CN111495396A - Ultrasonic/microwave-assisted preparation of NaYF4:Yb3+,Tb3+/TiO2Method for preparing composite photocatalytic material - Google Patents
Ultrasonic/microwave-assisted preparation of NaYF4:Yb3+,Tb3+/TiO2Method for preparing composite photocatalytic material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 45
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 6
- 239000011941 photocatalyst Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 51
- 239000000843 powder Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000002604 ultrasonography Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 7
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002244 precipitate Substances 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000003756 stirring Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- ZMQBAPPSYGILGT-UHFFFAOYSA-N sodium;2,3-bis(hydroxymethyl)butanedioic acid Chemical compound [Na+].OCC(C(O)=O)C(CO)C(O)=O ZMQBAPPSYGILGT-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an ultrasonic/microwave-assisted preparation method of NaYF4:Yb3+,Tb3+/TiO2The method for preparing the composite photocatalytic material adopts ultrasonic/microwave assistance to prepare the hexagonal phase up-conversion photocatalytic material NaYF with uniform particle size (3-5 mu m) and regular appearance under the condition of not adding any surfactant4:Yb3+,Tb3+On the basis of the above, the photocatalyst TiO is coated2Particles. The composite catalytic material utilizes the up-conversion material to absorb near infrared light for conversion to emit ultraviolet light, and shows excellent photocatalytic activity under the irradiation of 980nm light. The invention has simple process and reactionThe method is short in time, does not need to add any surfactant, is environment-friendly, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of up-conversion luminescence and photocatalysis, and particularly relates to a preparation method of a near-infrared up-conversion composite photocatalytic material.
Background
Solar energy is the cleanest energy source, the utilization of which is one of the most important science and technology in the 21 st century, and the current search for semiconductor photocatalytic materials for realizing high-efficiency solar energy conversion is urgent. TiO 22Is a very representative one due to its strong catalytic performance, good chemical and thermal stability, nontoxicity and low costThe photocatalytic material of (1). However, TiO2The solar energy collector has a forbidden band width of about 3.2eV, and can only be activated by high-energy ultraviolet light, wherein the ultraviolet light only accounts for 3-5% of the total solar spectrum, and the percentage of visible light and near infrared light is about 95-98%. Therefore, more than 95% of solar energy cannot be directly used for photocatalysis.
NaYF4:Yb3+,Tb3+Is an up-conversion light material, has the function of converting near infrared light into ultraviolet light, and leads the near infrared light and TiO to be mixed2Compounding in a certain mode. Utilizing upconversion light NaYF4:Yb3+,Tb3+The material has the characteristics of absorbing near infrared light and emitting high-energy ultraviolet light, so that the semiconductor TiO2Indirectly utilizes near infrared light, and improves the comprehensive utilization rate of solar energy.
Disclosure of Invention
The invention mainly aims to solve the problems that the particle size distribution of the composite catalytic material is not uniform, a surfactant is required to be used for preparation, and the like, and provides a preparation method of the composite catalytic material which is uniform in particle size and has good photocatalytic performance. The method is simple to operate, environment-friendly and easy to industrialize, and is applied to the field of environmental management.
In order to realize the purpose, the invention provides an ultrasonic/microwave-assisted NaYF preparation method4:Yb3+,Tb3+/TiO2The method for preparing the composite photocatalytic material specifically comprises the following steps.
(1) According to NaYF4:Yb3+,Tb3+Weighing Y in stoichiometric ratio2O3、Yb2O3、Tb(NO3)3·6H2Dissolving O in nitric acid solution, and performing ultrasonic magnetic stirring at 70-90 ℃ to obtain solution A.
(2) And (3) weighing disodium ethylene diamine tetraacetate according to the mass ratio of L n to EDTA =1: 0.85-1.20, and dissolving the disodium ethylene diamine tetraacetate in water to prepare a solution B, wherein L n represents all rare earth elements in the solution A.
(3) Weighing NH according to the mass ratio of L n: F =1: 8-124HF2Dissolving in water to obtain solution C.
(4) Under the assistance of ultrasound/microwave, the microwave power is 300-800W, the ultrasound frequency is 10-20 kHz, the liquid B is slowly added into the stirred liquid A, the temperature is controlled at 60-80 ℃, the time is kept for 20-40 min, EDTA-RE complex precipitation is formed, the liquid C is added into the stirred A, B mixed liquid, after milky precipitation is generated, the magnetic stirring is carried out for 30-60 min at 50-65 ℃, and the pH value of the mixed liquid A, B, C is adjusted to 0.5-1.5.
(5) And (3) placing the A, B, C mixed solution into a lining of a hydrothermal reaction kettle, screwing a reaction kettle cover, and placing the reaction kettle cover into an oven, wherein the temperature is controlled at 160-200 ℃ and the time is 12-20 hours.
(6) And removing the supernatant in the inner liner of the reaction kettle, washing the lower precipitate with water, performing centrifugal separation, and washing with absolute ethyl alcohol. Then putting the mixture into a vacuum drying oven, controlling the temperature at 60-100 ℃ for 8-20h, drying and grinding the mixture into powder to obtain the up-conversion material NaYF4:Yb3+,Tb3+。
(7) According to NaYF4:Yb3+,Tb3+With TiO2The molar ratio of the titanium dioxide to the water is 10: 2-6, weighing tetra-n-butyl titanate, dropwise adding absolute ethyl alcohol, uniformly mixing, under the assistance of ultrasound/microwave, wherein the microwave power is 300-800W, the ultrasound frequency is 10-20 kHz, and the reaction time is 30-60 min until the mixed solution is clear and transparent, so that a solution D can be obtained.
(8) NaYF is added4:Yb3+,Tb3+Adding the powder into the solution D, and reacting for 0.5-3 h under the assistance of ultrasound/microwave, wherein the microwave power is 300-800W, the ultrasound frequency is 10-20 kHz, and the temperature is controlled to be 50-95 ℃; then placing the mixture in a vacuum drying oven for drying; grinding the dried powder into powder, putting the powder into a muffle furnace, controlling the temperature at 500-700 ℃ for 2-4 h, and roasting to obtain the composite photocatalytic material NaYF4:Yb3+,Tb3+/TiO2。
Further, the composite photocatalytic material is made of an up-conversion luminescent material NaYF4:Yb3+,Tb3+And photocatalyst TiO2Formed by compounding of TiO2The coating is uniformly coated on the surface of the up-conversion optical material.
Further, the NaYF4:Yb3+,Tb3+/TiO2Crystals of composite photocatalytic materialThe form is hexagonal phase, and the particle size is 3-5 μm.
The preparation method does not need to add any surfactant, and is used for synthesizing the up-conversion luminescent material NaYF by an ultrasonic/microwave-assisted hydrothermal method4:Yb3+,Tb3+Adding TiO to2Coating the surface of the NaYF to prepare the composite photocatalytic material NaYF4:Yb3+,Tb3+/TiO2. The composite photocatalytic material can be applied to the field of photocatalytic environment treatment, can convert near infrared light into ultraviolet light and then excite TiO2Generates catalytic activity and indirectly expands TiO2The light response range of (a). The method provides a new technical method for the field of semiconductor catalysts by utilizing near infrared light, and has important significance for solving the increasingly serious problem of environmental pollution.
Drawings
FIG. 1 is an SEM image of a light conversion material in example 1 of the present invention.
Fig. 2 is an XRD pattern of the optical material converted in example 1 of the present invention.
FIG. 3 is a fluorescence spectrum of the upconversion optical material of example 1 of the present invention.
FIG. 4 is an SEM photograph of the composite photocatalytic material of example 1 according to the present invention.
FIG. 5 is a fluorescence spectrum of the composite photocatalytic material according to example 1 of the present invention.
FIG. 6 is a graph showing the degradation curve of the composite photocatalytic material in example 1 of the present invention.
Detailed Description
Example 1
(1) According to NaYF4:Yb3+,Tb3+Stoichiometrically weigh 2g of Y2O3、Yb2O3、Tb(NO3)3·6H2Dissolving the O in nitric acid solution of 30m L, and dissolving by ultrasonic magnetic stirring at 80 deg.C to obtain solution A.
(2) According to the mass ratio of L n to EDTA =1:1, disodium ethylene diamine tetraacetate is weighed and dissolved in 30m L distilled water to prepare solution B.
(3) Weighing NH according to the mass ratio of L n: F =1:104HF2Dissolve in 30m L distilled water to obtain solution C.
(4) Under the ultrasonic/microwave auxiliary condition, setting the microwave power to be 600W and the ultrasonic frequency to be 15kHz, dripping the B liquid into the stirred A liquid to form EDTA-RE complex precipitation, and magnetically stirring for 30min at 70 ℃. Slowly adding the solution C into the A, B mixture solution, generating milky white precipitate, magnetically stirring at 60 deg.C for 40min, and adding concentrated HNO3And NaOH solution to adjust the pH of the mixture to 1.0.
(5) And putting the mixed solution into the inner liner of the hydrothermal reaction kettle, screwing the cover of the reaction kettle, putting the reaction kettle into an oven, and controlling the temperature at 180 ℃ for 15 hours.
(6) Taking out the reaction kettle after hydrothermal treatment, naturally cooling to room temperature, removing the supernatant in the lining, transferring the lower precipitate to a centrifugal test tube, and performing centrifugal separation; washing with distilled water, centrifuging for 3-5 times, naturally settling, and washing with anhydrous ethanol for 2 times. Putting the cleaned precipitate into a vacuum drying oven, controlling the temperature at 80 ℃ for 12h, taking out and grinding the precipitate into powder to obtain the upconversion light material NaYF4:Yb3+,Tb3+. The obtained upconversion optical material is subjected to characterization test, wherein figure 1 is an SEM picture, figure 2 is an XRD picture, and figure 3 is a fluorescence spectrum.
(7) According to NaYF4:Yb3+,Tb3+With TiO2Weighing tetrabutyl titanate at a molar ratio of 7:3, adding anhydrous ethanol dropwise, mixing uniformly, setting the microwave power at 600W, the ultrasonic frequency at 15kHz, and the holding time at least 30min until the mixed solution is clear and transparent, thus obtaining a solution D.
(8) NaYF is added4:Yb3+,Tb3+Adding the powder into the solution D, washing with absolute ethyl alcohol, and completely adding the powder into the solution D, wherein the solution is white and turbid; under the assistance of ultrasound/microwave, setting the microwave power at 600W and the ultrasound frequency at 15kHz, and adding 10 drops of distilled water (the solution becomes milk-shaped) at 80 ℃ for 1 h; then drying the whole mixed solution in a vacuum drying oven for 12 hours at the temperature of 60 ℃; taking out the powder, carefully grinding the powder into fine powder, placing the fine powder in a crucible, and roasting the fine powder in a muffle furnace at 550 ℃ for 3 hours to obtain the composite photocatalytic material NaYF4:Yb3+,Tb3+/TiO2. The obtained upconversion optical material is subjected to characterization test, and fig. 4 is an SEM image, and fig. 5 is a fluorescence spectrum.
The activity test of photocatalytic degradation of dye is carried out on the composite photocatalytic material, namely, a methyl orange solution with the concentration of 0.01 mg/L and the concentration of 50m L is measured by a using cylinder, the methyl orange solution is slowly poured into a quartz tube, then 0.05g of the composite photocatalytic material is weighed into the quartz tube filled with the methyl orange solution, the quartz tube is placed into a 500m L beaker and then placed into an ultrasonic cleaner, ultrasonic dispersion is carried out for 1h under the condition of the frequency of 15kHz, the ultrasonic dispersion is kept in a dark state, the ultrasonic dispersion is carried out, the quartz tube is placed into a dark box for full pre-adsorption for 12h, after the catalyst adsorbs the methyl orange to reach balance, the photocatalytic activity test can be started, after dark treatment, the mixed solution is placed into a 300W fluorescent high-pressure xenon lamp photochemical reaction instrument for photocatalytic degradation at room temperature and normal pressure, magnetic stirring is adopted, the illuminated methyl orange solution is taken out every 10min, the supernatant is centrifugally separated, and the absorbance of the supernatant is measured by ultraviolet visibleX). This was repeated, and 5-7 sets of data were recorded, and FIG. 5 is a graph of degradation.
Example 2
(1) According to NaYF4:Yb3+,Tb3+Stoichiometrically weigh 1.8g of Y2O3、Yb2O3、Tb(NO3)3·6H2Dissolving the O in nitric acid solution of 30m L, and dissolving the solution at 65 ℃ by ultrasonic magnetic stirring to obtain solution A.
(2) According to the mass ratio of L n to EDTA =1: 1.2, disodium ethylene diamine tetraacetate is weighed and dissolved in 30m L distilled water to prepare solution B.
(3) Weighing NH according to the mass ratio of L n: F =1:124HF2Dissolve in 30m L distilled water to obtain solution C.
(4) Under the ultrasonic/microwave auxiliary condition, setting the microwave power to be 400W and the ultrasonic frequency to be 20kHz, dripping the B liquid into the stirred A liquid to form EDTA-RE complex precipitation, and magnetically stirring for 40min at the temperature of 60 ℃. Slowly adding the solution C into the A, B mixture solution, generating milky precipitate, magnetically stirring at 50 deg.C for 90min, and adding concentrated HNO3Mixing with NaOH solutionThe pH of the resultant solution was 1.0.
(5) And putting the mixed solution into the inner liner of the hydrothermal reaction kettle, screwing the cover of the reaction kettle, putting the reaction kettle into an oven, and controlling the temperature at 200 ℃ for 10 hours.
(6) Taking out the reaction kettle after hydrothermal treatment, naturally cooling to room temperature, removing the supernatant in the lining, transferring the lower precipitate to a centrifugal test tube, and performing centrifugal separation; washing with distilled water, centrifuging for 3-5 times, naturally settling, and washing with anhydrous ethanol for 2 times. Putting the cleaned precipitate into a vacuum drying oven, controlling the temperature at 70 ℃ for 12h, taking out and grinding the precipitate into powder to obtain the upconversion light material NaYF4:Yb3+,Tb3+。
(7) According to NaYF4:Yb3+,Tb3+With TiO2Weighing tetrabutyl titanate according to the molar ratio of 6:4, dropwise adding absolute ethyl alcohol, uniformly mixing, setting the microwave power at 400W, the ultrasonic frequency at 20kHz, and the holding time for more than 20min until the mixed solution is clear and transparent, thus obtaining a solution D.
(8) NaYF is added4:Yb3+,Tb3+Adding the powder into the solution D, washing with absolute ethyl alcohol, and completely adding the powder into the solution D, wherein the solution is white and turbid; under the assistance of ultrasound/microwave, setting the microwave power at 600W and the ultrasound frequency at 10kHz, and adding 10 drops of distilled water (the solution becomes milk-shaped) at 60 ℃ for 1.5 h; then drying the whole mixed solution in a vacuum drying oven at 70 ℃ for 10 h; taking out the powder, carefully grinding the powder into fine powder, placing the fine powder in a crucible, and roasting the fine powder in a muffle furnace for 4 hours at the temperature of 500 ℃ to obtain the composite photocatalytic material NaYF4:Yb3+,Tb3+/TiO2。
Example 3
(1) According to NaYF4:Yb3+,Tb3+Stoichiometrically weigh 2.2g of Y2O3、Yb2O3、Tb(NO3)3·6H2Dissolving the O in nitric acid solution of 30m L, and dissolving by ultrasonic magnetic stirring at 85 deg.C to obtain solution A.
(2) According to the mass ratio of L n to EDTA =1: 1.2, disodium ethylene diamine tetraacetate is weighed and dissolved in 30m L distilled water to prepare solution B.
(3) Weighing NH according to the mass ratio of L n: F =1:124HF2Dissolve in 30m L distilled water to obtain solution C.
(4) Under the ultrasonic/microwave auxiliary condition, setting the microwave power to be 700W and the ultrasonic frequency to be 10kHz, dripping the B liquid into the stirred A liquid to form EDTA-RE complex precipitation, and magnetically stirring for 20min at the temperature of 60 ℃. Slowly adding the solution C into the A, B mixture solution, generating milky precipitate, magnetically stirring at 50 deg.C for 60min, and adding concentrated HNO3And NaOH solution to adjust the pH of the mixture to 1.0.
(5) And putting the mixed solution into the inner liner of the hydrothermal reaction kettle, screwing the cover of the reaction kettle, putting the reaction kettle into an oven, and controlling the temperature at 160 ℃ for 18 hours.
(6) Taking out the reaction kettle after hydrothermal treatment, naturally cooling to room temperature, removing the supernatant in the lining, transferring the lower precipitate to a centrifugal test tube, and performing centrifugal separation; washing with distilled water, centrifuging for 3-5 times, naturally settling, and washing with anhydrous ethanol for 2 times. Putting the cleaned precipitate into a vacuum drying oven, controlling the temperature at 80 ℃ for 6h, taking out and grinding the precipitate into powder to obtain the upconversion light material NaYF4:Yb3+,Tb3+。
(7) According to NaYF4:Yb3+,Tb3+With TiO2Weighing tetrabutyl titanate at a molar ratio of 5:5, adding anhydrous ethanol dropwise, mixing uniformly, setting the microwave power at 500W, the ultrasonic frequency at 15kHz, and the holding time at least 35min until the mixed solution is clear and transparent, thus obtaining a solution D.
(8) NaYF is added4:Yb3+,Tb3+Adding the powder into the solution D, washing with absolute ethyl alcohol, and completely adding the powder into the solution D, wherein the solution is white and turbid; under the assistance of ultrasound/microwave, setting the microwave power at 700W and the ultrasound frequency at 10kHz, adding 10 drops of distilled water (the solution becomes milk-like) at 60 deg.C, and maintaining for 50 min; then drying the whole mixed solution in a vacuum drying oven for 6 hours at the temperature of 80 ℃; taking out the powder, carefully grinding the powder into fine powder, placing the fine powder in a crucible, and roasting the fine powder in a muffle furnace for 2 hours at the temperature of 600 ℃ to obtain the composite photocatalytic material NaYF4:Yb3+,Tb3+/TiO2。
Claims (3)
1. Ultrasonic/microwave-assisted NaYF preparation method4:Yb3+,Tb3+/TiO2The method for preparing the composite photocatalytic material is characterized by comprising the following steps of:
(1) according to NaYF4:Yb3+,Tb3+Weighing Y in stoichiometric ratio2O3、Yb2O3、Tb(NO3)3·6H2Dissolving O in nitric acid solution, and performing ultrasonic magnetic stirring at the temperature of 70-90 ℃ to obtain solution A;
(2) weighing disodium ethylene diamine tetraacetate according to the mass ratio of L n to EDTA =1: 0.85-1.20, and dissolving the disodium ethylene diamine tetraacetate in water to prepare solution B;
(3) weighing NH according to the mass ratio of L n: F =1: 8-124HF2Dissolving in water to obtain solution C;
(4) under the assistance of ultrasound/microwave, the microwave power is 300-800W, the ultrasound frequency is 10-20 kHz, the liquid B is slowly added into the stirred liquid A, the temperature is controlled at 60-80 ℃, the time is kept for 20-40 min, EDTA-RE complex precipitation is formed, the liquid C is added into the stirred A, B mixed solution, after milky precipitation is generated, the mixture is magnetically stirred for 30-60 min at 50-65 ℃, and the pH value of the mixed solution A, B, C is adjusted to 0.5-1.5;
(5) placing A, B, C mixed solution into a lining of a hydrothermal reaction kettle, screwing a reaction kettle cover, and placing the reaction kettle cover into an oven, wherein the temperature is controlled at 160-200 ℃ and the time is 12-20 hours;
(6) removing supernatant liquid in the inner liner of the reaction kettle, washing lower-layer sediment with water, performing centrifugal separation, and washing with absolute ethyl alcohol; then putting the mixture into a vacuum drying oven, controlling the temperature at 60-100 ℃ for 8-20h, drying and grinding the mixture into powder to obtain the up-conversion material NaYF4:Yb3+,Tb3+；
(7) According to NaYF4:Yb3+,Tb3+With TiO2The molar ratio of the titanium dioxide to the water is 10: 2-6, the tetrabutyl titanate is weighed, the absolute ethyl alcohol is dripped and uniformly mixed, under the assistance of ultrasound/microwave, the microwave power is 300-800W, the ultrasound frequency is 10-20 kHz, the reaction time is 30-60 min, and the mixture is mixedThe solution is clear and transparent, and a solution D can be obtained;
(8) NaYF is added4:Yb3+,Tb3+Adding the powder into the solution D, and reacting for 0.5-3 h under the assistance of ultrasound/microwave, wherein the microwave power is 300-800W, the ultrasound frequency is 10-20 kHz, and the temperature is controlled to be 50-95 ℃; then placing the mixture in a vacuum drying oven for drying; grinding the dried powder into powder, putting the powder into a muffle furnace, controlling the temperature at 500-700 ℃ for 2-4 h, and roasting to obtain the composite photocatalytic material NaYF4:Yb3+,Tb3+/TiO2。
2. The method of claim 1, wherein the composite photocatalytic material is NaYF (NaYF) which is an up-conversion luminescent material4:Yb3+,Tb3+And photocatalyst TiO2Formed by compounding of TiO2The coating is uniformly coated on the surface of the up-conversion optical material.
3. The method of claim 1, wherein said NaYF is present in a sample4:Yb3+,Tb3+/TiO2The crystal form of the composite photocatalytic material is a hexagonal phase, and the particle size is 3-5 mu m.
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