CN103818896A - Method for asymmetrically modifying grapheme or oxidized grapheme - Google Patents
Method for asymmetrically modifying grapheme or oxidized grapheme Download PDFInfo
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Abstract
The invention relates to a method for modifying grapheme, and particularly relates to a method for asymmetrically modifying two opposite planes of grapheme. Aiming at the problems that grapheme has high surface energy, grapheme is easy to conglobate and corrugate and is not easy to flatly lay, and two planes of grapheme can not be simultaneously and asymmetrically modified in the prior art, the invention provides a method for asymmetrically modifying two planes of grapheme. The method comprises the following concrete steps: firstly, providing an aqueous dispersion solution of grapheme or oxidized grapheme, secondly, feeding an organic phase that is not dissolved in water, thirdly, feeding a quaternary ammonium salt cationic surface active agent containing C10-C18 alkyl chain, vibrating or stirring, so as to ensure that the surface active agent reacts with the grapheme and the grapheme is transferred and assembled onto the organic phase/water interface from an aqueous phase, fourthly, respectively feeding different modifying material into the aqueous phase and organic phase, so as to ensure that the modifying material is respectively adhered to two planes of the grapheme through adsorption, and fifthly, separating the grapheme to which the modifying material is adhered after adsorption equilibrium.
Description
Technical field
The present invention relates to a kind of grapheme modified method, especially to contrary two methods that plane is carried out asymmetric modification of Graphene.
Background technology
Graphene only has single or several atoms as a kind of thickness, size but can reach several even two-dimensional nano films of tens microns, have advantages of outstanding, as good conductivity, physical strength is high, in the using value widely of electronics, optics, sensor, electrical condenser etc.Graphene through functionalization or modification more highlights excellent characteristic.But, because Graphene (GS) or graphene oxide (GO) surface can be large, easily be agglomerated into multilayer or wrinkling, thereby the modification/functionalization of most is in homogeneous system, in symmetrical and non-selective level.The symmetry of Graphene is modified very important, if but can realize its asymmetric or optionally modification, can greatly expand the application of Graphene.As Graphene plane is carried out to N-shaped doping, and contrary another side is carried out to the doping of P type, will certainly greatly improve the crystal field effects of Graphene.How by Graphene or these two-dimensional nano materials of graphene oxide with individual layer mode and corrugationless sprawl, be the key that realizes GS or the asymmetric modification of GO.
In prior art, mainly that Graphene two-dimensional material is spread over to smooth smooth solid substrate, on silicon face, first the exposed one side of Graphene is modified with a kind of material, then this face polymkeric substance of having modified is covered, and solid substrate is dissolved, make the another side of Graphene out exposed, and it is modified with another kind of material, finally again polymkeric substance is also removed, so just can realize the modification of two planar unsymmetricals that Graphene is contrary.The method adopts the carrier of solid silicon substrate as tiling Graphene, be conducive to Graphene in individual layer mode and without crinkled sprawling, for its asymmetric modification lays the foundation, but the step that this method relates to is more, two planes that Graphene is contrary must be modified by proceed step by step, and the condition of removal solid silicon substrate and polymkeric substance is all more violent.Therefore search out suitable carrier, can make the tiling that Graphene can corrugationless, and without relating to the step of complexity like this and violent reaction conditions, be the key issue of the asymmetric modification of Graphene.
Summary of the invention
Object of the present invention is exactly to crease easily because surface energy great Yi reunites for Graphene as above, is difficult for tiling; With and prior art in can not carry out the problems such as asymmetric modification to Graphene two sides simultaneously, a kind of method of Graphene being carried out to the asymmetric modification in two sides is proposed.
The present invention adopts the phase interface of two immiscible moving phases as the carrier of tiling Graphene, realizes the asymmetric modification on Graphene two sides, specifically comprises the steps:
1) provide the aqueous dispersion solution of Graphene or graphene oxide;
2) add the organic phase immiscible with water;
3) add the quaternary cationics containing C10-C18 alkyl chain, vibration or stirring make tensio-active agent react with Graphene, make Graphene shift and be assembled into organic phase/water termination from water;
4) in water and organic phase, add respectively different decorative materials, decorative material is attached to respectively on the two sides of Graphene by absorption;
5) etc., after adsorption equilibrium, isolating absorption has the Graphene of decorative material.
Of the present invention and immiscible the referring to of water can form stable organic phase/water termination with water, and generally speaking, the mutual solubility between water and organic phase two-phase is the smaller the better, and polarity differs and is the bigger the better.
Further, organic phase of the present invention can be selected from toluene, methylene dichloride, 1,2 ethylene dichloride.
Further, the volume of organic phase of the present invention and water substantially equates or is unequal, and preferred volume is substantially equal.
Further, quaternary cationics containing C10-C18 alkyl chain of the present invention is Trimethyllaurylammonium bromide, Dodecyl trimethyl ammonium chloride, dodecyl trimethylammonium hydroxide, dodecyl triethyl brometo de amonio, dodecyl triethyl ammonium chloride, dodecyl triethyl ammonium hydroxide, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, cetyltrimethylammonium hydroxide; Cetyltriethylammonium bromide, hexadecyl triethyl ammonium chloride, hexadecyl triethyl ammonium hydroxide; Preferably Trimethyllaurylammonium bromide or cetyl trimethylammonium bromide.
Further, the concentration of cats product of the present invention is 0.1-1mg/mL, and the volume ratio of its consumption and water volume is 0.01-0.1:100.The consumption of tensio-active agent very little, cannot make Graphene or graphene oxide effectively be assembled into organic phase/aqueous phase interface, and consumption can cause the mixed flow of water and organic phase too much.
Further, the concentration of Graphene of the present invention or graphene oxide aqueous dispersion solution is 0.0001-0.005mg/L.The consumption of Graphene or graphene oxide has influence on it at interfacial assembly state, appropriate consumption can make its assembling in organic-aqueous interface remain individual layer state, can make like this two sides of single-layer graphene be exposed to respectively in different systems, be convenient to asymmetric modification.As too much in consumption, it is in organic-aqueous interface or in the mode of multilayer, or wrinkling, is unfavorable for follow-up asymmetric modification.
Further, decorative material of the present invention is can be dissolved in the conventional decorative material in organic phase and can be dissolved in the conventional decorative material in water; Preferably, a kind of decorative material will have larger solvability in organic phase, and solvability is lower in water; And another kind of decorative material will have larger solvability in water, and solvability is lower in organic phase; Preferred, a kind of decorative material will dissolve in organic phase, and dissolves hardly in water; And another kind of decorative material will dissolve in water, and dissolve hardly in organic phase; Most preferred, a kind of decorative material is porphyrin, and another kind of decorative material is Cadmium Sulfide;
Further, decorative material Cadmium Sulfide of the present invention can be the Nano cadmium sulphide of preparing by reacting original position in water.
General, the polarity of these two kinds of decorative materials and different from the two sides mode of action of Graphene or graphene oxide, the decorative material that is dissolved in organic phase is preferably nonpolar, contains unsaturated link(age) or phenyl ring, can with graphene oxide nonpolarity element, as π key adsorbs with π-πconjugation; And preferably polarity of the decorative material being soluble in the aqueous phase, can with the polar component on Graphene or graphene oxide surface, as hydroxyl, ketone group, carboxyl etc. interact and adsorb with Van der Waals force or electrostatic force containing oxygen negative electricity group.
Beneficial effect
The carrier of the present invention using two immiscible organic phase/aqueous phase interfaces as tiling Graphene, to realize the asymmetric modification in its two sides, has following outstanding performance characteristics compared with the method that " adopts solid silicon substrate to carry out asymmetric modification as the carrier point multistep of tiling Graphene " in having been reported:
(1) the carrier difference of tiling Graphene.The present invention adopts the carrier of two immiscible organic-aqueous interfaces as tiling Graphene, molecule liveness between two organic-aqueous interfaces is high, can effectively repair Graphene defect in assembling process, be conducive to Graphene and tile in individual layer mode in organic-aqueous interface; In addition Graphene is assembled in organic-aqueous interface, can make two planes that Graphene is contrary simultaneously exposed, can be to its modification simultaneously.And in having been reported, adopt the carrier of solid silicon substrate as tiling Graphene, once produce defect in assembling, almost cannot repair; And Graphene only has a plane exposed, once can only modify a plane.
(2) the asymmetric modification of Graphene relates to step and complexity difference.The step that the present invention relates to the asymmetric modification of Graphene is few and gentle, mainly contains two committed steps, and the one, complete the assembling of Graphene in organic-aqueous interface, two is exactly to select suitable decorative material to add two immiscible organic phase water two-phases.And in having been reported, the asymmetric modification of Graphene is related to step various and violent.Because can only modify the one side of Graphene at every turn, and another side need to be hidden, therefore step is more, and silicon substrate need to be dissolved, and generally adopts hydrogen fluoride, reacts more violent.
(3) between Graphene and decorative material, reactive force is different.Reactive force in the present invention between Graphene and decorative material is also gentleer, is generally π-πconjugation, or electrostatic attraction.Generally, the Graphene plane of oil phase one side is modified, between decorative material and Graphene mainly with π-πconjugation; The Graphene plane of water one side is modified, between decorative material and Graphene mainly with electrostatic attraction.And in having been reported, because relate to, step is many and reaction process is comparatively strong, therefore generally adopt chemical bond, need to be first that Graphene is surface-functionalized, and then utilize these functional groups and decorative material to interact.
(4) two of Graphene of the present invention contrary planes can be modified simultaneously, also can modify by proceed step by step; And in having been reported, can only proceed step by step to two of Graphene planes.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of asymmetric modifying method of the present invention;
Fig. 2 a is the assembling situation of graphene oxide (GO) in toluene/water interface;
Fig. 2 b only uses graphene oxide (GO) after the porphyrin modified situation in toluene/water interface;
Fig. 2 c is the situation in toluene/water interface with the graphene oxide (GO) after porphyrin and Cadmium Sulfide modification;
Fig. 3 is the mode of action of porphyrin (porphyrin) and Cadmium Sulfide (CdS) and oxidation state Graphene.
Determine after solvent system, inductor, Graphene consumption and decorative material by mentioned above principle, the step that two contrary planar unsymmetricals of Graphene are modified of the present invention is shown in accompanying drawing 1: the first, first Graphene is assembled in organic-aqueous interface, what Fig. 1 demonstrated is that graphene oxide is assembled in organic-aqueous interface, because graphene oxide rich surface contains oxy radical, easily be scattered in water, because being first scattered in water, add again a certain amount of organic solvent immiscible with it, form flat organic-aqueous interface; Then in this system, add appropriate cats product, control the consumption of graphene oxide, can realize it and assemble in individual layer mode in organic-aqueous interface.The second, the decorative material different with difference in water at oil phase, decorative material 1 has great solvability in oil phase, but is insoluble to water; Decorative material 2 has great solvability at water, but is insoluble to oil phase, can guarantee that so the contrary two sides of Graphene that is laid in organic-aqueous interface can be exposed in different decorative materials.Different reactive forces by decorative material from Graphene two sides, two kinds of decorative materials can spontaneously be adsorbed in the two sides of Graphene, thereby realize the asymmetric modification of contrary two planes of Graphene.
The Graphene (GO) of Fig. 2 a oxidation state is in toluene/water interface assembling situation, can find out that the GO thickness that is assembled in toluene/water interface is about 1nm, show that it is to be assembled in organic-aqueous interface in individual layer mode, and sprawl evenly, zero lap, corrugationless; 2b, is only added to porphyrin at toluene, and after modification, thickness is about 1.5nm, and than the many 0.5nm of pure GO, this thickness is just in time the thickness of individual layer porphyrin, illustrate that porphyrin only optionally modified the one side of GO by toluene, leans on the one side of water not modified; 2c, in toluene phase and water, add respectively porphyrin and Cadmium Sulfide, thickness is about 4.5nm, than the many 3nm of Fig. 2 b, and the 3nm having more characterizes the thickness that it is just in time CdS nano particle through alternate manner as scanning electron microscope, transmission electron microscope and UV spectrum, show that GO one side is by porphyrin modified, one side is nano-particle modified by CdS, is asymmetric modification.
Fig. 3 is the mode of action of porphyrin (porphyrin) and Cadmium Sulfide (CdS) and oxidation state Graphene.The large π key on Porphyrin and GO surface adsorbs with π-πconjugation; CdS acts on electrostatic attraction (electrostatic attraction) containing oxygen negative electricity group mutually with GO surface.
Embodiment
Can there is better elaboration to the present invention by the following examples, but can not be interpreted as limiting the scope of the invention.
Embodiment 1
Adopt the method for the invention to adopt respectively Cadmium Sulfide (CdS) and porphyrin modified to two contrary planes of graphene oxide, obtain the asymmetric modification mixture of Cadmium Sulfide/graphene oxide/porphyrin.
In the present embodiment, adopt graphene oxide, there are the electronegative oxy radicals such as hydroxyl, ketone group, carboxyl on its surface.First be assembled in two immiscible organic-aqueous interfaces, the organic phase of herein selecting is toluene, and concrete steps are:
The graphene oxide water dispersion solution of 1mL0.001mg/L and 1mL toluene are placed in to an internal diameter and only have the Glass Containers of 12mm, adding the cats product cetyl trimethylammonium bromide CTAB that 0.5 μ L concentration is 0.5mg/mL, vibrate after 2 minutes, graphene oxide just shifts and is assembled into the interface of toluene/water from water.In macroscopic view, in toluene/water interface, form the film of one deck flexibility; On microcosmic, Graphene is sprawled with form of single sheet in toluene/water interface, and has each other certain spacing, not overlapping, corrugationless, and thickness is approximately 1nm.Secondly the porphyrin and the 20 μ L concentration that are 25mmol/L by 10 μ L concentration are 50mmol/L cadmium nitrate (CdNO
3) join respectively in toluene and water, toluene becomes pink colour mutually immediately, is adsorbed in Graphene by the one side of oil phase, the cadmium ion (Cd of positively charged in this while porphyrin with π-πconjugation
2+) in the mode of electrostatic attraction, be adsorbed in the surface of Graphene with the electronegative oxy radical interaction in Graphene surface.Place after the night, then be that 50mmol/L sodium sulphite (NaS) is added to the water by 20 μ L concentration, water is yellowing immediately.Cd
2+with S
2-interact and generate CdS nano particle, and be adsorbed on the Graphene surface by water one side.
Claims (10)
1. the method for an asymmetric grapheme modified or graphene oxide, it is characterized in that, adopt the phase interface of two immiscible moving phases as the carrier of tiling Graphene or graphene oxide, realize the asymmetric modification on Graphene or graphene oxide two sides, specifically comprise the steps:
1) provide the aqueous dispersion solution of Graphene or graphene oxide;
2) add the organic phase immiscible with water;
3) add the quaternary cationics containing C10-C18 alkyl chain, vibration or stirring make tensio-active agent react with Graphene, make Graphene shift and be assembled into organic phase/water termination from water;
4) in water and organic phase, add respectively different decorative materials, two kinds of decorative materials are attached to respectively on the two sides of Graphene;
5), after adsorption equilibrium, isolating absorption has the Graphene of decorative material.
2. according to the method for claim 1, it is characterized in that described organic phase is selected from toluene, methylene dichloride or 1,2 ethylene dichloride.
3. according to the method for claim 1 or 2, the volume that it is characterized in that organic phase and water substantially equates or is unequal.
4. according to the method for any one in claim 1-3, it is characterized in that the described quaternary cationics containing C10-C18 alkyl chain is Trimethyllaurylammonium bromide, Dodecyl trimethyl ammonium chloride, dodecyl trimethylammonium hydroxide, dodecyl triethyl brometo de amonio, dodecyl triethyl ammonium chloride, dodecyl triethyl ammonium hydroxide, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, cetyltrimethylammonium hydroxide; Cetyltriethylammonium bromide, hexadecyl triethyl ammonium chloride or hexadecyl triethyl ammonium hydroxide.
5. according to the method for claim 4, it is characterized in that cats product is Trimethyllaurylammonium bromide or cetyl trimethylammonium bromide.
6. according to the method for any one in claim 1-5, it is characterized in that, the concentration of described cats product is 0.1-1mg/mL, and the volume ratio of its consumption and water volume is 0.01-0.1: 100.
7. according to the method for any one in claim 1-6, it is characterized in that, the concentration of Graphene or graphene oxide aqueous dispersion solution is 0.0001-0.005mg/L.
8. according to the method for any one in claim 1-7, it is characterized in that, two kinds of decorative materials are different from the mode of action of Graphene two planes.
9. according to the method for any one in claim 1-8, it is characterized in that, a kind of decorative material is porphyrin, and another kind of decorative material is Cadmium Sulfide.
10. according to the method for claim 9, it is characterized in that, decorative material Cadmium Sulfide is Nano cadmium sulphide prepared by soluble salt by react cadmium in water and dissolvable sulfide original position.
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Cited By (7)
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| CN104386672A (en) * | 2014-10-22 | 2015-03-04 | 复旦大学 | Preparation method of graphite oxide alkene materials in dissymmetrical structure |
| CN105331447A (en) * | 2015-11-20 | 2016-02-17 | 李碧丹 | Sterilizing cleaning composition with rich and stable foam |
| CN105502376A (en) * | 2016-02-04 | 2016-04-20 | 成都新柯力化工科技有限公司 | Method for preparing large-sized thin film by mechanically exfoliating graphene nanoplatelets and solar cell |
| CN107108219A (en) * | 2014-08-08 | 2017-08-29 | 奥兰雷瓦朱·W·塔尼莫拉 | From asphaltene, Graphene derivative, the method for 2D materials synthesis paraffin derivatives and application |
| CN109256546A (en) * | 2018-09-03 | 2019-01-22 | 山西煤炭进出口集团科学技术研究院有限公司 | A kind of molybdenum disulfide/graphene composite material and its preparation method and application |
| CN110371963A (en) * | 2019-06-20 | 2019-10-25 | 宁波锋成先进能源材料研究院 | A kind of preparation method and application of parental graphite oxide alkene nano material |
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| CN105331447A (en) * | 2015-11-20 | 2016-02-17 | 李碧丹 | Sterilizing cleaning composition with rich and stable foam |
| CN105502376A (en) * | 2016-02-04 | 2016-04-20 | 成都新柯力化工科技有限公司 | Method for preparing large-sized thin film by mechanically exfoliating graphene nanoplatelets and solar cell |
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| CN109256546A (en) * | 2018-09-03 | 2019-01-22 | 山西煤炭进出口集团科学技术研究院有限公司 | A kind of molybdenum disulfide/graphene composite material and its preparation method and application |
| CN110371963A (en) * | 2019-06-20 | 2019-10-25 | 宁波锋成先进能源材料研究院 | A kind of preparation method and application of parental graphite oxide alkene nano material |
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