface
Water contact angle reduces 57 degree and 63 degree respectively.
Test results are shown in figure 3 for compression-reply of the graphene aerogel prepared in comparative example 1.Graphene aerogel
Compressive strength under 80% compression ratio when the first second compression is 0.003MPa.Compare known to Fig. 3 and Fig. 2: attapulgite enhancing
The intensity of graphene aerogel matrix, graphene aerogel and graphene/attapulgite clay compounded elastic aeroge are in 80% pressure
There is same good resilience performance under shrinkage.
Embodiment 2
Graphene/sodium-based montmorillonite composite elastic aeroge is made by following methods:
1) 2.0g sodium-based montmorillonite is added in 100g deionized water, at 300W after ultrasound 30min under 1000rpm
It is centrifuged 10min, the ultrasound 30min at 300W again is taken after the dispersion liquid of upper layer, is then centrifuged 10min at 2000rpm, upper layer is taken to divide
Dispersion liquid, obtaining concentration is 12mg ml-1Sodium-based montmorillonite dispersion liquid；
2) by 1.5ml, 12mg ml-1Sodium-based montmorillonite dispersion liquid, 6.0ml deionized water and 2.5ml, 8mg ml-1Preparation example 1 graphene oxide dispersion be uniformly mixed, then be added 40mg ascorbic acid, stirring and dissolving, obtains at room temperature
Mixed dispersion liquid；
3) mixed dispersion liquid is placed in 90 DEG C of oil baths and heats 7min, be subsequently placed in -75 DEG C and taken out after pre-freeze 30min,
It thaws to be placed in 70 DEG C of oil baths at room temperature and heats 20h, obtain graphene/sodium-based montmorillonite composite hydrogel；
4) graphene/sodium-based montmorillonite composite hydrogel is dialysed 5 days in deionized water, it is then dry at -75 DEG C
60min is gradually heated to 30 DEG C and drying in 48h from -15 DEG C, and vacuum degree when dry is 20Pa；It is finally that freezing is dry
Aeroge after dry is heat-treated 2h in 200 DEG C of baking ovens, obtains graphene/sodium-based montmorillonite composite elastic aeroge and (is denoted as sample
Product 3).The graphene/sodium-based montmorillonite composite elastic aeroge density is 4.0mg cm after tested-3。
Graphene/sodium-based montmorillonite composite elastic aeroge prepared by embodiment 2 the first second compression under 80% compression ratio
When compressive strength be 0.009MPa, enhance the intensity of graphene aerogel matrix, and have under 80% compression ratio good
Resilience performance.
Water static contact angle inside graphene/sodium-based montmorillonite composite elastic aeroge prepared by embodiment 2 is 120
Degree, the water static contact angle on surface are 103 degree.Composite sodium-based montmorillonite contacts graphene aerogel intrinsic silicon and surface water
Angle reduces 16 degree and 18 degree respectively.
Graphene/sodium-based montmorillonite composite elastic aeroge prepared by embodiment 2 can adsorb the toluene (oil red in water
Dyeing).Experiment is as it can be seen that before absorption, and the toluene of soudan III dyeing is pink colour liquid float on the water surface, after absorption, on the water surface
Pink colour liquid disappears；Show that the aeroge has adsorbed the toluene in the water.
Embodiment 3
Graphene/lithium diatomaceous earth composite elastic aeroge is made by following methods:
1) 0.5g lithium diatomaceous earth is added in 100g deionized water, is centrifuged under 1000rpm after ultrasound 20min at 300W
10min, taking upper layer dispersion liquid to obtain concentration is 5mg ml-1Lithium diatomaceous earth dispersion liquid；
2) by 4.0ml, 5mg ml-1Lithium diatomaceous earth dispersion liquid, 3.5ml deionized water and 2.5ml, 8mg ml-1Preparation
The graphene oxide dispersion of example 1 is uniformly mixed, and 40mg ascorbic acid is then added, at room temperature stirring and dissolving, obtains mixing point
Dispersion liquid；
3) mixed dispersion liquid is placed in 90 DEG C of oil baths and heats 8min, be subsequently placed in -70 DEG C and taken out after pre-freeze 30min,
It thaws to be placed in 70 DEG C of oil baths at room temperature and heat for 24 hours, obtain graphene/lithium diatomaceous earth composite hydrogel；
4) graphene/lithium diatomaceous earth composite hydrogel is dialysed 5 days in deionized water, it is then dry at -70 DEG C
60min is gradually heated to 30 DEG C and drying in 48h from -15 DEG C, and vacuum degree when dry is 20Pa；It is finally that freezing is dry
Aeroge after dry is heat-treated 2h in 200 DEG C of baking ovens, obtains graphene/lithium diatomaceous earth composite elastic aeroge (being denoted as sample 4).
The graphene/lithium diatomaceous earth composite elastic aeroge density is 3.0mg cm after tested-3。
Graphene/lithium diatomaceous earth composite elastic aeroge prepared by embodiment 3 is under 80% compression ratio when the first second compression
Compressive strength is 0.006MPa, enhances the intensity of graphene aerogel matrix, and is had good time under 80% compression ratio
Elastic energy.
Water static contact angle inside graphene/lithium diatomaceous earth composite elastic aeroge prepared by embodiment 3 is 115 degree, table
The water static contact angle in face is 109 degree.Complex lithium diatomaceous earth drops graphene aerogel intrinsic silicon and surface water contact angle respectively
It is 21 degree and 12 degree low.
Above-described embodiment is used to illustrate the present invention, rather than limits the invention, in spirit of the invention and
In scope of protection of the claims, to any modifications and changes that the present invention makes, protection scope of the present invention is both fallen within.
Claims (17)
1. a kind of graphene/clay composite elastic aeroge, which is characterized in that the aeroge is using graphene aerogel as base
Body, hydrophilic clay are dispersed phase；
The hydrophilic clay is attached to the abscess wall surface of graphene aerogel；
The density of the aeroge is 2~10mg cm-3, aperture is 10~100 μm, and water static contact angle is 50 °~120 °.
2. aeroge according to claim 1, which is characterized in that the hydrophilic clay is selected from attapulgite, sodium Ji Mengtuo
At least one of soil, calcium-base montmorillonite, lithium base montmorillonite, magnesium-based montmorillonite and lithium diatomaceous earth.
3. aeroge according to claim 1, wherein the density of the aeroge is 2.5~10mg cm-3。
4. aeroge according to claim 3, wherein the density of the aeroge is 3.0~6.0mg cm-3。
5. aeroge according to claim 1-4, wherein the aeroge is back and forth pressed under 80% compression ratio
Permanent deformation will not occur after contracting 10 times.
6. a kind of any one of claim 1-5 graphene/clay composite elastic aeroge preparation method, feature exist
In the described method comprises the following steps:
(1) in deionized water by hydrophilic clay dispersion, clay dispersion is obtained；
(2) graphene oxide dispersion is prepared with Hummers method or improved Hummers method；
(3) clay dispersion of step (1) is added in the graphene oxide dispersion of step (2) preparation, is obtained after stirring
Graphene oxide/clay mixed dispersion liquid；
(4) dissolve reduce agent in graphene oxide made from step (3)/clay mixed dispersion liquid, heating, pre-freeze, defrosting and
It heats again, obtains graphene/clay composite hydrogel；
(5) graphene made from step (4)/clay composite hydrogel is successively dialysed, is freeze-dried and is heat-treated, obtained
The graphene/clay composite elastic aeroge.
7. preparation method according to claim 6, which is characterized in that in step (1), hydrophilic clay is dispersed in deionized water
In after, through ultrasonic disperse and centrifugal purification, obtain clay dispersion.
8. preparation method according to claim 7, in step (1), the time of ultrasonic disperse is 10~30min；Centrifugation
Rate is 500~3000rpm；The concentration of the clay dispersion is 4~20mg ml-1。
9. preparation method according to claim 6, which is characterized in that in step (2), the graphene oxide dispersion
Concentration is 4~13mg ml-1。
10. preparation method according to claim 6, which is characterized in that in step (3), graphene oxide/clay mixing point
The solid content of dispersion liquid is 4~18mg ml-1。
11. preparation method according to claim 6, wherein graphene oxide and the mass ratio of hydrophilic clay are 1:4~4:
1。
12. preparation method according to claim 6, which is characterized in that in step (4), heating is added at 70~100 DEG C
5~10min of heat；Pre-freeze is 30~60min of pre-freeze at -50~-196 DEG C；Again heating be at 70~100 DEG C heating 12~
24h。
13. preparation method according to claim 6, in step (4), the reducing agent is selected from ascorbic acid, ascorbic acid
At least one of sodium, thioacetic acid, ethylenediamine, p-phenylenediamine and amino acid.
14. preparation method according to claim 6, in step (4), the mass ratio of reducing agent and graphene oxide be (2~
10): 1.
15. preparation method according to claim 6, which is characterized in that in step (5), the specific steps of the dialysis are such as
Under: deionized water is added in Xiang Suoshu graphene/clay composite hydrogel, immersion 2~for 24 hours afterwards pour out water repeats 5~10
It is secondary.
16. preparation method according to claim 6, in step (5), specific step is as follows for the freeze-drying: will be saturating
The graphene obtained after analysis/clay composite hydrogel dry 10~60min at -50~-75 DEG C, from -15 in 24~72h
50 DEG C and dry DEG C are gradually increased to, vacuum degree when dry is 0.1~50Pa.
17. preparation method according to claim 6, in step (5), specific step is as follows for the heat treatment: will pass through
Dialysis 1~5h of constant pressure and dry at 100~300 DEG C with graphene/clay composite hydrogel after freeze-drying process.
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| CN110152613A (en) * | 2018-04-16 | 2019-08-23 | 兰州理工大学 | A kind of aeroge adsorbent and preparation method thereof |
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| CN113908780A (en) * | 2021-11-01 | 2022-01-11 | 山东第一医科大学(山东省医学科学院) | Graphene-attapulgite composite elastic aerogel and application thereof in seawater desalination |
| CN115282925B (en) * | 2022-07-15 | 2023-08-22 | 山东第一医科大学(山东省医学科学院) | Three-dimensional graphene/clay composite aerogel for water treatment |
| CN115672289A (en) * | 2022-10-17 | 2023-02-03 | 大连理工大学 | Preparation method and application of super-hydrophilic high-elasticity graphene aerogel |
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