A zirconia-based composite material with fluorescence properties, preparation method and application thereof

Abstract

The present invention discloses a zirconia-based composite material with fluorescence characteristics, a preparation method and an application thereof. The preparation method of the zirconia-based composite material with fluorescence characteristics uses nano-zirconia powder and benzophenone derivative solid powder as raw materials and is prepared by a solid-phase composite method, which specifically includes the following steps: S1, weighing a certain amount of nano-zirconia powder and benzophenone derivative solid powder; S2, grinding the weighed nano-zirconia powder and benzophenone derivative solid powder evenly to obtain a mixture; S3, washing the evenly ground mixture evenly with a washing solvent; S4, drying the solid product obtained after washing to obtain a zirconia-based composite material with fluorescence characteristics; the zirconia-based composite material with fluorescence characteristics prepared by this method has a photoluminescence property, and the specific combination of zirconia and benzophenone derivatives enables the composite material to have excellent luminescence characteristics on the basis of maintaining the stable physical and chemical properties of the inorganic carrier.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparation of optical functional materials and nanocomposites, and particularly relates to a zirconia-based composite material with fluorescence characteristics, a preparation method and applications thereof. Background Art

[0002] Zirconia (ZrO2) is a metal oxide with a wide bandgap (5.0 - 5.5 eV), high melting point and stable chemical properties. ZrO2 has polymorphism, commonly including cubic phase, tetragonal phase and monoclinic phase, etc. Therefore, it has the characteristics of adjustable structure and customizable properties, and has great application prospects in the fields of high-performance ceramics, photocatalysis, thermal protection, etc. In the field of optoelectronic materials, this material is considered a potential luminescent matrix material. However, ZrO2 itself does not have photoluminescence characteristics and often needs to be doped or surface-modified to endow it with luminescence characteristics.

[0003] Doping is one of the main means to endow ZrO2 with luminescence characteristics. Currently, for luminescent materials based on ZrO2, mainly rare earth ions such as Eu 3+ , Tb 3+ , Sm 3+ , Yb 3+ etc. are used as luminescence centers and are incorporated into the ZrO2 lattice or lattice interstices. The research group of inventor Chen Xueyuan (CN102676166B) used high-temperature solvothermal and ligand exchange methods to incorporate Eu 3+ , Tb 3+Incorporated into zirconia nanocrystals, a monodisperse, water-soluble zirconia nano-fluorescent material with strong luminescence of rare-earth ions was obtained. This method achieved strong visible light emission of rare-earth ions sensitized by the matrix by exciting the ZrO2 matrix. The research group of Chen Weifan (CN103553594B) heated and dissolved Y2O3, Tb4O7 and ZrOCl2·8H2O in nitric acid, and obtained yttrium- and terbium-codoped zirconia nano-fluorescent ceramic powder through operations such as thermal concentration and high-temperature combustion. The powder prepared by this method has good dispersibility, small particle size, and good luminescence performance. The research group of He Dannong (CN108329906B) dissolved zirconium salt and erbium salt in a certain proportion, and obtained a zirconia fluorescent labeling material with small particle size, uniform particle distribution and photoluminescence performance after hydrothermal reaction at 120 °C for 24 - 36 hours. The powder obtained by this method has a large specific surface area and high luminescence efficiency. The research group of the inventor He Lingling (CN113101230A) selected Er2O3, Tb4O7 and Nd2O3 as stabilizers, and Y2O3, Yb2O3, Gd2O3 and Tm2O3 as fluorescent agents, and prepared a series of double-doped or multi-component doped fluorescent zirconia by dry pressing and high-temperature sintering methods. The prepared zirconia dental material can effectively meet the requirements of the inherent luminescence of dental materials. The research group of the inventor Liu Lu (CN102660273A) mixed and stirred Er(NO3)3 and Zr(NO3)4 solutions to form a sol, and then obtained rare-earth doped nano-zirconia upconversion phosphor through steps such as drying, sintering and high-temperature calcination. This method effectively weakens the fluorescence quenching effect of highly doped rare-earth ions, and the obtained finished product has a high luminescence efficiency. The above inventions can all illustrate that doping rare-earth ions is an effective way to endow ZrO2 with photoluminescence performance, but the synthesis processes of the above inventions all involve high-temperature treatment steps, which have problems such as cumbersome processes and high costs, and the above inventions are all in-situ doping during the ZrO2 synthesis process, and cannot perform post-doping on existing zirconia materials.

[0004] Composite of ZrO2 powder and fluorescent material is another common strategy to endow it with fluorescent properties. The research group led by Wang Xixin (CN113234434B) used zirconia film as a carrier, coated with a rhodamine B mixed solution after treatment with a silane coupling agent, and obtained a water-resistant rhodamine B / zirconia composite fluorescent film. The obtained composite film has high water resistance and photoluminescence intensity. The research group led by Feng Yakai (CN112210365B) prepared a solid-state stable zirconia carbon quantum dot composite material by a one-step hydrothermal method. The obtained composite material has stable fluorescent properties and is resistant to acid and alkali corrosion. The research group led by Jia Qiong (CN116023933A) mixed the porous zirconia hollow microspheres prepared by hydrothermal method with a copper nanocluster solution evenly, and obtained a fluorescence composite probe with enhanced emission of copper nanoclusters induced by the spatial confinement effect. This method uses the porous zirconia hollow microspheres as a host carrier to spatially confine the copper nanoclusters, effectively overcoming the disadvantages of weak fluorescence intensity and poor stability of copper nanoclusters. The research group led by Ye Weihao (CN113122227A) obtained a fluorescent material with high quantum efficiency by composite of inorganic quantum dots and mesoporous oxide materials with wrinkled structures such as zirconia. The wrinkled structure of the mesoporous oxide material can avoid the aggregation of quantum dots and ensure its good optical stability. The research group led by Wang Zhenhua (CN112812203B) mixed metal oxide nanoparticles such as zirconia modified with an organic initiator with a copper catalyst, a monomer and a solvent, and added a reducing agent to initiate radical transfer polymerization to grow a polymer under anaerobic conditions, and obtained a polymer / metal oxide composite material with fluorescent properties. The obtained material has good mechanical properties and fluorescent properties and can be applied to the fields of anti-counterfeiting and biological imaging. The above inventions all show that composite with fluorescent materials is an effective strategy to endow zirconia with fluorescent properties. However, in the above inventions, zirconia basically acts as a matrix material, and the fluorescent properties of the composite material basically come from the composite object itself, and the optical properties of zirconia have not been effectively developed. And the above methods all have problems such as cumbersome and complex preparation processes and high costs.

[0005] Based on the above situation, it is urgent to develop a composite material that can develop the optical properties of zirconia, has a simple preparation process, low cost, and good photoluminescence properties. Summary of the Invention

[0006] To solve the above problems, the present invention provides a zirconia-based composite material with fluorescent properties, a preparation method and an application thereof.

[0007] The present invention adopts the following technical solutions:

[0008] A method for preparing a zirconia-based composite material with fluorescence properties, which uses nano-zirconia powder and benzophenone derivative solid powder as raw materials and is prepared by a solid-phase composite method, specifically including the following steps:

[0009] S1. Weigh a certain amount of nano-zirconia powder and benzophenone derivative solid powder;

[0010] S2. Grind the weighed nano-zirconia powder and benzophenone derivative solid powder evenly to obtain a mixture;

[0011] S3. Wash the evenly ground mixture evenly with a washing solvent;

[0012] S4. Dry the solid product obtained after washing to obtain a zirconia-based composite material with fluorescence properties.

[0013] Preferably, the benzophenone derivative in step S1 is a benzophenone molecule containing an o-hydroxy group, and the benzophenone molecule containing an o-hydroxy group is one or a mixture of several of 2-hydroxybenzophenone, 2,2'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,2’,4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2’-dihydroxy-4-methoxybenzophenone, 2,2”-dihydroxy-4,4”-dimethoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 5-chloro-2-hydroxybenzophenone, 4-allyloxy-2-hydroxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone.

[0014] Preferably, the particle size of the nano-zirconia powder in step S1 is 2 - 500 nm.

[0015] Preferably, the mass ratio of the nano-zirconia powder to the benzophenone derivative solid powder weighed in step S1 is 1:(0.01 - 100).

[0016] Preferably, when the mass ratio of the nano-zirconia powder to the benzophenone derivative solid powder weighed in step S1 is 1:0.01 to 1:1, the mixture after grinding can be dried without washing.

[0017] Preferably, the grinding time in step S2 is 0.1 - 100 minutes.

[0018] Preferably, the washing solvent in step S3 is one or a mixture of several of methanol, ethanol, propanol, isopropanol, butanol, acetone, n-hexane, propylene glycol methyl ether, ethyl acetate, butyl acetate, isobutyl acetate, toluene, xylene.

[0019] Preferably, the temperature for drying in step S4 is 30 - 100 °C, and the drying time is 10 - 600 minutes.

[0020] A zirconia-based composite material with fluorescence properties, which is prepared by using the preparation method of the zirconia-based composite material with fluorescence properties; the main body of the zirconia-based composite material with fluorescence properties is nano-zirconia powder, and the surface of the nano-zirconia powder is modified by organic molecules of benzophenone derivatives.

[0021] An application of a zirconia-based composite material with fluorescence properties. The zirconia-based composite material with fluorescence properties emits bright yellow-green light under ultraviolet excitation, and it is assembled with an ultraviolet light-emitting diode to prepare a yellow light illumination device; the zirconia-based composite material with fluorescence properties emits bright yellow-green light under ultraviolet excitation, and after mixing it with a blue phosphor, it is then assembled with an ultraviolet light-emitting diode to prepare a white light illumination device.

[0022] After adopting the above technical solutions, compared with the background technology, the present invention has the following advantages:

[0023] 1. The zirconia-based composite material with fluorescence properties prepared by the present invention has photoluminescence performance. The specific binding of zirconia and benzophenone derivatives endows the composite material with excellent luminescence properties on the basis of maintaining the stable physical and chemical properties of the inorganic carrier.

[0024] 2. The preparation process of the present invention is simple, the reaction is fast, there is no pollution, the cost is low, the yield is high, and the obtained zirconia-based composite material with fluorescence properties has good stability and is easy to store. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 X-ray powder diffraction patterns of the zirconia-based composite materials with fluorescence properties obtained in Examples 1 - 5;

[0026] Figure 2 Infrared spectra of the zirconia-based composite materials with fluorescence properties obtained in Examples 1 - 5;

[0027] Figure 3 Raman spectra of the zirconia-based composite materials with fluorescence properties obtained in Examples 1 - 5;

[0028] Figure 4 Fluorescence spectra of the zirconia-based composite materials with fluorescence properties obtained in Examples 1 - 5;

[0029] Figure 5 UV-Vis diffuse reflectance spectra of the zirconia-based composite materials with fluorescence properties obtained in Examples 1 - 5;

[0030] Figure 6Fluorescence spectrum of the zirconia-based composite material with fluorescence properties obtained in Example 6;

[0031] Figure 7 Fluorescence spectrum of the zirconia-based composite material with fluorescence properties obtained in Example 7;

[0032] Figure 8 Fluorescence spectrum of the zirconia-based composite material with fluorescence properties obtained in Example 8;

[0033] Figure 9 Fluorescence spectrum of the zirconia-based composite material with fluorescence properties obtained in Example 9;

[0034] Figure 10 Fluorescence spectrum of the zirconia-based composite material with fluorescence properties obtained in Example 10;

[0035] Figure 11 UV-Vis diffuse reflectance spectrum of the zirconia-based composite material with fluorescence properties obtained in Example 6;

[0036] Figure 12 UV-Vis diffuse reflectance spectrum of the zirconia-based composite material with fluorescence properties obtained in Example 7;

[0037] Figure 13 UV-Vis diffuse reflectance spectrum of the zirconia-based composite material with fluorescence properties obtained in Example 8;

[0038] Figure 14 UV-Vis diffuse reflectance spectrum of the zirconia-based composite material with fluorescence properties obtained in Example 9;

[0039] Figure 15 UV-Vis diffuse reflectance spectrum of the zirconia-based composite material with fluorescence properties obtained in Example 10. Detailed implementation mode

[0040] In order to make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0041] Example 1: Preparation of ZrO2 / 2-hydroxy-4-methoxybenzophenone (mass ratio 1:0.05)

[0042] Accurately weigh 1 g of zirconia with a particle size of 10 nm and 0.05 g of 2-hydroxy-4-methoxybenzophenone and place them in an agate mortar. Grind them thoroughly for 3 min until the reaction is complete to obtain a zirconia-based composite material with fluorescence properties.

[0043] Example 2: Preparation of ZrO2 / 2-hydroxy-4-methoxybenzophenone (mass ratio 1:0.1)

[0044] Accurately weigh 1 g of zirconia with a particle size of 10 nm and 0.1 g of 2-hydroxy-4-methoxybenzophenone and place them in an agate mortar. Grind thoroughly for 5 min to complete the reaction, and a zirconia-based composite material with fluorescence properties is obtained.

[0045] Example 3: Preparation of ZrO2 / 2-hydroxy-4-methoxybenzophenone (mass ratio 1:0.2)

[0046] Accurately weigh 1 g of zirconia with a particle size of 10 nm and 0.2 g of 2-hydroxy-4-methoxybenzophenone and place them in an agate mortar. Grind thoroughly for 10 min to complete the reaction, and a zirconia-based composite material with fluorescence properties is obtained.

[0047] Example 4: Preparation of ZrO2 / 2-hydroxy-4-methoxybenzophenone (mass ratio 1:0.3)

[0048] Accurately weigh 1 g of zirconia with a particle size of 10 nm and 0.3 g of 2-hydroxy-4-methoxybenzophenone and place them in an agate mortar. Grind thoroughly for 20 min to complete the reaction, and a zirconia-based composite material with fluorescence properties is obtained.

[0049] Example 5: Preparation of ZrO2 / 2-hydroxy-4-methoxybenzophenone (mass ratio 1:0.5)

[0050] Accurately weigh 1 g of zirconia with a particle size of 10 nm and 0.5 g of 2-hydroxy-4-methoxybenzophenone and place them in an agate mortar. Grind thoroughly for 30 min to complete the reaction, and a zirconia-based composite material with fluorescence properties is obtained.

[0051] Example 6: Preparation of ZrO2 / 2-hydroxybenzophenone (mass ratio 1:0.7)

[0052] Accurately weigh 1 g of zirconia with a particle size of 5 nm and 0.7 g of 2-hydroxybenzophenone and place them in an agate mortar. Grind thoroughly for 50 min to complete the reaction, and a zirconia-based composite material with fluorescence properties is obtained.

[0053] Example 7: Preparation of ZrO2 / 2,2”-dihydroxy-4,4”-dimethoxybenzophenone (mass ratio 1:0.9)

[0054] Accurately weigh 1 g of zirconia with a particle size of 20 nm and 0.9 g of 2,2”-dihydroxy-4,4”-dimethoxybenzophenone and place them in an agate mortar. Grind thoroughly for 70 min to complete the reaction, and a zirconia-based composite material with fluorescence properties is obtained.

[0055] Example 8: Preparation of ZrO2 / 2,4-dihydroxybenzophenone (mass ratio 1:1)

[0056] Accurately weigh 1 g of zirconia with a particle size of 50 nm and 1 g of 2,4-dihydroxybenzophenone and place them in an agate mortar. Grind thoroughly for 90 min until the reaction is complete to obtain a zirconia-based composite material with fluorescence characteristics.

[0057] Example 9: Preparation of ZrO2 / 2-hydroxy-4-n-octyloxybenzophenone (mass ratio 1:3)

[0058] Accurately weigh 1 g of zirconia with a particle size of 80 nm and 3 g of 2-hydroxy-4-n-octyloxybenzophenone and place them in an agate mortar. Grind thoroughly for 100 min until the reaction is complete. Wash with ethanol and then dry in a vacuum drying oven at 45 °C for 500 minutes to obtain a zirconia-based composite material with fluorescence characteristics.

[0059] Example 10: Preparation of ZrO2 / 5-chloro-2-hydroxybenzophenone (mass ratio 1:5)

[0060] Accurately weigh 1 g of zirconia with a particle size of 100 nm and 5 g of 5-chloro-2-hydroxybenzophenone and place them in an agate mortar. Grind thoroughly for 10 min until the reaction is complete. Wash with ethanol and then dry in a vacuum drying oven at 55 °C for 600 minutes to obtain a zirconia-based composite material with fluorescence characteristics.

[0061] Figure 1 is the X-ray powder diffraction pattern of the zirconia-based composite materials with fluorescence characteristics obtained in Examples 1-5, and is compared with the X-ray patterns of the used nano-zirconia and 2-hydroxy-4-methoxybenzophenone raw materials. From Figure 1 It can be seen that the zirconia-based composite materials with fluorescence characteristics obtained in Examples 1-5 are all pure phases. Only the diffraction peaks belonging to nano-zirconia are observed, and no diffraction peaks belonging to 2-hydroxy-4-methoxybenzophenone are seen.

[0062] Figure 2 is the infrared spectrum of the zirconia-based composite materials with fluorescence characteristics obtained in Examples 1-5, and is compared with the infrared spectra of the used nano-zirconia and 2-hydroxy-4-methoxybenzophenone raw materials. From Figure 2 It can be seen that the obtained zirconia-based composite materials with fluorescence characteristics are all pure phases, and the characteristic peaks originating from nano-zirconia and 2-hydroxy-4-methoxybenzophenone can be observed simultaneously.

[0063] Figure 3 is the Raman spectrum of the zirconia-based composite materials with fluorescence characteristics obtained in Examples 1-5, and is compared with the Raman spectra of the used nano-zirconia and 2-hydroxy-4-methoxybenzophenone raw materials. FromFigure 3 It can be seen that the obtained zirconia-based composite material with fluorescence characteristics has characteristic peaks of both nano-zirconia and 2-hydroxy-4-methoxybenzophenone.

[0064] Figure 4 FIG. is the fluorescence spectrogram of the zirconia-based composite material with fluorescence characteristics obtained in Examples 1-5, and is compared with the fluorescence spectrograms of the nano-zirconia and 2-hydroxy-4-methoxybenzophenone raw materials used. From Figure 4 It can be seen that compared with nano-zirconia and 2-hydroxy-4-methoxybenzophenone, the obtained zirconia-based composite material with fluorescence characteristics has obvious fluorescence characteristics. The fluorescence emission peak shapes of the zirconia-based composite materials with fluorescence characteristics in different examples are consistent, and there are only differences in fluorescence intensity.

[0065] Figure 5 FIG. is the ultraviolet-visible diffuse reflection spectrogram of the zirconia-based composite material with fluorescence characteristics obtained in Examples 1-5, and is compared with the nano-zirconia and 2-hydroxy-4-methoxybenzophenone raw materials used. From Figure 5 It can be seen that the diffuse reflection spectra of the obtained zirconia-based composite materials with fluorescence characteristics are all smooth curves, and no obvious mechanical superposition characteristics are seen.

[0066] Figures 6 - 10 FIG. is the fluorescence spectrogram of the zirconia-based composite material with fluorescence characteristics obtained in Examples 6-10, and is compared with the fluorescence spectrograms of the nano-zirconia and benzophenone derivative raw materials used. From Figures 6 - 10 It can be seen that compared with nano-zirconia and benzophenone derivatives, the obtained zirconia-based composite material with fluorescence characteristics has obvious fluorescence characteristics.

[0067] Figures 11 - 15 FIG. is the ultraviolet-visible diffuse reflection spectrogram of the zirconia-based composite material with fluorescence characteristics obtained in Examples 6-10. And it is compared with the nano-zirconia and benzophenone derivative raw materials used. From Figures 11 - 15 It can be seen that the diffuse reflection spectra of the obtained zirconia-based composite materials with fluorescence characteristics are all smooth curves, and no obvious mechanical superposition characteristics are seen.

[0068] As mentioned above, it is only the preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. A method for preparing a zirconia-based composite material with fluorescence properties, characterized in that, It is prepared from nano-zirconia powder and benzophenone derivative solid powder by a solid-phase composite method, specifically including the following steps: S1. Weigh a certain amount of nano-zirconia powder and benzophenone derivative solid powder; S2. Grind the weighed nano-zirconia powder and benzophenone derivative solid powder evenly to obtain a mixture; S3. Wash the evenly ground mixture evenly with a washing solvent; S4. Dry the solid product obtained after washing to obtain a zirconia-based composite material with fluorescence characteristics.

2. The preparation method of a zirconia-based composite material with fluorescence characteristics according to claim 1, characterized in that: The benzophenone derivative in step S1 is a benzophenone molecule containing an o-hydroxy group, and the benzophenone molecule containing an o-hydroxy group is one or a mixture of 2-hydroxybenzophenone, 2,2'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,2’, 4, 4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2’-dihydroxy-4-methoxybenzophenone, 2,2''-dihydroxy-4,4''-dimethoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 5-chloro-2-hydroxybenzophenone, 4-allyloxy-2-hydroxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone.

3. The preparation method of a zirconia-based composite material with fluorescence characteristics as described in claim 1, characterized in that: The particle size of the nano-zirconia powder described in step S1 is 2 - 500 nm.

4. The preparation method of a zirconia-based composite material with fluorescence characteristics according to claim 1, characterized in that: The mass ratio of the nano-zirconia powder to the benzophenone derivative solid powder weighed in step S1 is 1:(0.01 - 100).

5. The preparation method of a zirconia-based composite material with fluorescence characteristics according to claim 4, characterized in that: When the mass ratio of the nano-zirconia powder to the benzophenone derivative solid powder weighed in step S1 is 1:0.01 to 1:1, the mixture after grinding can be dried without washing.

6. The preparation method of a zirconia-based composite material with fluorescence characteristics as described in claim 1, characterized in that: The grinding time in step S2 is 0.1 - 100 minutes.

7. The preparation method of a zirconia-based composite material with fluorescence characteristics as described in claim 1, wherein: The washing solvent in step S3 is one or a mixture of methanol, ethanol, propanol, isopropanol, butanol, acetone, n-hexane, propylene glycol methyl ether, ethyl acetate, butyl acetate, isobutyl acetate, toluene, xylene.

8. The preparation method of a zirconia-based composite material with fluorescence properties as described in claim 1, characterized in that: The drying temperature in step S4 is 30 - 100 °C, and the drying time is 10 - 600 minutes.

9. A zirconia-based composite material with fluorescence characteristics, characterized in that: It is prepared by using the preparation method of the zirconia-based composite material with fluorescence characteristics described in any one of claims 1 - 8; the main body of the zirconia-based composite material with fluorescence characteristics is nano-zirconia powder, and the surface of the nano-zirconia powder is modified by benzophenone derivative organic molecules.

10. Use of a zirconia-based composite material with fluorescence characteristics as described in claim 9, characterized in that: The zirconia-based composite material with fluorescence characteristics emits bright yellow-green light under ultraviolet excitation, and it is assembled with an ultraviolet light-emitting diode to prepare a yellow light illumination device.

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