CN102190296B - Hydrothermal method for preparing water-soluble graphene quantum dots - Google Patents
Hydrothermal method for preparing water-soluble graphene quantum dots Download PDFInfo
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- CN102190296B CN102190296B CN201110159907.9A CN201110159907A CN102190296B CN 102190296 B CN102190296 B CN 102190296B CN 201110159907 A CN201110159907 A CN 201110159907A CN 102190296 B CN102190296 B CN 102190296B
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Abstract
The invention discloses a hydrothermal method for preparing water-soluble graphene quantum dots. The invention relates to the preparation method of graphene quantum dots, and especially relates to a hydrothermal method for preparing water-soluble graphene quantum dots. The method provided by the present invention is characterized in that: 0.01 to 1.0M of an aqueous solution of polyhydroxyl carbohydrate is added to a hydrothermal reaction vessel; the aqueous solution is heated for 10 to 600 minutes under a temperature of 120 to 220 DEG C; sugar molecules are polymerized into graphene quantum dots with sizes of 1 to 10nm, such that target products are obtained. The graphene quantum dots prepared with the method provided by the present invention has characteristics of water-solubility, monodispersity and special photoelectrical characteristics. The raw materials are cheap, and the sources of the raw materials are wide. With environmental-protective technology, the method is suitable for volume production.
Description
Technical field
The present invention relates to the technology of preparing of graphene quantum dot, especially a kind of hydro-thermal technology of preparing of water-soluble graphene quantum dots.
Background technology
Graphene is a class carbon-based material, and carbon atom is with sp
2hydridization form composition bond distance is the two dimensional surface film of the cellular lattice structure of hexangle type of 0.142nm.The technology of preparing of Graphene mainly contains tape stripping method, chemical vapour deposition technique, SiC heating, graphene oxide reducing process etc., often kind of a technology of preparing has pluses and minuses, and wherein chemical vapour deposition technique technology prepares the major technique of large area single-layer graphene at present.Because Graphene is the special material with carbon element of a class, its special electricity, optics, calorifics, mechanical property demonstrate important potential using value at present in transistor, monomolecular gases detection, integrated circuit, transparency conductive electrode, biological devices, ultracapacitor and stress-electric coupling device etc.But the semimetal zero of Graphene can limit its application at photoelectric field with character.Recently, the research of Rice Univ USA (Rice University) shows, graphene quantum dot can realize monomolecular sensor.Carbon quantum dot has also been prepared by electrochemical method by the group of City University of Hong Kong (CityU) professor Li Shutang leader, and observed the luminescence generated by light phenomenon of carbon quantum dot.At present, it is openable that the breakthrough obtained about preparation and the photoelectric property research of graphene quantum dot in the world also imply that Graphene can be with, and has huge using value.
Existingly open the technology that Graphene can be with and mainly contain two kinds of methods, first is introduce size and quantum confined effect, forms nanobelt or quantum dot; Second is chemical doping.Many breakthrough important research have been done in the Synthesis and applications research of graphene nanobelt by the research group of Stanford Univ USA professor Dai Hongjie leader, they all achieve the graphene nanobelt of one fixed width by multinomial technology, and the field-effect transistor prepared based on graphene nanobelt has up to 10
7the on-off ratio of the order of magnitude, these researchs fully show Graphene can with the importance of cutting.
Water-soluble graphene quantum dots is a kind of graphene quantum dot that can be dissolved or dispersed in water.By controlling preparation condition, dispersed narrower quantum dot can be prepared.Due to the existence of quantum confined effect, graphene quantum dot has certain energy gap, has the characteristic of semiconductor such as obvious light absorption and photoluminescence property.It can be widely used in the aspects such as biological fluorescent labelling, opto-electronic device, over capacity battery, advanced composite material (ACM).
Summary of the invention
The present invention solves current Graphene can be with and not easily open, do not have semiconductor property, optics and electric property and the problem such as not easily to modulate, by the shrink polymerisation by glycan molecule under hydrothermal condition, and the water-soluble graphene quantum dots that preparation size is controlled.
The hydrothermal preparing process of a kind of water-soluble graphene quantum dots of the present invention, it is characterized in that the method is the aqueous solution adding 0.01 ~ 1.0M polyhydroxy carbohydrate in hydrothermal reaction kettle, heat 10 ~ 600 minutes at 120 ~ 220 DEG C of temperature, allow glycan molecule shrink and aggregate into the graphene quantum dot that is of a size of 1 ~ 10nm and be prepared into.
Described polyhydroxy carbohydrate is glucose, sucrose or fructose.
In described preparation method, polyhydroxy carbohydrate is reactant, and water is solvent, and reaction system is sealing system.
The graphene quantum dot that inventive method is prepared into is the zero dimension grapheme material that a kind of three dimensions are all subject to quantum confinement effect, and its particle size range is 1.0 ~ 10nm, has following feature:
1, water-soluble, graphene quantum dot can disperse, be dissolved in water, forms stable graphene quantum dot dispersion.
2, monodispersity, the average grain diameter of the graphene quantum dot of preparation is 2.3nm, and it is narrow that quantum dot is evenly distributed size, by controlling quantum dot synthesis condition, obtains the quantum dot solution that size is controlled.
3, raw material sources are extensive and cheap, and the raw material of use is sugar, as polyhydroxy carbohydrate such as glucose, sucrose, fructose.
4, technique environmental protection, preparation technology's one-step synthesis, does not relate to the process such as preparation and purifying of intermediate.
5, be easy to batch production, only need high voltage bearing hydrothermal reaction kettle just can complete preparation technology.
6, special photoelectric characteristic, graphene quantum dot has semiconductor property, has the features such as light absorption, luminescence generated by light, field-effect, can be widely used at optoelectronic areas.
Accompanying drawing explanation
Fig. 1 is the graphene quantum dot prepared under different heating time conditions.
Fig. 2 is the UV-vis absorption spectrum of graphene quantum dot.
Fig. 3 is that the low enlargement ratio TEM of graphene quantum dot schemes.
Fig. 4 is that the high magnification TEM of graphene quantum dot schemes.
Fig. 5 is the graphene quantum dot high-resolution-ration transmission electric-lens figure containing Graphene lattice fringe.
Fig. 6 is the electron diffraction diagram of graphene quantum dot 101 diffraction ring.
The graphene quantum dot domain size distribution statistical chart of Fig. 7 to be average-size be 2.3nm.
Detailed description of the invention
Embodiment 1: preparation 0.5M D/W, in the polytetrafluoroethyllining lining container of hydrothermal reaction kettle, add 40ml solution, cover tightly lid and form confined space, reactor is put in the stove of 190 DEG C, heat 120 minutes, namely obtain the graphene quantum dot that average-size is 2.3nm.
Embodiment 2: preparation 0.01M aqueous sucrose solution, gets 40ml solution in reactor, covers tightly lid and form confined space, put into by reactor in the stove of 220 DEG C, heat 600 minutes.Obtain the graphene quantum dot that average-size is 4.3nm.
Embodiment 3: preparation 1.0M fructose water solution, the solution getting certain volume, in reactor, covers tightly lid and forms confined space, put into by reactor in the stove of 150 DEG C, heat 120 minutes.Obtain the graphene quantum dot that average-size is 3.8nm.
Embodiment 4: preparation 0.01M D/W, the solution getting certain volume, in reactor, covers tightly lid and forms confined space, put into by reactor in the stove of 200 DEG C, heat 500 minutes.Obtain the graphene quantum dot that average-size is 3.5nm.
Embodiment 5: preparation 1.0M fructose water solution, the solution getting certain volume, in reactor, covers tightly lid and forms confined space, put into by reactor in the stove of 120 DEG C, heat 120 minutes.Obtain the graphene quantum dot that average-size is 2.0 nm.
Embodiment 6: preparation 0.01M D/W, the solution getting certain volume, in reactor, covers tightly lid and forms confined space, put into by reactor in the stove of 220 DEG C, heat 10 minutes.Obtain the graphene quantum dot that average-size is 1.6 nm.
Claims (6)
1. the hydrothermal preparing process of a water-soluble graphene quantum dots, it is characterized in that preparation 0.5M D/W, 40ml solution is added in the polytetrafluoroethyllining lining container of hydrothermal reaction kettle, cover tightly lid and form confined space, reactor is put in the stove of 190 DEG C, heat 120 minutes, namely obtain the graphene quantum dot that average-size is 2.3nm.
2. the hydrothermal preparing process of a water-soluble graphene quantum dots, it is characterized in that preparation 0.01M aqueous sucrose solution, get 40ml solution in reactor, cover tightly lid and form confined space, reactor is put in the stove of 220 DEG C, heat 600 minutes, namely obtain the graphene quantum dot that average-size is 4.3nm.
3. the hydrothermal preparing process of a water-soluble graphene quantum dots, it is characterized in that preparation 1.0M fructose water solution, get the solution of certain volume in reactor, cover tightly lid and form confined space, reactor is put in the stove of 150 DEG C, heat 120 minutes, namely obtain the graphene quantum dot that average-size is 3.8nm.
4. the hydrothermal preparing process of a water-soluble graphene quantum dots, it is characterized in that preparation 0.01M D/W, get the solution of certain volume in reactor, cover tightly lid and form confined space, reactor is put in the stove of 200 DEG C, heat 500 minutes, namely obtain the graphene quantum dot that average-size is 3.5nm.
5. the hydrothermal preparing process of a water-soluble graphene quantum dots, it is characterized in that preparation 1.0M fructose water solution, get the solution of certain volume in reactor, cover tightly lid and form confined space, reactor is put in the stove of 120 DEG C, heat 120 minutes, namely obtain the graphene quantum dot that average-size is 2.0nm.
6. the hydrothermal preparing process of a water-soluble graphene quantum dots, it is characterized in that preparation 0.01M D/W, get the solution of certain volume in reactor, cover tightly lid and form confined space, reactor is put in the stove of 220 DEG C, heat 10 minutes, namely obtain the graphene quantum dot that average-size is 1.6nm.
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