CN103113887A - Preparation method of nitrogenous graphene quantum dot composite particles with controlled structure and fluorescence - Google Patents
Preparation method of nitrogenous graphene quantum dot composite particles with controlled structure and fluorescence Download PDFInfo
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Abstract
The invention belongs to the technical field of nanometer material preparation, and particularly relates to a preparation method of nitrogenous graphene quantum dot composite particles with controlled structure and fluorescence. The preparation method comprises the following specific steps that: ammonia-water reacts with and cut epoxy groups on the surfaces of graphene quantum dots by taking a low-concentration ammonia-water solution as an etching agent and controlling reaction conditions under mild conditions so that lots of graphene quantum dot flakes are generated, the graphene quantum dot flakes gather and are assembled into spherical graphene quantum dots under a hydrothermal condition, so that the surfaces of the formed flaky graphene quantum dots are loaded with the lots of the spherical graphene quantum dots. The structure and appearance of the composite particles can be simply controlled by changing correspondingly experimental parameters; and the products have controlled fluorescence, good water-solubility, uniform and stable property and potential application prospect in fields of electronics, catalysis and bio-imaging. The raw materials in the method are wide in source, and the preparation method is simple, easy in operation and beneficial to batching and large-scale production and has good industrial production basis and wide application prospect.
Description
Technical field
The invention belongs to the nano material preparing technical field, be specially controlled nitrogenous graphene quantum dot composite particles of a kind of structure and fluorescence and preparation method thereof, more specifically, be etching agent by the low concentration ammonia aqueous solution, control reaction conditions, the flake graphite alkene quantum dot area load that obtains a series of fluorescence between gold-tinted and blue light the nitrogenous graphene quantum dot composite particles of the pattern of a large amount of globular graphite alkene quantum dots.
Background technology
In recent years, Graphene receives increasing concern because of excellent performance, as large specific surface area, and good conduction and thermal conductivity, excellent mechanical property and environment amenable characteristic etc.Graphene quantum dot, as a member in Graphene family, owing to having significant quantum confined effect and fringing effect, thereby in a lot of fields as bio-imaging, fuel cell, photodiode and biosensor etc. have tempting prospect, and at present the synthetic method of graphene quantum dot mainly is divided into two large classes: from bottom to top and top-to-bottom method.Method is by physics or chemical process, the big size graphene sheet to be cut into the small size graphene quantum dot from bottom to top, comprises the strong acid oxidation, microwave method, ultrasonic, hydro-thermal and electrochemical process.Bottom-to-top method refers to that small molecules prepares graphene quantum dot as presoma by series of chemical.In these reactions, graphene quantum dot surface is introduced a large amount of solubilizing groups thereby is had good water-soluble.Based on above various preparation methods, the fluorescence scope of graphene quantum dot obtains very large expansion, but still be confined to blue and yellow fluorescence scope, and the fluorescence quantum kind of independent a kind of method preparation seldom, often can only obtain one or both fluorescence.In order graphene quantum dot to be expanded in whole UV, visible light and near infrared spectral range and to develop new attribute and function, a kind of possible selection is by Heteroatom doping and surface modification.
" American Chemical Society's proceedings " (Journal of the American Chemical Society, 2011, 134, 15-18) taken the lead in reporting a kind of nitrating graphene quantum dot for preparing by electrochemical method, this graphene quantum dot aqueous solution is blue light-emitting under 365 nm ultra violet lamps, and with same method preparation without nitrogen graphene quantum dot aqueous solution green light, and because nitrogen-atoms can well change the chemically reactive site, it is active that thereby the nitrating graphene quantum dot has good redox catalysis, but it is not high that the method that adopts prepares the quantum dot productive rate, be difficult to reach the requirement of extensive preparation.
" advanced material " (AdvancedMaterials, 2012,24,5333-5338) reported by hydrothermal method under the high strength ammonia water condition and prepared the nitrating graphene quantum dot, introducing due to primary amine, graphene quantum dot has very strong fluorescence quantum yield (~ 29 – 19%) and very narrow fluorescence halfwidth (~ 65 – 80nm), but the quantum dot productive rate of preparation is not high equally.
" the materials chemistry magazine: B collects " (Journal of Materials Chemistry B, 2013,1,39 – 42) reported that the fragment by single stage method hydrothermal oxidization Graphene makes nitrogenous graphene quantum dot, productive rate is 8.7%, but its fluorescence is only single blue light, and same productive rate is still on the low side.
Although aforesaid method can be regulated fluorescence and doping nitrogen-atoms effectively, productive rate is all very low, thereby all obtains in actual applications considerable restraint, and most important is the regulation and control report that up to the present has no about nitrogenous graphene quantum dot structure and morphology.Therefore, we here provide, and a kind of direct method by acid oxidase makes nitrogenous graphene quantum dot with nitrogenous PAN-based carbon fiber, again under the cutting action of lower concentration ammoniacal liquor, control the experiment conditions such as hydrothermal temperature and time, can obtain having unique texture, the graphene quantum dot composite particles that fluorescence is controlled.This method is because raw material sources are extensive, and can control simply reaction conditions and realize regulation and control to microgranular texture pattern and fluorescence therefore potential application prospect being arranged on fuel cell, photodiode and bio-imaging.
Summary of the invention
The invention provides the preparation method of the nitrogenous graphene quantum dot composite particles of the controlled unique morphology of a kind of fluorescence.
Nitrogenous graphene quantum dot composite particles of the present invention is characterized in that on nitrogenous graphene quantum dot surface, and the corrasion by lower concentration ammoniacal liquor builds special appearance, and fluorescence is regulated and controled simultaneously.
The preparation method of the nitrogenous graphene quantum dot composite particles of the unique morphology that fluorescence provided by the invention is controlled, its concrete scheme is as follows:
(1) raw materials pretreatment:
PAN-based carbon fiber is placed in muffle furnace under argon gas atmosphere protection 350 ~ 500
oC temperature lower calcination 0.5 ~ 2 h is down to subsequently room temperature and takes out, the PAN-based carbon fiber of the sizing agent that is removed;
(2) prepare nitrogenous graphene quantum dot:
1～2 g polyacrylonitrile carbon fiber of processing is scattered in 65 ~ 68% concentrated nitric acids of 100～200 mL, supersound process 1 ~ 5 h, then in 100 ~ 150
o24 ~ 72 h reflux under C, after being cooled to room temperature, the concentrated nitric acid solution underpressure distillation is reclaimed, add the water of 30 ~ 100 mL and the ammoniacal liquor of 1 ~ 10 mL to regulate pH value for neutral in product, centrifugal 10 ~ 30 min under 5000 ~ 9000 rpm, dialyse mixing solutions and obtain the nitrogenous graphene quantum dot of yellow fluorescence again;
(3) the graphene quantum dot composite particles of the surperficial special appearance of preparation:
The nitrogenous graphene quantum dot of the yellow fluorescence that step (2) is obtained and the ammonia soln of 28wt% join in 20 ~ 100 mL water, the nitrogenous graphene quantum dot consumption of yellow fluorescence is 5 ~ 100 mg, the ammonia soln consumption of 28wt% is 0.05 ~ 1.5 mL, be placed in baking oven hydro-thermal reaction 2 ~ 24 h, oven temperature is 150 ~ 220
oC just obtains having the graphene quantum dot composite particles of the unique morphology of different fluorescence.
The method of the nitrogenous graphene quantum dot composite particles of the unique morphology that above-mentioned preparation fluorescence is controlled, described PAN-based carbon fiber is powdered for grinding after carbon fiber is shredded.
The method of the nitrogenous graphene quantum dot composite particles of the unique morphology that above-mentioned preparation fluorescence is controlled, the graphene quantum dot of described yellow fluorescence are that median size is the single-layer graphene quantum dot of 35 nm.
The method of the nitrogenous graphene quantum dot composite particles of the unique morphology that above-mentioned preparation fluorescence is controlled, described dialysis are the cut-off molecular weight: 1000～10000 Da.
The method of the nitrogenous graphene quantum dot composite particles of the unique morphology that above-mentioned preparation fluorescence is controlled is characterized in that prepared composite particles is a series of fluorescence between gold-tinted and blue light.
The method of the nitrogenous graphene quantum dot composite particles of the unique morphology that above-mentioned preparation fluorescence is controlled is characterized in that prepared composite particles is the pattern that flake graphite alkene quantum dot area load a large amount of globular graphite alkene quantum dots.
The nitrogenous graphene quantum dot of the special appearance that the prepared fluorescence of the present invention is controlled, productive rate can reach 50%, characterize through transmission electron microscope (HRTEM) and atomic force microscope (AFM), result shows that prepared nitrogenous graphene quantum dot has good dispersiveness, granular size is 35 ~ 60 nm, the quantum dot height between 0.5 ~ 2.5 nm, the pattern that flake graphite alkene quantum dot area load a large amount of globular graphite alkene quantum dots occurs mostly when hydrothermal treatment consists 6 ~ 10 h.Detect by fluorescence spectrophotometer, result shows that prepared nitrogenous graphene quantum dot is at the fluorescence between a series of gold-tinteds of emission and blue light under 365 nm ultra violet lamps.
The invention provides the preparation method of the nitrogenous graphene quantum dot of the controlled and unique morphology of a kind of fluorescence, the advantage such as the method is convenient, and is controlled, and raw material sources are extensive.It is dispersed that prepared nitrogenous graphene quantum dot has the good aqueous solution, and good fluorescence controllability and unique morphology can be applicable to the aspects such as fluorescent mark and dye cell.
Description of drawings
Fig. 1 is the nitrogenous graphene quantum dot TEM figure of yellow fluorescence of the present invention.
Fig. 2 is the nitrogenous graphene quantum dot hydrothermal treatment consists of the yellow fluorescence of the present invention TEM of 10 hours figure.
Fig. 3 is the nitrogenous graphene quantum dot AFM figure of yellow fluorescence of the present invention.
Fig. 4 is the nitrogenous graphene quantum dot hydrothermal treatment consists of the yellow fluorescence of the present invention AFM of 10 hours figure.
Fig. 5 is the fluorescence spectrum figure of the nitrogenous graphene quantum dot under the exciting of 365 nm wavelength.A wherein, B, C, D and E are respectively the yellow fluorescence graphene quantum dot, hydrothermal treatment consists 2 h, 6 h, the fluorescence spectrum figure of the nitrogenous graphene quantum dot of 10 h and 14 h.
Fig. 6 is yellow fluorescence graphene quantum dot x-ray photoelectron power spectrum.
Embodiment
The preparation of the nitrogenous graphene quantum dot composite particles of the unique morphology that embodiment 1. fluorescence are controlled.
(1) raw materials pretreatment:
PAN-based carbon fiber is placed in muffle furnace under argon gas atmosphere protection 350 ~ 500
oC temperature lower calcination 0.5 ~ 2 h is down to subsequently room temperature and takes out, the PAN-based carbon fiber of the sizing agent that is removed.
(2) prepare nitrogenous graphene quantum dot:
The polyacrylonitrile carbon fiber that 1g was processed is scattered in 65～68% concentrated nitric acids of 100 mL, supersound process 1 ~ 5 h, then in 100 ~ 150
o24 ~ 72 h reflux under C, after being cooled to room temperature, the concentrated nitric acid solution underpressure distillation is reclaimed, adding in the product ammoniacal liquor of the water of 30 ~ 100 mL and 1 ~ 10 mL to regulate pH value is 7, centrifugal 10 ~ 30 min under 5000 ~ 9000 rpm, dialyse mixing solutions and obtain two days later the nitrogenous graphene quantum dot of yellow fluorescence again;
(3) the graphene quantum dot composite particles of the surperficial special appearance of preparation:
Step (2) is obtained the nitrogenous graphene quantum dot of yellow fluorescence and the ammonia soln of 28wt% joins in 20 ~ 100 mL water, the nitrogenous graphene quantum dot consumption of yellow fluorescence is 5 ~ 20 mg, the ammonia soln consumption of 28wt% is 0.05 ~ 1mL, hydro-thermal reaction 2 ~ 24 h in baking oven again, oven temperature is 150 ~ 220
oC obtains having the graphene quantum dot composite particles of the unique morphology of different fluorescence.
The preparation of the nitrogenous graphene quantum dot composite particles of the unique morphology that embodiment 2. fluorescence are controlled.
" polyacrylonitrile carbon fiber that 1g processed " in embodiment 1 changed into " polyacrylonitrile carbon fiber that 2g processed ", and other condition of preparation obtains being similar to the product of embodiment 1 with embodiment 1.
The preparation of the nitrogenous graphene quantum dot composite particles of the unique morphology that embodiment 3. fluorescence are controlled.
" 65～68% concentrated nitric acids of 100 mL " in embodiment 1 are changed into " 65～68% concentrated nitric acids of 200 mL ", and other condition of preparation obtains being similar to the product of embodiment 1 with embodiment 1.
The preparation of the nitrogenous graphene quantum dot composite particles of the unique morphology that embodiment 4. fluorescence are controlled.
" the nitrogenous graphene quantum dot consumption of yellow fluorescence is 5 ~ 20 mg " in embodiment 1 changed into " the nitrogenous graphene quantum dot consumption of yellow fluorescence is 20 ~ 100 mg ", and other condition of preparation obtains being similar to the product of embodiment 1 with embodiment 1.
The preparation of the nitrogenous graphene quantum dot composite particles of the unique morphology that embodiment 5. fluorescence are controlled.
" the ammonia soln consumption of 28wt% is 0.05 ~ 1 mL " in embodiment 1 changed into " the ammonia soln consumption of 28wt% is 1ml ~ 1.5 mL ", and other condition of preparation obtains being similar to the product of embodiment 1 with embodiment 1.
Claims (6)
1. the preparation method of a nitrogenous graphene quantum dot composite particles is characterized in that concrete steps are:
(1) raw materials pretreatment:
PAN-based carbon fiber is placed in muffle furnace under argon gas atmosphere protection 350 ~ 500
oC temperature lower calcination 0.5 ~ 2 h is down to subsequently room temperature and takes out, the PAN-based carbon fiber of the sizing agent that is removed;
(2) prepare nitrogenous graphene quantum dot:
1～2 g polyacrylonitrile carbon fiber of processing is scattered in 65 ~ 68% concentrated nitric acids of 100～200 mL, supersound process 1 ~ 5 h, then in 100 ~ 150
o24 ~ 72 h reflux under C, after being cooled to room temperature, the concentrated nitric acid solution underpressure distillation is reclaimed, add the water of 30 ~ 100 mL and the ammoniacal liquor of 1 ~ 10 mL to regulate pH value for neutral in product, centrifugal 10 ~ 30 min under 5000 ~ 9000 rpm, dialyse mixing solutions and obtain the nitrogenous graphene quantum dot of yellow fluorescence again;
(3) the graphene quantum dot composite particles of the surperficial special appearance of preparation:
The nitrogenous graphene quantum dot of the yellow fluorescence that step (2) is obtained and the ammonia soln of 28wt% join in 20 ~ 100 mL water, the nitrogenous graphene quantum dot consumption of yellow fluorescence is 5 ~ 100 mg, the ammonia soln consumption of 28wt% is 0.05 ~ 1.5 ml, be placed in baking oven hydro-thermal reaction 2 ~ 24 h, oven temperature is 150 ~ 220
oC just obtains having the graphene quantum dot composite particles of the unique morphology of different fluorescence.
2. the preparation method of nitrogenous graphene quantum dot according to claim 1, is characterized in that described PAN-based carbon fiber is powdered for grinding after carbon fiber is shredded.
3. the preparation method of nitrogenous graphene quantum dot according to claim 1, the nitrogenous graphene quantum dot that it is characterized in that described yellow fluorescence is that median size is the single-layer graphene quantum dot of 35 nm.
4. the preparation method of nitrogenous graphene quantum dot according to claim 1, is characterized in that described dialysis is cut-off molecular weight: 1000～10000Da.
5. the preparation method of nitrogenous graphene quantum dot according to claim 1, is characterized in that prepared composite particles is a series of fluorescence between gold-tinted and blue light.
6. the preparation method of nitrogenous graphene quantum dot according to claim 1, is characterized in that prepared composite particles is the pattern that flake graphite alkene quantum dot area load a large amount of globular graphite alkene quantum dots.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104150473A (en) * | 2014-08-04 | 2014-11-19 | 江苏大学 | Chemical preparation method for nitrogen-doped graphene quantum dot |
| CN104401981A (en) * | 2014-11-10 | 2015-03-11 | 朱熹 | Preparation method of nitrogen-containing oxidative graphene quantum dot capable of giving off fluorescence in three primary colors |
| CN104861967A (en) * | 2015-04-14 | 2015-08-26 | 中国工程物理研究院化工材料研究所 | Preparation method and application of nitrogen-doped graphene quantum dots |
| CN105502356A (en) * | 2015-12-18 | 2016-04-20 | 上海交通大学 | Method for preparing graphene quantum dots from sp<2>-hybridized carbon materials |
| CN107431211A (en) * | 2014-11-06 | 2017-12-01 | 威廉马歇莱思大学 | By the method for various carbon sources manufacture graphene quantum dot |
| CN108097245A (en) * | 2017-11-13 | 2018-06-01 | 天津宝兴威科技股份有限公司 | A kind of preparation method of graphene quantum dot load Nano silver grain |
| CN111019650A (en) * | 2019-12-17 | 2020-04-17 | 中原工学院 | Synthesis method and application of red fluorescent carbon dots |
| CN113238047A (en) * | 2021-05-10 | 2021-08-10 | 深圳市光明区疾病预防控制中心 | Graphene quantum dot immunochromatography test strip for rapidly detecting Escherichia coli O157H 7 |
-
2013
- 2013-02-19 CN CN2013100528677A patent/CN103113887A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| YAN LI等: "Nitrogen-doped Graphene Quantum Dots with Oxygen-rich Functional Groups", 《JACS》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104150473A (en) * | 2014-08-04 | 2014-11-19 | 江苏大学 | Chemical preparation method for nitrogen-doped graphene quantum dot |
| CN107431211A (en) * | 2014-11-06 | 2017-12-01 | 威廉马歇莱思大学 | By the method for various carbon sources manufacture graphene quantum dot |
| CN104401981A (en) * | 2014-11-10 | 2015-03-11 | 朱熹 | Preparation method of nitrogen-containing oxidative graphene quantum dot capable of giving off fluorescence in three primary colors |
| CN104861967A (en) * | 2015-04-14 | 2015-08-26 | 中国工程物理研究院化工材料研究所 | Preparation method and application of nitrogen-doped graphene quantum dots |
| CN105502356A (en) * | 2015-12-18 | 2016-04-20 | 上海交通大学 | Method for preparing graphene quantum dots from sp<2>-hybridized carbon materials |
| CN108097245A (en) * | 2017-11-13 | 2018-06-01 | 天津宝兴威科技股份有限公司 | A kind of preparation method of graphene quantum dot load Nano silver grain |
| CN111019650A (en) * | 2019-12-17 | 2020-04-17 | 中原工学院 | Synthesis method and application of red fluorescent carbon dots |
| CN111019650B (en) * | 2019-12-17 | 2022-11-01 | 中原工学院 | Synthesis method and application of red fluorescent carbon dots |
| CN113238047A (en) * | 2021-05-10 | 2021-08-10 | 深圳市光明区疾病预防控制中心 | Graphene quantum dot immunochromatography test strip for rapidly detecting Escherichia coli O157H 7 |
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Application publication date: 20130522 |