CN106809820A - The preparation and its application of graphene quantum dot solution - Google Patents
The preparation and its application of graphene quantum dot solution Download PDFInfo
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- CN106809820A CN106809820A CN201710012878.0A CN201710012878A CN106809820A CN 106809820 A CN106809820 A CN 106809820A CN 201710012878 A CN201710012878 A CN 201710012878A CN 106809820 A CN106809820 A CN 106809820A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/132—Chemical colour-forming components; Additives or binders therefor
- B41M5/136—Organic colour formers, e.g. leuco dyes
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The invention belongs to information material field, the preparation and its application of specifically a kind of graphene quantum dot solution with new structure.Phenol type organic is added in absolute ethyl alcohol, after dissolving completely, is transferred in hydrothermal reaction kettle, 10 ~ 18h is reacted at 160 ~ 220 DEG C, obtain graphene quantum dot solution.The preparation and its application of graphene quantum dot solution of the present invention, compared with the similar technique of current report, have the following technical effect that:(1) compared to other nano-luminescent materials, the characteristics of graphene quantum dot has easy preparation, low toxicity, low cost, so using graphene quantum dot as secrecy ink low cost, and environmental protection.(2) secrecy ink prepared by the present invention can using inkjet printing, write or print by the way of, and can very easily enter the encryption and decryption of row information, including the reagent that needs of encryption and decryption and equipment are conveniently easy to get, and encrypt fast with decryption time.
Description
Technical field
The invention belongs to information material field, the preparation of specifically a kind of graphene quantum dot solution with new structure
And its application.
Background technology
Based on luminous secrecy ink because decrypt-encrypt is simple, in the neck such as information security, information Store, anti-counterfeiting mark
Domain has wide application prospect, thus obtains extensive concern and research recent years.It is presently used for developing luminous secrecy ink
Material mainly includes engine dyeing material and its compound, rare earth compound etc..But organic dyestuff and its compound are in the presence of luminous steady
The problems such as qualitative difference, luminous intensity are weaker, bio-toxicity is high;There is preparation process pollution greatly and less stable in rare earth compound
The problems such as, these problems limit their development and application.Graphene quantum dot is the nearest nano luminescent material for rising, by
The features such as its easily preparation, stable luminescence, low cost, hypotoxicity, it is widely studied.But, at present on graphene quantum dot
Research focus mostly in fields such as catalysis, electrochemistry, biologies, the rare report of application study in terms of secrecy ink.Additionally, stone
Also there are following two bottleneck problems as secrecy ink in black alkene quantum dot:(1)Pure graphene quantum dot is difficult to be attached to from branch
On support medium, cause the less stable of written information, and written information is luminous weaker;(2)How security information letter is realized
Encryption and the manner of decryption of list, environmental protection, and high selectivity.
Regarding to the issue above, the present invention starts with from the structure control of graphene quantum dot and writing medium, made Graphene
Quantum dot solution by the way of spraying printing, printing or writing, and can also can simply, highly selectively to information enter
Row encryption and decryption, will be with a wide range of applications in fields such as information privacy, information Store and anti-counterfeiting marks.
The content of the invention
The problem that the present invention exists for graphene quantum dot as secrecy ink, there is provided a kind of graphene quantum dot is molten
The preparation and its application of liquid.
The present invention is achieved by the following technical solutions:A kind of preparation method of graphene quantum dot solution, by phenol
Type organic is added in absolute ethyl alcohol, dissolving completely after, be transferred in hydrothermal reaction kettle, at 160 ~ 220 DEG C react 10 ~
18h, obtains graphene quantum dot solution.
Preferably, the reaction density of the phenol type organic is 10mg/ml ~ 200mg/ml.
In addition, the phenol type organic is preferably phenol or catechol.During specific implementation, the invention is not limited in
Foregoing phenol type organic.
Further, the invention provides the Graphene quantum that the preparation method of above-mentioned graphene quantum dot solution is prepared
Application of the point solution in secrecy ink is prepared.
In addition, the invention provides a kind of graphene quantum dot secrecy ink, the secrecy ink is molten graphene quantum dot
What the graphene quantum dot solution that the preparation method of liquid is prepared was prepared from.
For clearer explanation technology contents of the invention, this hair provides a kind of graphene quantum dot secrecy ink
Preparation method, the graphene quantum dot solution allocation obtained by the preparation method of graphene quantum dot solution is into graphene quantum dot
Concentration is the solution of 0.1 ~ 2.0mg/ml, as graphene quantum dot secrecy ink.
Further, the invention provides a kind of information security method, in warp in the way of spraying printing, print or write
The information of need for confidentiality is write on the wood fibre paper of peracid treatment using above-mentioned graphene quantum dot secrecy ink, is carried
There is the information carrier of security information.
Wherein, the acid treatment method of the wood fibre paper is:Impregnation process 1 ~ 2 hour in 35 ~ 50wt% nitric acid, it
It is neutral to be washed till pH with clear water afterwards, is dried.Wood fibre paper of the present invention is by chemistry by natural reproducible timber
The paper being made up of organic wadding fibrous material that reason, mechanical means processing are obtained.Preferably, the thickness of the paper is less than
500μm。
And then, present invention also offers a kind of information ciphering method, by the above-mentioned information carrier for being loaded with security information(Write
There is the wood fibre paper of security information)It is immersed in 0.5 ~ 2.0M acid, until can't see security information under the irradiation of ultraviolet light
Untill, acquisition is loaded with the information carrier of encryption information.
During concrete application, the acid employed in information ciphering method is any one weak acid, such as oxalic acid, acetic acid, boric acid, sheet
Invention is comprising upper but be not limited to above-mentioned acid.
Further, the invention provides a kind of decryption method of information, by the above-mentioned information carrier for being loaded with encryption information
(With the wood fibre paper of encryption information)It is immersed in 0.3 ~ 1.5M sodium hydroxide solutions, until can be in the irradiation of ultraviolet light
Down it can be seen that security information.
The preparation and its application of graphene quantum dot solution of the present invention, compared with the similar technique of current report, tool
There is following technique effect:
(1) compared to other nano-luminescent materials, the characteristics of graphene quantum dot has easy preparation, low toxicity, low cost, so adopting
With graphene quantum dot as secrecy ink low cost, and environmental protection.
(2) secrecy ink prepared by the present invention can using inkjet printing, write or print by the way of, and can be very convenient
The encryption and decryption of entering row information, including encryption and decryption need reagent and equipment be conveniently easy to get, encryption and decryption time
Hurry up.
(3) compared to other nano-luminescent materials, the message structure good stability that graphene quantum dot secrecy ink is write,
Including acid and alkali-resistance, heatproof, resistance to irradiation etc., and can for a long time preserve, will not fail.
Experiment one:The information heatproof of graphene quantum dot secrecy ink, resistance to radiation research
1.1 by with the wood fibre paper of security information(Through peracid treatment)Heated 24 hours in 60 DEG C of baking ovens, then ultraviolet
After being processed 24 hours under light radiation, the symbol write on wood fibre paper is " WCX ", is showed under ultraviolet radiation enough
The white of colour developing degree(As shown in a in Fig. 1), and information intensity of giving out light is basically unchanged in whole radiative process.
1.2 will be processed 24 hours with the wood fibre paper of security information at subzero 30 degree, then be located under ultraviolet radiation
After 24 hours, the symbol write on wood fibre paper is " WCX " to reason, and the white of colour developing degree enough is showed under ultraviolet radiation
Color(As shown in b in Fig. 1), and information intensity of giving out light is basically unchanged in whole radiative process.
1.3 will be immersed in acid with the wood fibre paper of security information, then be heated 24 hours in 60 DEG C of baking ovens, then
After being processed 24 hours under ultraviolet radiation, information remains at encrypted state(As shown in c in Fig. 1).Further using use
Alkali process are decrypted, and out, the symbol write on wood fibre paper is " WCX " to presentation of information, is showed under ultraviolet radiation
The white of colour developing degree enough(As shown in d in Fig. 1), luminous intensity is basically unchanged.
In summary it can be seen, this secrecy ink and the information write, with temperature tolerance, radiotolerant advantage.
Experiment two:The written information of graphene quantum dot secrecy ink preserves research
The wood fibre paper of security information is write under ultraviolet light, the symbol write on wood fibre paper is " WCX ",
The white of colour developing degree enough is showed under uviol lamp(As shown in a in Fig. 2).After further preserving one week, in ultraviolet light
Under, still show the white of colour developing degree enough(As shown in b in Fig. 2), before and after storage, information luminous intensity is basically unchanged.So
After encrypting and preserve one week through peracid treatment again afterwards, under ultraviolet light, information remains at encrypted state(Such as c institutes in Fig. 2
Show).Further decrypted using alkali process, out, information luminous intensity is basic with initial written information luminous intensity for presentation of information
Unanimously(As shown in d in Fig. 2).Illustrate that this secrecy ink and the information stability write can be preserved for a long time.
Experiment three:The acid and alkali-resistance research of graphene quantum dot secrecy ink
After writing security information on wood fibre paper, and after through acid treatment encrypt, further with alkali process decrypt, circulate 5 times
Afterwards, information luminous intensity is basically identical with initial written information luminous intensity.Illustrate, this secrecy ink and the information write are resistance to
Acid-base property is good.
Brief description of the drawings
Fig. 1 is information heatproof, the resistance to radiation research result figure of graphene quantum dot secrecy ink.
The written information of Fig. 2 graphene quantum dot secrecy inks preserves result of study figure.
Fig. 3 is the ultraviolet-visible spectrogram of graphene quantum dot secrecy ink in the embodiment of the present invention 1.
Fig. 4 is the pictorial diagram of graphene quantum dot secrecy ink in the embodiment of the present invention 1.Liquid shown in figure is that yellow is glimmering
The translucent solution of light.
Fig. 5 is the flow chart of information encryption and decryption in the embodiment of the present invention 1.Figure a is the wooden fibre with security information
Photo of the dimension paper under natural light irradiation.Figure b is photo of the wood fibre paper under ultraviolet light with security information, wood
The symbol write in matter fibrous paper is " NUC ", and the white of colour developing degree enough is showed under uviol lamp.Figure c is security information
The photo of wood fibre paper after encrypted under ultraviolet light.Figure d is the wood fibre paper with encryption information in purple
Photo under outer light irradiation, the symbol write on wood fibre paper is " NUC ", and colour developing degree enough is showed under uviol lamp
White.
Specific embodiment
The present invention is further described with reference to instantiation, following instance is intended to prove the present invention, rather than restriction
The present invention.And this experiment experimental technique used is conventional method, experiment material used is commercially obtained.
Embodiment 1
(1)Prepare graphene quantum dot secrecy ink
0.1g o-phenols are dissolved in 10ml absolute ethyl alcohols, are positioned in ptfe autoclave, 180 DEG C of reactions
12h, obtains the graphene quantum dot solution of yellow fluorescence.The graphene quantum dot solution that 1ml is obtained is measured, it is dilute with absolute ethyl alcohol
Release, as graphene quantum dot secrecy ink(Concentration is 0.5mg/ml), now solution is close to colourless.
(2)The use of graphene quantum dot secrecy ink
By wood fibre paper in 35wt% salpeter solutions impregnation process 2 hours, it is neutral to be washed till pH with clear water afterwards, is dried.With
Writing brush dips in the information that above-mentioned graphene quantum dot secrecy ink writes need for confidentiality on wood fibre paper.Use concentration for
The oxalic acid of 1.0M is encrypted to security information, is then decrypted with the sodium hydrate aqueous solution that concentration is 0.8M.
Embodiment 2
(1)Prepare graphene quantum dot secrecy ink
1g phenol is dissolved in 10ml absolute ethyl alcohols, is positioned in ptfe autoclave, 180 DEG C of reaction 18h are obtained
The graphene quantum dot solution of yellow fluorescence.The graphene quantum dot solution that 1ml is obtained is measured, is diluted with absolute ethyl alcohol, as
Graphene quantum dot secrecy ink(Concentration is 0.1mg/ml), now solution is close to colourless.
(2)The use of graphene quantum dot secrecy ink
By wood fibre paper in 45wt% salpeter solutions impregnation process 1 hour, it is neutral to be washed till pH with clear water afterwards, is dried.With
Writing brush dips in the information that above-mentioned graphene quantum dot secrecy ink sprays printing need for confidentiality on wood fibre paper.Using concentration
For the acetic acid of 0.5M is encrypted to security information, then it is decrypted with the sodium hydrate aqueous solution that concentration is 0.3M.
Embodiment 3
(1)Prepare graphene quantum dot secrecy ink
2g o-phenols are dissolved in 10ml absolute ethyl alcohols, are positioned in ptfe autoclave, 220 DEG C of reaction 10h,
Obtain the graphene quantum dot solution of yellow fluorescence.The graphene quantum dot solution that 1ml is obtained is measured, is diluted with absolute ethyl alcohol,
As graphene quantum dot secrecy ink(Concentration is 2.0mg/ml), now solution is close to colourless.
(2)The use of graphene quantum dot secrecy ink
By wood fibre paper in 50wt% salpeter solutions impregnation process 1 hour, it is neutral to be washed till pH with clear water afterwards, is dried.With
Writing brush dips in the information that above-mentioned graphene quantum dot secrecy ink prints need for confidentiality on wood fibre paper.Use concentration for
The boric acid of 2.0M is encrypted to security information, is then decrypted with the sodium hydrate aqueous solution that concentration is 1.5M.
Claims (10)
1. a kind of preparation method of graphene quantum dot solution, it is characterised in that phenol type organic is added to absolute ethyl alcohol
In, after dissolving completely, it is transferred in hydrothermal reaction kettle, 10 ~ 18h is reacted at 160 ~ 220 DEG C, obtain graphene quantum dot molten
Liquid.
2. a kind of preparation method of graphene quantum dot solution according to claim 1, it is characterised in that the phenol
The reaction density of organic matter is 10mg/ml ~ 200mg/ml.
3. a kind of preparation method of graphene quantum dot solution according to claim 1, it is characterised in that the phenol
Organic matter is preferably phenol or catechol.
4. the graphene quantum dot solution that claim 1 or 2 or 3 any claims are prepared is in secrecy ink is prepared
Using.
5. a kind of graphene quantum dot secrecy ink, it is characterised in that prepared by claim 1 or 2 or 3 any claims
What the graphene quantum dot solution of acquisition was prepared from.
6. a kind of preparation method of graphene quantum dot secrecy ink, it is characterised in that by any right of claim 1 or 2 or 3
It is required that the graphene quantum dot solution allocation that obtains of the preparation method into graphene quantum dot concentration be 0.1 ~ 2.0mg/ml's
Solution, as graphene quantum dot secrecy ink.
7. a kind of information security method, it is characterised in that through peracid treatment in the way of spraying printing, print or write
The information of need for confidentiality is write on wood fibre paper using the graphene quantum dot secrecy ink described in claim 5, is carried
There is the information carrier of security information.
8. a kind of information security method according to claim 7, it is characterised in that the acid treatment side of the wood fibre paper
Method is:Impregnation process 1 ~ 2 hour in 35 ~ 50wt% nitric acid, it is neutral to be washed till pH with clear water afterwards, is dried.
9. a kind of information ciphering method, it is characterised in that by the information carrier for the being loaded with security information immersion described in claim 8
To in 0.5 ~ 2.0M acid, untill it can't see security information under the irradiation of ultraviolet light, acquisition is loaded with the information of encryption information
Carrier.
10. a kind of decryption method of information, it is characterised in that by the information carrier for being loaded with encryption information described in claim 9
It is immersed in 0.3 ~ 1.5M sodium hydroxide solutions, until can be under the irradiation of ultraviolet light it can be seen that security information.
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Cited By (2)
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CN108946708A (en) * | 2018-07-02 | 2018-12-07 | 上海理工大学 | A kind of preparation method of high sensitivity graphene quantum dot ultraviolet detector |
CN113459692A (en) * | 2021-06-30 | 2021-10-01 | 陕西科技大学 | Preparation method of fluorescent anti-counterfeiting coating based on leather waste |
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WO2016118214A2 (en) * | 2014-11-06 | 2016-07-28 | William Marsh Rice University | Methods of making graphene quantum dots from various carbon sources |
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WO2016118214A2 (en) * | 2014-11-06 | 2016-07-28 | William Marsh Rice University | Methods of making graphene quantum dots from various carbon sources |
CN105349138A (en) * | 2015-12-08 | 2016-02-24 | 安徽建筑大学 | Preparation method for m-chlorophenol source hyper-fluorescent carbon dots |
Non-Patent Citations (2)
Title |
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SANKARAPILLA MAHESH ET AL.: "Simple and Cost-Effective Synthesis of Fluorescent Graphene Quantum Dots from Honey: Application as Stable Security Ink and White-Light Emission", 《PART. PART. SYST. CHARACT.》 * |
SANKARAPILLA MAHESH ET AL.: "Simple and Cost-Effective Synthesis of Fluorescent Graphene Quantum Dots from Honey: Application as Stable Security Ink and White-Light", 《PART. PART. SYST. CHARACT》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108946708A (en) * | 2018-07-02 | 2018-12-07 | 上海理工大学 | A kind of preparation method of high sensitivity graphene quantum dot ultraviolet detector |
CN113459692A (en) * | 2021-06-30 | 2021-10-01 | 陕西科技大学 | Preparation method of fluorescent anti-counterfeiting coating based on leather waste |
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