CN108046244A - A kind of method for synthesizing Janus graphenes - Google Patents
A kind of method for synthesizing Janus graphenes Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 34
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- 239000000377 silicon dioxide Substances 0.000 claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
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- 238000000926 separation method Methods 0.000 claims abstract description 4
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 5
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- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
The present invention relates to material synthesis method fields, provide a kind of method for synthesizing Janus graphenes, include the following steps：1) silicon dioxide microsphere is taken to be dispersed in toluene ultrasonic, then adds in APTES, mixture is stirred, and reacted at 95 DEG C, obtained product SiO2APTES is for use after being washed with ethyl alcohol；2) suitable SiO is taken2APTES is added in ultra-pure water and ultrasound, separately takes the GO monodisperses aqueous solution and ultrasound of low concentration, adds in SiO2It in APTES aqueous solutions, and is stirred at room temperature, precipitated solid product SiO is collected by centrifugation2@GO, and with after milli-Q water to SiO2@GO are unprotected to be modified on one side；3) SiO of single side modified is taken2@GO are stirred to react to dissolve SiO with aqueous slkali in a heated condition2, reaction finish after washing separation it is former to graphene oxide it is shielded modify on one side, obtain Janus graphenes.The present invention is easy to operate, can be synthesized on a large scale in the liquid phase.The Janus graphene nanometer sheets two sides of synthesis has different functional groups, and modification is efficient, and is easily dispersed the operation and application for, being conducive to carry out next step in the solution.
Description
Technical field
The present invention relates to material synthesis method fields, and in particular to a kind of method for synthesizing Janus graphenes.
Background technology
Graphite is repeatedly removed, obtains the thin slice-graphene being made of one layer of carbon atom.Graphene is a kind of two dimension
The sp of atom thick2It is conjugated the sheet material of carbon web frame.Due to surface area (the theoretical value 2360m of its super large2/ g) and outstanding electric conductivity
Deng making graphene that all there is application value well in many aspects.Graphene oxide be by powdered graphite through chemical oxidation and
Product after stripping, after peroxidating, oxygen-containing functional group thereon increases and makes its property more active compared with graphene, can be by each
It plants the reaction with oxygen-containing functional group and improves the property of itself.
The particle on the two sides with different structure or chemical composition is referred to as Janus particles, in recent years in physics, chemistry
Huge interest is caused in terms of each research with bioscience.Compared with the particle uniformly modified, Janus particles can be set
Count into has anisotropic electricity with unique amphiphilic character and due to its dissymmetrical structure, magnetically or optically
Property.Therefore, Janus particles are in medicine targeted delivery, biosensor, imaging nano-probe, autokinesis colloidal materials and skin
The wide range of areas such as crin interfacial catalysis agent have potential application.
Present inventor has found that the preparation method at present on Janus graphenes is also seldom under study for action, it is known that have
A kind of method of the single-layer graphene on asymmetric functionalization is reported within 2013, it is that polymethyl methacrylate is auxiliary
The method for helping transfer, but this method is complicated for operation, requirement is fine, cost is higher, for realizing that industrial mass production is difficult
It spends larger, and needs to use a large amount of organic solvents, it is not friendly enough to environment.
The content of the invention
The present invention provides a kind of method for synthesizing Janus graphenes, and this method is synthesized with silicon dioxide microsphere is template
The graphene of the asymmetric functional modification in two sides, this method is easy to operate, at low cost, can be closed on a large scale in the liquid phase
Into.The Janus graphene nanometer sheets two sides of synthesis has different functional groups, and modification is efficient, and is easily dispersed in the solution,
Be conducive to carry out the operation and application of next step.
The present invention provides a kind of method for synthesizing Janus graphenes, includes the following steps：
1) silicon dioxide microsphere is taken to be dispersed in toluene ultrasonic, then adds in 3-aminopropyltriethoxysilane
(APTES), mixture is stirred, and is reacted at 95 DEG C, obtained product SiO2After-APTES is washed with ethyl alcohol
For use；
2) suitable SiO is taken2- APTES is added in ultra-pure water and ultrasound, separately takes single point of the graphene oxide (GO) of low concentration
Aproll solution and ultrasound, are then slowly added dropwise to SiO with dropping funel by graphene oxide monodisperse liquid2- APTES aqueous solutions
In, and be stirred at room temperature, precipitated solid product SiO is collected by centrifugation2@GO, and with after milli-Q water to SiO2@GO are not affected by
Protection is modified on one side；
3) SiO of single side modified is taken2@GO are stirred to react to dissolve SiO with aqueous slkali in a heated condition2, expose oxygen
Graphite alkene shielded one side originally, reaction finish former to graphene oxide after washing separation shielded repair on one side
Decorations, obtain Janus graphenes.
Further, described in step 2) to SiO2@GO are unprotected to be modified on one side, including by with GO
The mode being chemically bonded is modified, such as：
Take the appropriate SiO2@GO are added to ultrasonic disperse 1h in ethyl alcohol, then add in N- (trimethoxy silicon third thereto
Base) ethylenediamine triacetic acid sodium salt (EDTA-silane), simultaneously condensing reflux is stirred, after completion of the reaction, precipitation solid is collected by centrifugation,
Washing obtains SiO2@GO·EDTA-silane。
Further, described in step 3) it is former to graphene oxide it is shielded modify on one side, including by with
The mode that GO is chemically bonded is modified, such as：
Suitable GOEDTA-silane is dispersed in water and n,N-Dimethylformamide, then adds in suitable ten
Eight amine and N, N'- dicyclohexylcarbodiimide, and be ultrasonically treated, simultaneously condensing reflux is stirred the mixture for, after completion of the reaction
Lower floor's solid product is collected by centrifugation, product Janus graphenes are obtained after washing.
Further, the aqueous slkali described in step 3) is potassium hydroxide, sodium hydroxide, calcium hydroxide strong base solution.
The stone of the asymmetric functional modification in two sides is synthesized for template using silicon dioxide microsphere the present invention provides a kind of
The method of black alkene.Pass through SiO2Microballoon carries out un-symmetrical change as template and synthesis medium to graphene oxide (GO) nanometer sheet
Learn modification.It is template with silica, it is cheap and be easy to be modified, and this method is easy to operate, at low cost, it can be
It is synthesized on a large scale in liquid phase.The Janus graphene nanometer sheets two sides of synthesis has different functional groups, and modification is efficient,
And it is easily dispersed the operation and application for, being conducive to carry out next step in the solution.
Description of the drawings
It 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 attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments, for those of ordinary skill in the art, without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is a kind of synthetic route chart for the method for synthesizing Janus graphenes of the embodiment of the present application；
Fig. 2 is intermediate product SiO in a kind of building-up process for the method for synthesizing Janus graphenes of the embodiment of the present application2@
The scanning electron microscope (SEM) photograph of GO；
Fig. 3 is intermediate product SiO in a kind of building-up process for the method for synthesizing Janus graphenes of the embodiment of the present application2@
The scanning electron microscope (SEM) photograph of GOEDTA-silane；
Fig. 4 is intermediate product GO in a kind of building-up process for the method for synthesizing Janus graphenes of the embodiment of the present application
The transmission electron microscope picture of EDTA-silane；
Fig. 5 is the Zeta electricity of each product in a kind of building-up process for the method for synthesizing Janus graphenes of the embodiment of the present application
The change curve of place value.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the attached drawing in the present invention, to this
Technical solution in inventive embodiments is clearly and completely described, it is clear that described embodiment is that a part of the invention is real
Example is applied, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not paying creation
Property work under the premise of all other embodiments obtained, belong to the scope of protection of the invention.
The embodiment of the present application provides a kind of method for synthesizing Janus graphenes, includes the following steps：
1) silicon dioxide microsphere is taken to be dispersed in toluene ultrasonic, then adds in 3-aminopropyltriethoxysilane
(APTES), mixture is stirred, and is reacted at 95 DEG C, obtained product SiO2After-APTES is washed with ethyl alcohol
For use；
2) suitable SiO is taken2- APTES is added in ultra-pure water and ultrasound, separately takes single point of the graphene oxide (GO) of low concentration
Aproll solution and ultrasound, are then slowly added dropwise to SiO with dropping funel by graphene oxide monodisperse liquid2- APTES aqueous solutions
In, and be stirred at room temperature, precipitated solid product SiO is collected by centrifugation2@GO, and with after milli-Q water to SiO2@GO are not affected by
Protection is modified on one side；
It in the embodiment of the present application, can be by way of being chemically bonded with graphene oxide unprotected
Upper various functions molecule is modified on one side.
3) SiO of single side modified is taken2@GO are stirred to react to dissolve SiO with aqueous slkali in a heated condition2, expose oxygen
Graphite alkene shielded one side originally, reaction finish former to graphene oxide after washing separation shielded repair on one side
Decorations, obtain Janus graphenes.
It in the embodiment of the present application, can be by way of being chemically bonded with graphene oxide in original shielded one
The upper various functions molecule of face modification.
Wherein, described in step 2) to SiO2The modification that carries out on one side unprotected@GO includes：
Take the appropriate SiO2@GO are added to ultrasonic disperse 1h in ethyl alcohol, then add in N- (trimethoxy silicon third thereto
Base) ethylenediamine triacetic acid sodium salt (EDTA-silane), simultaneously condensing reflux is stirred, after completion of the reaction, precipitation solid is collected by centrifugation,
Washing obtains SiO2@GO·EDTA-silane。
Wherein, former to graphene oxide described in step 3) shielded carry out modification and includes on one side：
Suitable GOEDTA-silane is dispersed in water and n,N-Dimethylformamide, then adds in suitable ten
Eight amine and N, N'- dicyclohexylcarbodiimide, and be ultrasonically treated, simultaneously condensing reflux is stirred the mixture for, after completion of the reaction
Lower floor's solid product is collected by centrifugation, product Janus graphenes are obtained after washing.
The method of the invention is described in detail with reference to specific embodiment.
Embodiment 1：
Real offer of the invention is a kind of to synthesize the graphene oxide of the asymmetric modification in two sides with silicon dioxide microsphere is template
Method, include the following steps：
1) silica is surface modified (SiO2-APTES)
By the silicon dioxide microsphere of 5g silicon dioxide microspheres, such as 200-600nm, it is analytically pure to be dispersed in 200mL
When ultrasound 1 is small in toluene, the 3-aminopropyltriethoxysilane (APTES) of 2.5mL is then added in.By mixture in 400rpm
Lower magnetic agitation, and when reflux 24 is small at 95 DEG C, obtain the SiO of aminofunctional2-APTES.Product washs three with ethyl alcohol
It is secondary, and be freeze-dried and be placed in sample cell, it is preserved in drier for use.
2) graphene oxide is coated on silicon dioxide microsphere surface (SiO2@GO)
By 1g SiO2- APTES is added in 100mL ultra-pure waters and ultrasound 1h, by the oxidation that 100mL concentration is 0.2mg/mL
Graphene (piece footpath be 50-200nm) monodisperse aqueous solution ultrasound 1h, then with dropping funel by graphene oxide dispersion slowly
(drop speed is about 0.017mL/s) is added dropwise and enters SiO2- APTES aqueous solutions, and 3h is stirred at room temperature at 500 rpm with mechanical agitation.From
The heart (6000rpm, 10min) collects precipitation solid (SiO2@GO), and with milli-Q water five times, remove unbonded GO.Then
It is for use that freeze-drying is placed on sample cell.
3) graphene oxide single side is modified into upper EDTA-silane (SiO2@GO·EDTA-silane)
By 1g SiO2@GO are added in 200mL ethyl alcohol, and pass through ultrasonic disperse 1h.Then 3mL 40% is added in thereto
N- (trimethoxy silicon propyl) ethylenediamine triacetic acid sodium salt (EDTA-silane), magnetic agitation under 1200rpm, and at 65 DEG C
When lower condensing reflux 24 is small.After having reacted, precipitation solid is collected in centrifugation (6000rpm, 10min), then with milli-Q water three
Time, methanol washs three times to remove unreacted EDTA-silane, for use after being then freeze-dried.
4) silica (GOEDTA-silane) is dissolved
The potassium hydroxide of 56.11g top pure grades is dissolved in 200mL water and is made into 5mol/L potassium hydroxide solutions, is added
0.9g SiO2@GO·EDTA-silane.In 80 DEG C, magnetic agitation under 1200rpm.After reaction six or seven days, reaction was completed, mixes
It closes liquid and 50min is first centrifuged under 12000rpm, lower floor's solid is washed twice with water, and is then filtered with 50nm filter membranes with nearly one
It walks and removes potassium hydroxide, the filter cake (GOEDTA-silane) after suction filtration on filter membrane is for use after being freeze-dried.
5) by the upper octadecylamine (Janus graphenes) of another side modification of the graphene oxide of single side modification
The GOEDTA-silane of 30mg is dispersed in 8mL water and 75mLN, in dinethylformamide, is then added in
450mg octadecylamines and 60mg N, N'- dicyclohexylcarbodiimides, and after being ultrasonically treated suspension 30min, mixture is existed
Magnetic agitation under 1200rpm, condensing reflux is for 24 hours at 70 DEG C.50min collections lower floor is centrifuged after having reacted under 12000rpm to consolidate
Body product adds and is washed several times to dissolve the complete octadecylamine of unreacted with anhydrous ether, obtains product Janus graphite to the end
Alkene.
Electronic Speculum characterization is carried out to some key intermediate species of building-up process by more than synthesis step.Fig. 2 is SiO2@GO
Scanning electron microscope (SEM) photograph, show graphene oxide by with SiO2The effect of-APTES electrostatic force relatively closely fits together, and rises
The effect of protection graphene oxide single side is arrived.Attached drawing 3 is SiO2The scanning electron microscope (SEM) photograph of@GOEDTA-silane, show into
Being about to the upper EDTA-silane of graphene oxide single side modification, this is walked in building-up process, and graphene oxide is also fitted in well
SiO2Microsphere surface is not fallen off.Fig. 4 is the transmission electron microscope picture of GOEDTA-silane, shows SiO2Microballoon is complete
It dissolves, the graphene oxide of single side modification disperses in the solution.
By by the product in building-up process with ultra-pure water carry out dissolving it is scattered after, survey its Zeta potential, obtained characterization
The results are shown in table below：
It is consistent by the characterization result carried out to its Zeta potential with theory, SiO2Since there is depositing for hydroxyl on surface in water
It is negative in Zeta potential；SiO2After carrying out aminofunctional, surface becomes just for amino Zeta potential；Graphene oxide is coated
In SiO2Microsphere surface, due to surface of graphene oxide there are many oxygen-containing functional group such as：Hydroxyl, carboxyl and epoxide group, so
SiO2The Zeta potential of@GO becomes negative, by its Zeta potential after the upper hydrophilic EDTA-silane of graphene oxide single side modification
Value further becomes smaller, by SiO2After microballoon dissolving, the Zeta potential value variation of GOEDTA-silane is little, finally by single side
After the upper hydrophobic octadecylamine of another side modification of the graphene oxide of modification, Zeta potential value becomes larger.
The stone of the asymmetric functional modification in two sides is synthesized for template using silicon dioxide microsphere the present invention provides a kind of
The method of black alkene.Pass through SiO2Microballoon carries out asymmetric chemistry to stannic oxide/graphene nano piece and repaiies as template and synthesis medium
Decorations, are supported on SiO by graphene oxide by electrostatic interaction first2Microsphere surface is protected it, is exposed on one side
Outer another side modifies upper functional molecular by way of chemical bonding, then using highly basic by SiO2Microballoon dissolves, by original by
The one side of protection modifies upper functional molecular by way of chemical bonding, obtains Janus graphenes.It is template with silica,
It is cheap and be easy to be modified, and this method is easy to operate, at low cost, can be synthesized on a large scale in the liquid phase.It closes
Into Janus graphene nanometer sheets two sides there is different functional groups, modification is efficient, and is easily dispersed in the solution, favorably
In the operation and application that carry out next step.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
The present invention is described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that：It still may be used
To modify to the technical solution recorded in foregoing embodiments or carry out equivalent substitution to which part technical characteristic；
And these modification or replace, do not make appropriate technical solution essence depart from various embodiments of the present invention technical solution spirit and
Scope.
Claims (4)
- A kind of 1. method for synthesizing Janus graphenes, which is characterized in that include the following steps：1) silicon dioxide microsphere is taken to be dispersed in toluene ultrasonic, then adds in 3-aminopropyltriethoxysilane (APTES), it will Mixture is stirred, and is reacted at 95 DEG C, obtained product SiO2It is for use after-APTES washings；2) suitable SiO is taken2- APTES is added in ultra-pure water and ultrasound, separately takes graphene oxide (GO) monodisperse water of low concentration Solution and ultrasound, are then slowly added dropwise to SiO with dropping funel by graphene oxide monodisperse liquid2In-APTES aqueous solutions, and It is stirred at room temperature, precipitated solid product SiO is collected by centrifugation2@GO, and with after milli-Q water to SiO2@GO are unprotected It is modified on one side；3) SiO of single side modified is taken2@GO are stirred to react to dissolve SiO with aqueous slkali in a heated condition2, expose oxidation stone Black alkene shielded one side originally, reaction finish after washing separation it is former to graphene oxide it is shielded modify on one side, obtain To Janus graphenes.
- 2. according to the method described in claim 1, it is characterized in that, described in step 2) to SiO2@GO it is unprotected one Face is modified, including being modified by way of being chemically bonded with GO, such as：Take the appropriate SiO2@GO are added to ultrasonic disperse 1h in ethyl alcohol, then add in N- (trimethoxy silicon propyl) second thereto Ethylenediamine triacetic acid sodium salt (EDTA-silane) stirs simultaneously condensing reflux, after completion of the reaction, precipitation solid is collected by centrifugation, washs To SiO2@GO·EDTA-silane。
- 3. method according to claim 1 or 2, which is characterized in that being protected to graphene oxide original described in step 3) Shield is modified on one side, including being modified by way of being chemically bonded with GO, such as：Suitable GOEDTA-silane is dispersed in water and n,N-Dimethylformamide, then adds in suitable octadecylamine And N, N'- dicyclohexylcarbodiimide, and be ultrasonically treated, simultaneously condensing reflux is stirred the mixture for, is centrifuged after completion of the reaction Lower floor's solid product is collected, product Janus graphenes are obtained after washing.
- 4. according to the method described in one of claim 1-3, which is characterized in that the aqueous slkali described in step 3) is hydroxide Potassium, sodium hydroxide, calcium hydroxide strong base solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810141755.1A CN108046244B (en) | 2018-02-11 | 2018-02-11 | Method for synthesizing Janus graphene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810141755.1A CN108046244B (en) | 2018-02-11 | 2018-02-11 | Method for synthesizing Janus graphene |
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| CN108046244A true CN108046244A (en) | 2018-05-18 |
| CN108046244B CN108046244B (en) | 2020-09-04 |
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| CN110026236A (en) * | 2019-03-23 | 2019-07-19 | 大连理工大学 | A kind of Pd composite nano-catalyst and preparation method thereof for formic acid decomposing hydrogen-production |
| CN110342505A (en) * | 2019-06-20 | 2019-10-18 | 宁波锋成先进能源材料研究院 | A kind of preparation method of parents' unsymmetric structure graphene oxide, parents' unsymmetric structure graphene oxide and its application |
| CN113694824A (en) * | 2020-05-20 | 2021-11-26 | 中国石油天然气股份有限公司 | Double-sided anisotropic nanosheet and preparation method thereof |
| CN113905982A (en) * | 2019-03-15 | 2022-01-07 | 沙特阿拉伯石油公司 | Batch synthesis of JANUS nanomaterials |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113905982A (en) * | 2019-03-15 | 2022-01-07 | 沙特阿拉伯石油公司 | Batch synthesis of JANUS nanomaterials |
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| CN110026236B (en) * | 2019-03-23 | 2021-09-10 | 大连理工大学 | Pd composite nano catalyst for hydrogen production by formic acid decomposition and preparation method thereof |
| CN110342505A (en) * | 2019-06-20 | 2019-10-18 | 宁波锋成先进能源材料研究院 | A kind of preparation method of parents' unsymmetric structure graphene oxide, parents' unsymmetric structure graphene oxide and its application |
| CN113694824A (en) * | 2020-05-20 | 2021-11-26 | 中国石油天然气股份有限公司 | Double-sided anisotropic nanosheet and preparation method thereof |
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