阅读说明：本技术 一种NH4Yb2F7基纳米颗粒及其制备方法和应用 (NH (hydrogen sulfide)4Yb2F7Base nano-particles and preparation method and application thereof ) 是由 李祥 王芸 葛万银 于 2020-05-06 设计创作，主要内容包括：本发明公开了一种NH4Yb2F7基纳米颗粒及其制备方法和应用,将稀土硝酸盐溶解在溶剂中配置成澄清溶液A,将氟铵盐分散在澄清溶液A中配成乳白色的混合溶液B；将乳白色的混合溶液B经固液分离获得白色的粉体C；对粉体C进行干燥后即得到球形的NH<Sub>4</Sub>Yb<Sub>2</Sub>F<Sub>7</Sub>基的纳米粉体。本发明工艺简单易行,重复性好,整个反应体系对环境无任何污染,所提出的工艺路线不仅具有较好的应用前景及经济效益,而且也具有重要的实用价值。(The invention discloses NH4Yb2F 7-based nano particles and a preparation method and application thereof, wherein rare earth nitrate is dissolved in a solvent to prepare a clear solution A, and fluorine ammonium salt is dispersed in the clear solution A to prepare a milky mixed solution B; carrying out solid-liquid separation on the milky mixed solution B to obtain white powder C; drying the powder C to obtain spherical NH 4 Yb 2 F 7 A base nano powder. The invention has simple and easy process, good repeatability, no pollution to the environment of the whole reaction system, and the proposed process route not only has better performanceGood application prospect and economic benefit, and also has important practical value.)

1. A preparation method of NH4Yb2F 7-based nanoparticles is characterized in that rare earth nitrate is dissolved in a solvent to prepare a clear solution A, and fluorine ammonium salt is dispersed in the clear solution A to prepare a milky mixed solution B; carrying out solid-liquid separation on the milky mixed solution B to obtain white powder C; drying the powder C to obtain spherical NH₄Yb₂F₇A base nano powder.

2. The method of claim 1, wherein the ratio of rare earth nitrate: the molar concentration ratio of ammonium fluoride is 1: (8-20).

3. The method of claim 1, wherein the clear solution a is prepared by:

dissolving 1mmol of rare earth nitrate in 20ml of solvent, wherein the solvent is distilled water or deionized water, and forming a clear solution A.

4. The method according to claim 1, wherein the milky white mixed solution B is prepared by the following steps:

and introducing the ammonium fluoride solution into the clear solution A, reacting for 1min, and stirring at the temperature of 10-40 ℃ to obtain a milky mixed solution B.

5. The method according to claim 1, wherein the centrifugal rate of the solid-liquid separation is 5000 to 9000 rpm when the white powder C is prepared.

6. The method according to claim 1, wherein the temperature of the drying treatment is 50 to 80 ℃.

7. An NH4Yb2F 7-based nanoparticle prepared according to the method of claim 1.

8. Use of NH4Yb2F 7-based nanoparticles in an up-conversion luminescent material according to claim 7, wherein the NH4Yb2F 7-based nanoparticles are doped in-situ with a rare earth element Tm.

9. The upconversion luminescent material according to claim 8, wherein the doped Tm content is 0 to 100 mol%.

10. The upconversion luminescent material according to claim 9, wherein the wavelength range is 200-1100 nm when a 980nm laser is used as an excitation source.

Technical Field

The present invention belongs to inorganic ternary NH₄Yb₂F₇The technical field of compound nano powder preparation, in particular to NH₄Yb₂F₇A base nanoparticle, a method for preparing the same and applications thereof.

Background

Up-conversion (UC) luminescent materials have received a great deal of attention in that their unique properties convert infrared bands, which are invisible to the naked eye, into visible bands. The UC material has the advantages of weak autofluorescence, high biological body penetration depth and the like, and has potential application prospects in the fields of biological imaging and detection. Therefore, many synthetic methods have been proposed to achieve upconversion nanoparticles. Particularly the ultra-fast synthetic route developed in recent years. A disadvantage is the potential threat to the environment of the Ethylene Glycol (EG) solvents used in the research, since EG has some toxicity. Therefore, it is necessary to develop a green process route and an inexpensive strategy to meet the needs of ultrafast synthesis.

From the angle of taking fluoride as a UC matrix, the lanthanide-doped NaYF₄The base compounds have been extensively studied in the last decade and realize three primary colors of blue, green and red. In particular, Er³⁺/Yb³⁺Activators/sensitizers are particularly popular for providing green and red UCL emissions. However, only limited research has focused on Tm³⁺/Yb³⁺This, in turn, typically provides blue emission and a greater anti-stokes shift. Ammonium fluoroytterbium NH₄Yb₂F₇The matrix is of a cubic structure. It is a layered compound, YbF₆Octahedron and NH₄The layers are staggered. For ammonium fluoroytterbium acid NH₄Yb₂F₇The literature on matrix synthesis is not very extensive. Some literature reports suggest NH₄Solid-phase reaction of F and rare earth oxide to obtain a series of NH₄Ln₂F₇(Ln ═ rare earth) compounds. However, the reaction period takes 1 to 3 days, which causes practical problems such as energy consumption and low efficiency. Subsequently, solvothermal methods to effect NH₄Ln₂F₇(Ln ═ Y, Ho, Er, Tm, Yb, Lu) nanoparticles, in a time period of at least 20 hours. In addition, pair Ln (OH)₃The nanoplates are fluorinated to obtain fluorolanthanates proposed to have mixed phases, but the obtained product is not a pure phase. These research works were directed to obtaining NH₄Yb₂F₇The compounds provide a useful reference.

Currently, there is a lack of realization of NH₄Yb₂F₇Ultra-fast, green synthetic routes to compounds and UCL.

Disclosure of Invention

Hair brushThe technical problem to be solved is to provide a NH against the above disadvantages in the prior art₄Yb₂F₇The base nano-particles and the preparation method and the application thereof provide a brand new solution for the green, environment-friendly and industrial production aspects of the novel up-conversion material.

The invention adopts the following technical scheme:

a preparation method of NH4Yb2F 7-based nanoparticles comprises the steps of dissolving rare earth nitrate in a solvent to prepare a clear solution A, and dispersing fluorine ammonium salt in the clear solution A to prepare a milky mixed solution B; carrying out solid-liquid separation on the milky mixed solution B to obtain white powder C; drying the powder C to obtain spherical NH₄Yb₂F₇A base nano powder.

Specifically, rare earth nitrates: the molar concentration ratio of ammonium fluoride is 1: (8-20).

Specifically, the preparation process of the clear solution A comprises the following steps:

dissolving 1mmol of rare earth nitrate in 20ml of solvent, wherein the solvent is distilled water or deionized water, and forming a clear solution A.

Specifically, the preparation process of the milky white mixed solution B comprises the following steps:

and introducing the ammonium fluoride solution into the clear solution A, reacting for 1min, and stirring at the temperature of 10-40 ℃ to obtain a milky mixed solution B.

Specifically, when the white powder C is prepared, the centrifugal rate of solid-liquid separation is 5000-9000 revolutions per minute.

Specifically, the temperature of the drying treatment is 50-80 ℃.

According to another technical scheme, the NH4Yb2F 7-based nano-particles are prepared according to the method.

The other technical scheme of the invention is that the NH4Yb2F 7-based nano-particles are applied to the up-conversion luminescent material, and the NH4Yb2F 7-based nano-particles are doped with the rare earth element Tm in situ.

Specifically, the doped Tm content is 0 to 100 mol%.

Furthermore, when a 980nm laser is used as an excitation source, the wavelength range is 200-1100 nm.

Compared with the prior art, the invention has at least the following beneficial effects:

the invention relates to a method for preparing pure NH at room temperature by using water as a solvent at ultra-fast speed₄Yb₂F₇Dissolving ytterbium nitrate in a solvent to prepare a solution A, and dispersing fluorine ammonium salt in the solution A to prepare a solution B; carrying out solid-liquid separation on the solution B to obtain white powder C; drying the powder C to obtain pure NH₄Yb₂F₇The nano powder of (1). NH with the nanometer size of 50nm can be obtained according to the process route₄Yb₂F₇The powder provides a brand new solution idea and process flow for green and environment-friendly industrial production of preparing novel up-conversion materials, avoids the use of glycol harmful to the environment, and provides an optimized, quick and low-cost choice for industrial production.

Furthermore, considering the requirements of industrial production and green synthesis process, the invention adopts distilled water or deionized water as solvent medium, solves the biological safety hidden trouble and environmental pollution hidden trouble of glycol with biological toxicity, and the solution immediately generates white precipitate by adding ammonium fluoride into the ytterbium nitrate water solution, indicating NH₄Yb₂F₇And (4) generating nano crystal grains. The whole reaction is carried out at room temperature, and a subsequent additional heat treatment process is not needed. The whole synthesis process is quick and simple, no special reaction equipment is needed, and NH can be realized by a common chemical instrument₄Yb₂F₇And (4) synthesizing the nanocrystal. From the industrial production perspective, the time of the synthesis process can be greatly shortened, and NH is fundamentally solved₄Yb₂F₇The cost of the synthesis of the nanocrystalline is increased, and the cost performance of the product is improved.

Furthermore, the stirring temperature is 10-40 ℃, and the subsequent high-temperature calcination process is avoided by performing at room temperature.

Furthermore, the reaction time is not more than 60 seconds, and pure NH can be obtained in a very short time through simple steps₄Yb₂F₇And (3) powder.

The invention also discloses an up-conversion luminescent material, and the pure NH prepared by the method₄Yb₂F₇The nanometer powder is doped with Tm element in situ to obtain functional material with up-conversion luminescence property without changing NH₄Yb₂F₇The structure of (1).

In conclusion, the process is simple and easy to implement, the repeatability is good, the whole reaction system has no pollution to the environment, and the proposed process route not only has good application prospect and economic benefit, but also has important practical value.

The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.

Drawings

FIG. 1 is a diagram of the rapid synthesis of NH at room temperature according to example 1 of the present invention₄Yb₂F₇X-ray diffraction spectrum of the powder;

FIG. 2 shows the rapid synthesis of NH at room temperature according to example 1 of the present invention₄Yb₂F₇Scanning Electron Microscopy (SEM) images of the powder;

FIG. 3 shows that the Tm element is doped with NH at room temperature in example 2 of the present invention₄Yb₂F₇X-ray diffraction spectrum of the powder;

FIG. 4 shows that the Tm element is doped with NH at room temperature in example 3 of the present invention₄Yb₂F₇X-ray diffraction spectrum of the powder;

FIG. 5 shows the rapid synthesis of NH at room temperature according to example 4 of the present invention₄Tm₂F₇X-ray diffraction spectrum of the powder;

FIG. 6 shows the rapid synthesis of NH at room temperature according to example 5 of the present invention₄Yb₂F₇EDS energy spectrum of the powder;

FIG. 7 shows the rapid synthesis of NH at room temperature according to example 6 of the present invention₄Yb₂F₇Scanning Electron Microscopy (SEM) images of the powder;

FIG. 8 is a diagram of the rapid synthesis of Tm doped NH at room temperature in example 6 of the present invention₄Yb₂F₇Up-conversion of powdersAnd exchanging the luminous performance graph.

Detailed Description

The invention provides a method for preparing pure NH at room temperature by using water as a solvent at ultra-fast speed₄Yb₂F₇Dissolving ytterbium nitrate in a solvent to prepare a solution A, and dispersing fluorine ammonium salt in the solution A to prepare a solution B; carrying out solid-liquid separation on the solution B to obtain white powder C; drying the powder C to obtain NH₄Yb₂F₇A base nano powder.

Distilled water or deionized water is used as a solvent medium, so that the biological potential safety hazard and the environmental pollution hazard of the ethylene glycol with biological toxicity are solved, the whole reaction process is carried out at room temperature, and the subsequent high-temperature calcination process is not needed. NH obtained₄Yb₂F₇The particle size of the powder is about 50nm, and the functional material with up-conversion luminescence property can be obtained by doping Tm element in situ. The method comprises the following specific steps:

s1, dissolving 1mmol of rare earth nitrate (such as ytterbium nitrate) in 20ml of solvent, wherein the solvent is distilled water or deionized water, and a clear solution A is formed;

s2, introducing 8-20 mmol of ammonium fluoride solution into the solution A, reacting for 1min, and stirring at 10-40 ℃ to obtain a milky mixed solution B, and rare earth nitrate (such as ytterbium nitrate): ammonium fluoride molar concentration ratio of 1: (8-20);

s3, washing the solution B, controlling the centrifugal rate to be 5000-9000 r/min, and performing solid-liquid separation to obtain white powder C;

s4, drying the powder C at 50-80 ℃ to obtain spherical NH₄Yb₂F₇And (3) nano powder.

To NH₄Yb₂F₇The nano powder is doped with a rare earth element Tm in situ to obtain up-conversion luminescence performance, and is excited by infrared light (such as 980nm laser) to obtain luminescence in a visible light band, wherein the visible light is green, the doped Tm content is 0-100 mol%, the phase and the purity of a product are analyzed by an X-ray diffractometer, and a Scherrer formula (D ═ K × (B × cos theta), K is a constant, λ is an X-ray wavelength, and β is a diffraction peakHalf height and width; theta is a diffraction angle) was calculated.

The invention provides a method for obtaining pure NH by using water to replace toxic solvents such as ethylene glycol and the like₄Yb₂F₇The green route of the main body and the derivatives thereof realizes the concept of green chemistry. Can be completed in one minute, providing a convenient ultra high speed route. A high molar yield of 97% was achieved and showed potential for large scale production. Furthermore, NH was excited by a 980nm laser₄Yb₂F₇Tm can realize strong blue and red UC luminescence. This work will provide a NH base that can be used on a large scale with other rare earths₄Ln₂F₇The ultra-fast green synthetic route of the compound and various up-conversion luminescence have potential application prospects in the fields of biological imaging, sensing and displaying.

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.