CN112618390A - Silicon dioxide/rare earth oxide light conversion composite material and preparation method thereof - Google Patents
Silicon dioxide/rare earth oxide light conversion composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of nano sunscreen composite materials, and particularly relates to a silicon dioxide/rare earth oxide light conversion composite material and a preparation method thereof. The composite material combines silicon dioxide and rare earth ions by a homogeneous precipitation method to synthesize a spherical silicon dioxide/rare earth oxide light conversion composite material, and has the advantages of controllable particle size, good dispersibility and difficult agglomeration; amphiphilic modification can be well realized, and the absorption and conversion of ultraviolet light can be realized within the ultraviolet full-spectrum range of 230-410 nm; in addition, the material has good chemical stability and thermal stability, is nontoxic and harmless to human bodies, and has good application prospect in the field of novel sun-proof materials.
Description
Technical Field
The invention belongs to the technical field of nano sun-proof composite materials. And more particularly, to a silica/rare earth oxide light conversion composite material and a method for preparing the same.
Background
The ultraviolet rays can be classified into long-wave ultraviolet rays (UVA) of 320-400 nm, medium-wave ultraviolet rays (UVB) of 280-320 nm, and short-wave ultraviolet rays (UVC) of 200-280 nm according to wavelength. Wherein, UVB and UVA are mainly harmful to the health of human skin, UVB ultraviolet rays can cause red swelling, blisters and skin aging, severe people can cause skin cancer, and the ultraviolet band is an important ultraviolet band for prevention; UVA has also been shown to decrease skin elasticity and accelerate skin aging with excessive exposure. Therefore, the realization of the full-range coverage protection of long-wave ultraviolet rays and medium-wave ultraviolet rays is the development trend and the inevitable requirement of the sunscreen products.
Sunscreen products are classified into chemical sunscreens and physical sunscreens depending on the mechanism of the sun protection. The chemical sunscreen agent mainly achieves the effect of absorbing ultraviolet photons based on reversible isomerization among organic matter molecules with aromatic rings or chromophoric structures, has a good sunscreen effect, but generally only aims at a specific wave band (UVA or UVB wave band), and most organic matters are easily decomposed and inactivated under illumination or high temperature to lose the sunscreen capacity, so that the chemical sunscreen agent is poor in stability and has certain irritation to the skin. The other physical sun-screening agent mainly achieves the effect of shielding ultraviolet rays through reflection and scattering, most typical is nano-scale titanium dioxide and zinc oxide powder materials, and has the advantages of stable chemical properties, high safety and capability of simultaneously covering full-spectrum shielding of UVA and UVB wave bands. For example, Chinese patent application CN109381361A discloses a refreshing sun block, the main sun block components of the sun block are butyl methoxy dibenzoyl methane, zinc oxide and nano titanium dioxide, and the sun block has good sun block effect; however, the nano titanium dioxide has the problem of phototoxicity, and the nano titanium dioxide can generate active oxygen free radicals (such as. OH, O) under the ultraviolet irradiation2-Etc.), on the one hand, active free radicals cause degradation of other organic substances in cosmetics, and on the other hand, active free radicals also accelerate skin aging, cause damage to skin, even human DNA, proteinsParenchyma or other cells.
Therefore, a new sunscreen material with large sunscreen wave band coverage, good stability and high safety is urgently needed to be provided.
Disclosure of Invention
The invention aims to solve the technical problems of small coverage area of sun-screening wave bands, poor stability and certain potential safety hazard of the existing sun-screening agent and provide a novel silicon dioxide/rare earth oxide photoconversion composite material with large coverage area of sun-screening wave bands, good stability and high safety.
The invention aims to provide a silicon dioxide/rare earth oxide light conversion composite material.
The invention also aims to provide a preparation method of the silicon dioxide/rare earth oxide light conversion composite material.
The invention also aims to provide application of the silica/rare earth oxide light conversion composite material.
The above purpose of the invention is realized by the following technical scheme:
a silicon dioxide/rare earth oxide light conversion composite material has a chemical composition expression of RE2O3-SiO2(ii) a Wherein RE is one or more rare earth elements selected from Y, Ce, Sm, Eu, Gd and Lu.
The silicon dioxide has better biocompatibility with human body, the rare earth ions have light conversion characteristics, and the inventor creatively combines the silicon dioxide and the rare earth ions by a homogeneous precipitation method to synthesize the spherical silicon dioxide/rare earth oxide light conversion composite material. The material has controllable particle size and good dispersibility, is not easy to agglomerate, and can better realize amphiphilic modification by utilizing the good compatibility of silicon dioxide; by adjusting the species and proportion of rare earth ions, the silicon dioxide/rare earth oxide light conversion composite material can realize the absorption and conversion of ultraviolet light in the full ultraviolet spectrum range, and can convert the ultraviolet light into visible red fluorescence emission after absorbing the ultraviolet light; in addition, the silicon dioxide/rare earth oxide light conversion composite material prepared by the invention has good chemical stability and thermal stability, is nontoxic and harmless to human bodies, and has good application prospect in the field of novel sun-proof materials.
Further, the composite material absorbs ultraviolet light within the range of 230-410 nm and converts the absorbed ultraviolet light into visible red fluorescence emission.
In addition, the invention also provides a preparation method of the silicon dioxide/rare earth oxide light conversion composite material, and the preparation method comprises the following steps:
the method comprises the following steps: firstly preparing a silicon dioxide ball template by a sol-gel method, then epitaxially growing a rare earth precipitate shell layer on the template by a coprecipitation method, and finally annealing to obtain the silicon dioxide/rare earth oxide photoconversion composite material;
or the second method: firstly, preparing a monodisperse rare earth precipitate by a coprecipitation method, then coating a silicon dioxide shell layer on the outer layer of the monodisperse rare earth precipitate, and finally annealing to obtain the silicon dioxide/rare earth oxide photoconversion composite material.
Further, the first method specifically comprises the following steps:
s1, dissolving Cetyl Trimethyl Ammonium Bromide (CTAB) in a mixed solution of ethanol and water, uniformly stirring, dropwise adding ammonia water, heating and stirring, then adding Tetraethoxysilane (TEOS), heating and stirring, and performing post-treatment after the reaction is finished to obtain a silicon dioxide ball;
s2, dispersing the silicon dioxide balls obtained in the step S1 in water, adding a rare earth salt solution, uniformly mixing, adding urea, heating and stirring, and performing post-treatment after the reaction is finished to obtain a precursor;
and S3, uniformly grinding the precursor obtained in the step S2, annealing and grinding to obtain the material.
Furthermore, in step S1, the ethanol solution is prepared by mixing water and ethanol according to a volume ratio of 14 (3-6).
Further, in step S1, the ratio of the amount of cetyltrimethylammonium bromide to the amount of water is (2.0 × 10)-3～1.0×10-2)mol：56ml。
Furthermore, in step S1, the heating and stirring temperature is 50-80 ℃, and the stirring reaction time is 2-6 h.
Further, in step S1, the ratio of the addition amount of tetraethyl orthosilicate (TEOS) to the amount of water used is (2.0 to 4.0) ml: 56 ml.
Furthermore, in step S2, the ratio of the silica spheres, water, urea, and the rare earth salt solution is (0.015 to 0.12) g: (25-100) ml: (0.729 to 3.645) g: (0.25 to 1.0) mmol.
Further, in the step S2, the heating and stirring temperature is 60-90 ℃, and the reaction time is 4-12 h.
Further, the second method specifically comprises the following steps:
adding urea into water, uniformly mixing, adding a rare earth salt solution, heating and stirring, and carrying out post-treatment after the reaction is finished to obtain a rare earth precipitate;
SII, adding the rare earth precipitate obtained in the step SI into ethanol for dispersion, adding water, heating and stirring, sequentially dropwise adding ammonia water and tetraethoxysilane, heating for reaction, and performing post-treatment after the reaction is finished to obtain a precursor;
and SIII, uniformly grinding the precursor obtained in the step SII, annealing and grinding to obtain the silicon nitride/.
Furthermore, in the step SI, the ratio of the water, the urea, the rare earth nitrate solution and the cerium nitrate solution is 50 ml: (1.1252-3.003) g: (4.00-4.99) ml: (0.005-1.250) ml.
Further, in the step SI, the heating and stirring temperature is 50-90 ℃, and the reaction time is 6-12 hours.
Furthermore, in the step SII, the dosage ratio of the rare earth precipitate, ethanol, water, ammonia water and ethyl orthosilicate is 0.0603 g: 50 ml: 10 ml: (0.5-2.5) ml: (0.075-0.200) ml.
Further, in the step SII, the heating and stirring temperature is 25-40 ℃, and the stirring time is 5-15 min.
Furthermore, in the step SII, the heating reaction temperature is 50-90 ℃ and the reaction time is 12-14 h.
Further, the concentration of the ammonia water is 10-28%, the dropping speed is 0.5-2 s/drop, the stirring time is 15-45 min, and the dosage is 0.05-0.20 ml.
Furthermore, the tetraethoxysilane is added dropwise at a speed of 5-15 s/drop.
Further, the stirring speed is 600-1300 rpm.
Furthermore, the rare earth salt solution is a rare earth nitrate solution or a rare earth acetate solution, and the concentration of the rare earth salt solution is 0.02-0.50M.
Further, the post-treatment comprises cooling, centrifuging, washing and drying. The washing is alternately washing by deionized water and ethanol; the drying is carried out for 8-12 h at the temperature of 60-90 ℃.
Furthermore, the annealing temperature is 950-1050 ℃, the heating rate is 1-10 ℃, and the reaction time is 8-20 hours.
In addition, the invention also provides application of the silicon dioxide/rare earth oxide light conversion composite material in a sunscreen product.
Further, the sunscreen product comprises sunscreen cosmetics and sunscreen plastics.
The invention has the following beneficial effects:
the silicon dioxide/rare earth oxide light conversion composite material has controllable particle size and good dispersibility, is not easy to agglomerate, can better realize amphiphilic modification by utilizing good compatibility of silicon dioxide, and realizes absorption and conversion of ultraviolet light within the ultraviolet full-spectrum range of 230-410 nm; in addition, the material has good chemical stability and thermal stability, is nontoxic and harmless to human bodies, and has good application prospect in the field of novel sun-proof materials.
Drawings
FIG. 1 shows SiO obtained in example 1 of the present invention2@Lu(OH)CO3TEM image of rare earth precipitate precursor powder.
FIG. 2 shows SiO obtained in example 1 of the present invention2@Lu1.86Ce0.04Eu0.1O3TEM images of the composite.
FIG. 3 shows SiO obtained in example 1 of the present invention2@Lu1.86Ce0.04Eu0.1O3Excitation spectrum of the composite material.
FIG. 4 shows SiO obtained in example 1 of the present invention2@Lu1.86Ce0.04Eu0.1O3Photograph of the composite material emitting red fluorescence under the irradiation of ultraviolet lamp.
FIG. 5 shows Lu (OH) CO obtained in example 2 of the present invention3TEM images of rare earth precipitates.
FIG. 6 shows Lu obtained in example 2 of the present invention1.86Ce0.04Eu0.1O3@SiO2TEM images of the composite.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1A spherical silica/rare earth oxide composite SiO2@Lu1.86Ce0.04Eu0.1O3(70nm) preparation
The preparation method specifically comprises the following steps:
s1, preparing a silicon dioxide template: measuring 56ml of deionized water in a single-neck flask, mixing with 14ml of absolute ethanol, weighing 1.146g of cetyltrimethylammonium bromide (CTAB) to dissolve, stirring at normal temperature for 10min, and slowly dropwise adding 0.1ml of 28% ammonia water (NH)3H2O), placing the single-neck flask on a magnetic heating stirrer, stirring for 30min at 60 ℃ to form a uniform solution, dropwise adding 2.92ml of Tetraethoxysilane (TEOS) at the speed of 10 s/drop under the stirring state, continuously heating for reaction for 3h, cooling, centrifuging, washing with deionized water and ethanol for several times, and drying in an oven at 70 ℃ for 12h to obtain silicon dioxide balls with the particle size of about 70 nm;
s2, weighing 0.030g of the silicon dioxide spheres obtained in the step S1, ultrasonically dispersing the silicon dioxide spheres in 25ml of deionized water, accurately weighing 2.325ml of the prepared silicon dioxide spheres0.2M Lu (NO)3)3、1.00ml 0.02M Ce(NO3)3And 0.50ml of 0.05M Eu (NO)3)3Putting the solution on an oil bath heating stirrer, stirring for 20min, adding 1.5g of urea, setting the oil bath temperature at 80 ℃, reacting for 6h under a strong stirring state, cooling, centrifuging, washing with deionized water and ethanol for several times, and drying in an oven at 70 ℃ for 12h to obtain SiO2@Lu(OH)CO3Precursor powder of rare earth precipitate;
s3, grinding the precursor powder obtained in the step S2 uniformly by using a mortar, transferring the precursor powder into an alumina crucible, placing the alumina crucible into a muffle furnace, setting the annealing temperature to 970 ℃, the heating rate to be 2 ℃/min, and the heat preservation time to be 20 hours; cooling and grinding to obtain white powder of about 70nm SiO2@Lu1.86Ce0.04Eu0.1O3A composite material.
TEM transmission electron microscope observation is carried out on the precursor powder and the composite material obtained in example 1, and excitation spectrum measurement and ultraviolet lamp irradiation are carried out on the composite material.
As can be seen from the graphs in FIGS. 1-2, the obtained precursor is spherical, has good monodispersity, and the particle size of the composite material is about 70nm, so that the good spherical morphology and the good dispersity are still maintained; as can be seen from FIG. 3, the composite material realizes full coverage absorption in the 230-410 nm wave band; as can be seen in fig. 4, the composite emits red fluorescence under uv light.
Embodiment 2 core-shell structure Lu1.86Ce0.04Eu0.1O3@SiO2Preparation of (200-230nm)
The preparation method specifically comprises the following steps:
s1, preparing rare earth precipitates by a coprecipitation method: 50ml of deionized water was weighed into a single-neck flask, and 1.5002g of urea (CH) was weighed4N2O), stirring for 10min at normal temperature, measuring 4.95ml of prepared 0.1M Lu (NO)3)3、2.0ml 0.02M Ce(NO3)3And 0.50ml of 0.05M Eu (NO)3)3Placing the solution in an oil bath heating stirrer, setting the oil bath temperature at 80 ℃, reacting for 6h under a strong stirring stateCooling, centrifuging, washing with deionized water and ethanol for several times, and oven drying at 70 deg.C for 12 hr to obtain white Lu (OH) CO with particle size of 180-210 nm3Rare earth precipitates;
s2, preparing a precursor with a core-shell structure by a Stober method: weighing 0.0603g of the rare earth precipitate obtained in the step S1 in 50ml of ethanol, adding 10ml of deionized water after ultrasonic dispersion for 30min, placing the mixture on a heating stirrer, setting the reaction temperature to 35 ℃, stirring for 10min, and slowly dropwise adding 2ml of 28% ammonia water (NH)3H2O), continuously stirring for 30min, dropwise adding 0.150ml of Tetraethoxysilane (TEOS) at the speed of 10 s/drop, reacting for 12h, centrifuging, washing with deionized water and ethanol for several times, and drying in an oven at 70 ℃ for 12h to obtain a precursor L @ SiO2；
S3, grinding the precursor obtained in the step S2 uniformly by using a mortar, transferring the precursor into an alumina crucible, placing the alumina crucible into a muffle furnace, setting the annealing temperature to be 1000 ℃, the heating rate to be 2 ℃/min, and keeping the temperature for 12 hours; cooling and grinding to obtain white powder of 200-210 nm Lu1.86Ce0.04Eu0.1O3@SiO2A composite material.
TEM transmission electron microscope observation is carried out on the rare earth precipitate and the composite material obtained in the example 2. As can be seen from the graphs of 5-6, the rare earth precipitate is spherical, has good monodispersity and obvious core-shell structure, and the light-color shell layer is SiO2A layer; the composite material keeps good monodispersity, and the shell is a silicon dioxide shell layer.
Examples 3-4 are methods for varying the particle size of the target product by varying the template silica sphere diameter:
example 3A spherical silica/rare earth oxide composite SiO2@Lu1.86Ce0.04Eu0.1O3(50nm) preparation
The preparation method specifically comprises the following steps:
s1, preparing a silicon dioxide template: 56ml of deionized water was weighed into a single-neck flask, mixed with 12ml of absolute ethanol, and 1.146g of urea (CH) was weighed4N2O) is dissolved in the solution, stirred for 10min at normal temperature, and then 0.1ml of 28 percent solution is slowly drippedAmmonia (NH)3H2O), placing the single-neck flask on a magnetic heating stirrer, stirring for 30min at 60 ℃ to form a uniform solution, dropwise adding 2.92ml of Tetraethoxysilane (TEOS) at the speed of 10 s/drop under the stirring state, continuously heating for reaction for 3h, cooling, centrifuging, washing with deionized water and ethanol for several times, and drying in an oven at 70 ℃ for 12h to obtain silicon dioxide balls with the particle size of about 50 nm;
s2, weighing 0.030g of the silicon dioxide spheres obtained in the step S1, ultrasonically dispersing the silicon dioxide spheres in 25ml of deionized water, and accurately weighing 2.325ml of prepared 0.2M Lu (NO)3)3、1.00ml 0.02M Ce(NO3)3And 0.50ml of 0.05M Eu (NO)3)3Putting the solution on an oil bath heating stirrer, setting the oil bath temperature at 80 ℃, reacting for 6h under a strong stirring state, cooling, centrifuging, washing with deionized water and ethanol for several times, and drying in an oven at 70 ℃ for 12h to obtain silicon dioxide @ Lu (OH) CO3Precursor powder of rare earth precipitate;
s3, grinding the precursor powder obtained in the step S2 uniformly by using a mortar, transferring the precursor powder into an alumina crucible, placing the alumina crucible into a muffle furnace, setting the annealing temperature to 970 ℃, the heating rate to be 2 ℃/min, and the heat preservation time to be 20 hours; cooling and grinding to obtain white powder of SiO about 50nm2@Lu1.86Ce0.04Eu0.1O3A composite material.
Example 4A spherical silica/rare earth oxide composite SiO2@Lu1.86Ce0.04Eu0.1O3(90nm) preparation
The preparation method specifically comprises the following steps:
s1, preparing a silicon dioxide template: 56ml of deionized water was weighed into a single-neck flask, mixed with 20ml of absolute ethanol, and 1.146g of urea (CH) was weighed4N2O), stirring at normal temperature for 10min, and slowly adding 0.1ml of 28% ammonia water (NH)3H2O), placing the single-neck flask on a magnetic heating stirrer, stirring at 60 deg.C for 30min to obtain a uniform solution, adding dropwise 2.92ml of tetraethyl orthosilicate (TEOS) at a speed of 10 s/drop while stirring, and heatingAfter reacting for 3h, cooling and centrifuging, washing with deionized water and ethanol for several times, and drying in an oven at 70 ℃ for 12h to obtain silicon dioxide spheres with the particle size of about 90 nm;
s2, weighing 0.030g of the silicon dioxide spheres obtained in the step S1, ultrasonically dispersing the silicon dioxide spheres in 25ml of deionized water, and accurately weighing 2.325ml of prepared 0.2M Lu (NO)3)3、1.00ml 0.02M Ce(NO3)3And 0.50ml of 0.05M Eu (NO)3)3Putting the solution on an oil bath heating stirrer, setting the oil bath temperature at 80 ℃, reacting for 6h under a strong stirring state, cooling, centrifuging, washing with deionized water and ethanol for several times, and drying in an oven at 70 ℃ for 12h to obtain silicon dioxide @ Lu (OH) CO3Precursor powder of rare earth precipitate;
s3, grinding the precursor powder obtained in the step S2 uniformly by using a mortar, transferring the precursor powder into an alumina crucible, placing the alumina crucible into a muffle furnace, setting the annealing temperature to 970 ℃, the heating rate to be 2 ℃/min, and the heat preservation time to be 20 hours; cooling and grinding to obtain white powder of about 90nm SiO2@Lu1.86Ce0.04Eu0.1O3A composite material.
Example 5A spherical silica/rare earth oxide composite SiO2@Lu1.82Ce0.04Eu0.14O3(70nm) preparation
The preparation method specifically comprises the following steps:
s1, preparing a silicon dioxide template: 56ml of deionized water was weighed into a single-neck flask, mixed with 14ml of absolute ethanol, and 1.146g of urea (CH) was weighed4N2O), stirring at normal temperature for 10min, and slowly adding 0.1ml of 28% ammonia water (NH)3H2O), placing the single-neck flask on a magnetic heating stirrer, stirring for 30min at 60 ℃ to form a uniform solution, dropwise adding 2.92ml of Tetraethoxysilane (TEOS) at the speed of 10 s/drop under the stirring state, continuously heating for reaction for 3h, cooling, centrifuging, washing with deionized water and ethanol for several times, and drying in an oven at 70 ℃ for 12h to obtain silicon dioxide balls with the particle size of about 70 nm;
s2, weighing 0.030g of the product obtained in the step S1Ultrasonically dispersing the silicon dioxide spheres in 25ml of deionized water, and accurately measuring 2.325ml of prepared 0.2M Lu (NO)3)3、1.00ml 0.02M Ce(NO3)3And 0.70ml of 0.05M Eu (NO)3)3Putting the solution on an oil bath heating stirrer, setting the oil bath temperature at 80 ℃, reacting for 6h under a strong stirring state, cooling, centrifuging, washing with deionized water and ethanol for several times, and drying in an oven at 70 ℃ for 12h to obtain silicon dioxide @ Lu (OH) CO3Precursor powder of rare earth precipitate;
s3, grinding the precursor powder obtained in the step S2 uniformly by using a mortar, transferring the precursor powder into an alumina crucible, placing the alumina crucible into a muffle furnace, setting the annealing temperature to 970 ℃, the heating rate to be 2 ℃/min, and the heat preservation time to be 20 hours; cooling and grinding to obtain white powder of about 70nm SiO2@Lu1.82Ce0.04Eu0.14O3A composite material.
Example 6A spherical silica/rare earth oxide composite SiO2@Lu1.86Ce0.04Sm0.1O3(70nm) preparation
The preparation method specifically comprises the following steps:
s1, preparing a silicon dioxide template: 56ml of deionized water was weighed into a single-neck flask, mixed with 14ml of absolute ethanol, and 1.146g of urea (CH) was weighed4N2O), stirring at normal temperature for 10min, and slowly adding 0.1ml of 28% ammonia water (NH)3H2O), placing the single-neck flask on a magnetic heating stirrer, stirring for 30min at 60 ℃ to form a uniform solution, dropwise adding 2.92ml of Tetraethoxysilane (TEOS) at the speed of 10 s/drop under the stirring state, continuously heating for reaction for 3h, cooling, centrifuging, washing with deionized water and ethanol for several times, and drying in an oven at 70 ℃ for 12h to obtain silicon dioxide balls with the particle size of about 70 nm;
s2, weighing 0.030g of the silicon dioxide spheres obtained in the step S1, ultrasonically dispersing the silicon dioxide spheres in 25ml of deionized water, and accurately weighing 2.325ml of prepared 0.2M Lu (NO)3)3、1.00ml 0.02M Ce(NO3)3And 0.50ml of 0.05M Sm (CH)3COO)3Putting the solution on an oil bath heating stirrer, setting the oil bath temperature at 80 ℃, reacting for 6h under a strong stirring state, cooling, centrifuging, washing with deionized water and ethanol for several times, and drying in an oven at 70 ℃ for 12h to obtain silicon dioxide @ Lu (OH) CO3Precursor powder of rare earth precipitate;
s3, grinding the precursor powder obtained in the step S2 uniformly by using a mortar, transferring the precursor powder into an alumina crucible, placing the alumina crucible into a muffle furnace, setting the annealing temperature to 970 ℃, the heating rate to be 2 ℃/min, and the heat preservation time to be 20 hours; cooling and grinding to obtain white powder of about 70nm SiO2@Lu1.86Ce0.04Sm0.1O3A composite material.
Example 7A silica/rare earth oxide composite SiO2@Lu1.82Ce0.04Sm0.14O3(70nm) preparation
The preparation method specifically comprises the following steps:
s1, preparing a silicon dioxide template: 56ml of deionized water was weighed into a single-neck flask, mixed with 14ml of absolute ethanol, and 1.146g of urea (CH) was weighed4N2O), stirring at normal temperature for 10min, and slowly adding 0.1ml of 28% ammonia water (NH)3H2O), placing the single-neck flask on a magnetic heating stirrer, stirring for 30min at 60 ℃ to form a uniform solution, dropwise adding 2.92ml of Tetraethoxysilane (TEOS) at the speed of 10 s/drop under the stirring state, continuously heating for reaction for 3h, cooling, centrifuging, washing with deionized water and ethanol for several times, and drying in an oven at 70 ℃ for 12h to obtain silicon dioxide balls with the particle size of about 70 nm;
s2, weighing 0.030g of the silicon dioxide spheres obtained in the step S1, ultrasonically dispersing the silicon dioxide spheres in 25ml of deionized water, and accurately weighing 2.325ml of prepared 0.2M Lu (NO)3)3、1.00ml 0.02M Ce(NO3)3And 0.70ml of 0.05M Sm (CH)3COO)3Placing the solution in an oil bath heating stirrer, setting the oil bath temperature at 80 deg.C, reacting under strong stirring for 6 hr, cooling, centrifuging, washing with deionized water and ethanol for several times, and oven drying at 70 deg.C for 12 hr to obtain the final productSilica @ Lu (OH) CO3Precursor powder of rare earth precipitate;
s3, grinding the precursor powder obtained in the step S2 uniformly by using a mortar, transferring the precursor powder into an alumina crucible, placing the alumina crucible into a muffle furnace, setting the annealing temperature to 970 ℃, the heating rate to be 2 ℃/min, and the heat preservation time to be 20 hours; cooling and grinding to obtain white powder of about 70nm SiO2@Lu1.82Ce0.04Sm0.14O3A composite material.
Embodiment 8 core-shell structure Lu1.86Ce0.04Eu0.1O3@SiO2Preparation of (140-170nm)
The preparation method specifically comprises the following steps:
s1, preparing rare earth precipitates by a coprecipitation method: 50ml of deionized water was weighed into a single-neck flask, and 2.2522g of urea (CH) was weighed4N2O), stirring at normal temperature for 10min, measuring 4.95ml of prepared 0.1M Lu (NO)3)3、0.25ml 0.02M Ce(NO3)3And 0.50ml of 0.05M Eu (NO)3)3Putting the solution into an oil bath heating stirrer, setting the oil bath temperature to be 80 ℃, reacting for 6h under a strong stirring state, cooling, centrifuging, washing with deionized water and ethanol for several times, and drying in an oven at 70 ℃ for 12h to obtain white Lu (OH) CO with the particle size of 120-150 nm3Rare earth precipitates;
s2, preparing a core-shell structure precursor with the particle size of 160-190 nm by a Stober method: weighing 0.0603g of the rare earth precipitate obtained in the step S1 in 50ml of ethanol, adding 10ml of deionized water after ultrasonic dispersion for 30min, placing the mixture on a heating stirrer, setting the reaction temperature to 35 ℃, stirring for 10min, and slowly dropwise adding 2ml of 28% ammonia water (NH)3H2O), continuously stirring for 30min, dropwise adding 0.100ml TEOS at the speed of 10 s/drop, reacting for 12h, centrifuging, washing with deionized water and ethanol for several times, and drying in an oven at 70 ℃ for 12h to obtain a core-shell structure precursor with the particle size of 160-190 nm;
s3, grinding the precursor powder obtained in the step S2 uniformly by using a mortar, transferring the precursor powder into an alumina crucible, placing the alumina crucible into a muffle furnace, setting the annealing temperature to be 1000 ℃, and setting the heating rate to be2 ℃/min, and the heat preservation time is 10 hours; cooling and grinding to obtain white powder of 140-170nm Lu1.86Ce0.04Eu0.1O3@SiO2A spherical composite material.
Example 9 core-shell Structure Lu1.86Ce0.04Sm0.1O3@SiO2Preparation of (140-170nm)
The preparation method specifically comprises the following steps:
s1, preparing rare earth precipitates by a coprecipitation method: 50ml of deionized water was weighed into a single-neck flask, and 2.2522g of urea (CH) was weighed4N2O), stirring at normal temperature for 10min, measuring 4.95ml of prepared 0.1M Lu (NO)3)3、0.25ml 0.02M Ce(NO3)3And 0.50ml of 0.05M Sm (CH)3COO)3Putting the solution into an oil bath heating stirrer, setting the oil bath temperature to be 80 ℃, reacting for 6h under a strong stirring state, cooling, centrifuging, washing with deionized water and ethanol for several times, and drying in an oven at 70 ℃ for 12h to obtain white Lu (OH) CO with the particle size of 120-150 nm3Rare earth precipitates;
s2, preparing a core-shell structure precursor with the particle size of 160-190 nm by a Stober method: weighing 0.0603g of the rare earth precipitate obtained in the step S1 in 50ml of ethanol, adding 10ml of deionized water after ultrasonic dispersion for 30min, placing the mixture on a heating stirrer, setting the reaction temperature to 35 ℃, stirring for 10min, and slowly dropwise adding 2ml of 28% ammonia water (NH)3H2O), continuously stirring for 30min, dropwise adding 0.100ml TEOS at the speed of 10 s/drop, reacting for 12h, centrifuging, washing with deionized water and ethanol for several times, and drying in an oven at 70 ℃ for 12h to obtain a core-shell structure precursor with the particle size of 160-190 nm;
s3, grinding the precursor powder obtained in the step S2 uniformly by using a mortar, transferring the precursor powder into an alumina crucible, placing the alumina crucible into a muffle furnace, setting the annealing temperature to be 1000 ℃, the heating rate to be 2 ℃/min, and the heat preservation time to be 10 hours; cooling and grinding to obtain white powder of 140-170nm Lu1.86Ce0.04Sm0.1O3@SiO2A spherical composite material.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The silicon dioxide/rare earth oxide light conversion composite material is characterized in that the chemical composition expression of the composite material is RE2O3-SiO2(ii) a Wherein RE is one or more rare earth elements selected from Y, Ce, Sm, Eu, Gd and Lu.
2. The silica/rare earth oxide light conversion composite of claim 1, wherein the composite absorbs ultraviolet light in the 230-410 nm range and converts the absorbed ultraviolet light into visible red fluorescent emission.
3. A method for preparing the silica/rare earth oxide light conversion composite material according to claim 1 or 2, wherein the method comprises:
the method comprises the following steps: firstly preparing a silicon dioxide ball template by a sol-gel method, then epitaxially growing a rare earth precipitate shell layer on the template by a coprecipitation method, and finally annealing to obtain the silicon dioxide/rare earth oxide photoconversion composite material;
or the second method: firstly, preparing a monodisperse rare earth precipitate by a coprecipitation method, then coating a silicon dioxide shell layer on the outer layer of the monodisperse rare earth precipitate, and finally annealing to obtain the silicon dioxide/rare earth oxide photoconversion composite material.
4. The preparation method according to claim 3, wherein the first method specifically comprises the following steps:
s1, dissolving cetyl trimethyl ammonium bromide in a mixed solution of ethanol and water, uniformly stirring, dropwise adding ammonia water, heating and stirring, adding tetraethoxysilane, heating and stirring, and performing post-treatment after the reaction is finished to obtain silicon dioxide spheres;
s2, dispersing the silicon dioxide balls obtained in the step S1 in water, adding a rare earth salt solution, uniformly mixing, adding urea, heating and stirring, and performing post-treatment after the reaction is finished to obtain a precursor;
and S3, uniformly grinding the precursor obtained in the step S2, annealing and grinding to obtain the material.
5. The preparation method according to claim 3, wherein the second method specifically comprises the following steps:
adding urea into water, uniformly mixing, adding a rare earth salt solution, heating and stirring, and carrying out post-treatment after the reaction is finished to obtain a rare earth precipitate;
SII, adding the rare earth precipitate obtained in the step SI into ethanol for dispersion, adding water, heating and stirring, sequentially dropwise adding ammonia water and tetraethoxysilane, heating for reaction, and performing post-treatment after the reaction is finished to obtain a precursor;
and SIII, uniformly grinding the precursor obtained in the step SII, annealing and grinding to obtain the silicon nitride/.
6. The production method according to claim 4 or 5, wherein the rare earth salt solution is a rare earth nitrate solution or a rare earth acetate solution.
7. The method according to claim 6, wherein the rare earth salt solution has a concentration of 0.02 to 0.50M.
8. The preparation method according to claim 4 or 5, wherein the annealing temperature is 950 to 1050 ℃, the heating rate is 1 to 10 ℃, and the reaction time is 8 to 20 hours.
9. Use of the silica/rare earth oxide photoconversion composite of claim 1 or 2 in a sunscreen product.
10. Use according to claim 9, wherein the sunscreen product comprises a sunscreen cosmetic, a sunscreen plastic.
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Application publication date: 20210409 Assignee: GUANGZHOU KING POWDER TECHNOLOGY Co.,Ltd. Assignor: SUN YAT-SEN University Contract record no.: X2021440000122 Denomination of invention: A silica / rare earth oxide light conversion composite and its preparation method License type: Common License Record date: 20210624 |
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