CN106809820B - Preparation and application of graphene quantum dot solution - Google Patents

Preparation and application of graphene quantum dot solution Download PDF

Info

Publication number
CN106809820B
CN106809820B CN201710012878.0A CN201710012878A CN106809820B CN 106809820 B CN106809820 B CN 106809820B CN 201710012878 A CN201710012878 A CN 201710012878A CN 106809820 B CN106809820 B CN 106809820B
Authority
CN
China
Prior art keywords
information
graphene quantum
quantum dot
preparation
ink
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710012878.0A
Other languages
Chinese (zh)
Other versions
CN106809820A (en
Inventor
孙友谊
王丛续
刘亚青
靳健丽
赵贵哲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
North University of China
Original Assignee
North University of China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by North University of China filed Critical North University of China
Priority to CN201710012878.0A priority Critical patent/CN106809820B/en
Publication of CN106809820A publication Critical patent/CN106809820A/en
Application granted granted Critical
Publication of CN106809820B publication Critical patent/CN106809820B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention belongs to the field of information materials, and particularly relates to preparation and application of a graphene quantum dot solution with a novel structure. Adding a phenol organic matter into absolute ethyl alcohol, completely dissolving, transferring to a hydrothermal reaction kettle, and reacting at 160-220 ℃ for 10-18 h to obtain a graphene quantum dot solution. Compared with the similar technology reported at present, the preparation and the application of the graphene quantum dot solution have the following technical effects: (1) compared with other nano fluorescent materials, the graphene quantum dots have the characteristics of easiness in preparation, low toxicity and low cost, so that the graphene quantum dots adopted as the confidential ink are low in cost and are green and environment-friendly. (2) The security ink prepared by the invention can adopt ink-jet printing, writing or printing modes, can conveniently encrypt and decrypt information, and has the advantages of convenient and easily obtained reagents and equipment required by encryption and decryption, and quick encryption and decryption time.

Description

Preparation and application of graphene quantum dot solution
Technical Field
The invention belongs to the field of information materials, and particularly relates to preparation and application of a graphene quantum dot solution with a novel structure.
Background
Because the luminescent-based secret ink is simple in decryption and encryption, the luminescent-based secret ink has wide application prospects in the fields of information security, information storage, anti-counterfeiting marks and the like, and therefore, the luminescent-based secret ink is widely concerned and researched in recent years. At present, materials for developing luminescent security ink mainly include organic dyes and compounds thereof, rare earth compounds, and the like. However, the organic dye and the compound thereof have the problems of poor luminous stability, weak luminous intensity, high biological toxicity and the like; rare earth compounds have the problems of great pollution, poor stability and the like in the preparation process, and the development and the application of the rare earth compounds are limited by the problems. Graphene quantum dots are recently emerging as nano luminescent materials, and are widely studied due to the characteristics of easy preparation, stable luminescence, low cost, low toxicity and the like. However, research on graphene quantum dots is mostly focused in the fields of catalysis, electrochemistry, biology and the like, and few reports are made on application research in the aspect of ink security. In addition, as security ink, graphene quantum dots have two bottleneck problems: (1) the pure graphene quantum dots are difficult to attach to a self-supporting medium, so that the stability of written information is poor, and the luminescence of the written information is weak; (2) how to realize the encryption and decryption modes with simple and environment-friendly secret information and high selectivity.
In order to solve the problems, the invention starts with the structural control of the graphene quantum dots and the writing medium, the prepared graphene quantum dot solution can adopt a spraying printing, printing or writing mode, and can also simply and highly selectively encrypt and decrypt information, thereby having wide application prospects in the fields of information confidentiality, information storage, anti-counterfeiting identification and the like.
Disclosure of Invention
The invention provides a preparation method and application of a graphene quantum dot solution, aiming at the problems of graphene quantum dots serving as confidential ink.
The invention is realized by the following technical scheme: a preparation method of a graphene quantum dot solution comprises the steps of adding a phenol organic matter into absolute ethyl alcohol, completely dissolving, transferring to a hydrothermal reaction kettle, and reacting for 10-18 hours at 160-220 ℃ to obtain the graphene quantum dot solution.
Preferably, the reaction concentration of the phenol organic substance is 10mg/ml to 200 mg/ml.
The phenol-based organic substance is preferably phenol or catechol. In practice, the present invention is not limited to the above-mentioned phenol-based organic compounds.
Further, the invention provides application of the graphene quantum dot solution prepared by the preparation method of the graphene quantum dot solution in preparation of security ink.
In addition, the invention provides the graphene quantum dot security ink which is prepared from the graphene quantum dot solution prepared by the preparation method of the graphene quantum dot solution.
In order to more clearly illustrate the technical content of the invention, the invention provides a preparation method of the graphene quantum dot security ink, the graphene quantum dot solution obtained by the preparation method of the graphene quantum dot solution is prepared into a solution with the graphene quantum dot concentration of 0.1-2.0 mg/ml, and the solution is the graphene quantum dot security ink.
Further, the invention provides an information security method, which is used for writing information needing to be kept secret on acid-treated wood fiber paper by adopting the graphene quantum dot security ink in a spraying, printing or writing mode to obtain an information carrier carrying the security information.
The acid treatment method of the wood fiber paper comprises the following steps: dipping in 35-50 wt% nitric acid for 1-2 hours, washing with clear water until the pH value is neutral, and drying. The wood fiber paper is made of organic flocculent fiber substances obtained by chemical treatment and mechanical processing of natural renewable wood. Preferably, the thickness of the paper is less than 500 μm.
Furthermore, the invention also provides an information encryption method, which comprises the step of immersing the information carrier (wood fiber paper written with the secret information) carrying the secret information into 0.5-2.0M acid until the secret information can not be seen under the irradiation of ultraviolet light, so as to obtain the information carrier carrying the encrypted information.
In a specific application, the acid used in the information encryption method is any weak acid, such as oxalic acid, acetic acid, and boric acid, and the invention includes, but is not limited to, the above acids.
Further, the invention provides an information decryption method, which comprises the step of immersing the information carrier (wood fiber paper written with the encrypted information) carrying the encrypted information into 0.3-1.5M sodium hydroxide solution until the confidential information can be seen under the irradiation of ultraviolet light.
Compared with the similar technology reported at present, the preparation and the application of the graphene quantum dot solution have the following technical effects:
(1) compared with other nano fluorescent materials, the graphene quantum dots have the characteristics of easiness in preparation, low toxicity and low cost, so that the graphene quantum dots adopted as the confidential ink are low in cost and are green and environment-friendly.
(2) The security ink prepared by the invention can adopt ink-jet printing, writing or printing modes, can conveniently encrypt and decrypt information, and has the advantages of convenient and easily obtained reagents and equipment required by encryption and decryption, and quick encryption and decryption time.
(3) Compared with other nanometer fluorescent materials, the information written by the graphene quantum dot security ink is good in structural stability, comprises acid and alkali resistance, temperature resistance, irradiation resistance and the like, can be stored for a long time, and cannot lose efficacy.
Test one: information temperature resistance and irradiation resistance research of graphene quantum dot security ink
1.1 after heating the lignocellulosic paper (acid-treated) on which the security information is written in an oven at 60 ℃ for 24 hours and then under UV irradiation for 24 hours, the symbol written on the lignocellulosic paper is "WCX", which exhibits a white color (shown as a in FIG. 1) of sufficient coloration under UV irradiation, and the information's luminous intensity is substantially constant throughout the irradiation.
1.2 after the lignocellulosic paper on which the security information is written is treated at-30 ℃ for 24 hours and then under ultraviolet radiation for 24 hours, the symbol written on the lignocellulosic paper is "WCX", which exhibits a white color (shown as b in FIG. 1) of sufficient coloration under ultraviolet radiation, and the information-emitting intensity is substantially constant throughout the irradiation.
1.3 the lignocellulosic paper on which the security information is written is immersed in an acid and then heated in an oven at 60 ℃ for 24 hours, after which the information remains encrypted after treatment under UV radiation for 24 hours (see c in FIG. 1). Further, by using alkali treatment for decryption, the information shows that the symbol written on the wood fiber paper is "WCX" and exhibits white color (as shown by d in fig. 1) with sufficient color development under the irradiation of ultraviolet light, and the luminous intensity is substantially unchanged.
In conclusion, the security ink and the written information have the advantages of temperature resistance and radiation resistance.
And (2) test II: written information storage research of graphene quantum dot security ink
The written symbol on the wood fiber paper is "WCX" under the irradiation of ultraviolet light, and the wood fiber paper with the secret information is white with enough color development under the ultraviolet lamp (as shown in a in figure 2). After further storage for one week, under the irradiation of ultraviolet light, the information still presents white color with enough color development (as shown in b in figure 2), and the luminous intensity of the information is basically unchanged before and after storage. Then, after being encrypted by acid treatment and stored for one week, the information is still in an encrypted state under the irradiation of ultraviolet light (as shown in c in fig. 2). And further decrypting by adopting alkali treatment, and displaying the information, wherein the luminous intensity of the information is basically consistent with that of the initial written information (shown as d in figure 2). It is shown that the security ink and the written information are stable and can be stored for a long time.
And (3) test III: acid and alkali resistance research of graphene quantum dot privacy ink
After the secret information is written on the wood fiber paper, the secret information is encrypted through acid treatment and decrypted through alkali treatment, and after circulation is carried out for 5 times, the luminous intensity of the information is basically consistent with that of the initially written information. It is said that the security ink and the written information have good acid and alkali resistance.
Drawings
FIG. 1 is a graph showing the research results of temperature resistance and irradiation resistance of information of the graphene quantum dot security ink.
FIG. 2 is a graph of the written information preservation research results of the graphene quantum dot security ink.
FIG. 3 is a UV-Vis spectrum of the security ink containing graphene quantum dots in example 1.
Fig. 4 is a diagram of a graphene quantum dot security ink in example 1 of the present invention. The liquid shown in the figure is a yellow fluorescent translucent solution.
Fig. 5 is a flowchart of information encryption and decryption in embodiment 1 of the present invention. Fig. a is a photograph of a lignocellulosic paper with security information written thereon under natural light. FIG. b is a photograph of a lignocellulosic paper bearing security information under UV light, the symbols written on the lignocellulosic paper being "NUC" and exhibiting a white color of sufficient coloration under UV light. Fig. c is a photograph of the lignocellulosic paper after the security information has been encrypted under uv light. Fig. d is a photograph of a lignocellulosic paper with encrypted information written thereon under uv light, the symbols written on the lignocellulosic paper being "NUC" and exhibiting a sufficiently colored white color under uv light.
Detailed Description
The invention is further illustrated by the following examples, which are intended to be illustrative of the invention and are not intended to be limiting. The experimental methods used in the experiment are all conventional methods, and the materials used in the experiment can be obtained from commercial sources.
Example 1
(1) Preparation of graphene quantum dot security ink
0.1g of o-diphenol is dissolved in 10ml of absolute ethyl alcohol, the obtained solution is placed in a polytetrafluoroethylene reaction kettle, and the reaction is carried out for 12 hours at 180 ℃ to obtain yellow fluorescent graphene quantum dot solution. Measuring 1ml of the obtained graphene quantum dot solution, and diluting with absolute ethyl alcohol to obtain the graphene quantum dot security ink (the concentration is 0.5 mg/ml), wherein the solution is nearly colorless.
(2) Use of graphene quantum dot security ink
The wood fiber paper is soaked in 35wt% nitric acid solution for 2 hours, then washed with clear water until the pH value is neutral, and dried. And (3) writing information needing to be kept secret on the wood fiber paper by dipping the graphene quantum dot secret ink with a writing brush. The secret information was encrypted with oxalic acid at a concentration of 1.0M and then decrypted with an aqueous solution of sodium hydroxide at a concentration of 0.8M.
Example 2
(1) Preparation of graphene quantum dot security ink
1g of phenol is dissolved in 10ml of absolute ethyl alcohol, the mixture is placed in a polytetrafluoroethylene reaction kettle, and the reaction is carried out for 18h at 180 ℃ to obtain yellow fluorescent graphene quantum dot solution. Measuring 1ml of the obtained graphene quantum dot solution, and diluting with absolute ethyl alcohol to obtain the graphene quantum dot security ink (the concentration is 0.1 mg/ml), wherein the solution is nearly colorless.
(2) Use of graphene quantum dot security ink
The wood fiber paper is soaked in 45wt% nitric acid solution for 1 hour, washed with clear water until the pH value is neutral, and dried. The information needing to be kept secret is printed on the wood fiber paper by dipping the graphene quantum dot secret ink with a writing brush and spraying. The secret information was encrypted with acetic acid at a concentration of 0.5M and then decrypted with an aqueous solution of sodium hydroxide at a concentration of 0.3M.
Example 3
(1) Preparation of graphene quantum dot security ink
2g of o-diphenol is dissolved in 10ml of absolute ethyl alcohol, the obtained solution is placed in a polytetrafluoroethylene reaction kettle, and the reaction is carried out for 10 hours at 220 ℃ to obtain yellow fluorescent graphene quantum dot solution. Measuring 1ml of the obtained graphene quantum dot solution, and diluting with absolute ethyl alcohol to obtain the graphene quantum dot security ink (the concentration is 2.0 mg/ml), wherein the solution is nearly colorless.
(2) Use of graphene quantum dot security ink
The wood fiber paper is soaked in 50wt% nitric acid solution for 1 hour, washed with clear water until the pH value is neutral, and dried. And (3) dipping the graphene quantum dot security ink with a writing brush to print information needing to be kept secret on the wood fiber paper. The secret information was encrypted with boric acid at a concentration of 2.0M and then decrypted with an aqueous solution of sodium hydroxide at a concentration of 1.5M.

Claims (3)

1. An information encryption method is characterized in that an information carrier carrying secret information is immersed in 0.5-2.0M acid until the secret information cannot be seen under the irradiation of ultraviolet light, and the information carrier carrying the secret information is obtained;
the preparation method of the information carrier carrying the encrypted information comprises the following steps: writing information needing to be kept secret on the wood fiber paper subjected to acid treatment by adopting graphene quantum dot secret ink in a spraying, printing or writing mode to obtain an information carrier carrying the secret information; the preparation method of the graphene quantum dot security ink comprises the following steps: adding a phenol organic matter into absolute ethyl alcohol, completely dissolving, transferring to a hydrothermal reaction kettle, reacting at 160-220 ℃ for 10-18 h to obtain a graphene quantum dot solution, and preparing the graphene quantum dot solution into a solution with the quantum dot concentration of 0.1-2.0 mg/ml, namely the graphene quantum dot security ink; the phenol organic matter is phenol or catechol; the acid treatment method of the wood fiber paper comprises the following steps: dipping in 35-50 wt% nitric acid for 1-2 hours, washing with clear water until the pH value is neutral, and drying.
2. The method according to claim 1, wherein the reaction concentration of the phenolic organic substance is 10mg/ml to 200 mg/ml.
3. A method for decrypting information, characterized in that an information carrier carrying encrypted information according to claim 1 or 2 is immersed in a 0.3 to 1.5M sodium hydroxide solution until the confidential information can be seen under the irradiation of ultraviolet light.
CN201710012878.0A 2017-01-09 2017-01-09 Preparation and application of graphene quantum dot solution Active CN106809820B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710012878.0A CN106809820B (en) 2017-01-09 2017-01-09 Preparation and application of graphene quantum dot solution

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710012878.0A CN106809820B (en) 2017-01-09 2017-01-09 Preparation and application of graphene quantum dot solution

Publications (2)

Publication Number Publication Date
CN106809820A CN106809820A (en) 2017-06-09
CN106809820B true CN106809820B (en) 2020-04-17

Family

ID=59110108

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710012878.0A Active CN106809820B (en) 2017-01-09 2017-01-09 Preparation and application of graphene quantum dot solution

Country Status (1)

Country Link
CN (1) CN106809820B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
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

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016118214A2 (en) * 2014-11-06 2016-07-28 William Marsh Rice University Methods of making graphene quantum dots from various carbon sources

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105349138A (en) * 2015-12-08 2016-02-24 安徽建筑大学 Preparation method for m-chlorophenol source hyper-fluorescent carbon dots

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016118214A2 (en) * 2014-11-06 2016-07-28 William Marsh Rice University Methods of making graphene quantum dots from various carbon sources

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Simple and Cost-Effective Synthesis of Fluorescent Graphene Quantum Dots from Honey: Application as Stable Security Ink and White-Light Emission;Sankarapilla Mahesh et al.;《Part. Part. Syst. Charact.》;20161231;第33卷;第73页右栏第2段及fig4 *

Also Published As

Publication number Publication date
CN106809820A (en) 2017-06-09

Similar Documents

Publication Publication Date Title
Li et al. A stimuli‐responsive smart lanthanide nanocomposite for multidimensional optical recording and encryption
Yu et al. Luminescence anti‐counterfeiting: from elementary to advanced
Liang et al. Lifetime‐engineered carbon nanodots for time division duplexing
Lou et al. Water‐Triggered luminescent “nano‐bombs” based on supra‐(carbon nanodots)
Tan et al. Time‐dependent phosphorescence colors from carbon dots for advanced dynamic information encryption
Zheng et al. Near‐infrared‐excited multicolor afterglow in carbon dots‐based room‐temperature afterglow materials
Li et al. Induction of long-lived room temperature phosphorescence of carbon dots by water in hydrogen-bonded matrices
Wang et al. Hybrid chloroantimonates (III): thermally induced triple‐mode reversible luminescent switching and laser‐printable rewritable luminescent paper
CN107746710B (en) Carbon nitride quantum dot and preparation method and application thereof
Chen et al. Facile synthesis of highly water‐soluble lanthanide‐doped t‐LaVO4 NPs for antifake ink and latent fingermark detection
Li et al. Surface ionization-induced tunable dynamic phosphorescence colors from carbon dots on paper for dynamic multimode encryption
Ji et al. An adaptable cryptosystem enabled by synergies of luminogens with aggregation‐induced‐emission character
Wang et al. Producing long afterglow by cellulose confinement effect: A wood-inspired design for sustainable phosphorescent materials
Du et al. Embellishment of upconversion nanoparticles with ultrasmall perovskite quantum dots for full‐color tunable, dual‐modal luminescence anticounterfeiting
CN106809820B (en) Preparation and application of graphene quantum dot solution
Juan et al. Near-infrared light-controlled circularly polarized luminescence of self-organized emissive helical superstructures assisted by upconversion nanoparticles
CN110982528B (en) Dual-mode fluorescent anti-counterfeiting material
CN104818653B (en) The ultraviolet light induced reusable paper of discoloration
Wan et al. Sustainable Afterglow Room‐Temperature Phosphorescence Emission Materials Generated Using Natural Phenolics
CN108070302B (en) Anti-counterfeiting ink with delayed fluorescence and application thereof
CN107209450A (en) The photocatalysis color switching of the redox imaging nano material of rewritable media
CN105344340B (en) A kind of non-metal carbon material catalyst and its preparation method and application
CN113444516A (en) Silicon dioxide/nitrogen-doped carbon nano composite and preparation method and application thereof
Hao et al. Durable room-temperature phosphorescence of nitrogen-doped carbon dots-silica composites for Fe3+ detection and anti-counterfeiting
Qiu et al. Ultraviolet and infrared excitable inorganic-organic hybrid materials: Synthesis, characterization and anti-counterfeiting applications

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant