CN105752978A - Modified graphene and preparation method thereof - Google Patents
Modified graphene and preparation method thereof Download PDFInfo
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- CN105752978A CN105752978A CN201610298441.3A CN201610298441A CN105752978A CN 105752978 A CN105752978 A CN 105752978A CN 201610298441 A CN201610298441 A CN 201610298441A CN 105752978 A CN105752978 A CN 105752978A
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Abstract
The invention discloses a modified graphene product which is prepared by modifying graphene with rutoside. The invention further discloses a surface modification method of graphene; the surface modification method comprises the steps of adding graphene subjected to plasma treatment into a rutoside aqueous solution, dispersing uniformly, leaving to stand, filtering, and taking out filter residues to be subjected to vacuum drying, so as to obtain surface-modified graphene. The modified graphene provided by the invention is good in dispersibility and low in impurity content; meanwhile, with the adoption of the method provided by the invention, the chemical damage to the graphene is avoided, the integrality of graphene is maintained, pollutants such as wastewater and waste acid are prevented from generation, the process is simple, the process parameters are easy to control, and a broad application prospect is achieved.
Description
Technical field
The invention belongs to field of nanometer technology, particularly relate to the surface modification method of a kind of Graphene.
Background technology
Desirable Graphene (CNFs) structure is plane hexagonal lattice, it is possible to being seen as the one layer of molecular layer stripped down from three-dimensional graphite, each carbon atom is sp2Hydridization, electronically forms big π key on one p track of contribution residue on the direction vertical with plane, and pi-electron can move freely, and gives Graphene good electric conductivity；In Graphene, each carbon atom is connected by very strong 3 carbon atoms of σ key (chemical bond the strongest in nature) and other, these very strong carbon-carbon bonds make graphene sheet layer have extremely excellent mechanical property and structural rigidity, its Young's modulus is about 1TPa, and intensity is about 130～180GPa.Owing to Graphene has above-mentioned excellent properties, it is made to can be used for the ultracapacitor manufacture in the fields such as automobile, machinery, electronics, military affairs, and can with various metals, nonmetal and the macromolecular material compound composition conductive material of excellent combination property, high strength composite, shielding material and stealth material etc..
But due to the nano-grade size of Graphene, big specific surface area, simultaneously stronger between graphene molecules van der Waals interaction, Graphene is easily occurred with reunion shape form, thus cause that Graphene is difficult to be distributed in various solvent, having had a strong impact on the practical application of Graphene, how effectively dispersed graphite alkene has great importance.
Graphenic surface modifiies the important method being to improve its dispersibility.Generally adopt after Graphene is carried out strong acid pretreatment so that it is surface, with functional groups such as carboxyls, then carries out the scion grafting such as amidatioon, esterification reaction, again thus improving the dispersibility of Graphene.But adopt strong acid or nitration mixture to process and Graphene is had certain destruction, and often need higher temperature and long period, when processing, easily produce the gas of contaminative simultaneously.
The mechanism of plasma modification CNT and Graphene is mainly by plasma bombardment CNT and Graphene, the direct grafting functional group on its surface, or produce avtive spot on the surface of CNT and Graphene by bombarding, then pass through and indirectly process in its surface graft-OH ,-COOH functional group.Felten etc. use O2Surface Modification of Carbon Nanotube By Plasma, after process, method its content of surface oxygen mutually substantially increases.Wu etc. use NH3Plasma treatment CNT, has found on its surface graft amido functional group after process.Wei Qinqin uses O2Cement Composite Treated by Plasma Graphene, introduces substantial amounts of defect at graphenic surface after process, thus improve possibility for grapheme modified further.
Summary of the invention
It is an object of the invention to overcome Graphene in prior art easily to reunite and difficulties in dispersion, and the deficiency of the infringement graphene molecules that existing method of modifying exists, it is provided that the graphene product of a kind of modifying and decorating, and prepare the surface modification method of this Graphene.The modified graphene good product dispersibility of the present invention, acrobatics content is few, best in quality.The method of modifying using plasma of the present invention processes, in conjunction with rutin aqueous solution soaking, Graphene is carried out finishing, and the modified graphene good dispersion obtained, impurity content is low.Graphene will not be caused chemical damage by the inventive method simultaneously, maintains the integrity of Graphene, and does not produce the pollutant such as waste water, spent acid, and technique is simple, and technological parameter is easily controlled.
In order to realize foregoing invention purpose, the invention provides techniques below scheme:
A kind of modified graphene product, it is obtained by rutin modified graphene.There is no the research about rutin modified graphene at present, Graphene is modified by the proposition of novelty of the present invention with rutin, in modifying process, rutin is attached to the graphenic surface of planar structure, the surface making Graphene can in conjunction with upper certain activity, hydrophilic functional group so that Graphene has better dispersibility.Meanwhile, in conjunction with on rutin change the planar π key of graphenic surface so that the absorption combination between lamellar graphite alkene molecule reduces, and the problem that multi-layer graphene molecule van der Waals interaction is closely attached onto no longer occurs.
Further, the method for rutin modified graphene is surface adsorption.Rutin molecule is by surface adsorption on the surface of graphene molecules, and adhesion is good, and the active function groups of modified reservation is many, has the physicochemical property of excellence.
Further, Graphene is the Graphene after Cement Composite Treated by Plasma.Graphene, through Cement Composite Treated by Plasma, then carries out surface adsorption and modifiies with rutin.Graphene molecules surface can be very low, and what typically directly combine is inefficient, and reaction time is long, and using plasma carries out activation processing and makes Graphene and rutin in hgher efficiency when combining.
Further, rutin is adsorbed onto the surface of Graphene and includes the π-π non-covalent bond effect on the combination of active function groups between the two and benzene ring structure.The mode that rutin and Graphene combine can be diversified, is mainly combined by above-mentioned combination, in conjunction with after firmness between rutin and Graphene good, the potentiality of secondary chemical reaction are big, have higher using value.Described Graphene is single-layer graphene or multi-layer graphene, also includes few layer graphene.
Meanwhile, present invention also offers a kind of method preparing this modified graphene, the method that namely graphenic surface is modified.
The surface modification method of a kind of Graphene, comprises the steps:
(1) take Graphene plasma its surface is processed.
(2) Graphene through Cement Composite Treated by Plasma is joined in rutin aqueous solution, be uniformly dispersed, stand.
(3) solution is filtered, take filtering residue and carry out vacuum drying, obtain the Graphene of surface modification.
The present invention prepares in the process of modified graphene, first with Cement Composite Treated by Plasma Graphene, by plasma, Graphene is bombarded, can on the surface of Graphene the functional group such as direct grafting hydroxyl, carboxyl and amino, some avtive spots or defect can be produced again, it is possible to carry out further modification and combine with rutin on the surface of Graphene.When Graphene joins after in rutin solution, rutin is combined by self phenolic hydroxyl group and graphenic surface defect sites on the one hand, and grafted functional group is thus carrying out finishing to Graphene；On the other hand, rutin is to utilize its big pi-conjugated structure and Graphene generation pi-pi accumulation effect, thus Graphene is modified, improves the dispersibility of Graphene.The rutin solution being to be understood that is not limited in aqueous solution, and application aqueous solution is for no other reason than that rutin aqueous solution easily obtains, and aqueous solution and Graphene interact, the advantage that side reaction is little.
The chemical formula of rutin is C27H30O16, its structure is such as shown in following formula 1, and relative molecular weight is 610.15, its character be yellow crystalline powder or without crystalline flour end, bitter in the mouth, be slightly soluble in water, hot water and ethanol can be dissolved in.Can go bad under light illumination, it is necessary to place it in and preserve under the environment in cool place.1g rutin is dissolved in 7mL methanol, 8000mL water, 200mL boiling water, 23mL boil in ethanol, the cold ethanol of 290mL.From formula 1 it can be seen that rutin contains phenyl ring, phenolic hydroxyl group and carbonyl, these groups are also expected to be used to modification Graphene.
The mechanism of rutin modification CNT and Graphene is to utilize active group grafting on rutin to CNT and graphenic surface, or by the π-π non-covalent bond effect of the phenyl ring on rutin and CNT and Graphene thus being adsorbed onto the surface of CNT and Graphene, rutin contains a lot of oxygen-containing functional group (hydroxyl, epoxy radicals and carbonyl), there are significantly high reactivity in these functional groups, with in the mechanism of CNT and Graphene, these functional groups can and CNT, Graphene reacts, play carbon nano-tube modified and Graphene effect；Rutin molecule contains two phenyl ring, benzene ring structure also can also and CNT, Graphene be adsorbed on the surface of CNT, Graphene by π-π non-covalent bond effect.
Modified gas different during Cement Composite Treated by Plasma knows from experience the modified effect that generation is different, selects suitable modified gas to be the key obtaining good dispersion effect according to actual requirement.In addition dispersion effect also can be produced critically important impact by plasma-treating technology parameter, and such as plasma treatment voltage, the process time, vacuum etc., good dispersion effect needs the combined effect of various factors.
Preferably, the plasma used when processing Graphene is Ar, NH3And O2One or more in three kinds of plasmas.Utilize single one or more to be jointly processed by Graphene and realize modified, it is ensured that the effectiveness of graphenic surface modification and adequacy.Ar is as noble gas, the surface of bombardment CNT and Graphene, although discord Graphene reaction, but can produce avtive spot, in order to follow-up modification.And NH3And O2Plasma then can introduce the functional groups such as-OH ,-COOH, improves the reactivity of Graphene.Further, it is preferred to Ar/NH3Plasma.Above-mentioned plasma is by Ar, NH3And O2The plasma that gas generates through plasma generator, as required, it is possible to adopt pure gas composition to obtain single plasma, it would however also be possible to employ blending constituent obtains the plasma of mixing.Graphene tiling is placed in clean vessel, together with vessel, Graphene is carried out plasma bombardment.
Preferably, Cement Composite Treated by Plasma power is 20W～150W.Plasma power is too low, and plasma bombardment power is weak, and graphenic surface etching is few, and the avtive spot of energy grafting functional group is just few；Power is too high, and graphenic surface activation is had certain upper limit by plasma, is further added by power activation effect inconspicuous, and the too high plasma bombardment of power can cause the destruction of graphenic surface at graphenic surface, causes quality of graphene to reduce.More preferably 40～80W, studies when controlling within the scope of this in conjunction with the lot of experiments of inventor, and graphenic surface activation effect is best.Best plasma power is 60W.
Preferably, plasma treatment time is 2min～15min.Control plasma treatment time at 2-15 minute, it is possible to effective guarantee plasma is for the adequacy of the activation of Graphene, and avoids overlong time to cause not good side effect and excessive energy resource consumption.Further, it is preferable that plasma treatment time is 5～8min, control more accurately within the scope of plasma Best Times, reach the target that activation effect is optimum.
Preferably, the weight of described Graphene is 0.05～0.5g:20～60mL with the ratio of the volume of rutin aqueous solution.Lot of experiments through inventor is studied, the technique that rutin is grapheme modified need in conjunction with the potential binding ability of Graphene itself, and rutin molecule carries out dual consideration for the new of Graphene and binding ability, the Graphene arranging aforementioned proportion can better mix with rutin, avoid unnecessary rutin cannot combine with Graphene and cause surface contamination, both improve the joint efficiency of Graphene and rutin, improve again the performance in combination with modified product.More preferably 0.05～0.2g:30～50mL, optimizes and revises the usage ratio of rutin and Graphene, it is achieved more excellent quality.Best preferably 0.1g:40mL.By above preferred, it is possible to improve the dispersibility of Graphene further.
Preferably, the time of described standing is 12～30h.Rutin stronger acids, character is comparatively gentle, and less than 12h between upon standing, the response time is too short, is unfavorable for the abundant combination of rutin and Graphene；Being longer than 30h between upon standing, its modification is not further added by.More preferably 20～25h；Best preferably 24h.
Preferably, described vacuum drying temperature is 60 DEG C～80 DEG C.When vacuum drying temperature is lower than 60 DEG C, drying efficiency is low；When baking temperature is higher than 80 DEG C, can cause that what non-chemically act between damage and rutin and the Graphene of grafted functional group weakens.More preferably 60～70 DEG C, best preferably 60 DEG C.
Preferably, the described vacuum drying time is 1～3h.When vacuum drying time is less than 1h, Graphene dries not exclusively, affects the performance of Graphene and to its phenetic analysis；It is longer than 3h between when drying, can cause that what non-chemically act between damage and rutin and the Graphene of grafted functional group weakens.More preferably 1～2h, between at this moment, in scope, range effect is good, and substantially without residual moisture, and the Van der Waals force bond strength between rutin and Graphene keeps preferably, and modification quality is more excellent.Best preferably 2h.
Described Graphene is single-layer graphene or multi-layer graphene.The Graphene of modifying and decorating of the present invention is not limited to single-layer graphene, it can also be multi-layer graphene, nanometer or the multi-layer graphene of micron-scale rank there is the fine quality of single-layer graphene equally, and in modification process, multilamellar mating surface is modified, the original Graphene characteristic of internal basic maintenance, has modified good, the feature that inherent character retentivity is good.
Preferably, in rutin aqueous solution, the concentration of rutin is 0.001～18 μ g/mL.Further, described rutin aqueous solution is prepared by deionized water.Applicant through test of many times find, when the concentration of rutin aqueous solution is too little, graphenic surface can due to the functional group of grafting very little, thus affecting the raising of its dispersibility, it is difficult to reach the set goal value.Although, increase along with rutin concentration of aqueous solution, the amount of the rutin of graphenic surface absorption can increase, when the concentration of rutin aqueous solution is more than 18 μ g/mL, solution there will be the rutin molecule that cannot be adsorbed onto graphenic surface in a large number, the rutin interaction of molecules that these dispersion rutin molecules in the solution can and adsorb, causes that the rutin molecule being adsorbed on graphenic surface comes off.Therefore, the concentration of rutin solution is excessive, on the contrary π-π the adsorption between rutin and Graphene is produced very adverse influence.The concentration of preferred described rutin aqueous solution is 0.02～2 μ g/mL, it is possible to 0.02,0.2, the 2 isocyatic rutins of μ g/mL enumerated are applied.When rutin concentration is too big time, the generation desorption of rutin of graphenic surface can be made, the phenomenon that modification amount reduces occurs, it is impossible to play the effect improving graphene dispersion.It is highly preferred that the concentration of described rutin aqueous solution is 0.02～0.2 μ g/mL, it is most preferred that, the concentration of described rutin aqueous solution is 0.02 μ g/mL.
Compared with prior art, beneficial effects of the present invention:
(1) the modified graphene product of the present invention, is obtained by rutin modified graphene, and degree of being firmly combined with is good, and modified graphene dispersion promotes notable, and the excellent physicochemical property that Graphene is inherently is effectively maintained.
(2) the modified graphene product of the present invention, raw material is natural product raw material and natural mineral raw, has wide material sources, the feature easily obtained.In conjunction with the easy enforcement that method of modifying itself has, high efficiency feature, there are the potentiality of good commercial application.
(3) method of modified graphene of the present invention utilizes Cement Composite Treated by Plasma graphene product, and the single activated carbon of graphenic surface is had good cleaning action.Through the Graphene sample high purity that the inventive method processes, modified application direction is varied.
(4) method of modified graphene of the present invention is by Graphene through Cement Composite Treated by Plasma, increases avtive spot at graphenic surface, provides for follow-up grafting more polyfunctional group and is likely to.Corresponding graphene product can well in conjunction with upper corresponding rutin molecule, and compared with the Graphene processed without rutin, this graphene dispersion is good, and impurities greatly reduces simultaneously.
(5) method of modified graphene of the present invention well maintains the integrity of Graphene, and after overcoming tradition strong acid treatment, the draw ratio of Graphene seriously reduces, thus causing the defect that Graphene properties reduces.
(6) method of modified graphene of the present invention does not produce the pollutant such as waste water, spent acid, and technique is simple simultaneously, and technological parameter is easily controlled.
Accompanying drawing illustrates:
Fig. 1 schemes without the Graphene sample TEM of any process.
Fig. 2 is Graphene Fourier transform infrared spectroscopy figure after gas with various Cement Composite Treated by Plasma.
Fig. 3 is Graphene Fourier transform infrared spectroscopy figure after variable concentrations rutin aqueous solution processes.
Fig. 4 is that the Graphene SEM without any process used in the present invention schemes.
Fig. 5 is Graphene SEM figure after rutin aqueous solution processes.
Fig. 6 is the Graphene SEM after rutin aqueous solution processes and corresponding point EDX figure.
Detailed description of the invention
Below in conjunction with test example and detailed description of the invention, the present invention is described in further detail.But this should not being interpreted as, the scope of the above-mentioned theme of the present invention is only limitted to below example, and all technology realized based on present invention belong to the scope of the present invention.
The multi-layer graphene and the single-layer graphene that relate in the embodiment of the present invention are purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.Original graphene product carrying out transmission electron microscope (TEM) characterize, result is Fig. 1 such as
Shown in.
Embodiment 1
A small amount of multi-layer graphene uniform spreading being sprinkling upon clean beaker bottom, is placed in plasma processing chambers by graphene ribbon beaker, arranging power is 60W, and the process time is 10min, and place's process gases is Ar.
Embodiment 2
A small amount of multi-layer graphene uniform spreading being sprinkling upon clean beaker bottom, is placed in plasma processing chambers by graphene ribbon beaker, arranging power is 60W, and first passing into Ar, to process the time be 5min, after pass into O2The process time is 5min, processes time 10min altogether.
Embodiment 3
A small amount of multi-layer graphene uniform spreading being sprinkling upon clean beaker bottom, is placed in plasma processing chambers by graphene ribbon beaker, arranging power is 60W, and first passing into Ar, to process the time be 5min, after pass into NH3The process time is 5min, processes time 10min altogether.
Fig. 1 be the Graphene without any process and after different disposal gas plasma process the infrared spectrum curve of Graphene.In figure, spectral line 1 is that original graphite alkene characterizes curve, the Graphene that spectral line 2 is after argon plasma processes characterizes curve, spectral line 3 is that the Graphene after argon and oxygen mix Cement Composite Treated by Plasma characterizes curve, and the Graphene that spectral line 4 is after argon and the process of ammonia hybrid plasma characterizes curve.Contrast four curves, it can be seen that the intensity through the infrared curve representation hydroxy of Graphene of Cement Composite Treated by Plasma and the peak of carboxyl has certain enhancing, wherein Ar-NH3The intensity at the peak of the infrared curve of the Graphene of Cement Composite Treated by Plasma is the strongest, 2, the peak of 3,4 curves is incremented by with this by force, this is possibly due to carry out again oxygen, ammonia plasma treatment bombardment through argon plasma bombardment, more functional group on the surface graft of Graphene, so that the dispersion effect of Graphene is better.
Embodiment 4
Being joined by multi-layer graphene in the rutin aqueous solution of 0.02 μ g/mL, be uniformly dispersed, wherein the weight of Graphene is 0.1g:40mL with the ratio of the volume of rutin aqueous solution；Stand 24h, filter, take filtering residue vacuum drying 2h at 60 DEG C, obtain the Graphene of surface modification.
The Graphene 0.1g of the surface modification prepared by the present embodiment 4 is dispersed in 100mL deionized water, after standing 5 days, precipitates under gravity and increases gradually, but remain in that dispersity between Graphene, it does not have reunite；Contrast with not modified Graphene simultaneously, namely precipitation occurs after standing 1 day, and agglomeration occurs between Graphene, it was shown that the Graphene of the surface modification of embodiment 4 preparation has the dispersibility of excellence.
Embodiment 5
Being joined by multi-layer graphene in the rutin aqueous solution of 0.2 μ g/mL, be uniformly dispersed, wherein the weight of Graphene is 0.1g:40mL with the ratio of the volume of rutin aqueous solution；Stand 24h, filter, take filtering residue vacuum drying 2h at 60 DEG C, obtain the Graphene of surface modification.
The Graphene 0.1g of the surface modification prepared by the present embodiment 5 is dispersed in 100mL deionized water, after standing 3 days, precipitates under gravity and increases gradually, but remain in that dispersity between Graphene, it does not have reunite.Show that the Graphene of surface modification prepared by embodiment 5 has the dispersibility of excellence.
Embodiment 6
Being joined by multi-layer graphene in the rutin aqueous solution of 2 μ g/mL, be uniformly dispersed, wherein the weight of Graphene is 0.1g:40mL with the ratio of the volume of rutin aqueous solution；Stand 24h, filter, take filtering residue vacuum drying 2h at 60 DEG C, obtain the Graphene of surface modification.
The Graphene 0.1g of the surface modification prepared by the present embodiment is dispersed in 100mL deionized water, after standing 2 days, precipitates under gravity and increases gradually, but remain in that dispersity between Graphene, it does not have reunite.Show that the Graphene of surface modification prepared by embodiment 6 has the dispersibility of excellence.
From embodiment 4～6, the Graphene of the surface modification of embodiment 4 preparation just increasingly generates precipitation after standing 5 days under gravity, and between Graphene, still well keep dispersity, do not reunite, and namely the Graphene of the surface modification of embodiment 5 and 6 preparation generated precipitation gradually under gravity after 2～3 days, therefore the method described in embodiment 4 is substantially better than the method described in embodiment 5 and 6.
Fig. 3 is the Graphene FTIR spectrum figure after variable concentrations rutin aqueous solution processes.Adopt the Graphene (pure CNFs) processed without rutin aqueous solution to contrast simultaneously.From figure 3, it can be seen that the Fourier transform infrared spectroscopy figure peak shape without the Graphene of rutin aqueous solution process is wider and peak value is more weak；And the Graphene after rutin aqueous solution (0.02 μ g/mL, 0.2 μ g/mL, 2 μ g/mL) processes is at 3430cm-1And 1640cm-1Neighbouring there is stronger absworption peak, is belonging respectively to stretching vibration absworption peak and the bending vibration absworption peak of-O-H, and wherein the peak value of 0.02 μ g/mL is the strongest；The more functional group of graphenic surface grafting or more rutin are adsorbed in graphenic surface by non-chemically effect as can be seen here, thus improve the dispersibility of Graphene.And continue the concentration increasing rutin aqueous solution to 2 μ g/mL, 3430cm-1And 1640cm-1Neighbouring absworption peak is substantially with the Graphene processed without rutin aqueous solution, this is after reaching capacity due to the amount of the rutin of graphenic surface absorption, dispersion unnecessary rutin molecule in the solution disturbs the rutin molecule adsorbed, cause that it occurs coming off, thus, after the concentration of rutin solution is excessive, the π-π adsorption between rutin and Graphene is produced very adverse influence, cause that the phenomenon that modification amount reduces occurs, and then affect the dispersibility of modifying and decorating Graphene.
According to embodiment 4 it can be seen that the Graphene processed through 0.02 μ g/mL rutin aqueous solution, just increasingly generate precipitation under gravity after standing five days, and between Graphene, remain in that good dispersity, it does not have reunite.And the situation according to embodiment 5 and embodiment 6 shows, namely Graphene after 0.2 μ g/mL rutin aqueous solution processes generates precipitation after 3 days gradually under gravity, after Graphene after 2 μ g/mL rutin aqueous solutions process stands 1 day, precipitating under gravity and increase gradually, there is slight agglomeration in Graphene gradually.Simultaneously according to FTIR spectrum figure it can be seen that the graphenic surface after 0.02 μ g/mL rutin aqueous solution processes has more functional group, thus further increasing the dispersibility of Graphene.To sum up, 0.02 μ g/mL and 0.2 μ g/mL and 2 μ g/mL compares, and obvious difference achieves unforeseeable effect, and therefore 0.02 μ g/mL is the optium concentration of rutin aqueous solution of the present invention.
More than analyze visible, no matter be the result from spectral characterization, or the result of conventional disperse test, the dispersibility performance of modified graphene is consistent, relevant with the concentration of bright rutin solution, but is not the bigger the better.
Fig. 4 is the Graphene low range SEM image without any process: the left figure of Fig. 4 is the SEM figure without any process Graphene amplification 5000 times；The right figure of Fig. 4 is the SEM figure without any process Graphene amplification 2000 times.Fig. 5 is Graphene high magnification SEM image before and after rutin aqueous solution processes: the left figure of Fig. 5 is that Graphene amplifies the SEM figure of 10,000 times after 0.02 μ g/mL rutin aqueous solution processes；The right figure of Fig. 5 is that Graphene amplifies the SEM figure of 20,000 times after 0.02 μ g/mL rutin aqueous solution processes.As can be seen from Figure 4 and Figure 5, the Graphene processed without rutin aqueous solution becomes reunion shape, and edge volume sticks up, bad dispersibility；And the graphene dispersion after rutin aqueous solution processes well is improved, can substantially observing many open and flat Graphenes under high magnification, the average area of Graphene is compared with before modifying simultaneously, and change is little, namely maintain the specific surface area before modification, do not shredded.After rutin aqueous solution processes, graphenic surface fineness increases, and impurity significantly reduces；Show that the inventive method can also purifying graphene.
Fig. 6 is the Graphene SEM after rutin aqueous solution processes and corresponding point EDX figure.The right figure of Fig. 6 is Graphene EDX figure after rutin aqueous solution processes.By the right figure of Fig. 6 it can be seen that Graphene is after rutin aqueous solution processes, impurity element greatly reduces, and only exists two kinds of elements of O, C, and its contained impurity greatly reduces.
Claims (10)
1. a modified graphene, it is characterised in that it is to be obtained by rutin modified graphene.
2. modified graphene according to claim 1, it is characterised in that: the method for rutin modified graphene is surface adsorption.
3. modified graphene according to claim 1, it is characterised in that: Graphene is the Graphene after Cement Composite Treated by Plasma.
4. modified graphene according to claim 1, it is characterised in that: Graphene is single-layer graphene or multi-layer graphene.
5. the surface modification method of a Graphene, it is characterised in that comprise the steps:
(1) take Graphene plasma its surface is processed；
(2) Graphene through Cement Composite Treated by Plasma is joined in rutin aqueous solution, be uniformly dispersed, stand；
(3) solution is filtered, take filtering residue and carry out vacuum drying, obtain the Graphene of surface modification.
6. method according to claim 1, it is characterised in that: the plasma used when processing Graphene is Ar, NH3And O2One or more in three kinds of plasmas.
7. method according to claim 1, it is characterised in that: Cement Composite Treated by Plasma power is 20W ~ 150W.
8. method according to claim 1, it is characterised in that: plasma treatment time is 2min ~ 15min.
9. method according to claim 1, it is characterised in that: the ratio of the weight of described Graphene and the volume of rutin aqueous solution is 0.05 ~ 0.5g:20 ~ 60mL.
10. method according to claim 1, it is characterised in that: in rutin aqueous solution, the concentration of rutin is 0.001 ~ 18 μ g/mL.
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| CN108611528A (en) * | 2018-05-09 | 2018-10-02 | 西南交通大学 | A kind of graphene enhancing titanium-based/nano HA composite material and preparation method |
| CN109266187B (en) * | 2018-08-10 | 2021-02-05 | 恒力盛泰（厦门）石墨烯科技有限公司 | Heat dissipation coating containing isocyanate modified graphene and preparation method thereof |
| CN109592675A (en) * | 2019-01-28 | 2019-04-09 | 江西理工大学 | The method and its application of plasma immersion injection modified graphene |
| CN109797452A (en) * | 2019-01-30 | 2019-05-24 | 浙江华峰氨纶股份有限公司 | The method of the microcosmic modified spandex of finely dispersed graphene |
| CN109797452B (en) * | 2019-01-30 | 2021-04-13 | 华峰化学股份有限公司 | Method for modifying spandex by virtue of graphene with uniform micro-dispersion |
| CN111234541A (en) * | 2020-02-28 | 2020-06-05 | 湖南省溆怀高速公路建设开发有限公司 | Odorless asphalt mixture, preparation method thereof and application of odorless asphalt mixture on road surface |
| CN111410517A (en) * | 2020-03-09 | 2020-07-14 | 西南交通大学 | Carbon nanotube and graphene synergistically enhanced aluminum oxide-based composite material and preparation method thereof |
| CN111410517B (en) * | 2020-03-09 | 2021-12-24 | 西南交通大学 | Carbon nanotube and graphene synergistically enhanced aluminum oxide-based composite material and preparation method thereof |
| CN111707724A (en) * | 2020-07-03 | 2020-09-25 | 深圳市溢鑫科技研发有限公司 | Vertical graphene glucolase working electrode, preparation method and biosensor |
| CN112679798A (en) * | 2020-12-10 | 2021-04-20 | 中国科学院深圳先进技术研究院 | Polyolefin-based graphite oriented thermal interface material and preparation method thereof |
| CN112933292A (en) * | 2021-01-25 | 2021-06-11 | 天琪(广东)科技发展有限公司 | Modified dental implant and preparation method thereof |
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