CN110813327A - Preparation method of near-infrared responsive photocatalyst with porous silica fiber as carrier and photocatalyst - Google Patents

Preparation method of near-infrared responsive photocatalyst with porous silica fiber as carrier and photocatalyst Download PDF

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CN110813327A
CN110813327A CN201810888339.8A CN201810888339A CN110813327A CN 110813327 A CN110813327 A CN 110813327A CN 201810888339 A CN201810888339 A CN 201810888339A CN 110813327 A CN110813327 A CN 110813327A
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photocatalyst
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温世鹏
苏玉仙
刘力
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Beijing University of Chemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B01J35/23—
    • B01J35/39—
    • B01J35/398—
    • B01J35/399—
    • B01J35/58—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Abstract

The invention provides a preparation method of a near-infrared responsive photocatalyst taking porous silica fiber as a carrier, belonging to the technical field of nano science. According to the method, rare earth oxide is used as a raw material, a hydrothermal method is adopted to obtain core-shell type nano-catalyst particles with uniform particle size distribution and near-infrared responsiveness, then a silica fiber with a porous structure is prepared by combining an electrostatic spinning technology and a template method, and finally the uniform core-shell type nano-catalyst particles are loaded on the porous silica fiber. The surface and the inner wall of the porous silicon dioxide fiber prepared by the invention are uniformly distributed with core-shell type nanometer catalyst particles, and the core-shell type nanometer catalyst particles show good dispersibility and stability. In addition, the preparation method is low in cost, and the photoresponse range of the photocatalyst can be expanded to a near infrared region.

Description

Preparation method of near-infrared responsive photocatalyst with porous silica fiber as carrier and photocatalyst
Technical Field
The invention relates to the field of inorganic photocatalytic materials, in particular to a preparation method of a near-infrared responsive photocatalyst taking porous silica fibers as a carrier and the photocatalyst.
Background
In recent years, various organic pollutants are increased, and the application of photocatalysis technology as an advanced oxidation engineering to the degradation of photocatalysis in the aspect of dyes is also increased. However, most of the materials can only be used under the condition of ultraviolet light, and have great limitation on practical application. Therefore, it has become necessary to prepare a catalyst having a good catalytic effect under sunlight.
Titanium dioxide (TiO)2) As an important semiconductor photocatalyst, the photocatalyst has the advantages of high catalytic activity, good stability, low price, no secondary pollution, wider band gap and the like, and is a semiconductor photocatalyst commonly used in the research of the technical field of photocatalysis at present. However, TiO2The wide forbidden band characteristic of the semiconductor limits the optical response range of the semiconductor, and only can absorb specific ultraviolet light (lambda)<387 nm). How to extend TiO2The range of light response is currently a focus of this area of research. At present, the TiO is doped with nonmetal, deposited with noble metal or compounded with semiconductor2The photoresponse range extends into the visible region.
To enhance the activity of the catalyst, nanoparticles with high surface area, up to 50m in specific surface area, are often used2In the order of/g. However, such small-sized particles are too fine to be easily agglomerated and deactivated in practical use and not easily sedimented, resulting in difficulty in separation, recovery and reuse thereof.
Disclosure of Invention
To overcome the above problems in the prior art, the present invention first employs an up-conversion material to convert TiO into TiO2The photoresponse range is expanded to a near infrared region, the up-conversion luminescent nano material can absorb long-wave radiation with low photon energy and then radiate short-wave radiation with high photon energy, so that near infrared light with low energy can be converted into ultraviolet light with high energy.
In addition, the present invention selectively uses porous adsorbent supports, wherein catalyzed molecules can be adsorbed near the photocatalytic sites, prolonging the reaction process and thereby enhancing the degradation process. In addition, the adsorbent support can retain reaction intermediates formed during photocatalytic oxidation, leading to better electron-hole separation, thereby also improving overall photocatalytic activity. The silica material has the characteristics of neutral framework, light hydrophobicity, transparency, light diffraction capability, wide aperture range and the like, and becomes an ideal choice of the photocatalytic carrier material.
Accordingly, the invention provides a hydrothermal method for synthesizing a near-infrared light-responsive up-conversion luminescent material with a core-shell structure, and aims to prepare nano particles with uniform appearance, small particle size and uniform dispersion, and then load the nano particles onto porous silica nano fibers prepared by combining an electrostatic spinning technology and a template method to obtain a near-infrared light-responsive photocatalyst taking the porous silica fibers as a carrier, which has important guiding significance for the application of the nano materials in sewage treatment.
One of the purposes of the invention is to provide a preparation method of a near-infrared responsive photocatalyst taking porous silica fiber as a carrier, which comprises the following steps:
(1) with rare earth oxides (RE)2O3) The upconversion crystal powder is prepared by a hydrothermal method.
The preparation method of the up-conversion crystal adopts a hydrothermal process commonly used in the field.
Preferably, the method comprises the steps of: mixing rare earth oxide (RE)2O3) Dissolving the mixture in strong acid, heating until water in the solution is evaporated, dissolving the mixture in water to obtain a rare earth salt dispersion liquid with the concentration of 0.01 mmol/L-10 mol/L, dissolving a surfactant in water to obtain a surfactant dispersion liquid with the concentration of 0.01 mmol/L-10 mol/L, dropwise adding the surfactant dispersion liquid into the rare earth salt dispersion liquid, violently stirring for 10 min-1 h until a white complex is formed, dropwise adding a NaF aqueous solution with 3-12 mmol of the NaF aqueous solution, continuously stirring for 1-10 h, heating the obtained mixed solution to 180-220 ℃, reacting for 2-14 h, centrifuging, washing and drying the obtained product to obtain the product with the upconversion conversion functionCrystalline powder of optical character.
The rare earth oxide is preferably Y2O3、Yb2O3、Tm2O3、Er2O3、Ho2O3More preferably, comprises Y2O3、Yb2O3And Tm2O3Wherein the molar ratio of Y, Yb and Tm is (74.9-80): (15-25): (0.1-10.1).
The strong acid is one of concentrated hydrochloric acid, concentrated nitric acid and concentrated sulfuric acid.
(2) Dispersing the upconversion crystal powder obtained in the step (1) in a solvent to obtain an upconversion crystal dispersion liquid, uniformly mixing a titanium dioxide precursor, a surfactant, water and absolute ethyl alcohol to obtain a titanium dioxide precursor liquid, mixing and stirring the upconversion crystal dispersion liquid and the titanium dioxide precursor liquid for 1-10 hours, reacting for 2-14 hours at 150-200 ℃, centrifuging, washing and drying a reaction product to obtain the upconversion luminescent material with the core-shell structure.
Wherein, the titanium dioxide precursor is preferably at least one of titanium isopropoxide, butyl titanate, titanium tetrachloride, titanium sulfate and diisopropyl di (acetylacetonato) titanate.
The mass ratio of the up-conversion crystal to the titanium dioxide precursor to the surfactant is 5: (2-20): (5-20), preferably 5: (2-10): (5-10).
The surfactant is preferably at least one selected from ethylenediaminetetraacetic acid (EDTA), trisodium citrate, polyvinylpyrrolidone (PVP), tartaric acid, oxalic acid, sulfosalicylic acid, cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC).
(3) Dissolving polyacrylonitrile and a water-soluble polymer in a solvent, performing electrostatic spinning to obtain composite fibers, dissolving the composite fibers in water to obtain porous polyacrylonitrile fibers, placing the porous polyacrylonitrile fibers in a mixed solution of a silicon dioxide precursor, a core-shell structure up-conversion luminescent material, a surfactant and an acidic aqueous solution, fully stirring, and calcining at 700-1200 ℃ for 30 min-3 h in an inert atmosphere to obtain the photocatalyst.
Preferably, the electrospinning process in the step (3) comprises: dissolving polyacrylonitrile and a water-soluble polymer into a solvent, stirring for 1-3 hours to obtain a uniform and transparent spinning solution, placing the spinning solution on an electrostatic spinning device, wherein the advancing speed is 1-10 mL/h, the distance between a needle point and a receiving device is 5-25 cm, and the rotating speed of a roller on the receiving device is 300-1000 rpm to obtain the composite fiber. The mass ratio of polyacrylonitrile to water-soluble polymer is (0.5-3): 1.
wherein the silica precursor is preferably at least one selected from the group consisting of methyl orthosilicate (TMOS), ethyl orthosilicate (TEOS), propyl orthosilicate (TPOS), and butyl orthosilicate (TBOS).
The proportion of the up-conversion luminescent material with the core-shell structure in the silicon dioxide precursor is 0.05-10 g/L, and preferably 0.2-4 g/L.
The water-soluble polymer is preferably at least one selected from polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride, polyquaternary ammonium salt and polyethylene glycol.
The concentration of the surfactant in the step (3) is preferably 0.01-0.2 mol/L.
The acidic aqueous solution is one or more of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, carbonic acid or acetic acid. The concentration of the acidic aqueous solution is preferably 0.1-0.5 mol/L.
The solvent is at least one of absolute ethyl alcohol, xylene, dimethyl sulfoxide (DMSO), cyclohexane, N-propanol, acetone, Tetrahydrofuran (THF), N-methylpyrrolidone (NMP), diethyl ether, propylene oxide, dichloromethane (CH2Cl2), trichloromethane (CHCl3), triethanolamine and N, N-Dimethylformamide (DMF).
The inert atmosphere is one or more of nitrogen, helium, neon, argon, krypton, xenon and radon.
The invention also aims to provide a photocatalyst obtained by the preparation method of the near-infrared response photocatalyst taking porous silica fiber as a carrier.
According to the invention, porous silica fiber is used as a nano carrier, and the core-shell type up-conversion crystal prepared by a hydrothermal method is loaded in the cavity and on the surface of the core-shell type up-conversion crystal, so that the core-shell type up-conversion luminescent material loaded porous silica fiber composite material is finally obtained. The process can obtain the core-shell up-conversion luminescent material with good crystal form stability, uniform particle size distribution and uniform shell thickness, and the core-shell up-conversion luminescent material is loaded on the porous silica fiber substrate with uniform diameter and uniform pore diameter, so that the obtained composite material has uniform diameter, the core-shell up-conversion luminescent material can be uniformly distributed on the surface and inside of the fiber, the specific surface area and the stability of the fiber are improved, the photodegradation of pollutants under sunlight can be realized, and a strong photocatalysis effect can be achieved. In addition, the invention has the advantages of simple equipment, easy operation, good controllability, recycling and the like.
Drawings
FIG. 1 is a Scanning Electron Micrograph (SEM) of upconverting nanocrystals prepared according to example 13 of the present invention.
FIG. 2 is a Transmission Electron Micrograph (TEM) of the upconversion luminescent material prepared in example 13 of the present invention.
FIG. 3 is a plot of upconversion fluorescence spectra of upconverting nanocrystals and core-shell upconversion phosphors prepared in example 13 of the present invention, excited with a 980nm diode.
NaYF4After coating titanium dioxide with Yb, Tm, the emission peak is reduced as a whole. The ultraviolet light almost disappears at 290 nm, 345 nm and 362nm, and 451 nm, 475 nm and 651 nm are obviously weakened, which shows that the core-shell upconversion luminescent material is successfully prepared, and the titanium dioxide can effectively absorb the purple light emitted by the upconversion crystal.
Fig. 4 is a scanning electron microscope (TEM) of the core-shell upconversion luminescent material-supported porous silica fiber composite prepared in example 13.
Detailed Description
The present invention will be further described with reference to the following specific embodiments, but the present invention is not limited to the following examples.
All the starting materials used in the examples were obtained commercially.
Example 1
1mmol of rare earth oxide with the chemical mol ratio of (Y: Yb: Tm ═ 79.5: 20: 0.5)RE2O3Dissolving in concentrated hydrochloric acid, heating until water in the solution is evaporated, and dissolving in deionized water to obtain 0.1mmol/L dispersion. Dissolving PVP in deionized water to obtain a dispersion liquid with the concentration of 0.1mmol/L, dropwise adding the dispersion liquid into the solution, and continuously stirring for 30min until a white precipitate is formed. Then, 4mmol of NaF aqueous solution was added dropwise, and stirring was continued for 1 hour. And (3) transferring the reaction precursor solution into a 40ml reaction kettle, heating to 180 ℃, reacting for 12 hours, centrifuging, washing and drying the obtained product to obtain a white powdery sample.
Collecting 50mg prepared NaYF4Yb, Tm powder is dispersed in 10ml of absolute ethyl alcohol by ultrasonic. Then weighing 0.086g of tetrabutyl titanate, 0.2g of PVP, 1ml of water and 10ml of absolute ethyl alcohol, uniformly mixing, adding the mixture into the solution, mixing and stirring for 2h, pouring the mixture into a 40ml reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing and drying the reaction product to obtain the core-shell NaYF4:Yb,Tm@TiO2。
Dissolving Polyacrylonitrile (PAN) and polyethylene glycol (PEG) (the mass ratio of PAN to PEG is 0.8: 1) in DMF, and stirring for 3h to obtain uniform and transparent spinning solution. And (3) placing the spinning solution on an electrostatic spinning experimental device, wherein the advancing speed is 1mL/h, the distance between the needle point and the receiving device is 15cm, and the rotating speed of a roller on the receiving device is 300rpm, so that the PAN/PEG composite fiber is obtained. And dissolving the composite fiber in water to fully dissolve out PEG to obtain the porous PAN fiber. It was placed in 50mL ethyl silicate, prepared NaYF4:Yb,Tm@TiO2Stirring thoroughly in mixed solution of (100mg), cetyltrimethylammonium chloride (CTAC, 0.2mol/L) and hydrochloric acid water solution (0.1mol/L), and calcining at 800 deg.C for 1h in nitrogen atmosphere to obtain NaYF4:Yb,Tm@TiO2Porous silica fiber composite.
Example 2
1mmol of rare earth oxide RE with a chemical molar ratio of (Y: Yb: Tm ═ 79.5: 20: 0.5)2O3Dissolving in concentrated hydrochloric acid, heating until water in the solution is evaporated, and dissolving in deionized water to obtain 0.1mmol/L dispersion. Dissolving PVP in deionized water to obtain dispersion with concentration of 0.1mmol/L, and dropwise adding the dispersionStirring was continued for 30min until a white precipitate formed. Then, 4mmol of NaF aqueous solution was added dropwise, and stirring was continued for 1 hour. And (3) transferring the reaction precursor solution into a 40ml reaction kettle, heating to 180 ℃, reacting for 12 hours, centrifuging, washing and drying the obtained product to obtain a white powdery sample.
Collecting 50mg prepared NaYF4Yb, Tm powder is dispersed in 10ml of absolute ethyl alcohol by ultrasonic. Then weighing 0.086g of tetrabutyl titanate, 0.2g of PVP, 1ml of water and 10ml of absolute ethyl alcohol, uniformly mixing, adding the mixture into the solution, mixing and stirring for 2h, pouring the mixture into a 40ml reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing and drying the reaction product to obtain the core-shell NaYF4:Yb,Tm@TiO2。
Dissolving Polyacrylonitrile (PAN) and polyethylene glycol (PEG) (the mass ratio of PAN to PEG is 1: 1) into DMF, and stirring for 3h to obtain uniform and transparent spinning solution. And (3) placing the spinning solution on an electrostatic spinning experimental device, wherein the advancing speed is 1mL/h, the distance between the needle point and the receiving device is 15cm, and the rotating speed of a roller on the receiving device is 300rpm, so that the PAN/PEG composite fiber is obtained. And dissolving the composite fiber in water to fully dissolve out PEG to obtain the porous PAN fiber. It was placed in 50mL ethyl silicate, prepared NaYF4:Yb,Tm@TiO2Stirring thoroughly in mixed solution of (100mg), cetyltrimethylammonium chloride (CTAC, 0.2mol/L) and hydrochloric acid water solution (0.1mol/L), and calcining at 800 deg.C for 1h in nitrogen atmosphere to obtain NaYF4:Yb,Tm@TiO2Porous silica fiber composite.
Example 3
1mmol of rare earth oxide RE with a chemical molar ratio of (Y: Yb: Tm ═ 79.5: 20: 0.5)2O3Dissolving in concentrated hydrochloric acid, heating until water in the solution is evaporated, and dissolving in deionized water to obtain 0.1mmol/L dispersion. Dissolving PVP in deionized water to obtain a dispersion liquid with the concentration of 0.1mmol/L, dropwise adding the dispersion liquid into the solution, and continuously stirring for 30min until a white precipitate is formed. Then, 4mmol of NaF aqueous solution was added dropwise, and stirring was continued for 1 hour. Transferring the reaction precursor solution into a 40ml reaction kettle, heating to 180 ℃, reacting for 12 hours, centrifuging and washing the obtained productWashing and drying to obtain a white powdery sample.
Collecting 50mg prepared NaYF4Yb, Tm powder is dispersed in 10ml of absolute ethyl alcohol by ultrasonic. Then weighing 0.086g of tetrabutyl titanate, 0.2g of PVP, 1ml of water and 10ml of absolute ethyl alcohol, uniformly mixing, adding the mixture into the solution, mixing and stirring for 2h, pouring the mixture into a 40ml reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing and drying the reaction product to obtain the core-shell NaYF4:Yb,Tm@TiO2。
Dissolving Polyacrylonitrile (PAN) and polyethylene glycol (PEG) (the mass ratio of PAN to PEG is 1.6: 1) in DMF, and stirring for 3h to obtain uniform and transparent spinning solution. And (3) placing the spinning solution on an electrostatic spinning experimental device, wherein the advancing speed is 1mL/h, the distance between the needle point and the receiving device is 15cm, and the rotating speed of a roller on the receiving device is 300rpm, so that the PAN/PEG composite fiber is obtained. And dissolving the composite fiber in water to fully dissolve out PEG to obtain the porous PAN fiber. It was placed in 50mL ethyl silicate, prepared NaYF4:Yb,Tm@TiO2Stirring thoroughly in mixed solution of (100mg), cetyltrimethylammonium chloride (CTAC, 0.2mol/L) and hydrochloric acid water solution (0.1mol/L), and calcining at 800 deg.C for 1h in nitrogen atmosphere to obtain NaYF4:Yb,Tm@TiO2Porous silica fiber composite.
Example 4
1mmol of rare earth oxide RE with a chemical molar ratio of (Y: Yb: Tm ═ 79.5: 20: 0.5)2O3Dissolving in concentrated hydrochloric acid, heating until water in the solution is evaporated, and dissolving in deionized water to obtain 0.1mmol/L dispersion. Dissolving PVP in deionized water to obtain a dispersion liquid with the concentration of 0.1mmol/L, dropwise adding the dispersion liquid into the solution, and continuously stirring for 30min until a white precipitate is formed. Then, 4mmol of NaF aqueous solution was added dropwise, and stirring was continued for 1 hour. And (3) transferring the reaction precursor solution into a 40ml reaction kettle, heating to 180 ℃, reacting for 12 hours, centrifuging, washing and drying the obtained product to obtain a white powdery sample.
Collecting 50mg prepared NaYF4Yb, Tm powder is dispersed in 10ml of absolute ethyl alcohol by ultrasonic. Then, 0.086g of butyl titanate, 0.2g of PVP, 1ml of water, 10ml of absolute ethanol were weighedUniformly mixing, adding the mixture into the solution, mixing and stirring for 2 hours, pouring the mixture into a 40ml reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing and drying a reaction product to obtain the core-shell NaYF4:Yb,Tm@TiO2。
Dissolving Polyacrylonitrile (PAN) and polyethylene glycol (PEG) (the mass ratio of PAN to PEG is 2.5: 1) in DMF, and stirring for 3h to obtain uniform and transparent spinning solution. And (3) placing the spinning solution on an electrostatic spinning experimental device, wherein the advancing speed is 1mL/h, the distance between the needle point and the receiving device is 15cm, and the rotating speed of a roller on the receiving device is 300rpm, so that the PAN/PEG composite fiber is obtained. And dissolving the composite fiber in water to fully dissolve out PEG to obtain the porous PAN fiber. It was placed in 50mL ethyl silicate, prepared NaYF4:Yb,Tm@TiO2Stirring thoroughly in mixed solution of (100mg), cetyltrimethylammonium chloride (CTAC, 0.2mol/L) and hydrochloric acid water solution (0.1mol/L), and calcining at 800 deg.C for 1h in nitrogen atmosphere to obtain NaYF4:Yb,Tm@TiO2Porous silica fiber composite.
Example 5
1mmol of rare earth oxide RE with a chemical molar ratio of (Y: Yb: Tm ═ 74.9: 25: 0.1)2O3Dissolving in concentrated hydrochloric acid, heating until water in the solution is evaporated, and dissolving in deionized water to obtain 0.1mmol/L dispersion. Dissolving PVP in deionized water to obtain a dispersion liquid with the concentration of 0.1mmol/L, dropwise adding the dispersion liquid into the solution, and continuously stirring for 30min until a white precipitate is formed. Then, 4mmol of NaF aqueous solution was added dropwise, and stirring was continued for 1 hour. And (3) transferring the reaction precursor solution into a 40ml reaction kettle, heating to 180 ℃, reacting for 12 hours, centrifuging, washing and drying the obtained product to obtain a white powdery sample.
Collecting 50mg prepared NaYF4Yb, Tm powder is dispersed in 10ml of absolute ethyl alcohol by ultrasonic. Then weighing 0.086g of tetrabutyl titanate, 0.2g of PVP, 1ml of water and 10ml of absolute ethyl alcohol, uniformly mixing, adding the mixture into the solution, mixing and stirring for 2h, pouring the mixture into a 40ml reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing and drying the reaction product to obtain the core-shell NaYF4:Yb,Tm@TiO2。
Dissolving Polyacrylonitrile (PAN) and polyethylene glycol (PEG) (the mass ratio of PAN to PEG is 1: 1) into DMF, and stirring for 3h to obtain uniform and transparent spinning solution. And (3) placing the spinning solution on an electrostatic spinning experimental device, wherein the advancing speed is 1mL/h, the distance between the needle point and the receiving device is 15cm, and the rotating speed of a roller on the receiving device is 300rpm, so that the PAN/PEG composite fiber is obtained. And dissolving the composite fiber in water to fully dissolve out PEG to obtain the porous PAN fiber. It was placed in 50mL ethyl silicate, prepared NaYF4:Yb,Tm@TiO2Stirring thoroughly in mixed solution of (100mg), cetyltrimethylammonium chloride (CTAC, 0.2mol/L) and hydrochloric acid water solution (0.1mol/L), and calcining at 800 deg.C for 1h in nitrogen atmosphere to obtain NaYF4:Yb,Tm@TiO2Porous silica fiber composite.
Example 6
1mmol of rare earth oxide RE with a chemical molar ratio of (Y: Yb: Tm: 75: 15: 10)2O3Dissolving in concentrated hydrochloric acid, heating until water in the solution is evaporated, and dissolving in deionized water to obtain 0.1mmol/L dispersion. Dissolving PVP in deionized water to obtain a dispersion liquid with the concentration of 0.1mmol/L, dropwise adding the dispersion liquid into the solution, and continuously stirring for 30min until a white precipitate is formed. Then, 4mmol of NaF aqueous solution was added dropwise, and stirring was continued for 1 hour. And (3) transferring the reaction precursor solution into a 40ml reaction kettle, heating to 180 ℃, reacting for 12 hours, centrifuging, washing and drying the obtained product to obtain a white powdery sample.
Collecting 50mg prepared NaYF4Yb, Tm powder is dispersed in 10ml of absolute ethyl alcohol by ultrasonic. Then weighing 0.086g of tetrabutyl titanate, 0.2g of PVP, 1ml of water and 10ml of absolute ethyl alcohol, uniformly mixing, adding the mixture into the solution, mixing and stirring for 2h, pouring the mixture into a 40ml reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing and drying the reaction product to obtain the core-shell NaYF4:Yb,Tm@TiO2。
Dissolving Polyacrylonitrile (PAN) and polyethylene glycol (PEG) (the mass ratio of PAN to PEG is 1: 1) into DMF, and stirring for 3h to obtain uniform and transparent spinning solution. Placing the spinning solution on an electrostatic spinning experimental device, wherein the advancing speed is 1mL/h, the distance between the needle tip and the receiving device is 15cm, and then connectingThe rotating speed of the roller on the collecting device is 300rpm, and the PAN/PEG composite fiber is obtained. And dissolving the composite fiber in water to fully dissolve out PEG to obtain the porous PAN fiber. It was placed in 50mL ethyl silicate, prepared NaYF4:Yb,Tm@TiO2Stirring thoroughly in mixed solution of (100mg), cetyltrimethylammonium chloride (CTAC, 0.2mol/L) and hydrochloric acid water solution (0.1mol/L), and calcining at 800 deg.C for 1h in nitrogen atmosphere to obtain NaYF4:Yb,Tm@TiO2Porous silica fiber composite.
Example 7
1mmol of rare earth oxide RE with a chemical molar ratio of (Y: Yb: Tm ═ 79.5: 20: 0.5)2O3Dissolving in concentrated hydrochloric acid, heating until water in the solution is evaporated, and dissolving in deionized water to obtain 0.1mmol/L dispersion. Trisodium citrate is dissolved in deionized water to obtain a dispersion liquid with the concentration of 0.75mmol/L, and the dispersion liquid is dropwise added into the solution and continuously stirred for 30min until a white precipitate is formed. Then, 4mmol of NaF aqueous solution was added dropwise, and stirring was continued for 1 hour. And (3) transferring the reaction precursor solution into a 40ml reaction kettle, heating to 180 ℃, reacting for 12 hours, centrifuging, washing and drying the obtained product to obtain a white powdery sample.
Collecting 50mg prepared NaYF4Yb, Tm powder is dispersed in 10ml of absolute ethyl alcohol by ultrasonic. Then weighing 0.086g of tetrabutyl titanate, 0.2g of PVP, 1ml of water and 10ml of absolute ethyl alcohol, uniformly mixing, adding the mixture into the solution, mixing and stirring for 2h, pouring the mixture into a 40ml reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing and drying the reaction product to obtain the core-shell NaYF4:Yb,Tm@TiO2。
Dissolving Polyacrylonitrile (PAN) and polyethylene glycol (PEG) (the mass ratio of PAN to PEG is 1: 1) into DMF, and stirring for 3h to obtain uniform and transparent spinning solution. And (3) placing the spinning solution on an electrostatic spinning experimental device, wherein the advancing speed is 1mL/h, the distance between the needle point and the receiving device is 15cm, and the rotating speed of a roller on the receiving device is 300rpm, so that the PAN/PEG composite fiber is obtained. And dissolving the composite fiber in water to fully dissolve out PEG to obtain the porous PAN fiber. It was placed in 50mL ethyl silicate, prepared NaYF4:Yb,Tm@TiO2(100mg), cetyltrimethylammonium chloride (CTAC, 0.2mol/L) and hydrochloric acid aqueous solution (0.1mol/L), fully stirring, and calcining at 800 ℃ for 1h in nitrogen atmosphere to obtain NaYF4:Yb,Tm@TiO2Porous silica fiber composite.
Example 8
1mmol of rare earth oxide RE with a chemical molar ratio of (Y: Yb: Tm ═ 79.5: 20: 0.5)2O3Dissolving in concentrated hydrochloric acid, heating until water in the solution is evaporated, and dissolving in deionized water to obtain 0.1mmol/L dispersion. Dissolving EDTA in deionized water to obtain 0.1mmol/L dispersion, adding dropwise into the above solution, and stirring for 30min until white precipitate is formed. Then, 4mmol of NaF aqueous solution was added dropwise, and stirring was continued for 1 hour. And (3) transferring the reaction precursor solution into a 40ml reaction kettle, heating to 180 ℃, reacting for 12 hours, centrifuging, washing and drying the obtained product to obtain a white powdery sample.
Collecting 50mg prepared NaYF4Yb, Tm powder is dispersed in 10ml of absolute ethyl alcohol by ultrasonic. Then weighing 0.086g of tetrabutyl titanate, 0.2g of PVP, 1ml of water and 10ml of absolute ethyl alcohol, uniformly mixing, adding the mixture into the solution, mixing and stirring for 2h, pouring the mixture into a 40ml reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing and drying the reaction product to obtain the core-shell NaYF4:Yb,Tm@TiO2。
Dissolving Polyacrylonitrile (PAN) and polyethylene glycol (PEG) (the mass ratio of PAN to PEG is 1: 1) into DMF, and stirring for 3h to obtain uniform and transparent spinning solution. And (3) placing the spinning solution on an electrostatic spinning experimental device, wherein the advancing speed is 1mL/h, the distance between the needle point and the receiving device is 15cm, and the rotating speed of a roller on the receiving device is 300rpm, so that the PAN/PEG composite fiber is obtained. And dissolving the composite fiber in water to fully dissolve out PEG to obtain the porous PAN fiber. It was placed in 50mL ethyl silicate, prepared NaYF4:Yb,Tm@TiO2Stirring thoroughly in mixed solution of (100mg), cetyltrimethylammonium chloride (CTAC, 0.2mol/L) and hydrochloric acid water solution (0.1mol/L), and calcining at 800 deg.C for 1h in nitrogen atmosphere to obtain NaYF4:Yb,Tm@TiO2Porous silica fiber composite materialAnd (5) feeding.
Example 9
1mmol of rare earth oxide RE with a chemical molar ratio of (Y: Yb: Tm ═ 79.5: 20: 0.5)2O3Dissolving in concentrated hydrochloric acid, heating until water in the solution is evaporated, and dissolving in deionized water to obtain 0.1mmol/L dispersion. Dissolving EDTA in deionized water to obtain 0.1mmol/L dispersion, adding dropwise into the above solution, and stirring for 30min until white precipitate is formed. Then, 4mmol of NaF aqueous solution was added dropwise, and stirring was continued for 1 hour. And (3) transferring the reaction precursor solution into a 40ml reaction kettle, heating to 180 ℃, reacting for 12 hours, centrifuging, washing and drying the obtained product to obtain a white powdery sample.
Collecting 50mg prepared NaYF4Yb, Tm powder is dispersed in 10ml of absolute ethyl alcohol by ultrasonic. Then weighing 0.086g of tetrabutyl titanate, 0.05g of CTAB, 1ml of water and 10ml of absolute ethyl alcohol, uniformly mixing, adding the mixture into the solution, mixing and stirring for 2 hours, pouring the mixture into a 40ml reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing and drying the reaction product to obtain the core-shell NaYF4:Yb,Tm@TiO2。
Dissolving Polyacrylonitrile (PAN) and polyethylene glycol (PEG) (the mass ratio of PAN to PEG is 1: 1) into DMF, and stirring for 3h to obtain uniform and transparent spinning solution. And (3) placing the spinning solution on an electrostatic spinning experimental device, wherein the advancing speed is 1mL/h, the distance between the needle point and the receiving device is 15cm, and the rotating speed of a roller on the receiving device is 300rpm, so that the PAN/PEG composite fiber is obtained. And dissolving the composite fiber in water to fully dissolve out PEG to obtain the porous PAN fiber. It was placed in 50mL ethyl silicate, prepared NaYF4:Yb,Tm@TiO2Stirring thoroughly in mixed solution of (100mg), cetyltrimethylammonium chloride (CTAC, 0.2mol/L) and hydrochloric acid water solution (0.1mol/L), and calcining at 800 deg.C for 1h in nitrogen atmosphere to obtain NaYF4:Yb,Tm@TiO2Porous silica fiber composite.
Example 10
1mmol of rare earth oxide RE with a chemical molar ratio of (Y: Yb: Tm ═ 79.5: 20: 0.5)2O3Dissolving in concentrated hydrochloric acid, and heating until the solution is evaporatedDissolving water in deionized water to obtain a dispersion liquid with the concentration of 0.1 mmol/L. Dissolving EDTA in deionized water to obtain 0.1mmol/L dispersion, adding dropwise into the above solution, and stirring for 30min until white precipitate is formed. Then, 4mmol of NaF aqueous solution was added dropwise, and stirring was continued for 1 hour. And (3) transferring the reaction precursor solution into a 40ml reaction kettle, heating to 180 ℃, reacting for 12 hours, centrifuging, washing and drying the obtained product to obtain a white powdery sample.
Collecting 50mg prepared NaYF4Yb, Tm powder is dispersed in 10ml of absolute ethyl alcohol by ultrasonic. Then weighing 0.172g of butyl titanate, 0.05g of CTAB, 1ml of water and 10ml of absolute ethyl alcohol, uniformly mixing, adding the mixture into the solution, mixing and stirring for 2 hours, pouring the mixture into a 40ml reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing and drying a reaction product to obtain the core-shell NaYF4:Yb,Tm@TiO2。
Dissolving Polyacrylonitrile (PAN) and polyethylene glycol (PEG) (the mass ratio of PAN to PEG is 1: 1) into DMF, and stirring for 3h to obtain uniform and transparent spinning solution. And (3) placing the spinning solution on an electrostatic spinning experimental device, wherein the advancing speed is 1mL/h, the distance between the needle point and the receiving device is 15cm, and the rotating speed of a roller on the receiving device is 300rpm, so that the PAN/PEG composite fiber is obtained. And dissolving the composite fiber in water to fully dissolve out PEG to obtain the porous PAN fiber. It was placed in 50mL ethyl silicate, prepared NaYF4:Yb,Tm@TiO2Stirring thoroughly in mixed solution of (100mg), cetyltrimethylammonium chloride (CTAC, 0.2mol/L) and hydrochloric acid water solution (0.1mol/L), and calcining at 800 deg.C for 1h in nitrogen atmosphere to obtain NaYF4:Yb,Tm@TiO2Porous silica fiber composite.
Example 11
1mmol of rare earth oxide RE with a chemical molar ratio of (Y: Yb: Tm ═ 79.5: 20: 0.5)2O3Dissolving in concentrated hydrochloric acid, heating until water in the solution is evaporated, and dissolving in deionized water to obtain 0.1mmol/L dispersion. Dissolving EDTA in deionized water to obtain 0.1mmol/L dispersion, adding dropwise into the above solution, and stirring for 30min until white precipitate is formed. Then, 4mm of a dispersion is added dropwiseThe olNaF aqueous solution was stirred for 1 h. And (3) transferring the reaction precursor solution into a 40ml reaction kettle, heating to 180 ℃, reacting for 12 hours, centrifuging, washing and drying the obtained product to obtain a white powdery sample.
Collecting 50mg prepared NaYF4Yb, Tm powder is dispersed in 10ml of absolute ethyl alcohol by ultrasonic. Then weighing 0.022g of tetrabutyl titanate, 0.05g of CTAB, 1ml of water and 10ml of absolute ethyl alcohol, uniformly mixing, adding the mixture into the solution, mixing and stirring for 2 hours, pouring the mixture into a 40ml reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing and drying the reaction product to obtain the core-shell NaYF4:Yb,Tm@TiO2。
Dissolving Polyacrylonitrile (PAN) and polyethylene glycol (PEG) (the mass ratio of PAN to PEG is 1: 1) into DMF, and stirring for 3h to obtain uniform and transparent spinning solution. And (3) placing the spinning solution on an electrostatic spinning experimental device, wherein the advancing speed is 1mL/h, the distance between the needle point and the receiving device is 15cm, and the rotating speed of a roller on the receiving device is 300rpm, so that the PAN/PEG composite fiber is obtained. And dissolving the composite fiber in water to fully dissolve out PEG to obtain the porous PAN fiber. It was placed in 50mL ethyl silicate, prepared NaYF4:Yb,Tm@TiO2Stirring thoroughly in mixed solution of (100mg), cetyltrimethylammonium chloride (CTAC, 0.2mol/L) and hydrochloric acid water solution (0.1mol/L), and calcining at 800 deg.C for 1h in nitrogen atmosphere to obtain NaYF4:Yb,Tm@TiO2Porous silica fiber composite.
Example 12
1mmol of rare earth oxide RE with a chemical molar ratio of (Y: Yb: Tm ═ 79.5: 20: 0.5)2O3Dissolving in concentrated hydrochloric acid, heating until water in the solution is evaporated, and dissolving in deionized water to obtain 0.1mmol/L dispersion. Dissolving EDTA in deionized water to obtain 0.1mmol/L dispersion, adding dropwise into the above solution, and stirring for 30min until white precipitate is formed. Then, 4mmol of NaF aqueous solution was added dropwise, and stirring was continued for 1 hour. And (3) transferring the reaction precursor solution into a 40ml reaction kettle, heating to 180 ℃, reacting for 12 hours, centrifuging, washing and drying the obtained product to obtain a white powdery sample.
Collecting 50mg prepared NaYF4Yb, Tm powder is dispersed in 10ml of absolute ethyl alcohol by ultrasonic. Then weighing 0.043g of tetrabutyl titanate, 0.05g of CTAB, 1ml of water and 10ml of absolute ethyl alcohol, uniformly mixing, adding the mixture into the solution, mixing and stirring for 2h, pouring the mixture into a 40ml reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing and drying the reaction product to obtain the core-shell NaYF4:Yb,Tm@TiO2。
Dissolving Polyacrylonitrile (PAN) and polyethylene glycol (PEG) (the mass ratio of PAN to PEG is 1: 1) into DMF, and stirring for 3h to obtain uniform and transparent spinning solution. And (3) placing the spinning solution on an electrostatic spinning experimental device, wherein the advancing speed is 1mL/h, the distance between the needle point and the receiving device is 15cm, and the rotating speed of a roller on the receiving device is 300rpm, so that the PAN/PEG composite fiber is obtained. And dissolving the composite fiber in water to fully dissolve out PEG to obtain the porous PAN fiber. It was placed in 50mL ethyl silicate, prepared NaYF4:Yb,Tm@TiO2Stirring thoroughly in the mixture of (50mg), cetyltrimethylammonium chloride (CTAC, 0.2mol/L) and hydrochloric acid aqueous solution (0.1mol/L), then calcining at 800 deg.C for 1h in nitrogen atmosphere to obtain NaYF4:Yb,Tm@TiO2Porous silica fiber composite.
Example 13
1mmol of rare earth oxide RE with a chemical molar ratio of (Y: Yb: Tm ═ 79.5: 20: 0.5)2O3Dissolving in concentrated hydrochloric acid, heating until water in the solution is evaporated, and dissolving in deionized water to obtain 0.1mmol/L dispersion. Dissolving EDTA in deionized water to obtain 0.1mmol/L dispersion, adding dropwise into the above solution, and stirring for 30min until white precipitate is formed. Then, 4mmol of NaF aqueous solution was added dropwise, and stirring was continued for 1 hour. And (3) transferring the reaction precursor solution into a 40ml reaction kettle, heating to 180 ℃, reacting for 12 hours, centrifuging, washing and drying the obtained product to obtain a white powdery sample.
Collecting 50mg prepared NaYF4Yb, Tm powder is dispersed in 10ml of absolute ethyl alcohol by ultrasonic. Then, 0.043g of tetrabutyl titanate, 0.05g of CTAB, 1ml of water and 10ml of absolute ethyl alcohol are weighed, evenly mixed, added into the solution, mixed and stirred for 2 hours, poured into a 40ml reaction kettleReacting for 6 hours at 160 ℃, centrifuging, washing and drying a reaction product to obtain the core-shell NaYF4:Yb,Tm@TiO2。
Dissolving Polyacrylonitrile (PAN) and polyethylene glycol (PEG) (the mass ratio of PAN to PEG is 1: 1) into DMF, and stirring for 3h to obtain uniform and transparent spinning solution. And (3) placing the spinning solution on an electrostatic spinning experimental device, wherein the advancing speed is 1mL/h, the distance between the needle point and the receiving device is 15cm, and the rotating speed of a roller on the receiving device is 300rpm, so that the PAN/PEG composite fiber is obtained. And dissolving the composite fiber in water to fully dissolve out PEG to obtain the porous PAN fiber. It was placed in 50mL ethyl silicate, prepared NaYF4:Yb,Tm@TiO2(200mg), cetyl trimethyl ammonium chloride (CTAC, 0.2mol/L) and hydrochloric acid aqueous solution (0.1mol/L), fully stirring, and calcining at 800 deg.C for 1h in nitrogen atmosphere to obtain NaYF4:Yb,Tm@TiO2Porous silica fiber composite.
Example 14
1mmol of rare earth oxide RE with a chemical molar ratio of (Y: Yb: Tm ═ 79.5: 20: 0.5)2O3Dissolving in concentrated hydrochloric acid, heating until water in the solution is evaporated, and dissolving in deionized water to obtain 0.1mmol/L dispersion. Dissolving EDTA in deionized water to obtain 0.1mmol/L dispersion, adding dropwise into the above solution, and stirring for 30min until white precipitate is formed. Then, 4mmol of NaF aqueous solution was added dropwise, and stirring was continued for 1 hour. And (3) transferring the reaction precursor solution into a 40ml reaction kettle, heating to 180 ℃, reacting for 12 hours, centrifuging, washing and drying the obtained product to obtain a white powdery sample.
Collecting 50mg prepared NaYF4Yb, Tm powder is dispersed in 10ml of absolute ethyl alcohol by ultrasonic. Then weighing 0.043g of tetrabutyl titanate, 0.05g of CTAB, 1ml of water and 10ml of absolute ethyl alcohol, uniformly mixing, adding the mixture into the solution, mixing and stirring for 2h, pouring the mixture into a 40ml reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing and drying the reaction product to obtain the core-shell NaYF4:Yb,Tm@TiO2。
Dissolving Polyacrylonitrile (PAN) and polyethylene glycol (PEG) (the mass ratio of PAN to PEG is 1: 1)Dissolving in DMF, and stirring for 3h to obtain uniform and transparent spinning solution. And (3) placing the spinning solution on an electrostatic spinning experimental device, wherein the advancing speed is 1mL/h, the distance between the needle point and the receiving device is 15cm, and the rotating speed of a roller on the receiving device is 300rpm, so that the PAN/PEG composite fiber is obtained. And dissolving the composite fiber in water to fully dissolve out PEG to obtain the porous PAN fiber. It was placed in 50mL ethyl silicate, prepared NaYF4:Yb,Tm@TiO2(500mg), cetyltrimethylammonium chloride (CTAC, 0.2mol/L) and hydrochloric acid aqueous solution (0.1mol/L), fully stirring, and calcining at 800 ℃ for 1h in nitrogen atmosphere to obtain NaYF4:Yb,Tm@TiO2Porous silica fiber composite.

Claims (10)

1. A method for preparing a near-infrared responsive photocatalyst by taking porous silica fiber as a carrier is characterized by comprising the following steps:
(1) preparing upconversion crystal powder by taking rare earth oxide as a raw material and adopting a hydrothermal method;
(2) dispersing the upconversion crystal powder obtained in the step (1) in a solvent to obtain an upconversion crystal dispersion liquid, uniformly mixing a titanium dioxide precursor, a surfactant, water and absolute ethyl alcohol to obtain a titanium dioxide precursor liquid, mixing and stirring the upconversion crystal dispersion liquid and the titanium dioxide precursor liquid for 1-10 hours, reacting for 2-14 hours at 150-200 ℃, centrifuging, washing and drying a reaction product to obtain an upconversion luminescent material with a core-shell structure;
(3) dissolving polyacrylonitrile and a water-soluble polymer in a solvent, performing electrostatic spinning to obtain composite fibers, dissolving the composite fibers in water to obtain porous polyacrylonitrile fibers, placing the porous polyacrylonitrile fibers in a mixed solution of a silicon dioxide precursor, a core-shell structure up-conversion luminescent material, a surfactant and an acidic aqueous solution, fully stirring, and calcining at 700-1200 ℃ for 30 min-3 h in an inert atmosphere to obtain the photocatalyst.
2. The photocatalyst preparation method according to claim 1, characterized in that:
the rare earth oxide is selected fromY2O3、Yb2O3、Tm2O3、Er2O3、Ho2O3At least one of (1).
3. The photocatalyst preparation method according to claim 2, characterized in that:
the rare earth oxide comprises Y2O3、Yb2O3And Tm2O3Wherein the molar ratio of Y, Yb and Tm is (74.9-80): (15-25): (0.1-10.1).
4. The photocatalyst preparation method according to claim 1, characterized in that:
the titanium dioxide precursor is selected from at least one of titanium isopropoxide, butyl titanate, titanium tetrachloride, titanium sulfate and diisopropyl di (acetylacetonate) titanate.
5. The photocatalyst preparation method according to claim 1, characterized in that:
the silicon dioxide precursor is selected from at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate.
6. The photocatalyst preparation method according to claim 1, characterized in that:
the water-soluble polymer is at least one selected from polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride, polyquaternary ammonium salt and polyethylene glycol.
7. The photocatalyst preparation method according to claim 1, characterized in that:
the surfactant is at least one selected from ethylenediamine tetraacetic acid, trisodium citrate, polyvinylpyrrolidone, tartaric acid, oxalic acid, sulfosalicylic acid, cetyl trimethyl ammonium bromide and cetyl trimethyl ammonium chloride.
8. The photocatalyst preparation method according to claim 1, characterized in that:
in the step (2), the mass ratio of the up-conversion crystal, the titanium dioxide precursor and the surfactant is 5: (2-20): (5-20).
9. The photocatalyst preparation method according to claim 1, characterized in that:
in the step (3), the proportion of the up-conversion luminescent material with the core-shell structure in the silicon dioxide precursor is 0.05-10 g/L.
10. A photocatalyst obtained by the method for preparing a near-infrared responsive photocatalyst using a porous silica fiber as a carrier according to any one of claims 1 to 9.
CN201810888339.8A 2018-08-07 2018-08-07 Preparation method of near-infrared responsive photocatalyst with porous silica fiber as carrier and photocatalyst Pending CN110813327A (en)

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