CN103359727A - Preparation method of oxygen and chlorine co-doped graphene quantum dots - Google Patents
Preparation method of oxygen and chlorine co-doped graphene quantum dots Download PDFInfo
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- CN103359727A CN103359727A CN2013103128360A CN201310312836A CN103359727A CN 103359727 A CN103359727 A CN 103359727A CN 2013103128360 A CN2013103128360 A CN 2013103128360A CN 201310312836 A CN201310312836 A CN 201310312836A CN 103359727 A CN103359727 A CN 103359727A
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Abstract
The invention discloses a preparation method of oxygen and chlorine co-doped graphene quantum dots, and relates to hydro-thermal preparation technology of the oxygen and chlorine co-doped graphene quantum dots. The hydro-thermal preparation technology of the oxygen and chlorine co-doped graphene quantum dots is characterized in that: under hydro-thermal conditions and hydrochloric acid catalysis conditions, a saccharide is used as a carbon source and an oxygen doping source, hydrochloric acid is used as a chlorine doping source, and water-soluble oxygen and chlorine co-doped graphene quantum dots are produced by water molecule-eliminating polymerization of saccharide molecules and the hydrochloric acid. The hydro-thermal preparation technology relates to simultaneous introduction of elements of oxygen and chlorine into the graphene quantum dots, so that electron transition effective energy levels in the graphene quantum dots can be increased, and furthermore the prepared oxygen and chlorine co-doped graphene quantum dots have more excellent luminescence and luminescence modulation performances.
Description
Technical field
The present invention relates to the preparation method of oxygen, chlorine co-doped graphene quantum dot, especially adopting cheap sugar and hydrochloric acid is raw material, with technique simple, environmental protection prepare water-soluble, monodispersity good, and has the oxygen of the characteristics of luminescence, the method for chlorine co-doped graphene quantum dot.
Background technology
Owing to have special optical property, characteristic electron, chemical stability and spin character etc., graphene quantum dot (GQDs) has become a focus in the numerous research fields of material at present.The technology of preparing of graphene quantum dot is various, wherein mainly comprises electron beam lithography, chemical synthesising technology, electrochemistry technology of preparing, graphene oxide (GO) reduction technique, polycyclic aromatic hydrocarbons pyrolytic technique etc.
At present, graphene quantum dot is not yet obtained widespread use at optoelectronic areas, traces it to its cause, and mainly is a kind of graphene quantum dot to be carried out effective level structure, optical property modulation technique means because still lack at present.In addition, produce in bulk graphene quantum dot and also have at present a series of technical barriers.
Doping is a kind of effective means that changes material level structure, optical property, electrical properties.Because Graphene is the semi-metallic of a class zero band gap, want the application of Graphene is expanded to field of optoelectronic devices from field of electronic devices, just must modulate being with of Graphene.At present, except adopting quantum confined effect and fringing effect, mixing also is used to change level structure, electrical properties and the optical property of grapheme material.Yet, with regard to present Graphene doping techniques, generally adopt high vacuum, plasma or high-temperature technology, synthetic and doping is carried out in two steps, and this not only consumes energy, danger, and step is numerous and diverse, is unfavorable for the application of doping type Graphene.
To obtain in large quantity the graphene quantum dot material in advance, just must be simple from technique, materials environmental protection, the preparation method that possesses batch production power start with.Obviously, the Hydrothermal Synthesis technology not only has the ability of batch production concurrently, also possesses technology environmental protection, the characteristics such as nontoxic.The new technology of the present invention's exploitation can be synthesized the controlled batch of graphene quantum dot and doping " unites two into one " effectively, and single step reaction is finished.
Chinese patent, the patent No. 201110159907.9, the hydrothermal preparing process of a kind of water-soluble graphene quantum dots of title, the method is the aqueous solution that adds 0.01～1.0M poly-hydroxy carbohydrate in hydrothermal reaction kettle, under 120～220 ℃ of temperature, heated 10～600 minutes, allow glycan molecule shrink to aggregate into the graphene quantum dot that is of a size of 1～10nm and be prepared into.Technology of the present invention is different with it, technology of the present invention relates in graphene quantum dot introduces oxygen and chlorine element simultaneously, compare with the graphene quantum dot that hydrothermal preparing process makes, graphene quantum dot of the present invention has increased effective energy level of transition of electron in the quantum dot, and then so that the oxygen that the present invention prepares, chlorine co-doped graphene quantum dot have better luminous and luminous modulating performance.
Summary of the invention
To be solved by this invention is that the effective energy level of graphene quantum dot transition of electron that makes of present hydrothermal preparing process is low, and the relatively poor problem of its luminous and luminous modulating performance provides the hydro-thermal synthetic preparation method of a kind of oxygen, chlorine co-doped graphene quantum dot.
The hydro-thermal synthetic preparation method of this oxygen of the present invention, chlorine co-doped graphene quantum dot, take low-cost sugar (fructose, glucose, sucrose) and hydrochloric acid as raw material, under hydrothermal reaction condition and hydrochloric acid catalysis condition, sugar is as carbon source and oxygen doped source, hydrochloric acid is as the chlorine source, and glycan molecule and hydrochloric acid shrink polymerization form water-soluble oxygen, chlorine co-doped graphene quantum dot.
The hydro-thermal synthetic preparation method of oxygen of the present invention, chlorine co-doped graphene quantum dot is characterized in that the method is to realize by following step:
The first step makes it be dissolved into sugar aqueous solution sugared water, and sugared concentration is 0.1-15% wt in this sugar aqueous solution;
Second step adds hydrochloric acid in the sugar aqueous solution of the first step gained, and 120 ~ 220 ℃ of lower reactions 0.5 ~ 10 hour, wherein, the chlorine in the hydrochloric acid and the carbon mol ratio in the sugar were 5:1 ~ 1:10;
In the 3rd step, reaction finishes, and the cooling reaction solution carries out dialysis purification to room temperature with dialysis tubing, namely collects to get oxygen, chlorine co-doped graphene quantum dot.
Described sugar is fructose, glucose or sucrose.
Among the described preparation method, can select the quanta point material that permeable membrane separates, purifying obtains different size of different cut-off molecular weight.Select the dialysis tubing by molecular weight 1000 to carry out dialysis purification, then collect and obtain the oxygen that mean sizes is 5.4 nm, chlorine co-doped graphene quantum dot.
The present invention is to have added hydrochloric acid in reaction compared with prior art, and hydrochloric acid plays two effects in this reaction, the one, and the carrying out of catalyzed reaction makes quick under acidic conditions, the effectively dehydration of glycan molecule, forms the Graphene matrix of hexagonal structure; Two provide doped element chlorine, namely introduce chlorine in the Graphene matrix, and hydrochloric acid is reactant effective and necessary in the reaction system of the present invention catalyzer of holding concurrently.
Oxygen, chlorine co-doped graphene quantum dot have increased effective energy level of transition of electron in the quantum dot, the transition of unadulterated graphene quantum dot electronic level is transition between the π of sp2 carbon and π * only, electron absorption can be 5. 4eV, photoluminescence wavelength is 303nm and 412nm, and emission wavelength is positioned at deep ultraviolet and blue wave band.By in graphene quantum dot, mixing simultaneously oxygen and chlorine, will can introduce simultaneously oxygen, chlorine energy level by inter-stage at π and the π * of sp2 carbon, 2.6eV(oxygen energy level occurs) and 3.5eV(chlorine energy level) transition of electronic energy, the variation so that the transition of electron pattern becomes, send the light of 600nm and 700nm, emission wavelength and then expand to gold-tinted, ruddiness.This is conducive to material in the application of the aspects such as bio-imaging, opto-electronic device, photonic device.
The product of preparation technology of the present invention and the method preparation has following advantage:
(1) monodispersity: the oxygen of the present invention's preparation, the median size of chlorine co-doped graphene quantum dot are 5.4nm, and it is narrow that quantum dot is evenly distributed size;
(2) technique is simple: the chlorine doped quantum dot of the present invention's preparation is simple to operate, and one step of reaction finishes;
(3) water-soluble: oxygen, the chlorine co-doped graphene quantum dot of the present invention's preparation are dissolved in water, have wide application space;
(4) preparation technology's environmental protection: the present invention prepares the synthetic technology of oxygen, chlorine co-doped graphene quantum dot, does not need the synthetic of intermediate, and reactant is simple, nontoxic;
(5) be easy to batch production: because the hydro-thermal reaction device can be according to industrial scale amplification, so can be used for industrial mass manufacture;
(6) the good characteristics of luminescence: oxygen, the chlorine co-doped graphene quantum dot of the present invention's preparation, at UV-light, visible light, infrared ray excited lower, all can be luminous.This special, excellent luminescent properties has been expanded it in the application in the fields such as bio-imaging, fluorescent mark, photochemical catalysis, nonlinear optics, photoelectron.
Oxygen, the chlorine co-doped graphene quantum dot of the present invention's preparation prove that being with of Graphene is openable.And, have the good characteristics of luminescence and water-soluble.And by the mixing of oxygen, chlorine element, graphene quantum dot is effectively modulated at aspects such as level structure, optical characteristics, thus efficient extn the application of graphene quantum dot.Present technique has very widely using value, and it is different from semimetallic Graphene, and it can be widely used in semi-conductor industry, bioluminescence, prepare composite.
Description of drawings
Fig. 1 is the x-ray photoelectron spectroscopy figure (Cl 2p XPS) of oxygen, chlorine co-doped graphene quantum dot.
Fig. 2 is the uv-visible absorption spectroscopy figure of oxygen, the chlorine co-doped graphene quantum dot aqueous solution.
Fig. 3 is the photoluminescence spectrum (Ex=325nm) of oxygen, the chlorine co-doped graphene quantum dot aqueous solution.
Fig. 4 is oxygen, chlorine co-doped graphene quantum dot low range transmission electron microscope picture.
Fig. 5 is oxygen, chlorine co-doped graphene quantum dot size distribution figure (mean sizes 5.4nm).
Fig. 6 is oxygen, chlorine co-doped graphene quantum dot high-resolution-ration transmission electric-lens figure.
Fig. 7 is outside drawing under oxygen, the chlorine co-doped graphene quantum dot solution natural light.
Fig. 8 is oxygen, chlorine co-doped graphene quantum dot solution ultraviolet lighting fluorogram.
Fig. 9 is X-ray energy spectrum (EDS) figure of embodiment 1 oxygen, chlorine co-doped graphene quantum dot, the content of oxygen and chlorine is respectively ~ and 5
Atm%, ~ 2
Atm%.
Embodiment
Embodiment 1: take by weighing 0.5 gram fructose, add 39.5 mL deionized waters, stir and make the sugar dissolving.Add in the sugar soln 0.5 mL hydrochloric acid (32%, wt), stir.Reaction solution was heated 4 hours under 170 ℃ of hydrothermal conditions.The cooling reaction solution uses the dialysis tubing by molecular weight 1000 to carry out dialysis purification to room temperature, collects sample, obtains the oxygen that mean sizes is 5.4 nm, chlorine co-doped graphene quantum dot.
Embodiment 2: take by weighing 1.5 gram glucose, add 38.5 mL deionized waters, stir and make the glucose dissolving.Add in the glucose solution 0.2 mL hydrochloric acid (32%, wt), stir.Reaction solution was heated 2 hours under 180 ℃ of hydrothermal conditions.The cooling reaction solution uses the dialysis tubing by molecular weight 3000 to carry out dialysis purification to room temperature, collects sample, obtains the oxygen that mean sizes is 7.2 nm, chlorine co-doped graphene quantum dot.
Embodiment 3: take by weighing 0.3 gram sucrose, add 39.7 mL deionized waters, stir and make sucrose dissolved.Add in the sucrose solution 0.6 mL hydrochloric acid (32%, wt), stir.Reaction solution was heated 3 hours under 190 ℃ of hydrothermal conditions.The cooling reaction solution uses the dialysis tubing by molecular weight 1000 to carry out dialysis purification to room temperature, collects sample, obtains the oxygen that mean sizes is 4.9 nm, chlorine co-doped graphene quantum dot.
Claims (2)
1. the hydro-thermal synthetic preparation method of an oxygen, chlorine co-doped graphene quantum dot is characterized in that the method is to realize by following step:
The first step makes it be dissolved into sugar aqueous solution sugared water, and sugared concentration is 0.1-15% wt in this sugar aqueous solution;
Second step adds hydrochloric acid in the sugar aqueous solution of the first step gained, and 120 ~ 220 ℃ of lower reactions 0.5 ~ 10 hour, wherein, the chlorine in the hydrochloric acid and the carbon mol ratio in the sugar were 5:1 ~ 1:10;
In the 3rd step, reaction finishes, and the cooling reaction solution carries out dialysis purification to room temperature with dialysis tubing, namely collects to get oxygen, chlorine co-doped graphene quantum dot.
2. the hydro-thermal synthetic preparation method of a kind of oxygen as claimed in claim 1, chlorine co-doped graphene quantum dot is characterized in that described sugar is fructose, glucose or sucrose.
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Cited By (13)
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| CN103833029A (en) * | 2014-01-10 | 2014-06-04 | 云南师范大学 | Preparation method of high-efficient multicolor-fluorescence water-soluble sulfur oxygen-codoped graphene quantum dot |
| CN104045076A (en) * | 2014-01-17 | 2014-09-17 | 中国科学院上海微***与信息技术研究所 | Graphene oxide quantum dot preparation method |
| CN104140084A (en) * | 2014-08-01 | 2014-11-12 | 中国人民解放军国防科学技术大学 | Method for preparing carbon nitride quantum dots |
| CN106601591A (en) * | 2016-12-21 | 2017-04-26 | 昆明物理研究所 | Preparation method of chlorine-doped multilayer graphene film |
| CN107011896A (en) * | 2016-01-27 | 2017-08-04 | 云南师范大学 | A kind of preparation method of potassium doped graphene quantum dot |
| CN107011897A (en) * | 2016-01-27 | 2017-08-04 | 云南师范大学 | A kind of preparation method of additive Mn graphene quantum dot |
| CN107572505A (en) * | 2016-07-04 | 2018-01-12 | 云南师范大学 | A kind of preparation method of Ag doping graphene quantum dot |
| CN108314005A (en) * | 2018-03-27 | 2018-07-24 | 广西师范大学 | A kind of method and its device preparing chlorine doped graphene quantum dot |
| CN108795421A (en) * | 2018-04-11 | 2018-11-13 | 北京科技大学 | A kind of Preparation method and use of chlorine doped graphene quantum dot |
| CN108911524A (en) * | 2018-08-30 | 2018-11-30 | 昆明理工大学 | A kind of preparation method of Cl doping Glucose Carbon base graphene |
| CN110437836A (en) * | 2019-08-21 | 2019-11-12 | 宁波石墨烯创新中心有限公司 | A kind of phosphor material and preparation method thereof based on graphene quantum dot |
| US10981139B2 (en) | 2014-09-19 | 2021-04-20 | National Cheng Kung University | Semiconductor quantum dot and method of carrying out chemical reaction or photoluminescence reaction by using the same |
| CN114316963A (en) * | 2021-12-03 | 2022-04-12 | 郑州大学 | Carbonized polymer dot and preparation method and application thereof |
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| CN103833029A (en) * | 2014-01-10 | 2014-06-04 | 云南师范大学 | Preparation method of high-efficient multicolor-fluorescence water-soluble sulfur oxygen-codoped graphene quantum dot |
| CN104045076A (en) * | 2014-01-17 | 2014-09-17 | 中国科学院上海微***与信息技术研究所 | Graphene oxide quantum dot preparation method |
| CN104045076B (en) * | 2014-01-17 | 2016-01-20 | 中国科学院上海微***与信息技术研究所 | The preparation method of graphene oxide quantum dot |
| CN104140084A (en) * | 2014-08-01 | 2014-11-12 | 中国人民解放军国防科学技术大学 | Method for preparing carbon nitride quantum dots |
| CN104140084B (en) * | 2014-08-01 | 2016-02-17 | 中国人民解放军国防科学技术大学 | A kind of preparation method of carbonitride quantum dot |
| US10981139B2 (en) | 2014-09-19 | 2021-04-20 | National Cheng Kung University | Semiconductor quantum dot and method of carrying out chemical reaction or photoluminescence reaction by using the same |
| CN107011896B (en) * | 2016-01-27 | 2019-12-10 | 云南师范大学 | Preparation method of potassium-doped graphene quantum dots |
| CN107011896A (en) * | 2016-01-27 | 2017-08-04 | 云南师范大学 | A kind of preparation method of potassium doped graphene quantum dot |
| CN107011897A (en) * | 2016-01-27 | 2017-08-04 | 云南师范大学 | A kind of preparation method of additive Mn graphene quantum dot |
| CN107572505A (en) * | 2016-07-04 | 2018-01-12 | 云南师范大学 | A kind of preparation method of Ag doping graphene quantum dot |
| CN106601591A (en) * | 2016-12-21 | 2017-04-26 | 昆明物理研究所 | Preparation method of chlorine-doped multilayer graphene film |
| CN108314005A (en) * | 2018-03-27 | 2018-07-24 | 广西师范大学 | A kind of method and its device preparing chlorine doped graphene quantum dot |
| CN108795421A (en) * | 2018-04-11 | 2018-11-13 | 北京科技大学 | A kind of Preparation method and use of chlorine doped graphene quantum dot |
| CN108911524A (en) * | 2018-08-30 | 2018-11-30 | 昆明理工大学 | A kind of preparation method of Cl doping Glucose Carbon base graphene |
| CN108911524B (en) * | 2018-08-30 | 2021-07-16 | 昆明理工大学 | Preparation method of Cl-doped glucose carbon-based graphene |
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| CN110437836B (en) * | 2019-08-21 | 2022-07-29 | 宁波石墨烯创新中心有限公司 | Phosphorescent material based on graphene quantum dots and preparation method thereof |
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