CN110257059A - A kind of biomass-based graphene quantum dot and its preparation method and application - Google Patents
A kind of biomass-based graphene quantum dot and its preparation method and application Download PDFInfo
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- CN110257059A CN110257059A CN201910548937.5A CN201910548937A CN110257059A CN 110257059 A CN110257059 A CN 110257059A CN 201910548937 A CN201910548937 A CN 201910548937A CN 110257059 A CN110257059 A CN 110257059A
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Abstract
The invention belongs to food and medicine anti-counterfeit field, a kind of biomass-based graphene quantum dot and its preparation method and application is disclosed.The biomass-based graphene quantum dot is will be in 2- aminobenzenesulfonic acid or p-methyl benzenesulfonic acid dissolution deionized water, it is then heated to 70~90 DEG C, it stirs evenly, alkali lignin is added to keep the temperature at 70~90 DEG C, acquired solution water system membrane filtration, filtrate is collected, lye is added to ultrasound in filtrate, in 180~220 DEG C of progress hydro-thermal reactions；Then acquired solution is filtered using water system filter membrane, collects filtrate, places it in the bag filter of retention, dialyse in deionized water, then carried out freeze-drying and be made.The present invention is not required to by high temperature pyrolysis technique, and safety easy to operate, process flow is short, low in cost, simple and effective.The biomass-based graphene quantum dot of the present invention has the advantages that good biocompatibility, low bio-toxicity and excellent photoluminescence performance, can be applied to food and medicine anti-counterfeit field.
Description
Technical field
The invention belongs to food and medicine field of anti-counterfeit technology, more particularly, to a kind of biomass-based graphene quantum dot
And its preparation method and application.
Background technique
Today's society fake and forged commodity event frequency shows space in a newspaper, this hope for pursuing high-quality life with people runs in the opposite direction, because
This, studies practical and reliable advanced anti-fake material and has received the extensive concern of domestic and foreign scholars, especially needle
For these fields closely bound up with our life of food and medicine.The anti-counterfeit measures of mainstream are numerous at present, wherein most common
Be using have luminescence generated by light behavior antifalsification label.With science and technology make rapid progress, this antifalsification label due to
Technology content is cheap, poor biocompatibility and increasingly denounced by people.To find more structurally sound antifalsification label material
Sight has been turned to field of nanometer material technology by material, people.Recent studies suggest that with excellent quantum hall effect and fluorescence property
Graphene quantum dot is expected into be applied as anti-fake material.However, the big over-borrowing of preparation process of graphene quantum dot at present
High temperature pyrolysis technology is helped, with high costs and complicated for operation, biocompatibility and practical application performance also need to be investigated.To sum up
Described, there are following technical problems for the research based on graphene quantum dot material developing food products drug anti-fake material: first, at
This is higher；Second, biocompatibility is to be improved；Its considerable fluorescence property is applied to the feasibility of anti-counterfeit field by third
It needs to assess.Based on the above status, finding a kind of prepare using the good raw material of cheap and biocompatibility can be applied to food
The method of the graphene quantum dot with excellent photoluminescence performance in anti-drug counterfeiting field is most important.
Summary of the invention
In order to solve above-mentioned the shortcomings of the prior art, primary and foremost purpose of the present invention is to provide a kind of biomass
Base graphene quantum dot.The good and excellent photoluminescence performance of the quanta point biological compatibility.
Another object of the present invention is to provide the preparation methods of above-mentioned biomass-based graphene quantum dot.The preparation method
Biomass-based graphene quantum dot is quickly and easily prepared by two-step method.
A further object of the present invention is to provide the applications of above-mentioned biomass-based graphene quantum dot.
The purpose of the present invention is realized by following technical proposals:
A kind of biomass-based graphene quantum dot, the biomass-based graphene quantum dot be by 2- aminobenzenesulfonic acid or
P-methyl benzenesulfonic acid dissolves in deionized water, is then heated to 70~90 DEG C, stirs evenly, and alkali lignin is added and protects at 70~90 DEG C
Temperature, acquired solution water system membrane filtration collect filtrate, lye are added to ultrasound in filtrate, in 180~220 DEG C of progress water
Thermal response；Then gained is filtered using water system filter membrane, collects filtrate, places it in the bag filter of retention, in deionized water
Middle dialysis, then carry out freeze-drying and be made.
Preferably, the 2- aminobenzenesulfonic acid or p-methyl benzenesulfonic acid and the mass ratio of deionized water are 1:(4~19)；Institute
The mass ratio of the alkali lignin and 2- aminobenzenesulfonic acid or p-methyl benzenesulfonic acid stated is (1~4): 4；The lye and 2- amino phenyl sulfonyl
The molar ratio of acid or p-methyl benzenesulfonic acid is (0.9~1): 1.
Preferably, the lye is sodium hydrate aqueous solution, hydrazine hydrate or ammonium hydroxide.
Preferably, the time of the heat preservation is 2~3h；The power of the ultrasound is 700~900W, the time of the ultrasound
For 1.5~2.5h, the time of the hydro-thermal reaction is 10~14h.
Preferably, the rate of the stirring is 300~400r/min.
Preferably, the time of the dialysis is 5~7 days.
Preferably, the molecular weight for matter of dialysing in the bag filter of the retention is 1000~1500.
Preferably, the aperture of the water system filter membrane is 0.8 μm or 0.45 μm.
The preparation method of the biomass-based graphene quantum dot, comprises the following specific steps that:
S1. by 2- aminobenzenesulfonic acid or p-methyl benzenesulfonic acid dissolution deionized water, 70~90 DEG C are then heated to, stirring is equal
It is even, alkali lignin is added and is kept the temperature at 70~90 DEG C, acquired solution water system membrane filtration collects filtrate, lye is added to filter
It is ultrasonic in liquid, in 180~220 DEG C of progress hydro-thermal reactions, obtain solution A；
S2. solution A is filtered using water system filter membrane, collects filtrate, places it in the bag filter of retention, in deionized water
Middle dialysis, then be freeze-dried, biomass-based graphene quantum dot is made.
Application of the biomass-based graphene quantum dot in the anti-counterfeit field that shines.
Compared with prior art, the invention has the following advantages:
1. biomass-based graphene quantum dot of the invention has good biocompatibility, biological non-toxicity, it is expected to answer
For many related fieldss including food and medicine including anti-fake.
2. the method that the present invention prepares biomass-based graphene quantum dot using two-step process, acid therein is to lignin knot
Ehter bond in structure is destroyed, and does not need to can be obtained by biomass-based graphene quantum by high temperature " thermal cracking " processing carbon source
A possibility that point, this method is environmentally protective, is effectively utilized cheap raw material, reduces environmental pollution.
Detailed description of the invention
Fig. 1 is the test chart that the resulting biomass-based graphene quantum dot of embodiment 3 is applied on filter paper.
Fig. 2 is the ultraviolet spectrogram and infrared spectrogram of the resulting biomass-based graphene quantum dot of embodiment 3.
Specific embodiment
The contents of the present invention are further illustrated combined with specific embodiments below, but should not be construed as limiting the invention.
Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.Except non-specifically
Illustrate, reagent that the present invention uses, method and apparatus is the art conventional reagents, method and apparatus.
Embodiment 1
1. the 2- aminobenzenesulfonic acid of 2g is dissolved in the deionized water of 8g, 80 DEG C are then heated to, is stirred evenly, then
The alkali lignin that 0.5g is added continues to keep former temperature 2h, obtains aterrimus solution；Solution is taken out, uses water system filter membrane mistake while hot
Filter collects filtrate, after liquid to be filtered is cooled to room temperature, filters to take filtrate again and be fitted into appropriate gauge hydrothermal reaction kettle liner, to
0.47g sodium hydroxide, ultrasound 2h after sealing are added in liner, then is transferred in 200 DEG C of baking ovens and keeps the temperature 10h progress hydro-thermal reaction.
2. after heat preservation, solution being taken out from liner, then further filter using water system filter membrane, filtrate being collected, by it
It is placed in the bag filter of 1000 molecular weight retention, dialysis 6 days in deionized water (daily to update), then transfer them to freezing and do
It is freeze-dried in dry machine, the lignin graphene quantum dot of solid state can be obtained.
Its biological (cell) toxicity index is tested using thiazolyl blue test method(s), with the 100 biomass-based graphene quantums of μ g/mL
Hydroponics Turnover of Mouse Peritoneal Macrophages is put, cell survival rate is more than 95% after 48hrs.
Embodiment 2
1. the 2- aminobenzenesulfonic acid of 2g is dissolved in the deionized water of 38g, 80 DEG C are then heated to, is stirred evenly, is connect
Be added 2g alkali lignin continue to keep former temperature 2h, obtain aterrimus solution；Solution is taken out, uses water system filter membrane mistake while hot
Filter collects filtrate, after liquid to be filtered is cooled to room temperature, filters to take filtrate again and be fitted into appropriate gauge hydrothermal reaction kettle liner, to
0.47g sodium hydroxide, ultrasound 2h after sealing are added in liner, then is transferred in 200 DEG C of baking ovens and keeps the temperature 12h progress hydro-thermal reaction.
2. after heat preservation, solution being taken out from liner, then further filter using water system filter membrane, filtrate being collected, by it
It is placed in the bag filter of 1000 molecular weight retention, dialysis 6 days in deionized water (daily to update), then transfer them to freezing and do
It is freeze-dried in dry machine to get the lignin graphene quantum dot of solid state is arrived.
Its biological (cell) toxicity index is tested using thiazolyl blue test method(s), with the 100 biomass-based graphene quantums of μ g/mL
Hydroponics Turnover of Mouse Peritoneal Macrophages is put, cell survival rate is more than 95% after 48hrs.
Embodiment 3
1. the 2- aminobenzenesulfonic acid of 2g is dissolved in the deionized water of 23g, 80 DEG C are then heated to, is stirred evenly, is connect
Be added 1.25g alkali lignin continue to keep former temperature 2h, obtain aterrimus solution；Solution is taken out, uses water system filter membrane while hot
Filtering collects filtrate, after liquid to be filtered is cooled to room temperature, filters to take filtrate again and be fitted into appropriate gauge hydrothermal reaction kettle liner,
0.47g sodium hydroxide, ultrasound 2h after sealing are added into liner, then is transferred in 200 DEG C of baking ovens and keeps the temperature 12h progress hydro-thermal reaction.
2. after heat preservation, solution being taken out from liner, then further filter using water system filter membrane, filtrate being collected, by it
It is placed in the bag filter of 1000 molecular weight retention, dialysis 6 days in deionized water (daily to update), then transfer them to freezing and do
It is freeze-dried in dry machine, the lignin graphene quantum dot of solid state can be obtained.
Its biological (cell) toxicity index is tested using thiazolyl blue test method(s), with the 100 biomass-based graphene quantums of μ g/mL
Hydroponics Turnover of Mouse Peritoneal Macrophages is put, cell survival rate is more than 95% after 48hrs.
Fig. 1 is the test chart that the resulting graphene quantum dot of the present embodiment is applied on filter paper.Wherein, (a) (b) is respectively
Before five months and present blank filter paper and the filter paper of graphene quantum dot in the present embodiment is coated, it can from Fig. 1
Out, the biomass-based graphene quantum dot of production is able to maintain prolonged stabilization, and superior performance.Fig. 2 is obtained by the present embodiment
Graphene quantum dot ultraviolet spectrogram and infrared spectrogram.Wherein, a is its ultraviolet spectrogram in Fig. 2, and pH is 3~13
In range, photoluminescence performance is all very stable, illustrates it with good environmental resistance；B is its fluorescence spectrum in Fig. 2
Figure, in 2~32min, photoluminescence performance is held essentially constant, and illustrates that graphene quantum dot is stablized with good long-range
Property.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination and simplify,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of biomass-based graphene quantum dot, which is characterized in that the biomass-based graphene quantum dot is by 2- ammonia
In base benzene sulfonic acid or p-methyl benzenesulfonic acid dissolution deionized water, 70~90 DEG C are then heated to, is stirred evenly, alkali lignin is added and exists
70~90 DEG C of heat preservations, acquired solution water system membrane filtration collect filtrate, lye is added in filtrate it is ultrasonic, 180~
220 DEG C of progress hydro-thermal reactions；Then acquired solution is filtered using water system filter membrane, collects filtrate, places it in the dialysis of retention
It in bag, dialyses in deionized water, then carries out freeze-drying and be made.
2. biomass-based graphene quantum dot according to claim 1, which is characterized in that the 2- aminobenzenesulfonic acid or
P-methyl benzenesulfonic acid and the mass ratio of deionized water are 1:(4~19)；The alkali lignin and 2- aminobenzenesulfonic acid or to toluene
The mass ratio of sulfonic acid is (1~4): 4；The molar ratio of the lye and 2- aminobenzenesulfonic acid or p-methyl benzenesulfonic acid is (0.9~1):
1。
3. biomass-based graphene quantum dot according to claim 1, which is characterized in that the lye is sodium hydroxide water
Solution, hydrazine hydrate or ammonium hydroxide.
4. biomass-based graphene quantum dot according to claim 1, which is characterized in that the time of the heat preservation be 2~
3h；The power of the ultrasound is 700~900W, and the time of the ultrasound is 1.5~2.5h, and the time of the hydro-thermal reaction is 10
~14h.
5. biomass-based graphene quantum dot according to claim 1, which is characterized in that the rate of the stirring is 300
~400r/min.
6. biomass-based graphene quantum dot according to claim 1, which is characterized in that the time of the dialysis is 5~7
It.
7. biomass-based graphene quantum dot according to claim 1, which is characterized in that in the bag filter of the retention thoroughly
The molecular weight for analysing matter is 1000~1500.
8. biomass-based graphene quantum dot according to claim 1, which is characterized in that the aperture of the water system filter membrane is
0.8 μm or 0.45 μm.
9. the preparation method of biomass-based graphene quantum dot according to claim 1-8, which is characterized in that packet
Include following specific steps:
S1. by 2- aminobenzenesulfonic acid or p-methyl benzenesulfonic acid dissolution deionized water, 70~90 DEG C is then heated to, is stirred evenly,
Alkali lignin is added to keep the temperature at 70~90 DEG C, acquired solution water system membrane filtration collects filtrate, lye is added in filtrate
Ultrasound obtains solution A in 180~220 DEG C of progress hydro-thermal reactions；
S2. solution A is filtered using water system filter membrane, collects filtrate, places it in the bag filter of retention, in deionized water thoroughly
Analysis, then be freeze-dried, biomass-based graphene quantum dot is made.
10. application of the described in any item biomass-based graphene quantum dots of claim 1-8 in the anti-counterfeit field that shines.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110589813A (en) * | 2019-10-08 | 2019-12-20 | 杭州高烯科技有限公司 | Preparation method of three-dimensional graphene |
| CN111039280A (en) * | 2019-12-16 | 2020-04-21 | 华南理工大学 | Lignin-based graphene quantum dot and preparation method and application thereof |
-
2019
- 2019-06-24 CN CN201910548937.5A patent/CN110257059A/en not_active Withdrawn
Non-Patent Citations (2)
| Title |
|---|
| WANG RUIBIN: "Direct transformation of lignin into fluorescence-switchable graphene quantum dots and their application in ultrasensitive profiling of a physiological oxidant", 《GREEN CHEMISTRY》 * |
| ZHEYUAN DING: "Gram-scale synthesis of single-crystalline graphene quantum dots derived from lignin biomass", 《GREEN CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110589813A (en) * | 2019-10-08 | 2019-12-20 | 杭州高烯科技有限公司 | Preparation method of three-dimensional graphene |
| CN111039280A (en) * | 2019-12-16 | 2020-04-21 | 华南理工大学 | Lignin-based graphene quantum dot and preparation method and application thereof |
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