CN103708447B - The method of purification of graphene oxide quantum dot - Google Patents
The method of purification of graphene oxide quantum dot Download PDFInfo
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Abstract
The invention provides a kind of method of purification of graphene oxide quantum dot, the method for purification of described graphene oxide quantum dot at least comprises: provide the graphene oxide quantum dot aqueous solution; Tensio-active agent is mixed into form mixing solutions in the described graphene oxide quantum dot aqueous solution; In described mixing solutions, add non-polar solvent, to be extracted in described non-polar solvent by described graphene oxide quantum dot, obtain graphene oxide quantum dot non-polar solution; Dry described graphene oxide quantum dot non-polar solution, to obtain graphene oxide quantum dot powder.The method of purification of above-mentioned graphene oxide quantum dot provided by the invention can obtain high-purity mangesium oxide graphene quantum dot powder.
Description
Technical field
The present invention relates to a kind of New Inorganic Materials technical field, particularly relate to a kind of method of purification of graphene oxide quantum dot.
Background technology
Graphene quantum dot is the zero dimension Graphene that lateral dimension is less than 100nm, is a kind of emerging carbon material.Compared with conventional large size two-dimensional graphene, graphene quantum dot has significant fringing effect and quantum confined effect, thus shows excellent optics and electric property.Simultaneously, for conventional carbon quantum dot and rare-earth oxide quantum dot, graphene quantum dot also has good water-soluble, the stable and biocompatibility of regulatable fluorescence, lower cytotoxicity and excellence, and these feature performance benefits make graphene quantum dot have application prospect widely at numerous areas such as photoelectric material and device, electrocatalysis, electrochemical biosensor and bio-imagings.
The preparation method of graphene quantum dot can be divided into Physical and chemical method.
Wherein, the Physical preparation method of graphene quantum dot mainly uses the physical etchings such as electron beam lithography, focused-ion-beam lithography method to carry out.But the features such as technique is loaded down with trivial details, cost intensive, output are lower that these methods exist, are therefore generally comparatively suitable as the preparation method of fundamental research, more difficultly realize large-scale mass production graphene quantum dot.
The chemical preparation process of graphene quantum dot is more, mainly contains strong acid oxidation style, Two-step anodization, hydrothermal method, solvent-thermal method, microwave method, chemical synthesis and electrochemical process etc.Wherein strong acid oxidation style, Two-step anodization and hydrothermal method prepare graphene oxide quantum dot solution by solution " cutting " various carbon source.
The graphene oxide quantum dot solution adopting chemical preparation process to obtain is generally containing a large amount of inorganic salt impurities ion.This is oxygenant owing to using in chemical preparation process, intercalator or auxiliaryly shear agent etc. and introduce, and these inorganic salt impurities ions are unfavorable for that sequential reduction prepares graphene quantum dot and the application in downstream photoelectric material and devices field thereof.
At present, in a large amount of bibliographical informations, the inorganic salt impurities ion in removing graphene oxide quantum dot solution generally adopts the method for dialysis.As at NanoLett.2012, in 12,844-849 mono-literary composition, Peng etc. report one concentrated nitric acid and sulfuric acid mixture carbon oxide fiber, then obtain the method for graphene quantum dot through ultrasonic and dialysis.In the same year, Shen etc. are at NewJ.Chem.2012, and the one step hydro thermal method reported in 36,97-101 is prepared in up-conversion fluorescence graphene quantum dot method, and the method also using dialysis is carried out except Ficus caricaL the graphene quantum dot aqueous solution.
But, dialysis be utilize the size difference of impurity salt ion and graphene quantum dot and to the selectivity perviousness of dialysis membrane to reach removal of impurities object, it is a kind of diffusion controlled process in essence, according to current report, general needs repeatedly, the dialysis of (a couple of days is even longer) for a long time just can reach removal of impurities requirement, dust removal rate is lower, is unfavorable for the extensive preparation of graphene quantum dot.Therefore, simple, the efficient graphene oxide quantum dot method of purification of research and development has important practical significance.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of method of purification of graphene oxide quantum dot, carries out the lower problem of graphene quantum dot aqueous solution purification efficiency for solving in prior art the mode adopting dialysis.
For achieving the above object and other relevant objects, the invention provides a kind of method of purification of graphene oxide quantum dot
The method of purification of described graphene oxide quantum dot at least comprises:
The graphene oxide quantum dot aqueous solution is provided;
Tensio-active agent is mixed into form mixing solutions in the described graphene oxide quantum dot aqueous solution;
In described mixing solutions, add non-polar solvent, to be extracted in described non-polar solvent by described graphene oxide quantum dot, obtain graphene oxide quantum dot non-polar solution;
Dry described graphene oxide quantum dot non-polar solution, to obtain graphene oxide quantum dot powder.
Preferably, described tensio-active agent is the quaternary ammonium salt ionogenic surfactant containing long chain alkane.
Preferably, described tensio-active agent is didodecyldimethylammbromide bromide, Trimethyllaurylammonium bromide, didecyl Dimethy brometo de amonio, DHAB or 4 bromide.
Preferably, described non-polar solvent is hexanaphthene, normal hexane, chloroform, ethyl acetate, benzene or toluene.
Preferably, the described graphene oxide quantum dot non-polar solution of described drying, to adopt rotary evaporation or distillation method to carry out drying in the step obtaining graphene oxide quantum dot powder.
Preferably, time dry, set temperature is 25 DEG C ~ 100 DEG C.
Preferably, the described graphene quantum dot aqueous solution is that strong acid oxidation style, Brodie method, Staudenmaier method, Hummers method or hydrothermal method are obtained.
Preferably, in the described graphene quantum dot aqueous solution, the lateral dimension of graphene quantum dot is less than 100nm, and in described graphene quantum dot, carbon and Sauerstoffatom ratio are 2:1 ~ 20:1.
Preferably, describedly add in the step of non-polar solvent in described mixing solutions, described non-polar solvent be described mixed liquor volume 0.5-10 doubly.
Preferably, tensio-active agent is mixed into be formed in the step of the first mixing solutions in the described graphene oxide quantum dot aqueous solution, the quality of described tensio-active agent is 1 ~ 20 times of described graphene oxide quantum dot quality, and adopts concussion, stir or ultrasonicly to mix.
As mentioned above, the method for purification of graphene oxide quantum dot of the present invention, has following beneficial effect:
Mainly utilize charge effect stronger between tensio-active agent and graphene oxide quantum dot surface anionic group, form the graphene oxide quantum dot of surface hydrophobicity, reduce the dispersiveness of graphene oxide quantum dot in water, graphene oxide quantum dot is shifted from the aqueous solution of impure lewis' acid in water-fast non-polar solvent, thus obtain not containing the graphene oxide quantum dot solution of inorganic salt impurities, high-purity mangesium oxide graphene quantum dot powder can be obtained after further drying process.
Accompanying drawing explanation
Fig. 1 to Fig. 3 is shown as the schematic diagram of the method for purification of graphene oxide quantum dot of the present invention.
Element numbers explanation
10 hexanaphthene layers
20 quantum dot aqueous layers
30 graphene oxide quantum dots/cyclohexane solution
40 salt-containing solutions
S10 ~ S20 step
Embodiment
A kind of method extracting graphene oxide quantum dot from the aqueous solution is provided in technical scheme of the present invention, mainly utilize charge effect stronger between cationic surfactant and graphene oxide quantum dot surface anionic group, form the graphene oxide quantum dot of surface hydrophobicity, reduce the dispersiveness of graphene oxide quantum dot in water, graphene oxide quantum dot is shifted from the aqueous solution from impure lewis' acid in water-fast non-polar solvent, thus obtain not containing the graphene oxide quantum dot solution of inorganic salt impurities, high-purity mangesium oxide graphene quantum dot powder can be obtained after further drying process.
Below by way of specific specific examples, embodiments of the present invention are described, those skilled in the art the content disclosed by this specification sheets can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by embodiments different in addition, and the every details in this specification sheets also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
Refer to Fig. 1.It should be noted that, the diagram provided in the present embodiment only illustrates basic conception of the present invention in a schematic way, then only the assembly relevant with the present invention is shown in graphic but not component count, shape and size when implementing according to reality is drawn, it is actual when implementing, and the kenel of each assembly, quantity and ratio can be a kind of change arbitrarily, and its assembly layout kenel also may be more complicated.
Concrete, as shown in Figure 1, the method for purification of graphene oxide quantum dot provided by the invention comprises;
First, step S10 is performed: provide the graphene oxide quantum dot aqueous solution;
General, the described graphene quantum dot aqueous solution is that strong acid oxidation style, Brodie method, Staudenmaier method, Hummers method or hydrothermal method are obtained.Wherein containing the inorganic salt impurities ion much introduced owing to using oxygenant, intercalator or auxiliary shearing agent etc. in chemical preparation process, these inorganic salt impurities ions are unfavorable for that sequential reduction prepares graphene quantum dot and the application in downstream photoelectric material and devices field thereof.
In addition, in the described graphene quantum dot aqueous solution, the lateral dimension of graphene quantum dot is less than 100nm, and in described graphene quantum dot, carbon and Sauerstoffatom ratio are 2:1 ~ 20:1.
Next, step S20 is performed: in the described graphene oxide quantum dot aqueous solution, be mixed into tensio-active agent to form mixing solutions;
Wherein, described tensio-active agent refers to have fixing hydrophilic and oleophilic group, aligns, and can make the material that surface tension significantly declines in the surface energy of solution.
The molecular structure of tensio-active agent has amphipathic: one end is hydrophilic radical, and the other end is hydrophobic group.Graphene oxide quantum dot itself is hydrophilic, well dispersed again in water, and can not disperse in non-polar solvent, in this step, after adding tensio-active agent, ionic bonding is formed between ionogenic surfactant energy and graphene oxide quantum dot, jointly be constructed to a hydrophobic entirety with quantum dot, make quantum dot be more prone to stable dispersion in the immiscible non-polar solvent of water, so, because energy minimization drives, quantum dot shifts in non-polar solvent.
In this step, described tensio-active agent is preferably adopted as the quaternary ammonium salt ionogenic surfactant containing long chain alkane, is specifically as follows didodecyldimethylammbromide bromide, Trimethyllaurylammonium bromide, didecyl Dimethy brometo de amonio, DHAB or 4 bromide.The part that such tensio-active agent works is positively charged ion, and its molecular structure major portion is a quinquevalent nitrogen atom.Described quaternary ammonium salt cationic surfactant by the impact of medium pH, remains the surfactant moiety with positive charge.
Concrete, the amphiphilic ions water-wet side that in quaternary ammonium salt, ionogenic surfactant can ionize out in water contains amido, positively charged, can and graphene oxide quantum dot on electronegative carboxyl, form ionic bonding between hydroxyl; The hydrophobic side of bonding back surface promoting agent is if chain alkyl, and hydrophobicity is stronger, more easily realizes quantum dot and shifts in hydrophobic non-polar solvent.
In other embodiments, other ammonium salt type cationic tensio-active agents may also can use.
The quality of described tensio-active agent determines according to the concentration of quantum dot in solution, is generally 1 ~ 20 times of described graphene oxide quantum dot quality.Too much, tensio-active agent is wasted; Very little, quantum dot hydrophobic modification is insufficient, can not realize the transfer of good quantum dot.And adopt concussion, stirring or ultrasonic disperse to mix.
Next, step S30 is performed: in described mixing solutions, add non-polar solvent, will be extracted in described non-polar solvent described graphene oxide quantum dot, obtain graphene oxide quantum dot non-polar solution; Wherein, the volume of described non-polar solvent is suitable for all graphene oxide quantum dots of dissolving that can try one's best, and don't as causing waste too much.Preferably, the volume of described non-polar solvent is described mixed liquor volume 0.5-5 times.
Because non-polar solvent is water insoluble, and the graphene oxide quantum dot of modified can be dissolved, thus can realize in this step extracting graphene oxide quantum dot, obtain the non-polar solution of graphene oxide quantum dot.
Next, step S40 is performed: dry described graphene oxide quantum dot non-polar solution, to obtain graphene oxide quantum dot powder.
Wherein, because the boiling point of non-polar solution is lower, in this step, drying process should be carried out at a lower temperature, otherwise easily produces the phenomenons such as blast or burning.Preferably, owing to adopting rotary evaporation or distillation method to operate more convenient, therefore adopt rotary evaporation or distillation method to carry out drying, time dry, set temperature is 25 DEG C ~ 100 DEG C.
Through above-mentioned technique, obtain graphene oxide quantum dot powder.
Embodiment 1
Get the 30mL graphene oxide quantum dot aqueous solution, the described graphene oxide quantum dot aqueous solution is that strong acid oxidation style prepares, wherein containing inorganic ion impurity;
In the described graphene oxide quantum dot aqueous solution, add the 100mg didodecyldimethylammbromide bromide aqueous solution, carry out ultrasonic disperse, the time of carrying out is 10min, obtains the mixing solutions of graphene quantum dot and didodecyldimethylammbromide bromide;
In the mixing solutions of described graphene quantum dot and didodecyldimethylammbromide bromide, add 30mL hexanaphthene, as shown in Figure 2, now upper strata is colourless hexanaphthene layer 10, and lower floor is brown quantum dot aqueous layer 20;
Carry out concussion 5min, then leave standstill 10min, to obtain upper strata be brown graphene oxide quantum dot/cyclohexane solution 30 and lower floor for close to water white salt-containing solution 40, as shown in Figure 2.
Get above-mentioned upper strata graphene oxide quantum dot/cyclohexane solution 30, join in 50mL round-bottomed flask, set temperature is 50 DEG C, carries out rotary evaporation, until solvent volatilizees completely, obtains dark-brown graphene oxide quantum dot powder.
The content of each element of front and back graphene oxide quantum dot solution of purifying in the present embodiment is analyzed, obtains as shown in following table table one:
Table one: the content balance table of each element of graphene oxide quantum dot solution before and after purifying.
Embodiment 2
Get the 20mL graphene oxide quantum dot aqueous solution, the described graphene oxide quantum dot aqueous solution is that the Staudenmaier method improved is prepared into, wherein containing inorganic ion impurity;
Add the 80mg Trimethyllaurylammonium bromide aqueous solution wherein, stir 30min, obtain the mixing solutions of graphene quantum dot and Trimethyllaurylammonium bromide;
40mL hexanaphthene is added in above-mentioned mixing solutions, now lower floor is colourless chloroform layer, and upper strata is brown quantum dot aqueous layer, concussion 5min, then leave standstill 10min, to obtain lower floor be brown graphene oxide quantum dot/chloroformic solution and upper strata for close to water white salt-containing solution;
Get above-mentioned lower floor brown solution, join in 50mL round-bottomed flask, set temperature is 50 DEG C, carries out distillation dry, until solvent volatilizees completely, obtains dark-brown graphene oxide quantum dot powder.
Embodiment 3
Get the 30mLHummers graphene oxide quantum dot aqueous solution, the described graphene oxide quantum dot aqueous solution is the saliferous graphene oxide quantum dot aqueous solution prepared, wherein containing inorganic ion impurity;
Add 120mg didecyl Dimethy bromize ammonium solution wherein, carry out ultrasonic disperse 10min, obtain the mixing solutions of graphene quantum dot and didecyl Dimethy brometo de amonio;
30mL hexanaphthene is added in above-mentioned mixing solutions, now upper strata is colourless toluene layer, and lower floor is brown quantum dot aqueous layer, concussion 5min, then leave standstill 10min, to obtain upper strata be brown graphene oxide quantum dot/toluene solution and lower floor for close to water white salt-containing solution;
Get above-mentioned upper strata brown solution, join in 50mL round-bottomed flask, in 50 DEG C of distillation evaporations until solvent volatilizees completely, obtain dark-brown graphene oxide quantum dot powder.
Embodiment 4
Get the 20mL graphene oxide quantum dot aqueous solution, the described graphene oxide quantum dot aqueous solution is hydrothermal method preparation, wherein containing inorganic ion impurity;
Add 80mg didecyl Dimethy bromize ammonium solution wherein, ultrasonic 10min, obtain the mixing solutions of graphene quantum dot and didecyl Dimethy brometo de amonio;
30mL hexanaphthene is added in above-mentioned mixing solutions, now upper strata is colourless hexanaphthene layer, and lower floor is brown quantum dot aqueous layer, concussion 5min, then leave standstill 10min, to obtain upper strata be brown graphene oxide quantum dot/cyclohexane solution and lower floor for close to water white salt-containing solution;
Get above-mentioned upper strata brown solution, join in 50mL round-bottomed flask, in 50 DEG C of distillation evaporations until solvent volatilizees completely, obtain dark-brown graphene oxide quantum dot powder.
In sum; the method of purification suitability of graphene oxide quantum dot provided by the invention is wide; the graphene oxide water solution that various method prepares can be purified; and operating procedure is simple; consuming time short; the quantum dot purity that purification obtains is high, is applicable to very much the large-scale production of graphene oxide quantum dot and graphene quantum dot.So the present invention effectively overcomes various shortcoming of the prior art and tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (10)
1. a method of purification for graphene oxide quantum dot, is characterized in that, the method for purification of described graphene oxide quantum dot at least
Comprise:
The graphene oxide quantum dot aqueous solution is provided;
Tensio-active agent is mixed into form mixing solutions in the described graphene oxide quantum dot aqueous solution;
In described mixing solutions, add non-polar solvent, to be extracted in described non-polar solvent by described graphene oxide quantum dot, obtain graphene oxide quantum dot non-polar solution;
Dry described graphene oxide quantum dot non-polar solution, to obtain graphene oxide quantum dot powder.
2. the method for purification of graphene oxide quantum dot according to claim 1, is characterized in that: described tensio-active agent is the quaternary ammonium salt ionogenic surfactant containing long chain alkane.
3. the method for purification of graphene oxide quantum dot according to claim 1 and 2, is characterized in that: described tensio-active agent is didodecyldimethylammbromide bromide, Trimethyllaurylammonium bromide, didecyl Dimethy brometo de amonio, DHAB or 4 bromide.
4. the method for purification of graphene oxide quantum dot according to claim 1, is characterized in that: described non-polar solvent is hexanaphthene, normal hexane, chloroform, ethyl acetate, benzene or toluene.
5. the method for purification of graphene oxide quantum dot according to claim 1, it is characterized in that: the described graphene oxide quantum dot non-polar solution of described drying, to adopt rotary evaporation or distillation method to carry out drying in the step obtaining graphene oxide quantum dot powder.
6. the method for purification of graphene oxide quantum dot according to claim 5, is characterized in that: time dry, set temperature is 25 DEG C ~ 100 DEG C.
7. the method for purification of graphene oxide quantum dot according to claim 1, is characterized in that: the described graphene quantum dot aqueous solution is that strong acid oxidation style, Brodie method, Staudenmaier method, Hummers method or hydrothermal method are obtained.
8. the method for purification of graphene oxide quantum dot according to claim 1, it is characterized in that: in the described graphene quantum dot aqueous solution, the lateral dimension of graphene quantum dot is less than 100nm, and in described graphene quantum dot, carbon and Sauerstoffatom ratio are 2:1 ~ 20:1.
9. the method for purification of graphene oxide quantum dot according to claim 1, is characterized in that: describedly add in the step of non-polar solvent in described mixing solutions, described non-polar solvent be described mixed liquor volume 0.5-10 doubly.
10. the method for purification of graphene oxide quantum dot according to claim 1, it is characterized in that: in the described graphene oxide quantum dot aqueous solution, be mixed into tensio-active agent to be formed in the step of the first mixing solutions, the quality of described tensio-active agent is 1 ~ 20 times of described graphene oxide quantum dot quality, and adopts concussion, stirring or ultrasonic disperse mode to mix.
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| CN104876212A (en) * | 2015-04-14 | 2015-09-02 | 上海大学 | Method for efficiently purifying and recycling graphene quantum dots based on extraction technique |
| CN105752958B (en) * | 2016-03-03 | 2018-06-15 | 中国烟草总公司郑州烟草研究院 | A kind of synthetic method of carbon nano-cluster and its application |
| CN107500274B (en) * | 2017-10-11 | 2020-05-22 | 江苏安纳泰环保科技有限公司 | Preparation method of graphene quantum dots with three primary colors of fluorescence |
| CN108163836A (en) * | 2018-02-12 | 2018-06-15 | 成都理工大学 | A kind of purifying technique of metal ion mixing carbon quantum dot |
| CN108423662B (en) * | 2018-04-09 | 2021-10-01 | 合肥国轩高科动力能源有限公司 | Method for preparing high-concentration graphene based on extraction technology |
| CN108864406B (en) * | 2018-07-25 | 2020-09-01 | 福州大学 | High-mechanical-strength GO/TPU in-situ polymerization method |
| CN113930240B (en) * | 2021-09-18 | 2024-05-14 | 深圳市彦博伟业科技有限公司 | Fluorescent carbon quantum dot, preparation method thereof and warm white light emitting LED |
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