CN115849358A - Amination modification method of graphene quantum dots and product thereof - Google Patents
Amination modification method of graphene quantum dots and product thereof Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000005576 amination reaction Methods 0.000 title claims abstract description 11
- 238000002715 modification method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000002096 quantum dot Substances 0.000 claims abstract description 20
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 5
- -1 amino modified graphene quantum dots Chemical class 0.000 claims abstract description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000502 dialysis Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 101710134784 Agnoprotein Proteins 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 125000001749 primary amide group Chemical group 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 7
- 150000003140 primary amides Chemical class 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract description 2
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 6
- 238000007167 Hofmann rearrangement reaction Methods 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 230000002862 amidating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Abstract
The invention discloses an amination modification method of graphene quantum dots and a product thereof, and the method comprises the following steps: (1) Neutralizing the graphene quantum dot dispersion liquid with carboxyl on the surface by ammonia water, and adding ammonium chloride; (2) Evaporating the dispersion liquid obtained in the step (1) to dryness and converting carboxyl on the surface of the graphene quantum dot into primary amide; (3) Re-dispersing the solid obtained in the step (2) and adding sodium hypobromite under the protection of an ice bath; (4) And filtering and dialyzing the reaction solution to obtain the amino modified graphene quantum dots. The reaction device is simple and has mild conditions. The existence form of nitrogen atoms in the product is clear.
Description
Technical Field
The invention relates to the field of carbon nanomaterials, in particular to a graphene quantum dot, and particularly relates to an amination modification method and an amination modification product of the graphene quantum dot.
Background
Graphene quantum dots are graphene nanoplatelets with lateral dimensions less than 100 nanometers, and various physicochemical properties of the graphene quantum dots are closely related to heteroatoms on the surface (Li B, wang Y, huang L, et al. View of performance improvement strategies for doped graphene quanta dots for fluorescent-based sensing [ J ]. Synthetic Metals, 2021, 276: 116758.). Nitrogen atom doped graphene quantum dots particularly have high catalytic and fluorescence activities and are widely concerned (Kaur M, kaur M, sharma V K. Nitrogen-doped graphene and graphene quantum dots: A new synthesis and applications in energy, sensors and environment [ J ]. Advances in colloidal and interface science, 2018, 259: 44-64.). In the preparation stage or after preparation, nitrogen atoms can be introduced into the graphene quantum dots through radical reaction under the conditions of high temperature, strong oxidant and the like, but the nitrogen introduced by the method often has various forms, such as pyridine form, amino group and the like, which is not favorable for more finely researching the function of the nitrogen atoms in the graphene quantum dots.
The Hofmann rearrangement reaction (Hofmann rearrangement) is a reaction of rearranging a primary amide to a corresponding primary amine in the presence of a hypohalite, and the general reaction formula can be represented as:
R-CO-NH 2 + NaOX + 2NaOH → R-NH 2 +Na 2 CO 3 + NaX +H 2 O （1）
this reaction is also referred to as hofmann degradation because it removes the carbonyl group located between the carbon backbone and the amine group, which is a "carbon reduction" reaction. Since the amine as a product is relatively fragile and is easily further oxidized into a nitroso group or a nitro group by hypohalite at a high temperature, the hofmann rearrangement reaction requires strict control of the reaction temperature.
Disclosure of Invention
Aiming at the problem that the form of nitrogen atoms in nitrogen-doped graphene quantum dots is not easy to control, the invention aims to provide an amination modification method of the graphene quantum dots, which is a method for amidating and modifying the graphene quantum dots and then converting amide groups into amido groups.
The purpose of the invention is realized by the following scheme: an amination modification method of graphene quantum dots comprises the following steps:
(1) Dispersing graphene quantum dots containing carboxyl in water;
(2) Adding ammonia water into the dispersion liquid obtained in the step (1) to neutralize the acidity of the dispersion liquid, and additionally adding ammonium chloride as a nitrogen source;
(3) Heating and drying the dispersion liquid obtained in the step (2) to dryness so as to convert carboxyl on the surface of the graphene quantum dot into a primary amide group;
(4) Adding the solid obtained in the water dispersion step (3) again, controlling the temperature, adding the newly prepared sodium hypobromite, and stirring quickly;
(5) Stopping AgNO from the reaction liquid obtained in the dialysis step (4) to the external liquid 3 And precipitating the solution, and obtaining the amino modified graphene quantum dots in a dialysis bag.
Preferably, the concentration of the graphene quantum dots in the step (1) is 0.4 g L -1 。
Preferably, the temperature in step (3) is controlled to 65 ℃.
Preferably, the permeability of the dialysis bag in step (6) is 14000 molecular weight.
In the step (4), the reaction temperature is controlled to be 0 ℃, and the reaction time is 1 h.
The invention provides an aminated modified graphene quantum dot prepared by any one of the methods.
The mechanism of the invention is as follows: converting carboxyl into amino by utilizing a Hofmann rearrangement reaction on the surface of the graphene quantum dot, firstly converting the carboxyl on the surface of the graphene quantum dot into primary amide, expressing the graphene quantum dot by GOD, and in the step (2):
GQD-COOH + NH 3 → GQD-COONH 4 （2）
the reaction is a reversible reaction.
Further converted to a primary amide in step (3) according to the formula:
GQD-COONH 4 → GQD-CO-NH 2 + H 2 O (↑) (3)
GQD-COOH + NH 4 Cl → GQD-CO-NH 2 + H 2 O (↑) + HCl (↑) (4)
in the condition of evaporation to dryness, water and hydrogen chloride molecules are continuously distilled out by utilizing the volatility of the water and the hydrogen chloride molecules, so that the reactions (3) and (4) are fully shifted to the right, and the conversion rate is improved. The infrared spectrum of the product shows that two adjacent carboxyl groups at a higher reaction temperature are easy to generate side reaction to generate more stable cyclic diimide, the generation of the substance can cause the reduction of the conversion rate of amine groups, and therefore, the evaporation process must be controlled at a lower temperature.
In the step (4), carrying out Hofmann rearrangement on primary amide on the surface of the graphene quantum dot to generate an amino group:
GQD-COONH 2 + NaBrO + 2NaOH → GQD-NH 2 + Na 2 CO 3 + NaBr + H 2 O (5)
the generated aminated graphene quantum dots have better dispersibility and can be recycled through dialysis.
Under the technical background, aiming at the problem that the form of nitrogen atoms in the nitrogen-doped graphene quantum dots is not easy to control, the invention provides an amination modification method of the graphene quantum dots, and the method has the advantages that:
(1) The reaction device is simple, and the conditions are mild;
(2) The existence form of nitrogen atoms in the product is clear.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Preparing graphene quantum dots: 100 mg of commercially available graphene oxide powder was dispersed in 100 mL of water, and 1 mL of 100 mg L of the solution was added -1 Stirring the manganese acetate solution for 2 hours; adding 200 uL of 30% hydrogen peroxide sold in the market, continuously stirring and heating until the solution is boiled, keeping boiling for 20 min, stopping stirring, performing ultrasonic treatment for 10 h, filtering the reaction solution with a 0.1 um filter membrane, and adding graphene quantum dots in the filtrate
Example 1.
The preparation method comprises the following steps of preparing an amino-modified graphene quantum dot by taking newly prepared sodium hypobromite as a Hoffman reagent:
(1) Dispersing 0.02 g of the graphene quantum dots in 50 mL of pure water at room temperature, and performing ultrasonic dispersion to obtain a graphene quantum dot dispersion liquid;
(2) Adding commercial concentrated ammonia water into the dispersion liquid obtained in the step (1) until the pH value of the solution is reached>7 to neutralize the acidity and 0.1 mL of 10 g L -1 Stirring the ammonium chloride for 15 min to serve as a nitrogen source;
(3) Transferring all the liquid obtained in the step (2) into a glass evaporation dish, keeping the temperature at 65 ℃ for drying until the moisture is completely disappeared, keeping the temperature for continuously drying for 0.5 h, and converting the carboxyl on the surface of the graphene quantum dot into a primary amide group;
(4) Dissolving 0.25 g of sodium hydroxide and 80 uL of liquid bromine in 5 mL of water at room temperature, stirring for 0.5 h, and cooling to 0 deg.C in a refrigerator ， Obtaining freshly prepared sodium hypobromite as a Hofmann reagent; adding 30 mL of pure water into the solid obtained in the step (3), cooling the solid to 0 ℃ in an ice-salt bath, adding newly prepared sodium hypobromite under the protection of an ice bath, quickly stirring the mixture for 15 min, placing the mixture in a refrigerator, and reacting the mixture for 1 h at 0 ℃;
(5) And (3) product purification: the reaction solution obtained in step (4) was stirred at room temperature, and 5 g L of the reaction solution was added -1 The sodium sulfite solution does not discolor the starch potassium iodide test paper until the reaction solution, the reaction solution is placed in a 14000 molecular weight dialysis bag for dialysis until the external solution is not mixed with 17 g L of the external solution -1 AgNO 3 And precipitating the solution, and obtaining the amino modified graphene quantum dots in a dialysis bag.
The above examples are merely illustrative for clearly illustrating the present invention and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (6)
1. An amination modification method of graphene quantum dots is characterized by comprising the following steps:
(1) Dispersing graphene quantum dots containing carboxyl in water;
(2) Adding ammonia water into the dispersion liquid obtained in the step (1) to neutralize the acidity of the dispersion liquid, and adding ammonium chloride as a nitrogen source;
(3) Heating and drying the dispersion liquid obtained in the step (2) to dryness so as to convert carboxyl on the surface of the graphene quantum dot into a primary amide group;
(4) Adding the solid obtained in the water dispersion step (3) again, adding sodium hypobromite under the protection of ice bath, and stirring quickly;
(5) The AgNO is not caused to be any longer from the reaction liquid obtained in the dialysis step (4) to the external liquid 3 And precipitating the solution, and obtaining the amino modified graphene quantum dots in a dialysis bag.
2. The amination modification method of graphene quantum dots according to claim 1, wherein the graphene quantum dots in the step (1) have a concentration of 0.4 g L -1 。
3. The amination modification method of graphene quantum dots according to claim 1, characterized in that,
in the step (3), the temperature for evaporation to dryness is 65 ℃.
4. The preparation method of the graphene quantum dot according to claim 1, wherein in the step (4), the reaction temperature is controlled to be 0 ℃ and the reaction time is 1 h.
5. The preparation method of the graphene quantum dot according to any one of claims 1 to 4, characterized by comprising the following steps:
(1) Dispersing 0.02 g of the graphene quantum dots in 50 mL of pure water at room temperature, and performing ultrasonic dispersion to obtain a graphene quantum dot dispersion liquid;
(2) Adding commercial concentrated ammonia water into the dispersion liquid obtained in the step (1) until the pH value of the solution is reached>7 to neutralize the acidity and 0.1 mL of 10 g L -1 Stirring the ammonium chloride for 15 min to serve as a nitrogen source;
(3) Transferring all the liquid obtained in the step (2) into a glass evaporation dish, keeping the temperature at 65 ℃ for drying until the moisture is completely disappeared, keeping the temperature for continuously drying for 0.5 h, and converting the carboxyl on the surface of the graphene quantum dot into a primary amide group;
(4) Dissolving 0.25 g of sodium hydroxide and 80 uL of liquid bromine in 5 mL of water at room temperature, stirring for 0.5 h, and cooling to 0 ℃ in a refrigerator to obtain newly prepared sodium hypobromite serving as a Hofmann reagent; adding 30 mL of pure water into the solid obtained in the step (3), cooling the solid to 0 ℃ in an ice salt bath, adding a Hofmann reagent under the protection of an ice bath, quickly stirring the mixture for 15 min, placing the mixture in a refrigerator, and reacting the mixture for 1 h at 0 ℃;
(5) And (3) purifying a product: the reaction solution obtained in step (4) was stirred at room temperature, and 5 g L of the reaction solution was added -1 Sodium sulfite solution does not discolor the potassium iodide starch test paper until the reaction solution, and the reaction solution is placed in a 14000 molecular weight dialysis bag for dialysis until the external solution does not react with 17 g L of the external solution -1 AgNO 3 And precipitating the solution, and obtaining the amino modified graphene quantum dots in a dialysis bag.
6. An aminated modified graphene quantum dot, characterized in that the aminated modified graphene quantum dot is prepared according to the method of any one of claims 1-5.
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| CN102616774A (en) * | 2012-04-12 | 2012-08-01 | 复旦大学 | Method for preparing graphene quantum dot |
| CN102660270A (en) * | 2012-05-03 | 2012-09-12 | 吉林大学 | Method for preparing fluorescent graphene quantum dots by solvothermal method |
| WO2016045045A1 (en) * | 2014-09-25 | 2016-03-31 | 深圳粤网节能技术服务有限公司 | Method for preparing graphene quantum dots |
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| CN108300463A (en) * | 2018-01-30 | 2018-07-20 | 浙江理工大学 | A kind of amphipathic graphene quantum dot and its preparation method and application |
| CN112409228A (en) * | 2020-12-25 | 2021-02-26 | 西北师范大学 | Preparation method of chiral sulfur and nitrogen co-doped graphene quantum dot |
| CN115074125A (en) * | 2022-08-16 | 2022-09-20 | 广东省科学院微生物研究所(广东省微生物分析检测中心) | GSH-based fluorescent nanoprobe and synthesis method and application thereof |
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2022
- 2022-12-26 CN CN202211674697.1A patent/CN115849358A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102616774A (en) * | 2012-04-12 | 2012-08-01 | 复旦大学 | Method for preparing graphene quantum dot |
| CN102660270A (en) * | 2012-05-03 | 2012-09-12 | 吉林大学 | Method for preparing fluorescent graphene quantum dots by solvothermal method |
| WO2016045045A1 (en) * | 2014-09-25 | 2016-03-31 | 深圳粤网节能技术服务有限公司 | Method for preparing graphene quantum dots |
| WO2017214389A1 (en) * | 2016-06-10 | 2017-12-14 | Ecolab USA, Inc. | Fluorescent water treatment compounds and method of use |
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| CN112409228A (en) * | 2020-12-25 | 2021-02-26 | 西北师范大学 | Preparation method of chiral sulfur and nitrogen co-doped graphene quantum dot |
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