CN113736465B - Dual-mode fluorescent nanoparticle composite material, preparation method and application - Google Patents
Dual-mode fluorescent nanoparticle composite material, preparation method and application Download PDFInfo
- Publication number
- CN113736465B CN113736465B CN202111060725.6A CN202111060725A CN113736465B CN 113736465 B CN113736465 B CN 113736465B CN 202111060725 A CN202111060725 A CN 202111060725A CN 113736465 B CN113736465 B CN 113736465B
- Authority
- CN
- China
- Prior art keywords
- dual
- composite material
- mode
- nanoparticle composite
- mode fluorescent
- 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
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
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a dual-mode fluorescent nanoparticle composite material, a preparation method and application, wherein the composite material is prepared from up-conversion luminescent nanoparticles and a EuSe semiconductor material, wherein the EuSe semiconductor material is uniformly coated on the surfaces of the up-conversion luminescent nanoparticles to form a heterogeneous particle structure; the fluorescent light can emit two kinds of fluorescent light with different colors under the excitation of two laser light sources with different wavelengths, and the emitted fluorescent light can be clearly seen by naked eyes, so that the fluorescent light can be widely applied to the fields of optical anti-counterfeiting, information safety and the like. The composite material provided by the invention has the advantages of uniform appearance, good dispersibility and high stability; the preparation method provided by the invention has the advantages of simple steps, easiness in control and high repeatability; the material of the invention ensures that the formed anti-counterfeiting pattern is bright and clear and has high aesthetic feeling through the synergistic effect of the components and the structure, and can meet the anti-counterfeiting requirement of high-grade products.
Description
Technical Field
The invention relates to the technical field of nano materials and optical anti-counterfeiting, in particular to a dual-mode fluorescent nano particle composite material, a preparation method and application.
Background
Counterfeiting and counterfeiting of high-grade commodities are increasingly serious and long-standing global problems, are common in daily life, and cause cheating to consumers, so that normal commodity circulation and brand reputation are seriously influenced. Currently, counterfeit products produced by the illegal counterfeiting of packaging, trademarks, documents, and the like have penetrated many industries, including medicine, food, clothing, luxury goods, jewelry, software, paper currency, diploma, certificates, and the like. The counterfeit goods not only disturb the normal economic development order, but also damage the reputation of enterprises, and even form a great threat to the health of consumers. Therefore, the security materials and technologies are receiving more and more attention, and governments are also striving to develop advanced security technologies to protect important documents from being copied.
The application of fluorescent materials to anti-counterfeiting is one of the most effective technical means at present. With the progress of research, more and more optical materials, such as carbon quantum dots, metal organic frameworks, etc., are increasingly used for anti-counterfeiting. Chinese patent application CN201810836592.9 discloses a rare earth doped NaYF 4 Preparation method and application of/carbon quantum dot dual-mode fluorescent nano composite material, wherein cationic surface activity is utilizedSex agent modified rare earth doped NaYF 4 Mixing the water dispersion of the up-conversion nano particles with the carbon quantum dot solution, then adding alkali liquor, ethyl acetate and ethyl orthosilicate into the mixed solution, and doping NaYF in the rare earth by utilizing the sol-gel chemistry principle 4 And coating a silicon dioxide shell layer on the surface of the particle, and encapsulating the carbon quantum dots in the shell layer to prepare the core-shell type nano composite material. The preparation method effectively avoids aggregation quenching of the carbon quantum dots, can be used for preparing ink, and applies the prepared composite material to the anti-counterfeiting field through ink-jet printing.
However, the preparation method provided by the technical scheme of the patent application has multiple steps, complex process and difficult control; the dual-mode fluorescent nano composite material provided by the invention has lower intensity under the excitation of near-infrared and ultraviolet dual-mode light sources, is not easy to directly identify by naked eyes, is dispersedly prepared into printing ink as fluorescent filler for outputting dim, lower definition and low aesthetic feeling of invisible fluorescent anti-counterfeiting patterns, can not meet the anti-counterfeiting requirements of high-grade products, and reduces the practicability.
Disclosure of Invention
Aiming at the problems that the preparation method is complex and the material performance is not enough in the prior art, and the formed pattern cannot meet the requirements of high-grade products on anti-counterfeiting patterns such as brightness, clearness and high aesthetic sensitivity, the invention aims to provide a dual-mode fluorescent nanoparticle composite material, a preparation method and application.
In order to realize the purpose, the technical scheme provided by the invention is as follows:
the dual-mode fluorescent nanoparticle composite material is characterized by being prepared from up-conversion luminescent nanoparticles and a EuSe semiconductor material, wherein the EuSe semiconductor material is uniformly coated on the surfaces of the up-conversion luminescent nanoparticles to form a heterogeneous particle structure.
The composite material can emit fluorescence clearly visible to naked eyes under the excitation of two light sources with different wavelengths, and forms dual-mode fluorescence of up-conversion luminescence and down-conversion luminescence respectively.
A method of preparing the dual-mode fluorescent nanoparticle composite, comprising the steps of:
(1) weighing selenium powder with a set amount, adding the selenium powder into a single-mouth bottle, adding tri-n-octylphosphine according to a set proportion, and placing the single-mouth bottle into an ultrasonic oscillator for ultrasonic treatment until the solution in the bottle is clear and transparent to form a first dispersion liquid;
(2) weighing a europium source with a set amount, adding the europium source into a three-neck flask, sequentially adding a first dispersion liquid, oleylamine, oleic acid, octadecene and a cyclohexane dispersion liquid of upconversion luminescent nanoparticles with surface ligands of oleic acid according to a set proportion, heating to 280-300 ℃ under the protection of argon atmosphere, reacting for 3 hours, cooling to room temperature, and adding acetone; and precipitating the sample, ultrasonically washing the sample by acetone, and centrifugally separating the sample to obtain the EuSe-coated rare earth up-conversion luminescent nano-particles, namely the dual-mode fluorescent nano-particle composite material.
The europium source in step (2) includes, but is not limited to, europium nitrate, europium chloride, europium acetate and hydrates thereof.
In the step (2), the dosage of the tri-n-octylphosphine is 2-3 mL relative to 1mmol of selenium powder.
The temperature during ultrasonic treatment in the step (2) is 15-35 ℃, the ultrasonic time is 20-40 minutes, and the frequency of ultrasonic waves is set to be 39-41 KHz.
In the step (2), the dosage of the first dispersion liquid is 2-3 mL, the dosage of oleylamine is 3-5 mL, the dosage of oleic acid is 1-2 mL, the dosage of octadecene is 30-35 mL, and the dosage of upconversion nanoparticles with surface ligands of oleic acid is 1-2 mmol relative to 1mmol of europium source.
The application of the dual-mode fluorescent nanoparticle composite material is characterized in that the dual-mode fluorescent nanoparticle composite material is used as a dual-mode fluorescent filler to prepare a solid or liquid product applied to up/down conversion dual-mode optical anti-counterfeiting.
The application of the dual-mode fluorescent nanoparticle composite material is characterized in that the dual-mode fluorescent nanoparticle composite material is used as a dual-mode fluorescent filler to prepare a solid or liquid product applied to up/down conversion dual-mode optical information storage or information safety.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the dual-mode fluorescent nanoparticle composite material and the preparation method provided by the invention, the components, the structure and the preparation process of the material are synchronously improved, the europium selenide (EuSe) is specifically adopted to coat the up-conversion nanoparticles, and the fluorescent luminous intensity of the composite material is improved through the mutual synergistic effect of specific components and structures; compared with the existing optical anti-counterfeiting material, the material has the following outstanding advantages: (1) the adopted raw materials are few in variety, the preparation process is simple and efficient, and the repeatability is high; (2) the material has stable structure, uniform shape and good monodispersity; (3) the material has the characteristic of up/down conversion dual-mode luminescence; (3) the structure and the components are mutually cooperated, so that the reduction of fluorescence intensity caused by cross relaxation among multiple lanthanide ions is avoided.
2. According to the preparation method of the dual-mode fluorescent nanoparticle composite material, the up-conversion nanoparticles are coated by the EuSe semiconductor to obtain the nanocomposite material with the up/down-conversion luminescence function, the method is simple in steps, convenient to operate, easy to control reaction conditions, high in repeatability, good in product consistency and dispersibility and easy to industrialize.
3. The dual-mode fluorescent nanoparticle composite material provided by the invention has the advantages of uniform size, good dispersibility, stable structure and performance, up/down conversion dual-mode luminescence and the like, wherein the rare earth up-conversion luminescent nanoparticles can emit up-conversion visible light under the irradiation of near infrared light, and the europium selenide semiconductor can emit macroscopic down-conversion blue light under the irradiation of ultraviolet light, so that the dual-mode fluorescent nanoparticle composite material can be widely applied to the fields of up/down conversion dual-mode optical anti-counterfeiting, information safety, storage and the like.
Drawings
FIG. 1 is a graph obtained in example 1 of the present inventionNaYF 4 Yb, Tm nanoparticles and EuSe-coated NaYF 4 Transmission Electron Microscopy (TEM) photographs of composites of Yb, Tm nanoparticles;
FIG. 2 is a EuSe-coated NaYF obtained from example 2 of the present invention 4 A fluorescence spectrum diagram of the composite material of Yb and Er nano particles under the excitation of a 980nm laser light source.
FIG. 3 is a EuSe-coated NaYF obtained from example 3 of the present invention 4 A fluorescence spectrogram of a composite material of Yb and Ho nano particles under the excitation of a 365nm laser light source;
FIG. 4 is EuSe-coated NaGdF according to example 7 of the present invention 4 Picture of anti-fake application of composite Yb, Tm nanometer particle material.
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Detailed Description
Example 1:
the dual-mode fluorescent nanoparticle composite material provided in this example is specifically a EuSe-coated NaYF 4 Yb, Tm upconversion luminescent nanoparticles.
The dual-mode fluorescent nanoparticle composite material provided in this example is composed of NaYF 4 Yb, Tm up-conversion luminescent nanoparticles and a EuSe semiconductor material, wherein the EuSe semiconductor material is uniformly coated on the NaYF 4 Yb, Tm nanoparticles to form a heterogeneous particle structure; the composite material can emit fluorescence clearly visible to naked eyes under the excitation of two laser light sources with different wavelengths, and forms dual-mode fluorescence of up-conversion luminescence and down-conversion luminescence respectively.
This EuSe-coated NaYF provided in this example 4 The preparation method of the Yb, Tm up-conversion luminescence nanoparticle composite material comprises the following steps:
(1) weighing 1mmol of selenium powder, adding into a single-neck bottle, adding 2mL of tri-n-octylphosphonium, placing the single-neck bottle into an ultrasonic oscillator for ultrasonic treatment, wherein the temperature is controlled at 25 ℃, the ultrasonic time is 20 minutes, and the frequency of ultrasonic wave is 40 KHz. Sonicate until the solution in the vial is clear and transparent to form a first dispersion.
(2) Weighing 1mmol of EuCl 3 ·6H 2 O is added into a three-mouth bottle, and then 2mL of first dispersion liquid, 3mL of oleylamine, 1mL of oleic acid, 30mL of octadecene and 1mmol of NaYF with surface ligand of oleic acid are added 4 A cyclohexane dispersion of Yb, Tm conversion luminescent nano particles, and reacting for 3 hours at a high temperature of 280-300 ℃ in an argon protection atmosphere. Cooling to room temperature, adding 40mL of acetone to precipitate the obtained composite material, placing the composite material in a high-speed centrifuge, setting the rotation speed of the centrifuge to 8000 rpm, and obtaining EuSe-coated NaYF by taking the lower-layer precipitate after the centrifugation is finished 4 Yb, Tm nanoparticle composites.
The inventor group finds that in the research process, in the previous research on a rare earth dual-mode luminescence anti-counterfeiting system, a plurality of rare earth elements with up-conversion and down-conversion characteristics are often uniformly mixed in the same material, and lanthanide elements often undergo cross relaxation, so that the luminescence intensity is reduced, and the formed anti-counterfeiting image and characters are unclear (low definition) and are difficult to distinguish. The rare earth luminescent material adopted by the invention has excellent optical characteristics such as narrow-band emission peak, long fluorescence life and high stability, but how to combine the rare earth luminescent material with lanthanide to avoid a cross relaxation field is a research focus of the invention and a technical problem to be solved. The dual-mode fluorescent nanoparticle composite material provided by the embodiment can emit fluorescence clearly visible to the naked eye under the excitation of two laser light sources with different wavelengths through the cooperation of material components and structures, and forms dual-mode fluorescence of up-conversion luminescence and down-conversion luminescence respectively, so that the technical problem is solved.
The invention is based on the defects that most of the existing rare earth luminescent systems for storing anti-counterfeiting information have single fluorescence mode, need specific expensive excitation light sources, have non-adjustable luminescent colors and the like, so that the problems of limited information storage and anti-counterfeiting capacity, cracking risk and the like are caused, and the research and development of new materials are started. The dual-mode luminescent material provided by the invention can fuse different fluorescent colors of up-conversion luminescence and down-conversion luminescence to the same luminescent platform, improve the technological content of anti-counterfeiting technology, establish a technical barrier for avoiding counterfeiting and fake behavior, and provide an efficient and convenient technical means for genuine product identification.
As shown in FIG. 1, (a) is NaYF 4 Transmission electron micrographs of Yb, Tm nanoparticles, (b) EuSe-coated NaYF 4 Transmission electron micrograph of composite of Yb, Tm nanoparticles shows that the morphology and properties of the composite obtained after EuSe semiconductor coating the nanoparticles are significantly changed into peanut (ellipsoid) nanoparticles.
The application of the dual-mode fluorescent nanoparticle composite material is used as a dual-mode fluorescent filler to prepare a solid or liquid product applied to up/down conversion dual-mode optical anti-counterfeiting, and can be particularly applied to manufacturing printing anti-counterfeiting ink, special anti-counterfeiting paper and the like.
Example 2:
the present example provides a dual-mode fluorescent nanoparticle composite material, a preparation method and applications thereof, which are substantially the same as those of example 1, except that the dual-mode fluorescent nanoparticle composite material, specifically, EuSe coated NaYF is used as the dual-mode fluorescent nanoparticle composite material 4 A composite material of Yb and Er up-conversion luminescent nano particles.
This example provides EuSe-coated NaYF 4 The synthesis and preparation process of the Yb and Er nano-particle composite material comprises the following steps:
(1) weighing 1mmol of selenium powder, adding into a single-neck bottle, adding 2mL of tri-n-octylphosphonium, placing the single-neck bottle into an ultrasonic oscillator for ultrasonic treatment, wherein the temperature is controlled at 25 ℃, the ultrasonic time is 20 minutes, and the frequency of ultrasonic wave is 40 KHz. Sonicate until the solution in the vial is clear and transparent to form a first dispersion.
(2) Weighing 1mmol of EuCl 3 ·6H 2 Adding O into a three-neck flask, and then adding 2mL of first dispersion, 3mL of oleylamine, 1mL of oleic acid, 30mL of octadecene and 1mmol of NaYF with surface ligand of oleic acid 4 A cyclohexane dispersion liquid of Yb and Er nano particles is reacted for 3 hours at a high temperature of 280-300 ℃ in an argon protection atmosphere. Cooling to room temperature, adding 40mL of acetone to precipitate the obtained composite material, placing the composite material in a high-speed centrifuge, setting the rotation speed of the centrifuge to 8000 rpm, and obtaining EuSe-coated NaYF by taking the lower-layer precipitate after the centrifugation is finished 4 Yb and Er nano-particle composite material.
As shown in FIG. 2, the EuSe-coated NaYF 4 Under the excitation of a 980nm laser light source, the Yb and Er nano-particle composite material mainly emits green light and red light, wherein the peak value of the green light is 545nm, and the peak value of the red light is 654 nm.
Example 3:
the present example provides a dual-mode fluorescent nanoparticle composite material, a preparation method and applications thereof, which are substantially the same as those of example 1, except that the dual-mode fluorescent nanoparticle composite material, specifically, EuSe coated NaYF is used as the dual-mode fluorescent nanoparticle composite material 4 Yb and Ho nano particle composite material.
This example provides a EuSe-coated NaYF 4 The synthesis and preparation method of the Yb and Ho nano-particle composite material comprises the following steps:
(1) weighing 1mmol of selenium powder, adding into a single-neck bottle, adding 2mL of tri-n-octylphosphonium, placing the single-neck bottle into an ultrasonic oscillator for ultrasonic treatment, wherein the temperature is controlled at 25 ℃, the ultrasonic time is 20 minutes, and the frequency of ultrasonic wave is 40 KHz. Sonicate until the solution in the vial is clear and transparent to form a first dispersion.
(2) Weighing 1mmol of EuCl 3 ·6H 2 O is added into a three-mouth bottle, and then 2mL of first dispersion liquid, 3mL of oleylamine, 1mL of oleic acid, 30mL of octadecene and 1mmol of NaYF with surface ligand of oleic acid are added 4 The cyclohexane dispersion liquid of Yb and Ho nano particles is reacted for 3 hours at the high temperature of 280-300 ℃ in the argon protection atmosphere. Cooling to room temperature, adding 40mL of acetone to precipitate the obtained composite material, placing the composite material in a high-speed centrifuge, setting the rotating speed of the centrifuge to 8000 rpm, and taking the lower layer precipitate after the centrifugation is finished to obtain the EuSe-coated NaYF 4 Yb, Ho nano particle composite material.
As shown in FIG. 3, the EuSe-coated NaYF 4 The Yb and Ho nano particle composite material mainly emits blue light under the excitation of a 365nm light source, and the highest emission peak is positioned at 425 nm.
Example 4:
the present example provides a dual-mode fluorescent nanoparticle composite material, a preparation method and applications thereof, which are substantially the same as example 1, except that the dual-mode fluorescent nanoparticle composite material, specifically, EuSe coatingNaErF 4 Tm nanoparticle composites.
This example provides EuSe-coated NaErF 4 The synthesis and preparation process of the Tm nanoparticle composite material comprises the following steps:
(1) weighing 1mmol of selenium powder, adding into a single-neck bottle, adding 2mL of tri-n-octylphosphonium, placing the single-neck bottle into an ultrasonic oscillator for ultrasonic treatment, wherein the temperature is controlled at 25 ℃, the ultrasonic time is 20 minutes, and the frequency of ultrasonic wave is 40 KHz. Sonicate until the solution in the vial is clear and transparent to form a first dispersion.
(2) Weighing 1mmol of EuCl 3 ·6H 2 Adding O into a three-neck flask, and adding 2mL of first dispersion, 3mL of oleylamine, 1mL of oleic acid, 30mL of octadecene and 1mmol of NaErF with surface ligand of oleic acid 4 The cyclohexane dispersion liquid of the Tm nano particles reacts for 3 hours at a high temperature of 280-300 ℃ under the protection of argon. Cooling to room temperature, adding 40mL of acetone to precipitate the obtained composite material, placing the composite material in a high-speed centrifuge, setting the rotation speed of the centrifuge to 8000 rpm, and taking the lower-layer precipitate after the centrifugation is finished to obtain the EuSe-coated NaErF 4 Tm nanoparticle composites.
Example 5:
the present example provides a dual-mode fluorescent nanoparticle composite, a method for preparing the same, and applications thereof, which are substantially the same as example 1, except that the dual-mode fluorescent nanoparticle composite, specifically EuSe-coated NaGdF, is prepared 4 Yb, Tm nanoparticle composite material.
This example provides EuSe-coated NaGdF 4 The synthesis and preparation process of the Yb, Tm nano particle composite material comprises the following steps:
(1) weighing 1mmol of selenium powder, adding into a single-mouth bottle, adding 2mL of tri-n-octylphosphine, placing the single-mouth bottle into an ultrasonic oscillator for ultrasonic treatment, wherein the temperature is controlled to be 25 ℃, the ultrasonic time is 20 minutes, and the frequency of ultrasonic waves is 40 KHz. Sonicate until the solution in the vial is clear and transparent to form a first dispersion.
(2) Weighing 1mmol EuCl 3 ·6H 2 O into a three-necked flask, and then 2mL of the first dispersion, 3mL of oleylamine, 1mL of oleic acid, and 30mL of decaNaGdF with octaene and 1mmol of surface ligand as oleic acid 4 The cyclohexane dispersion liquid of Yb and Tm nano particles reacts for 3 hours at the high temperature of 280-300 ℃ in the argon protection atmosphere. Cooling to room temperature, adding 40mL of acetone to precipitate the obtained composite material, placing the composite material in a high-speed centrifuge, setting the rotation speed of the centrifuge to 8000 rpm, and obtaining EuSe-coated NaGdF by taking the lower-layer precipitate after the centrifugation is finished 4 Yb, Tm nanoparticle composites.
Example 6:
the present example provides a dual-mode fluorescent nanoparticle composite, a method of making, and uses thereof, which are substantially the same as example 1, except that the dual-mode fluorescent nanoparticle composite, in particular, improved EuSe-coated NaGdF using PVP 4 Water solubility of Yb, Tm nanoparticle composites; the preparation method also comprises using PVP to improve EuSe coated NaGdF 4 The water-solubility of the Yb, Tm nano particle composite material comprises the following steps:
(3) the dual-mode fluorescent nanoparticle composite material synthesized in the step (2) (EuSe-coated NaGdF in example 5) 4 Yb, Tm nanoparticle composite material) dissolved in a cyclohexane solution to form a first dispersion;
(4) weighing 0.5mmol NOBF 4 Putting the mixture into a single-mouth bottle, adding 10mL of dichloromethane solution, and putting the single-mouth bottle into an ultrasonic oscillator for ultrasonic treatment, wherein the temperature is controlled to be 25 ℃, the ultrasonic time is 20 minutes, and the frequency of ultrasonic waves is 40 KHz. Performing ultrasonic treatment until the solution in the bottle is clear and transparent to form a second dispersion liquid;
(5) and (3) putting 5mL of the first dispersion liquid and 5mL of the second dispersion liquid into the same single-mouth bottle, and putting the single-mouth bottle into an ultrasonic oscillator for ultrasonic treatment, wherein the temperature is controlled to be 25 ℃ during ultrasonic treatment, the ultrasonic time is 20 minutes, and the frequency of ultrasonic waves is 40 KHz. Centrifuging at 15000 r/min to obtain solid precipitate, and dissolving the solid precipitate in 5-8 mL of deionized water to form a third dispersion;
(6) 0.1mmoL of polyvinylpyrrolidone is weighed and placed in a single-mouth bottle, 10mL of deionized water is added and stirred for 0.5 hour, and the temperature is controlled to be 30 ℃ while stirring. Forming a fourth dispersion;
(7) placing 2.5mL of the third dispersion and 2.5mL of the fourth dispersion in a single-mouth bottle for stirring; controlling the temperature to be 50 ℃ during stirring; the stirring time is controlled to be 24 hours, and the PVP modified dual-mode fluorescent nanoparticle composite material (EuSe coated NaGdF) is obtained 4 Yb, Tm nanoparticle composites).
Likewise, with this procedure, the water solubility of the bimodal fluorescent nanoparticle composites prepared in examples 1-4 can also be improved.
Example 7:
the embodiment provides a specific application of a dual-mode fluorescent nanoparticle composite material in the field of anti-counterfeiting, and the dual-mode fluorescent nanoparticle composite material is used as a dual-mode fluorescent filler to prepare a solid or liquid product applied to up/down conversion dual-mode optical anti-counterfeiting.
Specifically, this example provides coating NaGdF with EuSe 4 The process of anti-fake application of Yb, Tm nanometer particle composite material includes the following steps:
(1) EuSe-coated NaGdF synthesized as described in example 5 4 A composite of Yb, Tm nanoparticles dispersed in a cyclohexane solution to form a first dispersion (which may be further formulated with other components into a printing ink);
(2) the synthesis described in example 6 was carried out using EuSe-coated NaGdF modified with PVP 4 A Yb, Tm nanoparticle composite forming a second dispersion;
(3) respectively and uniformly coating the first dispersion liquid and the second dispersion liquid on different parts of the non-fluorescent paper, then placing the non-fluorescent paper in a drying oven for drying for 10 minutes, controlling the temperature of the drying oven to be 60 ℃, drying the non-fluorescent paper, and then carrying out fluorescence test.
As shown in FIG. 4, (a) is a coated EuSe-coated NaGdF 4 A photograph of a non-fluorescent paper of a Yb, Tm nanoparticle composite material under natural light; (b) the EuSe-coated NaGdF is coated under 365nm ultraviolet lamp 4 A photo of a non-fluorescent paper of the Yb, Tm nanoparticle composite material, which proves that the composite material emits blue light under the irradiation of an ultraviolet lamp of 365 nm; (c) the EuSe-coated NaGdF is coated under 980nm near infrared light 4 Photograph of a fluorescent-free paper of a Yb, Tm nanoparticle composite materialThe composite material is proved to emit purple light under the irradiation of 980nm near infrared light;
in other embodiments, the dual-mode fluorescent nanoparticle composite material is used as an anti-counterfeiting filler, and can be further prepared into liquid anti-counterfeiting products such as printing ink, water-based paint and the like together with other components, and the solid anti-counterfeiting products are formed after drying.
Example 8:
the application of the dual-mode fluorescent nanoparticle composite material provided by the embodiment is used as a dual-mode fluorescent filler to prepare a solid or liquid product applied to up/down conversion dual-mode optical information storage or information security. Specifically, EuSe-coated NaGdF prepared in example 6, with PVP to improve water solubility 4 Yb and Tm nano particle composite material is used as an anti-counterfeiting filler and added into aqueous papermaking slurry, a non-uniform and natural anti-counterfeiting pattern is formed in the papermaking forming process, and anti-counterfeiting special paper is obtained after drying.
The key point of the invention is that a layer of europium selenide semiconductor is coated on the surface of the rare earth up-conversion luminescent nano particle, and the two are cooperated, wherein the rare earth up-conversion luminescent nano particle can emit up-conversion visible light under the irradiation of near infrared light, and the europium selenide semiconductor can emit macroscopic down-conversion blue light under the irradiation of ultraviolet light. The europium selenide coated rare earth up-conversion nanoparticle composite material provided by the invention can be used in the fields of up/down conversion dual-mode optical anti-counterfeiting, information safety, storage and the like. The preparation method provided by the invention has the advantages of simple steps, easiness in control, high repeatability and the like.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Those skilled in the art can make many possible variations or modifications to the disclosed solution, using the methods and techniques disclosed above, to equivalents thereof without departing from the scope of the invention. Therefore, all equivalent modifications made according to the structure, structure and principle of the present invention should be covered within the protection scope of the present invention without departing from the contents of the technical scheme of the present invention.
Claims (9)
1. A dual-mode fluorescent nanoparticle composite material is characterized in that the composite material is made of up-conversion luminescent nanoparticles and a EuSe semiconductor material, wherein the EuSe semiconductor material is uniformly coated on the surfaces of the up-conversion luminescent nanoparticles to form a heterogeneous particle structure; the composite material can emit fluorescence clearly visible to naked eyes under the excitation of two laser light sources with different wavelengths, and forms dual-mode fluorescence of up-conversion luminescence and down-conversion luminescence respectively.
2. A method of preparing the dual-mode fluorescent nanoparticle composite of claim 1, comprising the steps of:
(1) weighing selenium powder with a set amount, adding the selenium powder into a single-mouth bottle, adding tri-n-octylphosphine according to a set proportion, and placing the single-mouth bottle into an ultrasonic oscillator for ultrasonic treatment until the solution in the bottle is clear and transparent to form a first dispersion liquid;
(2) weighing a europium source with a set amount, adding the europium source into a three-neck flask, sequentially adding a first dispersion liquid, oleylamine, oleic acid, octadecene and a cyclohexane dispersion liquid of upconversion luminescent nanoparticles with surface ligands of oleic acid according to a set proportion, heating to 280-300 ℃ under the protection of argon atmosphere, reacting for 3 hours, cooling to room temperature, and adding acetone; and precipitating the sample, ultrasonically washing the sample by using acetone, and centrifugally separating the sample to obtain the EuSe-coated rare earth up-conversion luminescent nano-particles, namely the dual-mode fluorescent nano-particle composite material.
3. The method for preparing a dual mode fluorescent nanoparticle composite according to claim 2, wherein the europium source in step (2) is one of europium nitrate, europium chloride, europium acetate, and hydrates thereof.
4. The preparation method of the dual-mode fluorescent nanoparticle composite material as claimed in claim 2, wherein in the step (1), the amount of tri-n-octylphosphine is 2-3 mL relative to 1mmol of selenium powder.
5. The preparation method of the dual-mode fluorescent nanoparticle composite material as claimed in claim 2, wherein the temperature during the ultrasonic treatment in the step (1) is 15 to 35 ℃, the ultrasonic time is 20 to 40 minutes, and the frequency of the ultrasonic wave is set to be 39 to 41 KHz.
6. The method for preparing a dual mode fluorescent nanoparticle composite material according to claim 2, wherein in step (2), the amount of the first dispersion liquid is 2 to 3mL, the amount of oleylamine is 3 to 5mL, the amount of oleic acid is 1 to 2mL, the amount of octadecene is 30 to 35mL, and the amount of upconversion nanoparticles with surface ligands of oleic acid is 1 to 2mmol relative to 1mmol of europium source.
7. The method of preparing the dual-mode fluorescent nanoparticle composite of claim 2, further comprising improving the EuSe coating NaGdF using PVP 4 The water-solubility of the Yb, Tm nano particle composite material comprises the following steps:
(3) dissolving the dual-mode fluorescent nanoparticle composite material synthesized in the step (2) in a cyclohexane solution to form a first dispersion liquid;
(4) weighing 0.5mmol NOBF 4 Placing the mixture into a single-mouth bottle, adding 10mL of dichloromethane solution, placing the single-mouth bottle into an ultrasonic oscillator for ultrasonic treatment, wherein the temperature is controlled to be 25 ℃ during ultrasonic treatment, the ultrasonic time is 20 minutes, and the frequency of ultrasonic wave is 40 KHz; performing ultrasonic treatment until the solution in the bottle is clear and transparent to form a second dispersion liquid;
(5) placing 5mL of the first dispersion and 5mL of the second dispersion in the same single-mouth bottle, and placing the single-mouth bottle in an ultrasonic oscillator for ultrasonic treatment, wherein the temperature is controlled to be 25 ℃, the ultrasonic time is 20 minutes, and the frequency of ultrasonic waves is 40 KHz; centrifuging at 15000 r/min to obtain solid precipitate, and dissolving the solid precipitate in 5-8 mL of deionized water to form a third dispersion;
(6) weighing 0.1mmoL of polyvinylpyrrolidone, placing into a single-mouth bottle, adding 10mL of deionized water, stirring for 0.5 h, and controlling the temperature to be 30 ℃ during stirring to form a fourth dispersion;
(7) placing 2.5mL of the third dispersion and 2.5mL of the fourth dispersion in a single-mouth bottle for stirring; controlling the temperature to be 50 ℃ during stirring; the stirring time is controlled to be 24 hours, and the PVP modified dual-mode fluorescent nano-particle composite material is obtained.
8. The application of the dual-mode fluorescent nanoparticle composite material as claimed in claim 1, wherein the dual-mode fluorescent nanoparticle composite material is used as a dual-mode fluorescent filler to prepare a solid or liquid product for up/down conversion dual-mode optical anti-counterfeiting.
9. Use of the dual-mode fluorescent nanoparticle composite material of claim 1 as a dual-mode fluorescent filler for the preparation of solid or liquid products for up/down conversion dual-mode optical information storage or information security.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111060725.6A CN113736465B (en) | 2021-09-10 | 2021-09-10 | Dual-mode fluorescent nanoparticle composite material, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111060725.6A CN113736465B (en) | 2021-09-10 | 2021-09-10 | Dual-mode fluorescent nanoparticle composite material, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113736465A CN113736465A (en) | 2021-12-03 |
| CN113736465B true CN113736465B (en) | 2022-09-23 |
Family
ID=78737867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111060725.6A Active CN113736465B (en) | 2021-09-10 | 2021-09-10 | Dual-mode fluorescent nanoparticle composite material, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113736465B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114560450B (en) * | 2022-02-23 | 2023-05-16 | 西安交通大学 | Preparation method and application of rare earth selenide nano material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115145B (en) * | 2010-11-23 | 2012-06-27 | 吉林大学 | Preparation method of rare earth europium nano crystal with fluorescence and magnetism |
-
2021
- 2021-09-10 CN CN202111060725.6A patent/CN113736465B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113736465A (en) | 2021-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xie et al. | Design of novel lanthanide-doped core–shell nanocrystals with dual up-conversion and down-conversion luminescence for anti-counterfeiting printing | |
| Liu et al. | Simultaneously excited downshifting/upconversion luminescence from lanthanide‐doped core/shell fluoride nanoparticles for multimode anticounterfeiting | |
| Gong et al. | Design of core/active-shell NaYF4: Ln3+@ NaYF4: Yb3+ nanophosphors with enhanced red-green-blue upconversion luminescence for anti-counterfeiting printing | |
| Zhang et al. | Near-infrared and visible dual emissive transparent nanopaper based on Yb (III)–carbon quantum dots grafted oxidized nanofibrillated cellulose for anti-counterfeiting applications | |
| Hu et al. | Synthesis and properties of transition metals and rare-earth metals doped ZnS nanoparticles | |
| Liu et al. | Facile synthesis and potential bioimaging applications of hybrid upconverting and plasmonic NaGdF4: Yb3+, Er3+/silica/gold nanoparticles | |
| Komahal et al. | Design of Bi-functional composite core–shell SiO2@ ZnAl2O4: Eu3+ array as a fluorescent sensors for selective and sensitive latent fingerprints visualization protocol | |
| Revathy et al. | Microwave-assisted synthesis of GdOF: Eu3+/Tb3+ ultrafine phosphor powders suitable for advanced forensic and security ink applications | |
| CN113736465B (en) | Dual-mode fluorescent nanoparticle composite material, preparation method and application | |
| Song et al. | Synthesis and inkjet printing of NaYF4: Ln3+@ NaYF4 core–shell nanoparticles with enhanced upconversion fluorescence for anti-counterfeiting applications | |
| Lavanya et al. | Applications for data security and latent fingerprint visualization using blue-emitting surface-modified LZO: Ce3+ nanophosphor | |
| Aljohani | Preparation of polylactic acid reinforced with cellulose nanofibers toward photochromic self-healing adhesive for anti-counterfeiting applications | |
| Mamatha et al. | Designing ultra-highly efficient Sm3+ activated SrLaAlO4 orange-red emitting phosphor towards security encoding, hydro-gels, flexible displays and personal identification | |
| Ansari et al. | A facile synthesis approach and impact of shell formation on morphological structure and luminescent properties of aqueous dispersible NaGdF 4: Yb/Er upconversion nanorods | |
| Han et al. | Tunable multicolor emission based on dual-mode luminescence Y2O3: Eu@ SiO2/Y2O3: Er (Tm/Yb) composite nanomaterials | |
| Alharbi et al. | Photoluminescent cellulose nanofibers-reinforced alginate hydrogel with color-tunable and self-healing properties for authentication applications | |
| Xie et al. | Water-borne, durable and multicolor silicon nanoparticles/sodium alginate inks for anticounterfeiting applications | |
| Hameed et al. | Preparation of persistently luminescent polyacrylic acid-based nanocomposite ink for secure encoding | |
| CN113105886B (en) | Up-conversion luminescent composite nano powder with variable luminescent color and preparation method and application thereof | |
| Al-Qahtani et al. | Information encryption strategy for optical security authentication using phosphor-encapsulated poly (N-isopropylacrylamide) nanoparticles | |
| EP3310878B1 (en) | Nanostructured phosphorescent pigment and uses thereof | |
| Kalaburgi et al. | Facile and eco-friendly PVA nanocomposites as a photo-luminescent: Anti-counterfeiting, LED and wettability applications | |
| CN108929678B (en) | Anti-counterfeiting ink for industrial and commercial management and preparation method thereof | |
| Molkenova et al. | Europium (III)-doped mesoporous silica nanoparticles (SiO2-Eu NPs) prepared via the soaking method | |
| Zhang et al. | NaYF4: Yb, Er with N-GQDs mixture: One-pot hydrothermal synthesis and its luminescent film |
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 |