CN109181680B - Silicon dioxide-rare earth-titanium dioxide hybrid material and preparation method thereof - Google Patents
Silicon dioxide-rare earth-titanium dioxide hybrid material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a silicon dioxide-rare earth-titanium dioxide hybrid material and a preparation method thereof. The composite material comprises silicon dioxide, a rare earth complex and titanium dioxide, wherein the silicon dioxide is used as a core, the rare earth complex is coated on the outer surface of the silicon dioxide to form a first shell, and the titanium dioxide is coated on the outer surface of the rare earth complex to form a second shell; the mass ratio of the silicon dioxide, the rare earth complex and the titanium dioxide in the hybrid material is 1:0.3:0.6-2:0.1: 1.7. The invention has a core-shell structure, uniform size distribution, good appearance and uniform dispersion; the rare earth complex coats the silicon dioxide spheres, so that the problem that the rare earth complex is easy to agglomerate is solved, the fluorescent material has good fluorescent property, and the fluorescent material has better application in the fields of energy storage, solar cells, photonic devices, catalysis and the like; the titanium dioxide is positioned at the outermost layer of the hybrid material, so that the nonradiative transition of the rare earth complex is effectively reduced, the luminous efficiency of the rare earth complex is optimized, and the stability is improved.
Description
Technical Field
The invention relates to the technical field of hybrid materials, in particular to a silicon dioxide-rare earth-titanium dioxide hybrid material with a core-shell structure and a preparation method thereof.
Background
Hybrid materials (Hybrid materials) are mixtures of two nano-or molecular-scale components, one composite containing two nano-or molecular-scale components, and are fourth generation materials following single component materials, composite materials and gradient materials. In nature, hybrid materials are usually made of an inorganic substance mixed with an organic substance. Thus, it differs from conventional composites or composites in that the components of the latter have macroscopic dimensions in the micrometer to millimeter range; the hybrid material is mixed on a microscopic scale, and the internal structure is relatively uniform. The hybrid material shows not a property between two phases but a new property.
Nano titanium dioxide (TiO)2) The material is an important inorganic functional material, and the particles of the material have the properties of surface effect, quantum size effect, small size effect, macroscopic quantum tunneling effect and the like; the crystal has the performances of ultraviolet resistance, good light absorptivity, angle dependent heterochromous effect, photocatalysis and the like; and it has better weather resistance, chemical resistance and chemical stability; therefore, the nano titanium dioxide is widely applied to the fields of photocatalysis, solar cells, organic pollutant degradation, coatings and the like. However, nano-titanium dioxide also has certain limitations, such as: the band gap is wide, the light absorption is limited to the ultraviolet region and the near ultraviolet region, and the available energy can not reach 10% of the sunlight irradiating the ground.
At present, some technologies for improving the nano titanium dioxide are also appeared in the prior art, such as: adding appropriate substances (such as resin, polyaniline, coupling agent, fluorocarbon resin and the like) into the nano titanium dioxide to modify the nano titanium dioxide; however, the technologies for modifying the nano titanium dioxide have the problems of long process flow, inconvenient operation and difficult control, the morphology of the obtained modified nano titanium dioxide is not controllable, the light absorption capacity of the nano titanium dioxide is basically not influenced, the fluorescence efficiency and the fluorescence intensity of the obtained nano titanium dioxide modified material are still very low, and the practical application of the titanium dioxide is limited.
Disclosure of Invention
The invention provides a silicon dioxide-rare earth-titanium dioxide hybrid material with a core-shell structure and a preparation method thereof, which solve the problem that the practical application of the titanium dioxide hybrid material is limited due to low fluorescence intensity of the titanium dioxide hybrid material in the prior art.
The invention relates to a silicon dioxide-rare earth-titanium dioxide hybrid material with a core-shell structure, which adopts the technical scheme that: the titanium dioxide-based composite material comprises silicon dioxide, a rare earth complex and titanium dioxide, wherein the silicon dioxide is used as a core, the rare earth complex is coated on the outer surface of the silicon dioxide to form a first shell, and the titanium dioxide is coated on the outer surface of the rare earth complex to form a second shell; the mass ratio of silicon dioxide, rare earth complex and titanium dioxide in the hybrid material is 1:0.3:0.6-2:0.1:1.7, the rare earth complex is formed in an organic ligand, the organic ligand comprises a first ligand and a second ligand, the molar ratio of the rare earth compound to the first ligand to the second ligand is 1:1:1-1:3:1, the first ligand is any one or two of 2-thenoyl trifluoroacetone and dibenzoyl methane, and the second ligand is any one or two of 1, 10-phenanthroline and acetylacetone.
The hybrid material has a core-shell structure, silicon dioxide is used as a core, a rare earth complex is wrapped on the outer surface of the silicon dioxide to form a first shell, and titanium dioxide is wrapped on the outer surface of the rare earth complex to form a second shell, wherein the second shell is uniform in size distribution; the silicon dioxide has good appearance and uniform dispersion; the rare earth complex coats the well-dispersed silicon dioxide spheres, so that the problem that the rare earth complex is easy to agglomerate is solved, and the rare earth complex has good fluorescence performance, so that the rare earth complex has better application in the fields of energy storage, solar cells, photonic devices, catalysis and the like; the titanium dioxide is positioned at the outermost layer of the hybrid material, so that the nonradiative transition of the rare earth complex can be effectively reduced, the quenching effect of the matrix on the rare earth complex is avoided, the luminous efficiency of the rare earth complex is optimized, and the stability of the hybrid material is improved.
In a preferred embodiment, the silica has a particle size of 120-140nm, the first shell has a thickness of 4-6nm, and the second shell has a thickness of 10-20 nm. The silicon dioxide is used as a template for synthesizing the hybrid material, so that the obtained hybrid material has a good appearance; under the action of silicon dioxide, the dispersibility of the hybrid material is improved and the hybrid material is uniformly dispersed.
In a preferred embodiment, the rare earth element in the rare earth complex is any one of europium, terbium, neodymium, samarium and gadolinium. The rare earth elements have various kinds, have the advantages of strong absorption capacity, high conversion efficiency and capability of emitting a spectrum from ultraviolet rays to infrared rays, and can obviously improve the fluorescence property of the hybrid material.
The invention relates to a preparation method of a silicon dioxide-rare earth-titanium dioxide hybrid material with a core-shell structure, which adopts the technical scheme that: the method comprises the following steps:
1) taking rare earth oxide, adding strong acid, stirring, dissolving, heating to separate out crystals until no liquid exists basically, drying, dissolving in an organic solvent to prepare a rare earth salt solution with the concentration of 0.08-0.12 mol/L;
2) taking a first ligand and a second ligand, and adding an organic solvent to prepare a first ligand solution and a second ligand solution respectively, wherein the concentration of the first ligand in the first ligand solution is 0.1-0.3mol/L, and the concentration of the second ligand in the second ligand solution is 0.1-0.3 mol/L;
3) dissolving silicon dioxide in organic solvent to obtain silicon dioxide solution with mass concentration of 3 × 10-3-5×10-3g/mL；
4) Adding the silicon dioxide solution obtained in the step 3) into the second ligand solution obtained in the step 2), stirring for 20-40min, then adding the first ligand solution obtained in the step 2) and the rare earth salt solution obtained in the step 1), wherein the molar ratio of the rare earth salt to the first ligand to the second ligand is 1:1:1-1:3:1, stirring for 5-7h, washing, and drying to obtain a primary product, wherein the mass ratio of silicon dioxide to the rare earth complex in the primary product is 1:0.3-2: 0.1;
5) dissolving the initial product obtained in the step 4) in an organic solvent to prepare a first solution, wherein the mass concentration of the initial product in the first solution is 3.1 multiplied by 10-3-5.6×10-3g/mL；
6) Adding hydroxypropyl cellulose and a solvent into the first solution obtained in the step 5), wherein the addition amount of the hydroxypropyl cellulose is 4-6 times of the mass of the initial product, and the addition amount of the solvent is 4-6 times of the volume of the first solution, and stirring for 20-40min to obtain a second mixed solution;
7) taking tetrabutyl titanate as a titanium source, adding an organic solvent to prepare a tetrabutyl titanate solution, wherein the volume ratio of tetrabutyl titanate to the organic solvent is 1:8-3: 8;
8) adding the tetrabutyl titanate solution obtained in the step 7) into the second mixed solution obtained in the step 6), wherein the volume ratio of the tetrabutyl titanate solution to the second mixed solution is 1:5-3:5, stirring for 80-120min at 80-90 ℃, washing, and drying to obtain the hybrid material.
The preparation method of the hybrid material takes rare earth oxide as a raw material, and the rare earth oxide is dissolved by strong acid to form a rare earth salt solution; then, respectively dissolving the organic ligand and the silicon dioxide by using an organic solvent; then, adding a second ligand solution into the silicon dioxide solution, and then adding the first ligand solution and the rare earth salt solution; the rare earth elements are hybridized to the surface of the silicon dioxide while being complexed, the silicon dioxide is well coated, and the rare earth elements are complexed on the surface of the silicon dioxide, so that the high dispersibility of the silicon dioxide is fully utilized, and the problem that the rare earth complex is easy to agglomerate is solved. In addition, the titanium dioxide is directly formed on the surface of the rare earth complex coated silicon dioxide product, and the titanium dioxide covers the surface of the rare earth complex to cover the rare earth complex to a certain degree, so that the nonradiative transition of the rare earth complex is effectively reduced, the quenching effect of a matrix on the rare earth complex is avoided, the luminous efficiency of the rare earth complex is optimized, and the stability of the hybrid material is improved. The preparation method is simple, short in process flow, convenient to operate and control, free of special requirements on equipment, clean and pollution-free, and easy to realize industrialization.
As a preferred embodiment, the preparation method of the silica microspheres comprises the following steps: adding ammonia water and deionized water into ethyl orthosilicate, adding absolute ethyl alcohol or methanol, wherein the addition amounts of the ammonia water, the deionized water, the absolute ethyl alcohol or the methanol are respectively 4.5-5.5 times, 1.8-1.2 times and 40-60 times of the dosage of the ethyl orthosilicate, stirring for 4-8h, washing, and drying at 55-65 ℃ to obtain the silicon dioxide microspheres. The silicon dioxide spheres have very high stability in aqueous solution and other media, the morphology of the silicon dioxide spheres is controllable in the reaction process, the dispersibility of the silicon dioxide spheres is good, and the precursors are low in price and easy to obtain.
In a preferred embodiment, in step 1), the strong acid is any one or more of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid, and the organic solvent is any one or two of absolute ethyl alcohol and methanol. The rare earth oxide is quickly dissolved under the action of strong acid to form rare earth salt, the purity of the rare earth salt is purified through crystal precipitation, and the rare earth salt is dissolved in absolute ethyl alcohol or methanol to form a solution, so that the subsequent reaction is facilitated.
As a preferred embodiment, in the step 1), the heating is carried out by using an oil bath, the oil bath temperature is 40-60 ℃, and the drying is carried out in an oven at 40-50 ℃. The method takes tetraethoxysilane as a silicon source, and controls the temperature of an oil bath by heating the tetraethoxysilane in the oil bath under the action of ammonia water, deionized water, absolute ethyl alcohol or methanol, and the product is washed for multiple times to obtain the silicon dioxide microspheres, so that the conditions are mild and the control is convenient.
In a preferred embodiment, the second stirring in step 4) is performed at room temperature by using a magnetic stirrer, and the stirring speed is 500-. According to the invention, after the rare earth salt solution, the first ligand solution and the second ligand solution are added, the mixture is stirred in the magnetic stirrer, the stirring time and the stirring temperature are controlled, the complexing and coating of rare earth elements are accelerated, the complexing action force is stronger, the coating is better and uniform, the dispersibility is better, and the agglomeration phenomenon is further avoided; moreover, the stirring is convenient, the control is easy, and the stirring efficiency is improved.
In a preferred embodiment, in step 4), the first stirring is performed under ultrasonic stirring at room temperature, and the drying temperature is 70-90 ℃. According to the invention, the second ligand solution is added into the silicon dioxide solution, and then the silicon dioxide solution is stirred by using ultrasound, so that the operation is easy and convenient to control, redundant energy is not consumed in room temperature operation, the experiment cost is reduced, the experiment efficiency is high, and the room temperature is usually 25 ℃.
As a preferred embodiment, in said step 6), the stirring is carried out at 30-40 ℃. Under the stirring temperature, the silica microspheres coated with the rare earth complex can be better dispersed into the solvent under the action of the surfactant, and the titanium dioxide can be more uniformly dispersed on the surface of the rare earth complex after the titanium source is added.
Compared with the prior art, the invention has the beneficial effects that: the hybrid material has a core-shell structure, silicon dioxide is used as a core, a rare earth complex is wrapped on the outer surface of the silicon dioxide to form a first shell, and titanium dioxide is wrapped on the outer surface of the rare earth complex to form a second shell, wherein the second shell is uniform in size distribution; the silicon dioxide has good appearance and uniform dispersion; the rare earth complex coats the well-dispersed silicon dioxide spheres, so that the problem that the rare earth complex is easy to agglomerate is solved, and the rare earth complex has good fluorescence performance, so that the rare earth complex has better application in the fields of energy storage, solar cells, photonic devices, catalysis and the like; the titanium dioxide is positioned at the outermost layer of the hybrid material, so that the nonradiative transition of the rare earth complex can be effectively reduced, the quenching effect of the matrix on the rare earth complex is avoided, the luminous efficiency of the rare earth complex is optimized, and the stability of the hybrid material is improved. The preparation method of the hybrid material is simple, short in process flow, convenient to operate and control, controls the structure of the hybrid material layer by layer, strictly controls the structure of the hybrid material, has no special requirements on equipment, is clean and pollution-free, and is easy to realize industrialization.
Drawings
FIG. 1 is a photograph of a transmission electron microscope of silica microspheres obtained according to the present invention;
FIG. 2 is a transmission electron micrograph of the rare earth complex obtained according to the present invention;
FIG. 3 is a transmission electron micrograph of the primary product obtained according to the present invention;
FIG. 4 is a transmission electron micrograph of the hybrid material obtained in the present invention;
FIG. 5 is a fluorescence image of the hybrid material obtained in the present invention.
Detailed Description
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 only a part of the embodiments of the present invention, and not all of the embodiments. 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.
The silicon dioxide-rare earth-titanium dioxide hybrid material with the core-shell structure comprises silicon dioxide, a rare earth complex and titanium dioxide, wherein the silicon dioxide is used as a core, the rare earth complex is wrapped on the outer surface of the silicon dioxide to form a first shell, and the titanium dioxide is wrapped on the outer surface of the rare earth complex to form a second shell; the mass ratio of silicon dioxide, rare earth complex and titanium dioxide in the hybrid material is 1:0.3:0.6-2:0.1:1.7, the rare earth complex is formed in an organic ligand, the organic ligand comprises a first ligand and a second ligand, the molar ratio of the rare earth compound to the first ligand to the second ligand is 1:1:1-1:3:1, the first ligand is any one or two of 2-thenoyl trifluoroacetone and dibenzoyl methane, and the second ligand is any one or two of 1, 10-phenanthroline and acetylacetone.
Preferably, the particle size of the silicon dioxide is 120-140nm, the thickness of the first shell is 4-6nm, and the thickness of the second shell is 10-20 nm.
Furthermore, the rare earth element in the rare earth complex is any one of europium, terbium, neodymium, samarium and gadolinium.
The invention relates to a preparation method of a silicon dioxide-rare earth-titanium dioxide hybrid material with a core-shell structure, which comprises the following steps:
1) taking rare earth oxide, adding strong acid, stirring, dissolving, heating to separate out crystals until no liquid exists basically, drying, dissolving in an organic solvent to prepare a rare earth salt solution with the concentration of 0.08-0.12 mol/L;
2) taking a first ligand and a second ligand, and adding an organic solvent to prepare a first ligand solution and a second ligand solution respectively, wherein the concentration of the first ligand in the first ligand solution is 0.1-0.3mol/L, and the concentration of the second ligand in the second ligand solution is 0.1-0.3 mol/L;
3) dissolving silicon dioxide in organic solvent to obtain silicon dioxide solution with mass concentration of 3 × 10-3-5×10-3g/mL；
4) Adding the silicon dioxide solution obtained in the step 3) into the second ligand solution obtained in the step 2), stirring for 20-40min, then adding the first ligand solution obtained in the step 2) and the rare earth salt solution obtained in the step 1), wherein the molar ratio of the rare earth salt to the first ligand to the second ligand is 1:1:1-1:3:1, stirring for 5-7h, washing, and drying to obtain a primary product, wherein the mass ratio of silicon dioxide to the rare earth complex in the primary product is 1:0.3-2: 0.1;
5) dissolving the initial product obtained in the step 4) in an organic solvent to prepare a first solution, wherein the mass concentration of the initial product in the first solution is 3.1 multiplied by 10-3-5.6×10-3g/mL；
6) Adding hydroxypropyl cellulose and a solvent into the first solution obtained in the step 5), wherein the addition amount of the hydroxypropyl cellulose is 4-6 times of the mass of the initial product, and the addition amount of the solvent is 4-6 times of the volume of the first solution, and stirring for 20-40min to obtain a second mixed solution;
7) taking tetrabutyl titanate as a titanium source, adding an organic solvent to prepare a tetrabutyl titanate solution, wherein the volume ratio of tetrabutyl titanate to the organic solvent is 1:8-3: 8;
8) adding the tetrabutyl titanate solution obtained in the step 7) into the second mixed solution obtained in the step 6), wherein the volume ratio of the tetrabutyl titanate solution to the second mixed solution is 1:5-3:5, stirring for 80-120min at 80-90 ℃, washing, and drying to obtain the hybrid material.
Preferably, the preparation method of the silica microspheres comprises the following steps: adding ammonia water and deionized water into ethyl orthosilicate, adding absolute ethyl alcohol or methanol, wherein the addition amounts of the ammonia water, the deionized water, the absolute ethyl alcohol or the methanol are respectively 4.5-5.5 times, 1.8-1.2 times and 40-60 times of the dosage of the ethyl orthosilicate, stirring for 4-8h, washing, and drying at 55-65 ℃ to obtain the silicon dioxide microspheres.
Further, in the step 1), the strong acid is one or more of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid, and the organic solvent is one or two of absolute ethyl alcohol and methanol.
Specifically, in the step 1), the heating is carried out by adopting oil bath heating, the oil bath temperature is 40-60 ℃, and the drying is finished in an oven at 40-50 ℃.
Still preferably, in the step 4), the second stirring is performed at room temperature by using a magnetic stirrer, and the stirring speed is 500-.
Still further, in the step 4), the first stirring is performed under ultrasonic stirring at room temperature, and the drying temperature is 70-90 ℃.
More specifically, in the step 6), the stirring is performed at 30 to 40 ℃.
Example one
The invention relates to a preparation method of a silicon dioxide-rare earth-titanium dioxide hybrid material with a core-shell structure, which comprises the following steps:
1) 1.3459g of neodymium oxide is taken, 3mL of concentrated sulfuric acid is added, stirring is carried out until the neodymium oxide is dissolved, heating is carried out in an oil bath at 50 ℃ to separate out crystals until no liquid exists basically, the crystals cannot be dried into powder, and drying is carried out in an oven at 40 ℃ to obtain neodymium sulfate for later use; dissolving neodymium sulfate in methanol to prepare a neodymium sulfate solution with the concentration of 0.08 mol/L;
2) taking a first ligand, namely acetylacetone, and a second ligand, namely 1, 10-phenanthroline, and adding methanol to prepare a first ligand solution and a second ligand solution respectively, wherein the concentration of the first ligand in the first ligand solution is 0.1mol/L, and the concentration of the second ligand in the second ligand solution is 0.3 mol/L;
3) dissolving silicon dioxide in methanol to prepare silicon dioxide solution, wherein the mass concentration of the silicon dioxide in the silicon dioxide solution is 3 multiplied by 10-3g/mL；
4) Adding the silicon dioxide solution obtained in the step 3) into the second ligand solution obtained in the step 2), stirring for 20min, then adding the first ligand solution obtained in the step 2) and the neodymium sulfate solution obtained in the step 1), wherein the molar ratio of neodymium sulfate to the first ligand to the second ligand is 1:1:1, stirring for 5h, washing, and drying to obtain an initial product, wherein the mass ratio of silicon dioxide to the rare earth complex in the initial product is 1: 0.3;
5) dissolving the primary product obtained in the step 4) in methanol to prepare a first solution, wherein the mass concentration of the primary product in the first solution is 3.1 multiplied by 10-3g/mL；
6) Adding hydroxypropyl cellulose and a solvent into the first solution obtained in the step 5), wherein the addition amount of the hydroxypropyl cellulose is 4 times of the mass of the initial product, and the addition amount of the solvent is 4 times of the volume of the first solution, and stirring for 20min to obtain a second mixed solution;
7) taking tetrabutyl titanate as a titanium source, adding an organic solvent to prepare a tetrabutyl titanate solution, wherein the volume ratio of tetrabutyl titanate to the organic solvent is 1: 8;
8) adding the tetrabutyl titanate solution obtained in the step 7) into the second mixed solution obtained in the step 6), wherein the volume ratio of the tetrabutyl titanate solution to the second mixed solution is 1:5, stirring for 80min at 80 ℃, washing, and drying to obtain the hybrid material.
Example two
The invention relates to a preparation method of a silicon dioxide-rare earth-titanium dioxide hybrid material with a core-shell structure, which comprises the following steps:
1) taking 0.2g of terbium oxide, adding 7mL of concentrated nitric acid, stirring until the terbium oxide is dissolved, heating in an oil bath at 50 ℃ to separate out crystals until no liquid exists basically, and drying the crystals into powder, and drying the crystals in a drying oven at 40 ℃ to obtain terbium nitrate for later use; dissolving terbium nitrate in absolute ethyl alcohol to prepare a terbium nitrate solution with the concentration of 0.12 mol/L;
2) respectively preparing a first ligand solution and a second ligand solution by adding absolute ethyl alcohol into a first ligand, namely 2-thenoyltrifluoroacetone and a second ligand, namely 1, 10-phenanthroline, wherein the concentration of the first ligand in the first ligand solution is 0.3mol/L, and the concentration of the second ligand in the second ligand solution is 0.1 mol/L;
3) preparing the silicon dioxide microspheres: taking 1mL of tetraethoxysilane, adding 5mL of ammonia water and 1mL of deionized water, adding 50mL of absolute ethyl alcohol, stirring for 6 hours at 25 ℃, washing for multiple times, and drying at 60 ℃ to obtain silicon dioxide microspheres;
4) dissolving the silica microspheres obtained in the step 3) in absolute ethyl alcohol to prepare a silica solution, wherein the silica is in the dioxygenThe mass concentration in the silicon solution is 5X 10-3g/mL；
5) Adding the silicon dioxide solution obtained in the step 4) into the second ligand solution obtained in the step 2), stirring for 40min, then adding the silicon dioxide solution into the first ligand solution obtained in the step 2) and the terbium nitrate solution obtained in the step 1), wherein the molar ratio of terbium nitrate to the first ligand to the second ligand is 1:3:1, stirring for 7h, washing, and drying to obtain a primary product, wherein the mass ratio of silicon dioxide to the rare earth complex in the primary product is 2: 0.1;
6) dissolving the initial product obtained in the step 5) in absolute ethyl alcohol to prepare a first solution, wherein the mass concentration of the initial product in the first solution is 5.6 multiplied by 10-3g/mL；
7) Adding hydroxypropyl cellulose and a solvent into the first solution obtained in the step 6), wherein the addition amount of the hydroxypropyl cellulose is 6 times of the mass of the primary product, and the addition amount of the solvent is 6 times of the volume of the first solution, and stirring for 40min to obtain a second mixed solution;
8) taking tetrabutyl titanate as a titanium source, adding an organic solvent to prepare a tetrabutyl titanate solution, wherein the volume ratio of tetrabutyl titanate to the organic solvent is 3: 8;
9) adding the tetrabutyl titanate solution obtained in the step 8) into the second mixed solution obtained in the step 7), wherein the volume ratio of the tetrabutyl titanate solution to the second mixed solution is 3:5, stirring for 120min at 90 ℃, washing, and drying to obtain the hybrid material.
EXAMPLE III
The invention relates to a preparation method of a silicon dioxide-rare earth-titanium dioxide hybrid material with a core-shell structure, which comprises the following steps:
1) taking 0.9g of europium oxide, adding 5mL of concentrated hydrochloric acid, stirring until the europium oxide is dissolved, heating in an oil bath at 50 ℃ to separate out crystals until no liquid exists basically and the crystals cannot be dried into powder, and drying in a drying oven at 40 ℃ to obtain europium chloride for later use; dissolving europium chloride in absolute ethyl alcohol to prepare a europium chloride solution with the concentration of 0.10 mol/L;
2) taking a first ligand, namely dibenzoylmethane, and a second ligand, namely acetylacetone, and adding absolute ethyl alcohol to prepare a first ligand solution and a second ligand solution respectively, wherein the concentration of the first ligand in the first ligand solution is 0.3mol/L, and the concentration of the second ligand in the second ligand solution is 0.1 mol/L;
3) preparing the silicon dioxide microspheres: taking 1mL of tetraethoxysilane, adding 5mL of ammonia water and 1mL of deionized water, adding 50mL of absolute ethyl alcohol, stirring for 6 hours at 25 ℃, washing for multiple times, and drying at 60 ℃ to obtain silicon dioxide microspheres;
4) dissolving the silicon dioxide obtained in the step 3) in absolute ethyl alcohol to prepare a silicon dioxide solution, wherein the mass concentration of the silicon dioxide in the silicon dioxide solution is 4 multiplied by 10-3g/mL；
5) Taking 50mL of the silicon dioxide solution obtained in the step 4), adding 200 mu L of the second ligand solution obtained in the step 2), ultrasonically stirring for 30min at room temperature, then adding 200 mu L of the first ligand solution obtained in the step 2) and 200 mu L of the europium chloride solution obtained in the step 1), stirring for 6h at 25 ℃ in a magnetic stirrer at the stirring speed of 600r/min, washing for multiple times, and drying at 80 ℃ to obtain an initial product;
6) dissolving the initial product obtained in the step 5) in absolute ethyl alcohol to prepare a first solution, wherein the mass concentration of the initial product in the first solution is 4.2 multiplied by 10-3g/mL；
7) Taking 5mL of the first solution obtained in the step 6), adding 0.1g of hydroxypropyl cellulose, 20mL of absolute ethyl alcohol serving as a solvent and 0.1mL of deionized water, and stirring for 30min at 30 ℃ to obtain a second mixed solution;
8) taking tetrabutyl titanate as a titanium source, adding an organic solvent to prepare a tetrabutyl titanate solution, wherein the volume ratio of tetrabutyl titanate to the organic solvent is 1: 4;
9) and (3) adding 5mL of tetrabutyl titanate solution obtained in the step 8) into the second mixed solution obtained in the step 7), stirring for 100min at 85 ℃, washing for multiple times, and drying to obtain the hybrid material.
The silica microspheres obtained in the embodiment are placed on a model JEM-2100 transmission electron microscope produced by a JEOL manufacturer for analysis, and the obtained transmission electron microscope photo is shown in figure 1, and as can be seen from figure 1, the silica microspheres obtained in the invention have the size of 120-140nm, are regular spherical particles, are uniform in particle size, are controllable in morphology, have good dispersibility and are good in stability. The rare earth complex obtained in the embodiment is placed on a model JEM-2100 transmission electron microscope produced by a JEOL manufacturer for analysis, the obtained transmission electron microscope photo is shown in figure 2, and as can be seen from figure 2, the rare earth complex obtained by the invention has very small particle size, the size is 4-6nm, the rare earth complex is easy to agglomerate and has poor dispersibility; the fluorescent material has good fluorescent property, but the fluorescent material is directly exposed in a matrix, so that the fluorescent material is easy to quench the rare earth luminescence, has poor stability and limits the application of the fluorescent material. The primary product obtained in the embodiment is placed on a transmission electron microscope of model JEM-2100 produced by a JEOL manufacturer for analysis, the obtained transmission electron microscope photo is shown in figure 3, and as can be seen from figure 3, the primary product obtained in the invention wraps a layer of rare earth complex on the outer layer of silicon dioxide, and the rare earth complex is wrapped on the surface of silicon dioxide microspheres and uniformly dispersed, so that the problem of agglomeration of the rare earth complex is solved; in addition, the fluorescent material has good fluorescent property, so that the fluorescent material has better application in the fields of energy storage, solar cells, photonic devices, catalysis and the like. The hybrid material obtained in the embodiment is placed on a transmission electron microscope of model JEM-2100 produced by a JEOL manufacturer for analysis, the obtained transmission electron microscope photo is shown in figure 4, and as can be seen from figure 4, the size of the hybrid material obtained in the invention is between 140-180nm, the hybrid material has a rough surface and good dispersibility, the titanium dioxide effectively coats the rare earth complex, the nonradiative transition of the rare earth complex can be effectively reduced, the luminous efficiency of the rare earth complex is optimized, and the stability of the hybrid material is improved. The hybrid material obtained in this example was placed in an Eclipse model fluorescence photometer manufactured by VARIAN of USA for fluorescence performance test, and the test result is shown in FIG. 5, and it can be seen from FIG. 5 that the hybrid material obtained in the present invention has emission at 614nm, and the fluorescence intensity is as high as about 300a.u.
The hybridization materials obtained in the first to third examples of the present invention were respectively subjected to fluorescence property test experiments, the fluorescence intensities thereof were measured on a fluorescence photometer, and the same test experiments were respectively performed on the rare earth complex (i.e., the first control) prepared in the third example and the inorganic rare earth-doped titanium dioxide (i.e., the second control), and the results of the experiments are shown in table 1. And calculating the coating rate according to the analysis result of the transmission electron microscope, calculating the number of the wrapped samples and the number of the unwrapped samples in the transmission electron microscope picture by observation, and calculating the coating rate according to a formula, wherein the coating rate is the number of the wrapped samples/(the number of the wrapped samples + the number of the unwrapped samples)) multiplied by 100%. Placing the sample in a natural environment for 30 days, measuring the fluorescence intensity of the sample on a fluorescence photometer again, and comparing the newly obtained data with the original data to obtain the stability of the sample; the agglomeration of the particles was counted and the results are also shown in Table 1.
TABLE 1 results of fluorescence Properties measurements of different materials
| Sample name | Particle size (nm) | Agglomeration of particles | Coating ratio (%) | Fluorescence intensity (a.u.) | Description of the stability |
| Example one | 155 | Does not agglomerate | 95 | 200 | Good effect |
| Example two | 163 | Does not agglomerate | 93 | 220 | Good effect |
| EXAMPLE III | 168 | Does not agglomerate | 97 | 290 | Good effect |
| Comparison sample one | 5 | Agglomeration | --- | 130 | Difference (D) |
| Control 2 | 160 | Slightly agglomerated | 90 | 20 | Difference (D) |
As can be seen from Table 1, the particle size of the hybrid material of the invention is 140-180nm, and the particles are uniformly distributed; the dispersibility is good, and the agglomeration phenomenon is avoided; the coating rate is high, is more than 93 percent and is uniform; the silicon dioxide is uniformly coated by the rare earth complex, and simultaneously, the surface of the rare earth complex is uniformly coated with a layer of titanium dioxide; the fluorescence intensity of the obtained hybrid material reaches 200-300a.u., and the hybrid material has obvious fluorescence property; meanwhile, as the rare earth complex is coated by the titanium dioxide layer, compared with the pure rare earth complex (namely a reference sample I), the fluorescence property of the rare earth complex effectively reduces the non-radiative transition of the rare earth complex and optimizes the luminous efficiency of the rare earth complex; the performance of the hybrid material of the invention is obviously superior to that of the titanium dioxide simply doped with inorganic rare earth (namely, the reference sample II), the stability, the coating rate and the fluorescence intensity of the hybrid material are improved, no agglomeration exists among particles, and the overall performance of the hybrid material is improved.
Therefore, compared with the prior art, the invention has the beneficial effects that: the hybrid material has a core-shell structure, silicon dioxide is used as a core, a rare earth complex is wrapped on the outer surface of the silicon dioxide to form a first shell, and titanium dioxide is wrapped on the outer surface of the rare earth complex to form a second shell, wherein the second shell is uniform in size distribution; the silicon dioxide has good appearance and uniform dispersion; the rare earth complex coats the well-dispersed silicon dioxide spheres, so that the problem that the rare earth complex is easy to agglomerate is solved, and the rare earth complex has good fluorescence performance, so that the rare earth complex has better application in the fields of energy storage, solar cells, photonic devices, catalysis and the like; the titanium dioxide is positioned at the outermost layer of the hybrid material, so that the nonradiative transition of the rare earth complex can be effectively reduced, the quenching effect of the matrix on the rare earth complex is avoided, the luminous efficiency of the rare earth complex is optimized, and the stability of the hybrid material is improved. The preparation method of the hybrid material is simple, short in process flow, convenient to operate and control, controls the structure of the hybrid material layer by layer, strictly controls the structure of the hybrid material, has no special requirements on equipment, is clean and pollution-free, and is easy to realize industrialization.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a silicon dioxide-rare earth-titanium dioxide hybrid material with a core-shell structure is characterized by comprising the following steps:
the hybrid material comprises silicon dioxide, a rare earth complex and titanium dioxide, wherein the silicon dioxide is used as a core, the rare earth complex is wrapped on the outer surface of the silicon dioxide to form a first shell, and the titanium dioxide is wrapped on the outer surface of the rare earth complex to form a second shell;
the mass ratio of silicon dioxide, rare earth complex and titanium dioxide in the hybrid material is 1:0.3:0.6-2:0.1:1.7, the rare earth complex is formed in an organic ligand, the organic ligand comprises a first ligand and a second ligand, the molar ratio of the rare earth compound to the first ligand to the second ligand is 1:1:1-1:3:1, the first ligand is any one or two of 2-thenoyl trifluoroacetone and dibenzoyl methane, and the second ligand is any one or two of 1, 10-phenanthroline and acetylacetone;
the preparation method of the hybrid material comprises the following steps:
1) taking rare earth oxide, adding strong acid, stirring, dissolving, heating to separate out crystals until no liquid exists basically, drying, dissolving in an organic solvent to prepare a rare earth salt solution with the concentration of 0.08-0.12 mol/L;
2) taking a first ligand and a second ligand, and adding an organic solvent to prepare a first ligand solution and a second ligand solution respectively, wherein the concentration of the first ligand in the first ligand solution is 0.1-0.3mol/L, and the concentration of the second ligand in the second ligand solution is 0.1-0.3 mol/L;
3) dissolving silicon dioxide in organic solvent to obtain silicon dioxide solution with mass concentration of 3 × 10-3-5×10-3g/mL；
4) Adding the silicon dioxide solution obtained in the step 3) into the second ligand solution obtained in the step 2), stirring for 20-40min, then adding the first ligand solution obtained in the step 2) and the rare earth salt solution obtained in the step 1), wherein the molar ratio of the rare earth salt to the first ligand to the second ligand is 1:1:1-1:3:1, stirring for 5-7h, washing, and drying to obtain a primary product, wherein the mass ratio of silicon dioxide to the rare earth complex in the primary product is 1:0.3-2: 0.1;
5) dissolving the initial product obtained in the step 4) in an organic solvent to prepare a first solution, wherein the mass concentration of the initial product in the first solution is 3.1 multiplied by 10-3-5.6×10-3g/mL；
6) Adding hydroxypropyl cellulose and a solvent into the first solution obtained in the step 5), wherein the addition amount of the hydroxypropyl cellulose is 4-6 times of the mass of the initial product, and the addition amount of the solvent is 4-6 times of the volume of the first solution, and stirring for 20-40min to obtain a second mixed solution;
7) taking tetrabutyl titanate as a titanium source, adding an organic solvent to prepare a tetrabutyl titanate solution, wherein the volume ratio of tetrabutyl titanate to the organic solvent is 1:8-3: 8;
8) adding the tetrabutyl titanate solution obtained in the step 7) into the second mixed solution obtained in the step 6), wherein the volume ratio of the tetrabutyl titanate solution to the second mixed solution is 1:5-3:5, stirring for 80-120min at 80-90 ℃, washing, and drying to obtain the hybrid material.
2. The preparation method of the silica-rare earth-titania hybrid material with the core-shell structure according to claim 1, characterized in that:
the particle size of the silicon dioxide is 120-140nm, the thickness of the first shell is 4-6nm, and the thickness of the second shell is 10-20 nm.
3. The preparation method of the silica-rare earth-titania hybrid material with the core-shell structure according to claim 1, characterized in that:
the rare earth element in the rare earth complex is any one of europium, terbium, neodymium, samarium and gadolinium.
4. The preparation method of the silica-rare earth-titania hybrid material with the core-shell structure according to any one of claims 1 to 3, wherein the preparation method of the silica microspheres comprises the following steps:
adding ammonia water and deionized water into ethyl orthosilicate, adding absolute ethyl alcohol or methanol, wherein the addition amounts of the ammonia water, the deionized water, the absolute ethyl alcohol or the methanol are respectively 4.5-5.5 times, 1.8-1.2 times and 40-60 times of the dosage of the ethyl orthosilicate, stirring for 4-8h, washing, and drying at 55-65 ℃ to obtain the silicon dioxide microspheres.
5. The preparation method of the silica-rare earth-titania hybrid material with the core-shell structure according to claim 1, characterized in that:
in the step 1), the strong acid is one or more of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid, and the organic solvent is one or two of absolute ethyl alcohol and methanol.
6. The preparation method of the silica-rare earth-titania hybrid material with the core-shell structure according to claim 1, characterized in that:
in the step 1), the heating is carried out by adopting oil bath heating, the oil bath temperature is 40-60 ℃, and the drying is finished in an oven at the temperature of 40-50 ℃.
7. The preparation method of the silica-rare earth-titania hybrid material with the core-shell structure according to claim 1, characterized in that:
in the step 4), the second stirring is performed at room temperature by using a magnetic stirrer, and the stirring speed is 500-.
8. The preparation method of the silica-rare earth-titania hybrid material with the core-shell structure according to claim 1, characterized in that:
in the step 4), the first stirring is completed at room temperature under ultrasonic stirring, and the drying temperature is 70-90 ℃.
9. The preparation method of the silica-rare earth-titania hybrid material with the core-shell structure according to claim 1, characterized in that:
in the step 6), stirring is completed at 30-40 ℃.
10. A silicon dioxide-rare earth-titanium dioxide hybrid material with a core-shell structure is characterized in that:
the hybrid material is prepared by the preparation method of the silicon dioxide-rare earth-titanium dioxide hybrid material with the core-shell structure according to any one of claims 1 to 9.
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