CN107500284A - A kind of carboxylated graphene oxide hydrogel and preparation method thereof - Google Patents
A kind of carboxylated graphene oxide hydrogel and preparation method thereof Download PDFInfo
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- CN107500284A CN107500284A CN201710800011.1A CN201710800011A CN107500284A CN 107500284 A CN107500284 A CN 107500284A CN 201710800011 A CN201710800011 A CN 201710800011A CN 107500284 A CN107500284 A CN 107500284A
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Abstract
The embodiments of the invention provide a kind of carboxylated graphene oxide hydrogel and preparation method thereof, wherein, the preparation method of the carboxylated graphene oxide hydrogel, including：Obtain carboxylated graphene oxide；Carboxylated graphite oxide is added to the water, is ultrasonically treated, is dispersed in water carboxylated graphene oxide, obtains the dispersion liquid of carboxylated graphite oxide；The dispersion liquid is reacted 24 96 hours at 80 120 DEG C, obtains the carboxylated graphene oxide hydrogel.Carboxylated graphene oxide hydrogel provided by the invention, it is compared with existing graphene oxide hydrogel, and shape is complete, and surface is more smooth, there is more preferable elasticity, it is contemplated that it has more preferable application prospect.
Description
Technical field
The present invention relates to carboxylated graphene oxide technical field, more particularly to a kind of carboxylated graphene oxide water-setting
Glue and preparation method thereof.
Background technology
For graphene as current most thin material known in the world, it is the discovery that the thing of Univ Manchester UK first
For neo-confucian in 2004, the method peeled off using microcomputer was separated into the state of individual layer.The structure of graphene has feature very much, is
By carbon atom with sp2Hybrid form connect to form monoatomic layer two-dimensional structure, its thickness only has 0.3354nm, once it is found that
As focus of attention.Structures shape property, due to the architectural feature of this special monoatomic layer of graphene so that graphene
With many novel physical arrangements, this is also exactly the reason for it is so attracted attention.Graphene is considered as in single-molecule detection
The quantum devices such as device, integrated circuit, field-effect transistor, functional composite material, energy storage material, catalyst carrier etc. have
It is widely applied prospect.Therefore, graphene is also referred to as " dark fund ", and some scientists even foretell that grapheme material will be thorough
Bottom changes 21 century.Hereafter the research on graphene emerges in an endless stream, however, graphene is not readily dissolved in polar organic solvent,
Easily reunite in polar solvent, limit the development of graphene to a certain extent, it is especially nano combined.Therefore, for stone
The modified aspect of black alkene, has substantial amounts of research to carry out, and graphene oxide equally has and stone as most common modified graphene
The carbon monoatomic layer of black alkene identical basic structure-extension, modified aspect are to be connected with a large amount of hydroxyls on aspect and edge
The hydrophilic radicals such as base, carboxyl, epoxy radicals, these groups cause graphene oxide to possess the property different from graphene, can also
Functional modification is continued to graphene oxide using these groups.Graphene oxide hydrogel is existed by graphene oxide
Under certain condition, surface functional group is cross-linked to form three-dimensional framework, effectively raises the specific surface area and electrical and thermal conductivity of material,
There is important application value in fields such as energy storage, catalysis and electronic devices, still, directly obtained using Hummers methods
The hydrogel surface of graphene oxide is coarse and compactness is poor, and hydrogel elastic is poor, frangible, is unfavorable for it and further applies.
The content of the invention
The purpose of the embodiment of the present invention is to provide a kind of carboxylated graphene oxide hydrogel and preparation method thereof, enters one
Step ground, carboxylated graphene oxide hydrogel provided in an embodiment of the present invention can solve the problem that the hydrogel of existing graphene oxide
Rough surface, poor flexibility, it is frangible the problem of.To reach above-mentioned at least one purpose, concrete technical scheme of the invention is as follows：
Present invention firstly provides a kind of carboxylated graphene oxide hydrogel, three formed comprising carboxylated graphite oxide
Tie up skeleton.
The present invention does not provide a kind of preparation method of carboxylated graphene oxide hydrogel, including：
Obtain carboxylated graphene oxide；
Carboxylated graphite oxide is added to the water, is ultrasonically treated, is dispersed in water carboxylated graphene oxide, obtains
The dispersion liquid of carboxylated graphite oxide；
The dispersion liquid is reacted into 24-96 hours at 80-120 DEG C, obtains the carboxylated graphene oxide hydrogel.
Alternatively, the concentration of carboxylated graphene oxide is (0.05-0.3) g/mL in the dispersion liquid.
Alternatively, the concentration of carboxylated graphene oxide is (0.1-0.2) g/mL in the dispersion liquid.
Alternatively, the concentration of carboxylated graphene oxide is (0.12-0.14) g/mL in the dispersion liquid.
Alternatively, the time of supersound process is 0.3-3 hours；Preferably 0.5-1 hours.
Alternatively, ultrasonic power 100-500W.
Alternatively, reaction temperature is 90-100 DEG C.
Alternatively, the reaction time is 48-72 hours.
Inventor is it was unexpectedly observed that carboxylated graphene oxide hydrogel provided by the invention, itself and existing oxidation stone
Black alkene hydrogel is compared, and shape is complete, and surface is more smooth, non-friable, and has more preferable elasticity, it is contemplated that it has preferably
Application prospect.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
The graphene oxide water-setting that Fig. 1 is carboxylated graphene oxide hydrogel prepared by embodiment 3 and prepared by comparative example
The photo of glue；
Fig. 2 is the infrared spectrogram of carboxylated graphene oxide hydrogel prepared by embodiment 3 and graphene oxide；
Fig. 3 is the XRD of carboxylated graphene oxide hydrogel prepared by embodiment 3 and graphene oxide.
Embodiment
Present invention firstly provides a kind of carboxylated graphene oxide hydrogel, it is formed comprising carboxylated graphene oxide
Three-dimensional framework, specifically, carboxylated graphene oxide is by its surface functional group, such as carboxyl is cross-linked to form three-dimensional bone
Frame, and micromolecular water calking is in three-dimensional framework, so as to form hydrogel.
Inventor is after carboxylated graphene oxide hydrogel is prepared, it has unexpectedly been found that, the oxidation of prepared carboxylated
Graphene hydrogel apparent property is much better than existing graphene oxide hydrogel, specifically, carboxylated prepared by the present invention
Graphene oxide hydrogel shape is complete, surface is smooth, flexible, and non-friable；Further, the water-setting prepared from the present invention
The excellently apparent property of glue can determine the space dense uniform of hydrogel, and mechanical property more preferably, thus is being catalyzed, the energy,
The fields such as sensing detection can have prior application value.
Present invention also offers a kind of preparation method of carboxylated graphene oxide hydrogel, above-mentioned carboxylic can be prepared
Base graphene oxide hydrogel, this method include：
Obtain carboxylated graphene oxide；
Carboxylated graphite oxide is added to the water, is ultrasonically treated, is dispersed in water carboxylated graphene oxide, obtains
The dispersion liquid of carboxylated graphite oxide；
The dispersion liquid is incubated 24-96 hours at 80-120 DEG C, obtains the carboxylated graphene oxide hydrogel.
In a kind of embodiment of the present invention, carboxylated graphene oxide can be by by graphene oxide carboxyl
Change and prepare；And graphene oxide then can pass through Hummers methods or improved Hummers methods etc. using graphite as raw material
It is prepared by method.
Technical scheme, after carboxylated graphene oxide is obtained, to add it in water, and pass through ultrasound
Processing, makes carboxylated graphene oxide fully be dispersed in water.For carboxylated graphene oxide and the ratio of water, the present invention
There is no particular/special requirement, as long as the amount of water disclosure satisfy that fully dispersed carboxylated graphene oxide, and the amount of water is no more than ability
The scope of hydrogel is suitably formed known to field technique personnel.In a kind of embodiment of the present invention, carboxylic in dispersion liquid
The concentration of base graphene oxide is (0.05-0.3) g/mL.In another embodiment of the present invention, in dispersion liquid
The concentration of carboxylated graphene oxide is (0.1-0.2) g/mL.In another embodiment of the present invention, in dispersion liquid
The concentration of carboxylated graphene oxide is (0.12-0.14) g/mL.
In a kind of embodiment of the present invention, inventor has found, when ultrasonic power is 100-500W, carboxylated oxygen
The dispersion effect of graphite alkene is more preferable.In a kind of embodiment of the present invention, inventor has found, the time of supersound process
For 0.3-3 hours, preferably 0.5-1 hours when, the dispersion effect of carboxylated graphene oxide is more preferable.
In order to obtain the preferable carboxylated graphene oxide hydrogel of appearance characteristics, after dispersion liquid is obtained, it is necessary to by its
Insulation reaction certain time at a certain temperature, such as 24-96 hours are incubated at 80-120 DEG C, to promote the contracting between carboxyl
Close to realize crosslinking.In a kind of embodiment of the present invention, reaction temperature is 90-100 DEG C.In a kind of tool of the present invention
In body embodiment, the reaction time is 48-72 hours.
By the preparation method in the specific embodiment of the invention, the carboxylated that can prepare apparent property protrusion aoxidizes
Graphene hydrogel.
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other under the premise of creative work is not made
Embodiment, belong to the scope of protection of the invention.
The preparation of the graphene oxide of embodiment 1
(1) the 230mL concentrated sulfuric acids, 5g sodium nitrate, 5g graphite powders are mixed in large beaker, after ice-water bath stirs 15 minutes,
30g potassium permanganate is uniformly added into 30 minutes while stirring.
(2) after removing ice-water bath, in 35 DEG C of stirred in water bath 30 minutes, 460ml water is added while stirring.
(3) 98 DEG C of oil baths are changed into, are stirred continuously insulation 15 minutes.
(4) after removing oil bath, warm water 1.4L is added.100ml hydrogen peroxide (30%) is slowly added dropwise, is stirred continuously, stands 3
My god.
(5) filter, washed three times, washed to not containing sulfate radicals particle with 2L 5% HCl.Washing removes HCl three times,
Using the method for centrifuge washing, hygrometric state graphene oxide GO is finally obtained.
(6) hygrometric state GO is transferred in surface plate, 60 DEG C of dry 24h.
The graphene oxide carboxylated of embodiment 2
(1) graphene oxide that graphene oxide prepared by embodiment 1 is configured to mass fraction 2.154% with water is molten
Liquid；
(2) the graphene oxide solution 16.7131g of mass fraction 2.154% is weighed, and is made into 8mg/ml water slurry
45ml, ultrasonic disperse is in 150ml water.
(3) 0.55g monoxones are added into suspension.
(4) by mixture 70 DEG C be heated to reflux 6 hours.
(5) in ultra-pure water, with dialysis membrane (cellulose dialysis film, molecular cut off 8000-14000) dialysis until PH is
About 3.5.
After (6) 60 DEG C rotate partial moisture, it is dried overnight in 70 DEG C of baking ovens.
The process of above-mentioned graphene oxide carboxylated refers to documents below：
Wang Zhengwei, Xiong Li, high clouds, wait the preparation of carboxylated oxygen graphenes and its electric property [J] Yunnan's Ethnics big
Journal nature section version, 2013,22 (2):86-90.
Embodiment 3
2g carboxylated graphene oxides are measured in 20ml vials, afterwards plus water constant volume is to 15mL, and bottle is twisted into lid,
Ultrasound 30 minutes, ultrasonic power 300W, is finally put into baking oven hydro-thermal reaction 3 days at 95 DEG C.Obtain product：Carboxylated aoxidizes
Graphene hydrogel.
Embodiment 4
2g carboxylated graphene oxides are measured in 20ml vials, afterwards plus water constant volume is to 15mL, and bottle is twisted into lid,
Ultrasound 30 minutes, ultrasonic power 300W, is finally put into baking oven hydro-thermal reaction 4 days at 80 DEG C.Obtain product：Carboxylated aoxidizes
Graphene hydrogel.
Embodiment 5
2g carboxylated graphene oxides are measured in 20ml vials, afterwards plus water constant volume is to 15mL, and bottle is twisted into lid,
Ultrasound 30 minutes, is finally put into baking oven hydro-thermal reaction 2 days at 120 DEG C.Obtain product：Carboxylated graphene oxide water-setting
Glue.
Embodiment 6
2g carboxylated graphene oxides are measured in 50ml vials, afterwards plus water constant volume is to 40mL, and bottle is twisted into lid,
Ultrasound 30 minutes, ultrasonic power 300W, is finally put into baking oven hydro-thermal reaction 3 days at 100 DEG C.Obtain product：Carboxylated oxygen
Graphite alkene hydrogel.
Embodiment 7
2g carboxylated graphene oxides are measured in 20ml vials, afterwards plus water constant volume is to 8mL, and bottle is twisted into lid,
Ultrasound 60 minutes, ultrasonic power 300W, is finally put into baking oven hydro-thermal reaction 3 days at 95 DEG C.Obtain product：Carboxylated aoxidizes
Graphene hydrogel.
It should be noted that carboxylated graphene oxide used in embodiment 3-7, according to the method system of embodiment 2
It is standby.
The preparation of comparative example graphene oxide hydrogel
2g graphene oxides (preparing as described in Example 1) are measured in 20ml vials, afterwards plus water constant volume is to 15mL,
Lid is twisted in bottle, ultrasound 30 minutes, ultrasonic power 300W, is finally put into baking oven hydro-thermal reaction 3 days at 95 DEG C.Obtain
Product：Graphene oxide hydrogel.
Characterize and analyze
Below by taking carboxylated graphene oxide hydrogel prepared by embodiment 3 as an example, phenetic analysis is carried out.
Apparent property is examined
(a) figure is graphene oxide hydrogel prepared by comparative example in Fig. 1；(b) figure is carboxylic prepared by embodiment 3 in Fig. 1
Base graphene oxide hydrogel；
Compare (a) in Fig. 1, (b) figure, it can be clearly seen that, carboxylated graphene oxide hydrogel tool prepared by embodiment 3
There is preferable integrity degree, surface is smooth, and compared with graphene oxide hydrogel prepared by comparative example, apparent property is more excellent；And
And by pressing two hydrogels, carboxylated graphene oxide hydrogel prepared by embodiment 3 has preferably elasticity, and
Elasticity is significantly better than graphene oxide hydrogel prepared by comparative example.
Infrared spectrum analysis
FTIS (the FT-IR) (model produced using Nicolet companies of the U.S.：Nicolet360)
Graphene oxide prepared by the carboxylated graphene oxide hydrogel and embodiment 1 prepared to embodiment 3 carries out IR Characterization and (adopted
With KBr pressed disc methods, scan at room temperature, test scope is 4000~400cm-1), infrared spectrogram is as shown in Figure 2.
(a) is the infrared spectrogram of carboxylated graphene oxide hydrogel prepared by embodiment 3 in Fig. 2；(b) is in Fig. 2
The infrared spectrogram of graphene oxide.
(a) is it can be found that in 1610-1560cm from Fig. 2-1Neighbouring and 1440-1360cm-1Nearby there is two strong absorb
Peak, it can be said that bright have-COO-, 3200-2500cm-1Nearby have one it is interior with 3000cm in a big way-1Centered on width and
Scattered peak, and this is absorbed in 2700-2500cm-1Often there are several small peaks, therefore can be identified as the hydroxyl peak in carboxyl.Pass through contrast
The infared spectrum (in Fig. 2 (b)) of graphene oxide it can be found that this carboxyl peak than before graphene oxide infared spectrum more
Substantially, and 1050cm-1Neighbouring C-O singly-bounds absworption peak and 1254cm-1Neighbouring C-O-C absworption peaks significantly decline.Therefore can
Illustrate that carboxylated graphene hydrogel is successfully prepared, the epoxy and hydroxy functional group on surface are oxidized to-COOH.It may finally obtain
Go out, the carboxyl intensity increase of carboxylated graphene oxide, hydroxyl and epoxy radicals remitted its fury, illustrate after chloroethene acid treatment,
So that part of hydroxyl and epoxy radicals, oxidation transformation is carboxyl, and carboxylated graphene oxide is prepared.
2nd, XRD (ray diffraction, X-ray diffraction) is analyzed
X-ray powder diffraction instrument (the model produced using Dutch PA Nalytical companies：X Pert PRO MPD) it is right
Graphene oxide prepared by carboxylated graphene oxide hydrogel and embodiment 1 prepared by embodiment 3 carries out XRD signs, XRD
As shown in Figure 3.
(a) is the XRD of carboxylated graphene oxide hydrogel prepared by embodiment 3 in Fig. 3；(b) is oxidation stone in Fig. 3
The XRD of black alkene.
Carboxylated oxygen graphene peak value is can be seen that in (a) from Fig. 3 to move to low-angle, is due to interlamellar spacing increase,
The reason for interlamellar spacing increase is the intercalation work that hydroxyl and epoxy radicals improve molecule by chemical conversion carboxyl, and after its water solubility increase
With.
Experiment shows above, and the present invention has successfully prepared carboxylated graphene oxide hydrogel, and prepared
For carboxylated graphene oxide hydrogel compared with the graphene oxide hydrogel of non-carboxylated, apparent property is more preferable, has more preferable
Application prospect.
A kind of carboxylated graphene oxide hydrogel provided by the present invention and preparation method thereof is carried out above in detail
Introduce.Specific embodiment used herein is set forth to the principle and embodiment of the present invention, and above example is said
It is bright to be only intended to help the method and its central idea for understanding the present invention.It should be pointed out that for one of ordinary skill in the art
For, under the premise without departing from the principles of the invention, some improvement and modification can also be carried out to the present invention, these improve and repaiied
Decorations are also fallen into the protection domain of the claims in the present invention.
Claims (9)
- A kind of 1. carboxylated graphene oxide hydrogel, it is characterised in that the three-dimensional bone formed comprising carboxylated graphene oxide Frame.
- A kind of 2. preparation method of carboxylated graphene oxide hydrogel, it is characterised in that including：Obtain carboxylated graphene oxide；Carboxylated graphite oxide is added to the water, is ultrasonically treated, is dispersed in water carboxylated graphene oxide, obtains carboxyl Change the dispersion liquid of graphite oxide；The dispersion liquid is reacted into 24-96 hours at 80-120 DEG C, obtains the carboxylated graphene oxide hydrogel.
- 3. method as claimed in claim 2, it is characterised in that the concentration of carboxylated graphene oxide is in the dispersion liquid (0.05-0.3)g/mL。
- 4. method as claimed in claim 3, it is characterised in that the concentration of carboxylated graphene oxide is in the dispersion liquid (0.1-0.2)g/mL。
- 5. method as claimed in claim 4, it is characterised in that the concentration of carboxylated graphene oxide is in the dispersion liquid (0.12-0.14)g/mL。
- 6. method as claimed in claim 2, it is characterised in that the time of supersound process is 0.3-3 hours；Preferably 0.5-1 Hour.
- 7. method as claimed in claim 2, it is characterised in that ultrasonic power 100-500W.
- 8. method as claimed in claim 2, it is characterised in that reaction temperature is 90-100 DEG C.
- 9. such as the method any one of claim 2-8, it is characterised in that the reaction time is 48-72 hours.
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