CN109181687A - A kind of rear-earth-doped NaYF4The preparation method and application of/carbon quantum dot double mode fluorescence nano composite material - Google Patents
A kind of rear-earth-doped NaYF4The preparation method and application of/carbon quantum dot double mode fluorescence nano composite material Download PDFInfo
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- CN109181687A CN109181687A CN201810836592.9A CN201810836592A CN109181687A CN 109181687 A CN109181687 A CN 109181687A CN 201810836592 A CN201810836592 A CN 201810836592A CN 109181687 A CN109181687 A CN 109181687A
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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
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
- C09K11/7773—Halogenides with alkali or alkaline earth metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
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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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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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
Abstract
The present invention relates to a kind of rear-earth-doped NaYF of nanocomposite technical field4The preparation method and applications of/carbon quantum dot double mode fluorescence nano composite material.The rear-earth-doped NaYF that cationic surfactant is modified4The aqueous dispersions of upper conversion nano particle are mixed with carbon quantum dot solution, lye, ethyl acetate and ethyl orthosilicate are then added into mixed solution, using sol-gel chemistry principle in rear-earth-doped NaYF4Particle surface coated silica shell, while carbon quantum dot being encapsulated in shell, core-shell nano-composite material is prepared.The aggregation that the preparation method efficiently avoids carbon quantum dot is quenched, and the optics of the composite material of preparation, chemical stability are good.The composite material of acquisition is prepared into ink, the composite material of preparation is applied in anti-counterfeit field by inkjet printing, has the characteristics of height concealment, the difficult replicability of double mode detection, antifalse effect is more preferably.
Description
Technical field
The present invention relates to nanocomposite technical fields, more particularly, to a kind of rear-earth-doped NaYF4/ carbon quantum
The preparation method and purposes of point double mode fluorescence nano composite material.
Background technique
Fluorescence falsification preventing technology is to resist personation, important means of poor quality, based on single rear-earth-doped up-conversion fluorescence material
The Antiforge fluorescent ink of material or carbon quantum dot fluorescent material, due to the transreplication of its single fluorescence mode be difficult to meet it is higher level
Anti-fake demand.Thus, occur the anti-forgery ink of double mode fluorescent material at present, is mainly by being excited in 980 nm
Up-conversion nanoparticles surface coats one layer of rear-earth-doped down-conversion fluorescent of up-conversion or cladding of one layer of 808 nm excitation
Material.Although this homogeneity crystal double mode fluorescent material performance is stablized, this material is usually high temperature pyrolysis legal system
It is standby, it needs accurately to control experiment condition, shell thickness, Doped ions ratio, preparation process is excessively complicated.Therefore, seek one kind
Easy double mode fluorescence composite material preparation method is most important.
Rear-earth-doped NaYF is prepared using hydro-thermal method in the prior art4With carbon quantum dot composite fluorescent material, two are combined
The fluorescent material that kind is had excellent performance, but there are, without strong interaction, carbon dots are easy to fall off between up-conversion and carbon quantum dot
The problems such as；And the spacing between carbon quantum dot is unable to control, and the phenomenon that aggregation is quenched easily occurs.In addition, this method preparation is compound
The size of material is larger, causes spray nozzle clogging for being very easy to when inkjet printing.Therefore, it is compound to seek a kind of suitable method
Rear-earth-doped NaYF4With carbon quantum dot material, the stability for improving composite material and the adaptation in inkjet printing fluorescence falsification preventing
Property is most important.
Summary of the invention
Aiming at the shortcomings in the prior art, the purpose of the present invention is to provide a kind of rear-earth-doped NaYF4/ carbon quantum dot is double
The preparation method of mode fluorescence nano composite material, and be used in anti-counterfeit field.
The purpose of the present invention is achieved through the following technical solutions:
A kind of rear-earth-doped NaYF4The preparation method of/carbon quantum dot double mode fluorescence nano composite material, specific preparation step
Are as follows:
S1. rare earth metal oleate presoma is prepared；
S2. rear-earth-doped NaYF is prepared4Upper conversion nano particle；
S3. carbon quantum dot is prepared；
S4. rear-earth-doped NaYF is prepared4/ carbon quantum dot double mode fluorescence nano composite material: by rear-earth-doped NaYF4Nanometer
After grain carries out Hydrophilic modification, it is mixed with carbon quantum dot solution, is added after ethyl acetate and mixed solution is adjusted using lye
PH value, ethyl orthosilicate is then added, stirs at room temperature to obtain the final product；
Wherein, rear-earth-doped NaYF described in step S24Upper conversion nano particle is prepared using high temperature pyrolytic cracking (HTP)；Step S3 institute
Stating carbon quantum dot is Water-soluble carbon quantum dot or alcohol-soluble carbon quantum dot.
Further, in step S4, the additional amount of the ethyl orthosilicate and rear-earth-doped NaYF4The quality of nano particle
Than for 3 ~ 5:1；The concentration of carbon quantum dot is 5 ~ 10 mg/mL in the mixed solution.
Further, the concrete operation step of rare earth metal oleate presoma is prepared described in step S1 are as follows: weigh rare earth
In a reservoir, water, ethyl alcohol and n-hexane is added in metal salt and enuatrol, stirs, and flow back 4 h at 70 DEG C, washes, obtains after cooling
Rare earth metal oleate presoma.
Further, rear-earth-doped NaYF is prepared described in step S24The concrete operation step of upper conversion nano particle are as follows: will
The rare earth metal oleate presoma of step S1 preparation is vacuumized to 140 DEG C and is removed with octadecylene, oleic acid mixing warming while stirring
Low boiling point solvent is removed, the methanol solution dissolved with sodium hydroxide and ammonium fluoride is added after being cooled to 50 DEG C, stirs 30 ~ 60min, rises
Temperature vacuumizes removing methanol to 110 DEG C, 300 ~ 310 DEG C is warming up under the protection of rare gas, 1 ~ 1.5h of heat preservation obtains rare earth
Adulterate NaYF4Particle uses the rear-earth-doped NaYF of ethanol precipitation after cooling4Particle, centrifugation, will be dilute using hexamethylene and ethanol washing
Soil doping NaYF4Upper conversion nano particle is dispersed in hexamethylene, spare；Prepared rear-earth-doped NaYF4Upper conversion nano
Grain coated with oleic acid.
Further, the rear-earth-doped NaYF4Nano particle is erbium thulium codope, ytterbium and erbium-codoped or ytterbium thulium codope
In any one.
Further, in the erbium thulium codope, the molar content of erbium is 10%, and the molar content of thulium is 2%；
It is described it is ytterbium and erbium-codoped in, the molar content of ytterbium is 20%, and the molar content of erbium is 2%；
In the ytterbium thulium codope, the molar content of ytterbium is 25%, and the molar content of thulium is 0.3%.
Further, the carbon quantum dot is prepared using solvent-thermal method or prepared by hydro-thermal method；
Wherein, the hydro-thermal method prepares the concrete operation step of the carbon quantum dot are as follows: using citric acid with ethylenediamine as raw material, water
For solvent, reaction temperature is 200 DEG C, and the aqueous solution of carbon quantum dot is prepared in reaction time 5h；
Wherein, the solvent-thermal method prepares the concrete operation step of the carbon quantum dot are as follows: using phenylenediamine as raw material, ethyl alcohol is molten
Agent, temperature are 180 DEG C, and the ethanol solution of carbon quantum dot is prepared in reaction time 12h.
Further, rear-earth-doped NaYF is prepared described in step S44/ carbon quantum dot double mode fluorescence nano composite material
Concrete operation step are as follows: containing rear-earth-doped NaYF4Cationic surface is added in the cyclohexane solution of upper conversion nano particle
Aqueous surfactant solutions, ultrasonic 2h, magnetic agitation removes hexamethylene at 70 DEG C, adds water, ethyl acetate and carbon quantum dot solution,
With lye adjusting pH value to certain value, mixed solution is stirred to get, continues to stir after ethyl orthosilicate is added dropwise, is centrifuged, washs,
It dries at 60 DEG C to get rear-earth-doped NaYF4/ carbon quantum dot double mode fluorescence nano composite material；
Preferably, the pH value is 9 ~ 10, continues 8 ~ 12h of stirring after ethyl orthosilicate is added dropwise；Preferably, the cationic surface
Activating agent is CnTAB or CPC, the n are 12 ~ 18；Preferably, the lye is potassium hydroxide aqueous solution, and sodium hydroxide is water-soluble
Any one in liquid or ammonium hydroxide.
A kind of rear-earth-doped NaYF4The application of/carbon quantum dot double mode fluorescence nano composite material, will be described rear-earth-doped
NaYF4/ carbon quantum dot double mode fluorescence nano composite material is dispersed in ethyl alcohol as fluorescence filler and glycerine volume ratio is 4:1
Mixed liquor in be equipped to ink for output invisible fluorescence falsification preventing pattern.
Rear-earth-doped NaYF of the invention4Upper conversion nano preparation method of granules can obtain spherical morphology, size distribution
It is narrow, the high upper conversion nano microballoon of crystallinity.The rear-earth-doped NaYF of coated with silica can be formed in preparation process4And carbon
Quantum dot nano composite material, the composite property being prepared are more stable.
Composite material and preparation method thereof of the invention is applicable in water soluble carbon quantum dot and alcohol-soluble carbon quantum dot and upper conversion
Material it is compound.
Compared with prior art, the beneficial effects of the present invention are:
1. technical solution of the present invention provides a kind of rear-earth-doped NaYF4/ carbon quantum dot double mode fluorescence nano composite material
Preparation method, utilize the rear-earth-doped NaYF of coated with silica4Upper conversion nano particle prepares hud typed receive with carbon quantum dot
Nano composite material, reaction condition is mild, easy to operate, available light, stable chemical performance, good hydrophilic property and have both other
The double mode fluorescent material of the high stability of physical property.Prepared hud typed composite fluorescent material, stability is good, water dispersion
Property it is good, it is easy to accomplish further application.
2. rear-earth-doped NaYF of the invention4The preparation of/carbon quantum dot double mode fluorescence nano composite material is in carbon amounts
It is carried out in the dispersion solution of son point, it is possible to prevente effectively from the aggregation of carbon quantum dot is quenched, and is suitable for a plurality of types of carbon quantums
Point material.
3. rear-earth-doped NaYF of the invention4The up-conversion fluorescence of/carbon quantum dot double mode fluorescence nano composite material is special
Property can be adjusted by changing rare earth ion doped ratio, the down-conversion fluorescent characteristic of double mode fluorescent material, which can pass through, changes carbon
Quantum dot type and the concentration in reaction solution are adjusted.In conjunction with up/down conversion fluorescence characteristic adjusting, it can be achieved that
The preparation of the double mode nano-composite fluorescent material of up/down conversion fluorescence characteristic customization.
4. the double mode fluorescence composite material of technical solution of the present invention preparation is nano material, water dispersible is good, can make
For at environmentally friendly ink, realize that individualized security pattern prints immediately, security pattern can be in near-infrared and ultraviolet bimodulus
It is detected under formula light source, anti-counterfeiting characteristic is more difficult to replicate, and antifalse effect is more preferably.
Detailed description of the invention
Fig. 1 is the rear-earth-doped NaYF prepared in 1 step S2 of embodiment4The transmission electron microscope of upper conversion nano particle
Figure；
Fig. 2 is the transmission electron microscope figure of the carbon quantum dot prepared in 1 step S3 of embodiment；
Fig. 3 is the rear-earth-doped NaYF prepared in 1 step S4 of embodiment4/ carbon quantum dot double mode fluorescence nano composite material
Transmission electron microscope figure；
Fig. 4 is the rear-earth-doped NaYF prepared in 1 step S4 of embodiment4/ carbon quantum dot double mode fluorescence nano composite material
Transmission electron microscope figure；
Fig. 5 is that the print image presented under natural light irradiation after pad-ink printing is made in the present invention in embodiment 1；
Fig. 6 is that the print image presented under 980nm laser irradiation after pad-ink printing is made in 1 present invention of embodiment；
Fig. 7 is that the print image presented under 360nm ultraviolet light after pad-ink printing is made in 1 present invention of embodiment；
Fig. 8 is the carbon quantum dot aqueous solution and composite material water that nitre acid for adjusting pH value is added and is 1 with nitre acid for adjusting pH value is not added
Solution fluorescence photo figure under the ultraviolet light irradiation of 360nm；
Detailed description of the invention: acid solution is added in the composite material aqueous solution c. that the non-acid liquid of composite material aqueous solution b. of acid solution is added in a.
The carbon quantum dot aqueous solution of the non-acid liquid of carbon quantum dot aqueous solution d..
Specific embodiment
Further detailed description is done to the present invention below with reference to embodiment, embodiments of the present invention are not limited thereto.
Embodiment 1
The present embodiment provides a kind of rear-earth-doped NaYF4The preparation method of/carbon quantum dot double mode fluorescence nano composite material, tool
Body the following steps are included:
S1. prepare rare earth metal oleate presoma: weigh 2mmol rare earth metal salt (specifically: 0.4732 g (1.56mmol)
YCl3·6H2O, 0.1549 g (0.4 mmol) YbCl3·6H2O, 0.0158 g (0.04 mmol) ErCl3·6H2O),
1.8570 g (6.1 mmol) enuatrol is placed in 100 mL round-bottomed flasks, be added 6 mL water, 7 mL ethyl alcohol and 14 mL just oneself
Alkane, magnetic agitation, flow back at 70 DEG C 4 h, stops that obtained mixed solution is poured into separatory funnel after heating is cooled to room temperature
In, washing is three times, spare；
S2. rear-earth-doped NaYF is prepared4Upper conversion nano particle: rare earth metal oleate presoma prepared by previous step is set
In 100 mL three-neck flasks, it is added 30 mL octadecylenes and 12 mL oleic acid, under magnetic agitation, is heated to 140 DEG C, vacuumizes and remove
The low boiling point solvent in solution is removed, then cools to 50 DEG C, then 20 mL of upper addition are dissolved with 0.2 g (5 mmol) hydroxide
The methanol solution of sodium and 0.2936 g (8 mmol) ammonium fluoride stirs 60 min, is then warming up to 110 DEG C, and it is molten to vacuumize removing
Methanol in agent is then under nitrogen protection warming up to 310 DEG C, keeps 1.5h, subsequent cooled to room temperature.Product is with second
Alcohol precipitating, centrifuge separation are washed 5 times with hexamethylene and alcohol mixeding liquid, are finally dispersed in spare in hexamethylene.
S3. preparing carbon quantum dot: weighing 1.1527 g(6 mmol) citric acid is placed in 100 mL round-bottomed flasks, it is added 30
The dissolution of mL water, is then added dropwise 1.602 mL(24 mmol) ethylenediamine, it is transferred in reaction kettle after mixing evenly, in 200 DEG C of baking
5 h are reacted in case, are naturally cooled to room temperature and are obtained carbon quantum dot aqueous solution.
S4. rear-earth-doped NaYF is prepared4/ carbon quantum dot double mode fluorescence nano composite material: it takes and is mixed containing 50 mg rare earths
Miscellaneous NaYF4The cyclohexane solution of upper conversion particles is placed in 150 mL conical flasks, and the water that 20 mL are dissolved with 0.5 g CTAB is added
Solution, ultrasonic 2h, then 70 DEG C of heating of magnetic agitation remove hexamethylene, 52 mL water, 4 mL acetic acid are then added in conical flask
Ethyl ester, the carbon quantum dot aqueous solution that 8 mL concentration are 0.4g/mL, are added a certain amount of ammonia water conditioning system pH value to 9, stir 2 h,
0.2 mL ethyl orthosilicate is added dropwise, stirs 12h, centrifuge separation three times with ethanol washing by precipitating, is drying to obtain at 60 DEG C.
To rear-earth-doped NaYF prepared by the present embodiment4/ carbon quantum dot double mode fluorescence nano composite material carries out glimmering
The discovery of light optical spectroscopy, rear-earth-doped NaYF provided in this embodiment4/ carbon quantum dot double mode fluorescence nano composite material exists
980 nm laser irradiation emitted green lights, blue light-emitting under 360 nm ultraviolet lights.
By rear-earth-doped NaYF prepared by the present embodiment4/ carbon quantum dot double mode fluorescence nano composite material is applied to
Inkjet printing is dispersed in 8 mL ethyl alcohol specific steps are as follows: taking 10 mg nanocomposite manufactured in the present embodiment
Ultrasonic 20min adds 2 mL glycerine, is uniformly mixed to get dual mode luminous ink is arrived.Ink obtained is packed into ink-jet
In the print cartridge of printer, that is, it can print out designed concealed anti-false pattern.
Fig. 1 is the rear-earth-doped NaYF prepared in 1 step S2 of embodiment4The transmission electron microscope of upper conversion nano particle
Figure, the rear-earth-doped NaYF of preparation4Upper conversion nano particle size uniformity, partial size are about 24nm.
Fig. 2 is the transmission electron microscope figure of the carbon quantum dot prepared in 1 step S3 of embodiment, the carbon quantum dot ruler of preparation
Very little uniform, partial size is about 1 ~ 2nm.
Fig. 3 is the rear-earth-doped NaYF prepared in 1 step S4 of embodiment4/ carbon quantum dot double mode fluorescence nano composite wood
The transmission electron microscope figure of material, the composite material of preparation are the core-shell type nano microballoon being evenly distributed, and partial size is about 45nm.
Fig. 4 is the rear-earth-doped NaYF prepared in 1 step S4 of embodiment4/ carbon quantum dot double mode fluorescence nano composite wood
The transmission electron microscope figure of material, it can be seen that being encapsulated in the carbon quantum dot of silica shell in the composite material of preparation.
Fig. 5 is the print image that presents under natural light irradiation after pad-ink printing is made prepared in the present embodiment,
Print image, almost without trace, there is very strong concealment under natural light, is conducive to the application in anti-counterfeit field.
Fig. 6 is the printing that presents under 980nm laser irradiation after pad-ink printing is made prepared in the present embodiment
Image, print image print clear image, are conducive to anti-counterfeit recognition in the laser irradiation emitted green light of 980nm.
Fig. 7 be prepared in the present embodiment be made pad-ink printing after presented under 360nm ultraviolet light beat
Watermark image, print image blue light-emitting under the ultraviolet light of 360nm print clear image, are conducive to anti-counterfeit recognition.
Embodiment 2
The present embodiment provides a kind of rear-earth-doped NaYF4The preparation method of/carbon quantum dot double mode fluorescence nano composite material, tool
Body the following steps are included:
S1. prepare rare earth metal oleate presoma: weigh 2mmol rare earth metal salt (specifically: 0.4532 g
(1.494mmol) YCl3·6H2O, 0.1937 g (0.50 mmol) YbCl3·6H2O, 0.0023 g (0.006 mmol)
TmCl3·6H2O), 1.8570 g (6.1 mmol) enuatrol is placed in 100 mL round-bottomed flasks, and 6 mL water, 7 mL ethyl alcohol are added
With 14 mL n-hexanes, magnetic agitation, flow back at 70 DEG C 4 h, stops falling obtained mixed solution after heating is cooled to room temperature
Enter in separatory funnel, washing is three times, spare；
S2. rear-earth-doped NaYF is prepared4Upper conversion nano particle: rare earth metal oleate presoma prepared by previous step is set
In 100 mL three-neck flasks, it is added 30 mL octadecylenes and 12 mL oleic acid, under magnetic agitation, is heated to 140 DEG C, vacuumizes and remove
Remove the low boiling point solvent in solution, then cool to 50 DEG C, add 20 mL dissolved with 0.2 g (5 mmol) sodium hydroxide and
The methanol solution of 0.2936 g (8 mmol) ammonium fluoride stirs 30min, is then warming up to 110 DEG C, vacuumizes and removes in solvent
Methanol be then under nitrogen protection warming up to 300 DEG C, keep 1h, subsequent cooled to room temperature.Product with ethanol precipitation,
Centrifuge separation is washed 3 times with hexamethylene and alcohol mixeding liquid, is finally dispersed in spare in hexamethylene.
S3. preparing carbon quantum dot: weighing 1.1527 g(6 mmol) citric acid is placed in 100 mL round-bottomed flasks, it is added 30
The dissolution of mL water, is then added dropwise 1.602 mL(24 mmol) ethylenediamine, it is transferred in reaction kettle after mixing evenly, in 200 DEG C of baking
5 h are reacted in case, are naturally cooled to room temperature and are obtained carbon quantum dot aqueous solution.
S4. rear-earth-doped NaYF is prepared4/ carbon quantum dot double mode fluorescence nano composite material: it takes and is mixed containing 50 mg rare earths
Miscellaneous NaYF4The cyclohexane solution of upper conversion particles is placed in 150 mL conical flasks, and 20 mL are added and are dissolved with 0.5 g C14TAB's
Aqueous solution, ultrasonic 2h, then 70 DEG C of heating of magnetic agitation remove hexamethylene, 52 mL water, 5.3 mL are then added in conical flask
Ethyl acetate, the carbon quantum dot aqueous solution that 8 mL concentration are 0.8g/mL, are added a certain amount of ammonia water conditioning system pH value to 10, stir
2 h are mixed, 0.2 mL ethyl orthosilicate is added dropwise, stir 8h, centrifuge separation, three times with ethanol washing by precipitating, drying is at 60 DEG C
?.
To rear-earth-doped NaYF prepared by the present embodiment4/ carbon quantum dot double mode fluorescence nano composite material carries out glimmering
The discovery of light optical spectroscopy, rear-earth-doped NaYF provided by the present embodiment4/ carbon quantum dot double mode fluorescence nano composite material exists
It is blue under 980 nm exciting lights to shine, the blue light-emitting under 360 nm ultraviolet lights.
By rear-earth-doped NaYF manufactured in the present embodiment4/ carbon quantum dot double mode fluorescence nano composite material is applied to spray
Ink printing, concrete operations are as follows: taking nanocomposite prepared by 10 mg the present embodiment, be dispersed in 8 mL ethyl alcohol ultrasonic
20min adds 2 mL glycerine, is uniformly mixed to get dual mode luminous ink is arrived.Ink obtained is packed into inkjet printing
In the print cartridge of machine, that is, it can print out designed concealed anti-false pattern.
Embodiment 3
The preparation method of the present embodiment reference embodiment 1, the difference is that: in step S1, weighed 2 mmol rare earth metal
Salt is specially 0.5339 g (1.76mmol) YCl3·6H2O, 0.0763 g (0.20 mmol) ErCl3·6H2O, 0.0154
g (0.04 mmol) TmCl3·6H2O；The carbon quantum dot solution being added in step S4 is the carbon quantum that 8mL concentration is 0.6g/mL
Point aqueous solution.
To rear-earth-doped NaYF prepared by the present embodiment4/ carbon quantum dot double mode fluorescence nano composite material carries out glimmering
The discovery of light optical spectroscopy, rear-earth-doped NaYF provided in this embodiment4/ carbon quantum dot double mode fluorescence nano composite material exists
It glows under 980 nm laser irradiations, blue light-emitting under 360 nm ultraviolet lights.
By rear-earth-doped NaYF manufactured in the present embodiment4/ carbon quantum dot double mode fluorescence nano composite material is applied to spray
Ink printing is dispersed in 8 mL ethyl alcohol and surpasses specific steps are as follows: taking 10 mg composite material manufactured in the present embodiment
Sound 20min adds 2 mL glycerine, is uniformly mixed to get dual mode luminous ink is arrived, is then packed into ink obtained and sprays
In the print cartridge of black printer, that is, it can print out designed concealed anti-false pattern.
Embodiment 4
The preparation method of the present embodiment reference embodiment 1, the difference is that: in step S3, weighs 0.45 g p-phenylenediamine and set
In 100 mL round-bottomed flasks, the dissolution of 45 mL ethyl alcohol is added, is then transferred into reaction kettle, reacts 12 in 180 DEG C of baking oven
H naturally cools to room temperature and obtains carbon quantum dot ethanol solution；In step S4, take containing the rear-earth-doped NaYF of 42 mg4Upper conversion
The cyclohexane solution of particle is placed in 150 mL conical flasks, and 20 mL are added and are dissolved with 0.5 g C18The aqueous solution of TAB, ultrasonic 2h,
Then 70 DEG C of heating of magnetic agitation remove hexamethylene, and it is dense that 52 mL water, 4 mL ethyl acetate, 8 mL are then added in conical flask
Degree is the carbon quantum dot ethanol solution of 0.4g/mL, and a certain amount of ammonia water conditioning system pH value is added to 10, stirs 2 h, is added dropwise certain
The ethyl orthosilicate of amount, stirs 10 h, and centrifuge separation three times with ethanol washing by precipitating, is drying to obtain at 60 DEG C.
To rear-earth-doped NaYF prepared by the present embodiment4/ carbon quantum dot double mode fluorescence nano composite material carries out glimmering
The discovery of light optical spectroscopy, rear-earth-doped NaYF provided in this embodiment4/ carbon quantum dot double mode fluorescence nano composite material exists
980 nm laser irradiation emitted green lights glow under 360 nm ultraviolet lights.
By rear-earth-doped NaYF manufactured in the present embodiment4/ carbon quantum dot double mode fluorescence nano composite material is applied to spray
Ink printing is dispersed in 8 mL ethyl alcohol and surpasses specific steps are as follows: taking 10 mg composite material manufactured in the present embodiment
Sound 20min adds 2 mL glycerine, is uniformly mixed to get dual mode luminous ink is arrived, is then packed into ink obtained and sprays
In the print cartridge of black printer, that is, it can print out designed concealed anti-false pattern.
Embodiment 5
The preparation method of the present embodiment reference embodiment 1, the difference is that: in step S3, weighs 0.45 g m-phenylene diamine (MPD) and set
In 100 mL round-bottomed flasks, the dissolution of 45 mL ethyl alcohol is added, is then transferred into reaction kettle, reacts 12 in 180 DEG C of baking oven
H naturally cools to room temperature and obtains carbon quantum dot ethanol solution；In step S4, take containing the rear-earth-doped NaYF of 59.5 mg4It is upper to turn
The cyclohexane solution for changing particle is placed in 150 mL conical flasks, and 20 mL are added and are dissolved with 0.5 g C12The aqueous solution of TAB, ultrasound
2h, then 70 DEG C of heating of magnetic agitation remove hexamethylene, 52 mL water, 4 mL ethyl acetate, 8 mL are then added in conical flask
Concentration is the carbon quantum dot ethanol solution of 0.4g/mL, and a certain amount of sodium hydroxide solution regulation system pH value is added to 9, stirs 2
A certain amount of ethyl orthosilicate is added dropwise in h, stirs 10 h, centrifuge separation, three times with ethanol washing by precipitating, drying is at 60 DEG C
?.
To rear-earth-doped NaYF prepared by the present embodiment4/ carbon quantum dot double mode fluorescence nano composite material carries out glimmering
The discovery of light optical spectroscopy, rear-earth-doped NaYF provided in this embodiment4/ carbon quantum dot double mode fluorescence nano composite material
It is in green emitting under 980 nm exciting lights, in 360 nm ultraviolet light emitted green lights.
By rear-earth-doped NaYF manufactured in the present embodiment4/ carbon quantum dot double mode fluorescence nano composite material is applied to spray
Ink printing is dispersed in 8 mL ethyl alcohol and surpasses specific steps are as follows: taking 10 mg composite material manufactured in the present embodiment
Sound 20min adds 2 mL glycerine, is uniformly mixed to get dual mode luminous ink is arrived, is then packed into ink obtained and sprays
In the print cartridge of black printer, that is, it can print out designed concealed anti-false pattern.
Embodiment 6
The preparation method of the present embodiment reference embodiment 4, the difference is that: in step S3, weighs 0.45 g o-phenylenediamine and set
In 100 mL round-bottomed flasks, the dissolution of 45 mL ethyl alcohol is added, is then transferred into reaction kettle, reacts 12 in 180 DEG C of baking oven
H naturally cools to room temperature and obtains carbon quantum dot ethanol solution；In step S4, take containing the rear-earth-doped NaYF of 42 mg4Upper conversion
The cyclohexane solution of particle is placed in 150 mL conical flasks, aqueous solution of 20 mL of addition dissolved with 0.5 g CTAB, ultrasonic 2h,
Then 70 DEG C of heating of magnetic agitation remove hexamethylene, and it is dense that 52 mL water, 4 mL ethyl acetate, 8 mL are then added in conical flask
Degree is the carbon quantum dot ethanol solution of 0.4g/mL, and a certain amount of potassium hydroxide aqueous solution regulation system pH value is added to 10, stirs 2
A certain amount of ethyl orthosilicate is added dropwise in h, stirs 10 h, centrifuge separation, three times with ethanol washing by precipitating, drying is at 60 DEG C
?.
To rear-earth-doped NaYF prepared by the present embodiment4/ carbon quantum dot double mode fluorescence nano composite material carries out glimmering
The discovery of light optical spectroscopy, rear-earth-doped NaYF provided in this embodiment4/ carbon quantum dot double mode fluorescence nano composite material
It is in green emitting, the blue light-emitting under 360 nm ultraviolet lights under 980 nm exciting lights.
By rear-earth-doped NaYF manufactured in the present embodiment4/ carbon quantum dot double mode fluorescence nano composite material is applied to spray
Ink printing is dispersed in 8 mL ethyl alcohol and surpasses specific steps are as follows: taking 10 mg composite material manufactured in the present embodiment
Sound 20min adds 2 mL glycerine, is uniformly mixed to get dual mode luminous ink is arrived, is then packed into ink obtained and sprays
In the print cartridge of black printer, that is, it can print out designed concealed anti-false pattern.
Comparative example 1
The preparation method of this comparative example reference embodiment 1, the difference from embodiment 1 is that, in step S4, positive silicic acid second is not added
Ester.
Rear-earth-doped NaYF prepared by this comparative example4/ carbon quantum dot double mode fluorescence nano composite material and embodiment 1
The composite material of preparation is compared, rear-earth-doped NaYF prepared by this comparative example4/ carbon quantum dot double mode fluorescence nano composite wood
Expect that stability is low, uniformity is low, carbon quantum dot is easy to fall off.
Comparative example 2
The preparation method of this comparative example reference embodiment 1, the difference from embodiment 1 is that, in step S4, the positive silicic acid second of addition
The amount of ester is 0.1mL.
Rear-earth-doped NaYF prepared by this comparative example4/ carbon quantum dot double mode fluorescence nano composite material and embodiment 1
The composite material of preparation is compared, and the silica shell thickness of the composite wood cladding of this comparative example preparation is too small and is difficult to all
Upper conversion particles form uniform cladding, and the composite material stability, uniformity of preparation reduces.
Comparative example 3
The preparation method of this comparative example reference embodiment 1, the difference from embodiment 1 is that, in step S4, the positive silicic acid second of addition
The amount of ester is 0.3mL.
Rear-earth-doped NaYF prepared by this comparative example4/ carbon quantum dot double mode fluorescence nano composite material and embodiment 1
The composite material of preparation is compared, this comparative example preparation composite material silica shell thickness it is excessive, composite material upper turn
Changing fluorescence intensity greatly reduces.
Comparative example 4
The preparation method of this comparative example reference embodiment 1, the difference from embodiment 1 is that, in step S4, the carbon of the 8mL of addition
Quantum dot concentration is 0.3g/mL.
Rear-earth-doped NaYF prepared by this comparative example4/ carbon quantum dot double mode fluorescence nano composite material and embodiment 1
The composite material of preparation is compared, and the concentration of composite material carbon quantum dot prepared by this comparative example is too small, prepared composite wood
The fluorescence intensity of material is low, and security pattern is unfavorable for detecting.
Comparative example 5
The preparation method of this comparative example reference embodiment 1, the difference from embodiment 1 is that, in step S4, the carbon of the 8mL of addition
Quantum dot concentration is 0.9g/mL.
Rear-earth-doped NaYF prepared by this comparative example4/ carbon quantum dot double mode fluorescence nano composite material and embodiment 1
The composite material of preparation is compared, and the concentration of carbon quantum dot is excessive in composite material prepared by this comparative example, and prepared is compound
Material color is too deep, is unfavorable for forming stealthy security pattern.
As shown in Figure 8, fluorescent quenching can occur for pure carbon quantum dot under strongly acidic conditions, and composite material will not occur it is glimmering
Optical quenching.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this
Made any modifications, equivalent replacements, and improvements etc., should be included in the claims in the present invention within the spirit and principle of invention
Protection scope within.
Claims (10)
1. a kind of rear-earth-doped NaYF4The preparation method of/carbon quantum dot double mode fluorescence nano composite material, which is characterized in that tool
The preparation step of body are as follows:
S1. rare earth metal oleate presoma is prepared；
S2. rear-earth-doped NaYF is prepared4Upper conversion nano particle；
S3. carbon quantum dot is prepared；
S4. rear-earth-doped NaYF is prepared4/ carbon quantum dot double mode fluorescence nano composite material: by rear-earth-doped NaYF4Nanometer
After grain carries out Hydrophilic modification, it is mixed with carbon quantum dot solution, is added after ethyl acetate and mixed solution is adjusted using lye
PH value, ethyl orthosilicate is then added, stirs at room temperature to obtain the final product；
Wherein, rear-earth-doped NaYF described in step S24Upper conversion nano particle is prepared using high temperature pyrolytic cracking (HTP)；Step S3 institute
Stating carbon quantum dot is Water-soluble carbon quantum dot or alcohol-soluble carbon quantum dot.
2. rear-earth-doped NaYF according to claim 14The preparation method of/carbon quantum dot double mode fluorescence nano composite material,
It is characterized in that, in step S4, the additional amount of the ethyl orthosilicate and rear-earth-doped NaYF4The mass ratio of nano particle be 3 ~
5:1；The concentration of carbon quantum dot is 5 ~ 10 mg/mL in the mixed solution.
3. rear-earth-doped NaYF according to claim 14The preparation method of/carbon quantum dot double mode fluorescence nano composite material,
It is characterized in that, preparing the concrete operation step of rare earth metal oleate presoma described in step S1 are as follows: weigh rare earth metal salt
In a reservoir with enuatrol, water, ethyl alcohol and n-hexane is added, stirs, flow back 4 h at 70 DEG C, washes after cooling, obtains rare earth gold
Belong to oleate presoma.
4. rear-earth-doped NaYF according to claim 14The preparation method of/carbon quantum dot double mode fluorescence nano composite material,
It is characterized in that, preparing rear-earth-doped NaYF described in step S24The concrete operation step of upper conversion nano particle are as follows: by step S1
The rare earth metal oleate presoma of preparation and octadecylene, oleic acid mixing warming while stirring vacuumize removing low boiling to 140 DEG C
The methanol solution dissolved with sodium hydroxide and ammonium fluoride is added after being cooled to 50 DEG C, stirs 30 ~ 60min, is warming up to for point solvent
110 DEG C vacuumize removing methanol, 300 ~ 310 DEG C are warming up under the protection of rare gas, 1 ~ 1.5h of heat preservation obtains rear-earth-doped
NaYF4Particle uses the rear-earth-doped NaYF of ethanol precipitation after cooling4Particle, centrifugation, using hexamethylene and ethanol washing, rare earth is mixed
Miscellaneous NaYF4Upper conversion nano particle is dispersed in hexamethylene, spare；Prepared rear-earth-doped NaYF4Upper conversion nano particle table
Face oleic acid-coated.
5. rear-earth-doped NaYF according to claim 14The preparation method of/carbon quantum dot double mode fluorescence nano composite material,
It is characterized in that, the rear-earth-doped NaYF4Nano particle is erbium thulium codope, any in ytterbium and erbium-codoped or ytterbium thulium codope
It is a kind of.
6. rear-earth-doped NaYF according to claim 54The preparation method of/carbon quantum dot double mode fluorescence nano composite material,
It is characterized in that, the molar content of erbium is 10% in the erbium thulium codope, the molar content of thulium is 2%；
It is described it is ytterbium and erbium-codoped in, the molar content of ytterbium is 20%, and the molar content of erbium is 2%；
In the ytterbium thulium codope, the molar content of ytterbium is 25%, and the molar content of thulium is 0.3%.
7. rear-earth-doped NaYF according to claim 14The preparation method of/carbon quantum dot double mode fluorescence nano composite material,
It is characterized in that, the carbon quantum dot is prepared using solvent-thermal method or hydro-thermal method preparation；
Wherein, the hydro-thermal method prepares the concrete operation step of the carbon quantum dot are as follows: using citric acid with ethylenediamine as raw material, water
For solvent, reaction temperature is 200 DEG C, and the aqueous solution of carbon quantum dot is prepared in reaction time 5h；
Wherein, the solvent-thermal method prepares the concrete operation step of the carbon quantum dot are as follows: using phenylenediamine as raw material, ethyl alcohol is molten
Agent, temperature are 180 DEG C, and the ethanol solution of carbon quantum dot is prepared in reaction time 12h.
8. rear-earth-doped NaYF according to claim 14The preparation method of/carbon quantum dot double mode fluorescence nano composite material,
It is characterized in that, preparing rear-earth-doped NaYF described in step S44The specific behaviour of/carbon quantum dot double mode fluorescence nano composite material
Make step are as follows: containing rear-earth-doped NaYF4Cationic surfactant is added in the cyclohexane solution of upper conversion nano particle
Aqueous solution, ultrasonic 2h, magnetic agitation removes hexamethylene at 70 DEG C, adds water, ethyl acetate and carbon quantum dot solution, uses lye
PH value is adjusted to certain value, mixed solution is stirred to get, continues to stir after ethyl orthosilicate is added dropwise, be centrifuged, wash, at 60 DEG C
Drying is to get rear-earth-doped NaYF4/ carbon quantum dot double mode fluorescence nano composite material；
Preferably, the pH value is 9 ~ 10, continues 8 ~ 12h of stirring after ethyl orthosilicate is added dropwise；Preferably, the cationic surface
Activating agent is CnTAB or CPC, the n are 12 ~ 18；Preferably, the lye is potassium hydroxide aqueous solution, and sodium hydroxide is water-soluble
Any one in liquid or ammonium hydroxide.
9. the rear-earth-doped NaYF that any one preparation method is prepared according to claim 1 ~ 84/ carbon quantum dot double mode
Fluorescence nano composite material.
10. rear-earth-doped NaYF described in a kind of claim 94The application of/carbon quantum dot double mode fluorescence nano composite material,
It is characterized in that, by the rear-earth-doped NaYF4/ carbon quantum dot double mode fluorescence nano composite material is dispersed in as fluorescence filler
Ink is equipped in the mixed liquor that ethyl alcohol and glycerine volume ratio are 4:1 for output invisible fluorescence falsification preventing pattern.
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