CN110694611B - Rare earth modified nRe-M x WO 3 F y Particles and method for producing same - Google Patents

Abstract

The invention relates to a rare earth modified nRe-M _x WO ₃ F _y particle and a preparation method thereof, belonging to the fields of new materials and energy conservation and environmental protection. A preparation method of rare earth modified nRe-M _x WO ₃ F _y particles, the tungstic acid solution is added into a reaction kettle, M salt, HF solution, inducer and solvent are added, and the reaction precursor is obtained after continuous stirring for 0.5-6 h The precursor reaction solution was reacted at 150-400°C, and the reacted precipitate was washed with water and alcohol in turn, and after centrifugal separation, dried to obtain M _x WO ₃ F _y particles; M _x WO ₃ F _y particles were obtained by drying The particles are added to the reaction kettle, the solvent is added, the rare earth salt and organic acid are added during the stirring process, and the reaction solution is obtained after stirring. Modified nRe‑M _x WO ₃ F _y particles. The rare earth modified M _x WO ₃ F _y (nRe-M _x WO ₃ F _y ) particles not only have high visible light transmittance and near-infrared shielding/transparent heat shielding function, but also have excellent photocatalytic degradation of organic Pollutant function.

Description

A rare earth modified nRe-MxWO3Fy particle and preparation method thereof

technical field

The invention relates to a rare earth modified nRe-M _x WO ₃ F _y particle and a preparation method thereof, belonging to the fields of new materials and energy conservation and environmental protection.

Background technique

With the development of society and the improvement of productivity, people's demand for energy is increasing. Due to the large amount of polluting smoke and harmful gases generated in the process of energy consumption, various environmental problems such as greenhouse effect and acid rain are caused. etc. are also increasingly concerned by the whole society. Therefore, energy conservation and consumption reduction are issues that must be considered in the sustainable economic development of various countries. Near-infrared light in the solar spectrum accounts for about 46%. In the energy consumption of many countries, building energy consumption accounts for about 30 to 40% of the national energy consumption, while the energy consumed through glass doors and windows accounts for 50% of building energy consumption. above. The energy saving and thermal insulation of building window glass is of great significance for energy saving and emission reduction.

At the same time, with the improvement of people's living conditions and the improvement of life quality requirements, people's requirements for their own living environment also increase accordingly. Indoor air quality has gradually become an important area of concern. The fumes from cooking in the kitchen and the formaldehyde emitted from indoor furniture are all invisibly endangering people's health. The window glass of the building occupies most of the area of the building, which is in close contact with the indoor air. If the transparent thermal insulation film coated on architectural window glass also has the function of photocatalytic degradation of harmful pollutants, indoor air quality will be greatly improved.

It has been reported in a patent that adding M _x WO ₃ F _y particles with transparent heat insulating properties to the coating can obtain a transparent heat insulating film that can transmit visible light and shield near-infrared light. Transparent thermal insulation film can be widely used in car film and building door and window film. However, the photocatalytic performance of M _x WO ₃ F _y particles is not ideal. Therefore, it is very necessary to study and prepare M _x WO ₃ particles with excellent transparent heat shielding function and photocatalytic degradation of organic pollutants.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a rare earth modified M _x WO ₃ F _y (nRe-M _x WO ₃ F _y ) particle with both transparent heat shielding performance and photocatalytic degradation of organic pollutants and a preparation method thereof, wherein, M can be lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) or ammonia (NH ₄ ), x=0.2-0.35; rare earth element Re can be lanthanum (La), Cerium (Ce), Praseodymium (Pr), Neodymium (Nd), Samarium (Sm), Europium (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), Erbium (Er), One or more of thulium (Tm), ytterbium (Yb) and lutetium (Lu), n=0.001-0.9; y=0-1.0, preferably y=0.01-0.95, most preferably y=0.20-0.75.

A preparation method of rare earth modified nRe-M _x WO ₃ F _y particles, the tungstic acid solution is added into a reaction kettle, M salt or M salt solution is added and stirred, HF solution, inducer or inducer solution and solvent, and continue stirring for 0.5 to 6 hours to obtain the reaction precursor solution; react the precursor reaction solution at 150 to 400 ° C for 5 to 72 hours, wash the reacted precipitate with water and alcohol in turn, and after centrifugal separation, at 50 Drying at ~100°C to obtain M _x WO ₃ F _y particles; adding the M _x WO ₃ F _y particles into the reaction kettle, adding a solvent, adding rare earth salt or rare earth salt solution and organic acid during stirring, and stirring for 0.5 to 3 hours A reaction solution is obtained, reacted at 150-350°C for 12-72 hours, the precipitate is washed with water, alcohol, centrifuged, and dried at 50-120°C to obtain rare earth modified nRe-M _x WO ₃ F _y particles, in,

The molar ratio of the inducer to W atoms in the reaction precursor solution is 0.05-15:1; the atomic molar ratio of F:M:W is 0-1:0.1-0.5:1; the concentration of tungstic acid in the reaction precursor solution is 0.1-1.5 mol/L; the concentration of the inducer in the reaction precursor solution is 0.3-1.8 mol/L; the molar concentration of the organic acid in the reaction solution is 0.1-3.0 mol/L; the M salt is Li , Na, K, Rb, Cs, NH ₄ salts, x=0.2～0.35, n=0.001～0.9, y=0～1.0.

In the above technical solution, in the nRe-M _x WO ₃ F _y , preferably y=0.01-0.95, most preferably y=0.20-0.75.

In the above technical scheme, the tungstic acid solution is prepared by the following method: dissolving tungstate in water to prepare a tungstate solution with a concentration of 0.1 to 2 mol/L, and converting the tungstate solution into tungsten by using a cation exchange resin. acid solution. Further, the tungstate is one or a mixture of sodium tungstate, potassium tungstate, ammonium metatungstate, ammonium orthotungstate, and ammonium paratungstate.

In the above technical scheme, the rare earth salts are nitrates, chlorides, sulfates, One or more of carbonate or acetate; or oxides containing La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu Salts formed by acid dissolution.

Further, the rare earth salt is most preferably one or more of nitrates, chlorides, carbonates, sulfates or acetates of ytterbium (Yb) or thulium (Tm); , Tm oxide salts generated by acid dissolution.

Furthermore, when rare earth Yb and Tm jointly modify M _x WO ₃ F _y , the molar ratio of Yb ³⁺ , Tm ³⁺ and M _x WO ₃ F _y in the reaction solution is: Yb ³⁺ : Tm ³⁺ : M _x WO ₃ F _y =0.001 to 0.6:0.0001 to 0.1:1.

Further, the M salts are sulfates, nitrates, carbonates and chlorides.

Further, the inducer is oxalic acid, formic acid, tartaric acid, acetic acid, lactic acid, citric acid, ascorbic acid, polyethylene glycol, sorbic acid, polypropylene glycol, potassium borohydride, sodium borohydride, N ₂ H ₄ ·H _{2 One} of _O , _N2H4.HCl , _N2H4.H2SO4 , _or a mixture thereof _.

Further, the concentration of the HF solution is 0.05-0.85 mol/L.

Further, the molar ratio of the inducer to W atom is 1-10:1.

Further, the solvent is one or more of deionized water, ethanol, isopropanol, ethylene glycol methyl ether, and ethylene glycol ethyl ether.

Further, the organic acid is one or more of oxalic acid, tartaric acid, acetic acid, benzoic acid, lactic acid, citric acid, ascorbic acid, sorbic acid, malic acid and the like.

Further, the concentration of M _x WO ₃ F _y in the reaction solution is 0.05-3 mol/L, and the molar ratio of rare earth Re ³⁺ to M _x WO ₃ F _y is Re ³⁺ : M _x WO ₃ F _y =0.001 ~0.9:1.

The preparation method of the rare earth modified nRe-M _x WO ₃ F _y particles of the present invention further comprises the step of heat treatment, specifically: the rare earth modified M _x WO ₃ F _y particles are heated in a reducing atmosphere or an inert atmosphere at 350-800° C. Heat treatment for 10min～3h.

Further, the reducing atmosphere includes a single mixed gas of H ₂ , NH ₃ gas or a combination thereof; the inert atmosphere includes a mixed gas of N ₂ , Ar or a combination thereof, which may also be N ₂ /H ₂ or Mixed gas such as N ₂ /HH ₃ .

Furthermore, the reducing atmosphere can also be obtained by adding an organic acid or an organic compound capable of generating reducing gases such as H ₂ , NH ₃ , CO and the like while passing an inert atmosphere into the heat treatment reactor.

Another object of the present invention is to provide rare earth-modified nRe-M _x WO ₃ F _y particles prepared by the above method, wherein the nRe-M _x WO ₃ F _y particles, wherein M is Li, Na, K, Rb, Cs , NH ₄ , x=0.2～0.35, n=0.001～0.9, y=0～1.0, preferably y=0.01～0.95, most preferably y=0.20～0.75; Re is La, Ce, Pr, Nd, Pm, One or more of Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu salts, the main crystal phase of the nRe-M _x WO ₃ F _y particles is hexagonal M _x WO ₃ crystals structure.

The nRe-M _x WO ₃ F _y particles prepared by the above method have the functions of visible light transmission, near-infrared shielding and transparent heat insulation.

The nRe-M _x WO ₃ F _y particles prepared by the above method have the function of photocatalytic degradation of organic pollutants.

The beneficial effects of the present invention are: the advanced nature and creativity of the present invention lie in that the rare earth modified M _x WO ₃ F _y (nRe-M _x WO ₃ F _y ) particles not only have high visible light transmittance and Infrared shielding/transparent heat shielding function, and has excellent photocatalytic degradation of organic pollutants. This is because the doping modification of rare earth ions expands the light absorption range of M _x WO ₃ F _y , increases the number of photogenerated electrons, suppresses the recombination of photo-generated electrons and holes, thereby improving the M _x WO ₃ F _y tungsten Photocatalytic properties of bronze particles. Therefore, the rare earth-modified M _x WO ₃ F _y (nRe-M _x WO ₃ F _y ) particles of the present invention are particularly suitable for preparing coatings and films with self-cleaning, air purification, sterilization, and transparent and heat-insulating functions at the same time Wait.

Description of drawings

Fig. 1 is the XRD pattern of Yb, Tm modified Cs _x WO ₃ (Yb, Tm-Cs _x WO ₃ ) particles synthesized in Examples 1-4 and Comparative Example 1. It can be seen from Fig. 1 that Example 1- 4 The main crystal phase of the synthesized Yb, Tm modified Cs _x WO ₃ particles is hexagonal Cs _0.2 WO ₃ .

Fig. 2 is the variation curve of the solution absorbance of the photocatalytic degradation of RhB under xenon lamp irradiation with the products of Examples 1-4 and Comparative Example 1. It can be seen that, compared with the Comparative Examples, the total amount of the synthesized products of Examples 1-4 is The spectral photocatalytic performance was improved to a certain extent.

Fig. 3 is the variation curve of the solution absorbance over time of photocatalytic degradation of RhB under UV lamp for the products of Examples 1-4 and Comparative Example 1. It can be seen that, compared with the Comparative Examples, the UV photocatalysis of the products of Example 1-4 Performance has been further enhanced.

Fig. 4 is the ultraviolet-visible-near-infrared transmission spectrum of the coated film on the glass surface after dispersion of the product particles corresponding to Examples 1-4 and Comparative Example 1. It can be seen that the product particles corresponding to Examples 1-4 are all It has good visible light transmission and near-infrared shielding performance.

Fig. 5 is the change curve of the solution absorbance with time of photocatalytic degradation of RhB by the corresponding products of embodiment 5-7 under UV lamp, it can be seen that the corresponding products of embodiment 5-7 have extremely strong UV photocatalytic degradation performance .

Detailed ways

The following non-limiting examples may enable those of ordinary skill in the art to more fully understand the present invention, but do not limit the present invention in any way.

The test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials can be obtained from commercial sources unless otherwise specified.

Preparation of Cs _x WO ₃ particles: take sodium tungstate as raw material, prepare sodium tungstate solution, obtain 0.5 mol/L tungstic acid solution through ion exchange, measure 38.5 mL of tungstic acid solution into the reaction kettle, add 49.5 mL Deionized water, add 1.4186g of cesium sulfate and stir, after high-speed stirring for 1 h, react at 190 ° C for 72 h, after the reaction kettle is cooled, take out the reactant, wash with ultrasonic water and alcohol three times each, and centrifuge dry to obtain Cs _0.33 WO ₃ powder body.

Preparation of Cs _x WO ₃ F _y particles: take sodium tungstate as raw material, obtain 0.5 mol/L tungstic acid solution by ion exchange, measure 50 mL of tungstic acid solution and add it to the reaction kettle, add 50 mL of tungstic acid solution to a concentration of 0.25 mol/L The HF solution was stirred for 30min, then 30mL of deionized water was added, and the stirring was continued; 1.074g of cesium carbonate was added to 20mL of deionized water to prepare a cesium carbonate solution, and 5mL of the cesium carbonate solution was measured, added to the reaction kettle, and continued to stir for 2 hours, and then reacted in an oven at 190 °C for 72 h. Three times of water washing and three times of alcohol washing, and finally drying at 60° C. to obtain Cs _0.33 WO ₃ F _0.5 powder. The above preparation process is similar, and 25 mL of HF solution with a concentration of 0.25 mol/L is added, and through a similar preparation process, Cs _0.33 WO ₃ F _0.25 powder is obtained.

_The preparation methods _of the above Cs _x WO ₃ and Cs _x WO ₃ F _y particles can also be prepared _by using other similar _{processes .} The content of the present invention is limited, but the type, preparation method and process of Cs _x WO ₃ and Cs _x WO ₃ F _y will affect the final performance of the product to a certain extent.

In the following examples, unless otherwise specified, in the determination of the performance parameters of the prepared rare earth modified Cs _x WO ₃ F _y nanoparticle products:

(1) Use an X-ray diffractometer to test the phase structure of the product. The X-ray diffractometer model is Shimadzu XRD-7000S, Shimadzu Corporation of Japan, using Cu Kα rays, λ=0.15406nm, and the scanning rate is 5°/min. The scanning step size was 0.01°, and the scanning range 2θ was 10°-70°.

(2) Photocatalytic performance test: add 0.2 g of sample powder to 300 mL of RhB solution with a molar concentration of 1×10 ^-5 mol/L, and transfer the resulting liquid to a dark room with magnetic stirring for 30 min for dark room adsorption. The dark room adsorption process begins The samples were centrifuged and the absorbance was measured as the first data point at a wavelength of 553 nm. After the adsorption process in the dark room, take a sample as the second data point, and then turn on the xenon light source for photocatalytic reaction, and take samples every 10 minutes to test the absorbance of the supernatant. , repeat the above steps until the end after 120min.

The UV photocatalytic process is similar to the photocatalytic experimental steps under xenon lamp irradiation, except that the UV photocatalytic reaction ends after 1 h.

(3) UV-VIS-NIR spectrometer (Perkin Elmer, Lambda 950, USA) was used to test the UV-Vis-NIR transmission spectrum of the powder dispersion after coating the glass surface.

Example 1

5.5g of the Cs _0.33 WO ₃ powder prepared above was added to the reaction kettle, 110 mL of deionized water was added, and 0.8982 g of Yb(NO ₃ ) ₃ ·5H ₂ O and 0.0185 g of Tm(NO ₃ were added during the stirring process. ) ₃ · 6H ₂ O, then add 21 g of citric acid monohydrate and stir for 1 h, react at 190 ° C for 24 h, after cooling, repeat washing with water and alcohol three times each, after centrifugal drying, heat treatment in a hydrogen atmosphere at 450 ° C for 30 min, cooling Then take out and grind to obtain Yb, Tm modified Cs _x WO ₃ powder final product 0.10Yb, 0.002Tm-Cs _0.33 WO ₃ .

Example 2

5.5g of the Cs _x WO ₃ powder prepared above was added to the reaction kettle, 110 mL of deionized water was added, and 0.8982g of Yb(NO ₃ ) ₃ .5H ₂ O and 0.0463g of Tm(NO ₃ ) were added during the stirring process. ₃ · 6H ₂ O, then add 21 g of citric acid monohydrate and stir for 1 h, react at 190 ° C for 24 h, after cooling, repeat washing with water and alcohol three times, after centrifugal drying, heat treatment in a hydrogen atmosphere at 450 ° C for 30 min, after cooling Take out and grind to obtain Yb, Tm modified Cs _x WO ₃ powder final product 0.10Yb, 0.005Tm-Cs _0.33 WO ₃ .

Example 3

Take 5.5g of the Cs _x WO ₃ powder prepared above and add it to the reaction kettle, add 110 mL of deionized water and add 0.8982g Yb(NO ₃ ) ₃ ·5H ₂ O and 0.0925g Tm(NO ₃ in the process of stirring ) ₃ 6H ₂ O, then added 21 g of citric acid monohydrate and stirred for 1 h, reacted at 190 ° C for 24 h, after cooling, repeated washing with water and alcohol three times, after centrifugal drying, heat treatment in a hydrogen atmosphere at 450 ° C for 30 min, cooling Then take out and grind to obtain Yb, Tm modified Cs _x WO ₃ powder final product 0.10Yb, 0.01Tm-Cs _0.33 WO ₃ .

Example 4

Take 5.5g of the Cs _x WO ₃ powder prepared above and add it to the reaction kettle, add 110 mL of deionized water and add 0.8982g Yb(NO ₃ ) ₃ .5H ₂ O and 0.1388g Tm(NO ₃ during the stirring process ) ₃ 6H ₂ O, then added 21 g of citric acid monohydrate and stirred for 1 h, reacted at 190 ° C for 24 h, after cooling, repeated washing with water and alcohol three times, after centrifugal drying, heat treatment in a hydrogen atmosphere at 450 ° C for 30 min, cooling Then take out and grind to obtain Yb, Tm modified Cs _x WO ₃ powder final product 0.10Yb, 0.015Tm-Cs _0.33 WO ₃ .

Example 5

Weigh a certain amount of YbCl ₃ ·6H ₂ O to prepare 0.109mol/L YbCl ₃ ·6H ₂ O solution; weigh a certain amount of TmCl ₃ ·6H ₂ O to prepare 0.052mol/L TmCl ₃ ·6H ₂ O solution; take 2.0 g of the Cs _0.33 WO ₃ F _0.5 powder prepared above, add 40 mL of deionized water, add it to the reaction kettle, add 3.3 mL of LYbCl ₃ ·6H ₂ O solution, and add 2.02 mL of TmCl ₃ ·6H ₂ O solution , add 70 mL of citric acid solution with a concentration of 1 mol/L, stir for 2 h, put it in an oven for 24 h at 180 °C; after the reaction, centrifugal washing, and drying at 80 °C for 2 h to obtain Yb, Tm modified Cs _0.33 WO ₃ F _0.5 powder body. The UV photocatalytic test showed that the photocatalytic degradation rate of the prepared 0.05Yb, 0.015Tm-Cs _0.33 WO ₃ F _0.5 powder was close to 100% in 100 min.

Example 6

Weigh a certain amount of YbCl ₃ ·6H ₂ O to prepare 0.109mol/L YbCl ₃ ·6H ₂ O solution; weigh a certain amount of TmCl ₃ ·6H ₂ O to prepare 0.052mol/L TmCl ₃ ·6H ₂ O solution; take 2.0 g of the Cs _0.33 WO ₃ F _0.25 powder prepared above, add 40 mL of deionized water, add it to the reaction kettle, add 3.3 mL of LYbCl ₃ ·6H ₂ O solution, and add 2.02 mL of TmCl ₃ ·6H ₂ O solution , add 70 mL of citric acid solution with a concentration of 1 mol/L, stir for 2 h, put it in an oven for 24 h at 180 °C; after the reaction, centrifugal washing, and drying at 80 °C for 2 h to obtain Yb, Tm modified Cs _0.33 WO ₃ F _0.25 powder body. The UV photocatalytic test showed that the photocatalytic degradation rate of the prepared 0.05Yb, 0.015Tm-Cs _0.33 WO ₃ F _0.25 powder was close to 99.5% in 100 min.

Example 7

Weigh a certain amount of YbCl ₃ ·6H ₂ O to prepare 0.109mol/L YbCl ₃ ·6H ₂ O solution; weigh a certain amount of TmCl ₃ ·6H ₂ O to prepare 0.052mol/l TmCl ₃ ·6H ₂ O solution; take 2.0 g of the Cs _0.33 WO ₃ powder prepared above, add 40 mL of deionized water, add it to the reaction kettle, add 3.3 mL of LYbCl ₃ ·6H ₂ O solution, add 2.02 mL of TmCl ₃ ·6H ₂ O solution, add 65mL of citric acid solution with a concentration of 1mol/L was stirred for 2h, put into an oven at 180°C for reaction for 24h; after the reaction, centrifuged and washed, and dried at 80°C for 2h to obtain Yb, Tm modified Cs _0.33 WO ₃ powder. The UV photocatalytic test showed that the photocatalytic degradation rate of the prepared 0.05Yb, 0.015Tm-Cs _0.33 WO ₃ powder was close to 99% in 100 min.

Comparative Example 1

Use sodium tungstate as raw material to prepare sodium tungstate solution, obtain 0.5mol/L tungstic acid solution by ion exchange, measure 38.5mL of tungstate solution and add it to the reaction kettle, add 49.5mL deionized water, add 1.4186g sulfuric acid Cesium and stirred, then added 25.427g of citric acid monohydrate, stirred at high speed for 1 hour, and reacted at 190 ° C for 72 hours. After the reaction kettle was cooled, the reactant was taken out, washed with ultrasonic water and alcohol three times, and centrifuged to dry to obtain Cs _x WO ₃ powder.

Claims (9)

1. a preparation method of rare earth modified nRe-M _x WO ₃ F _y particle, is characterized in that: adding tungstic acid solution in the reactor, adding M salt or M salt solution and stirring, adding HF solution, inducing After stirring continuously for 0.5 to 6 hours, the reaction precursor solution is obtained; the precursor reaction solution is reacted at 150 to 400 ° C for 5 to 72 hours, and the reacted precipitate is washed with water and alcohol in turn. After centrifugal separation, drying at 50-100° C. to obtain M _x WO ₃ F _y particles; adding the M _x WO ₃ F _y particles into the reaction kettle, adding a solvent, and adding rare earth salt or rare earth salt solution and organic acid, stirred for 0.5-3 hours to obtain a reaction solution, reacted at 150-350 °C for 12-72 hours, washed the precipitate with water, alcohol, centrifuged, and dried at 50-120 °C to obtain rare earth modified nRe-M _x WO ₃ F _y particles, where, The molar ratio of the inducer to W atoms in the reaction precursor solution is 0.05-15:1; the atomic molar ratio of F:M:W is 0-1:0.1-0.5:1; the concentration of tungstic acid in the reaction precursor solution is 0.1-1.5 mol/L; the concentration of the inducer in the reaction precursor solution is 0.3-1.8 mol/L; the molar concentration of the organic acid in the reaction solution is 0.1-3.0 mol/L; the M salt is Li , Na, K, Rb, Cs, NH ₄ salts, x=0.2～0.35, n=0.001～0.9, y=0～1.0; the inducers are oxalic acid, formic acid, tartaric acid, acetic acid, lactic acid, lemon Of acid, ascorbic _acid , polyethylene glycol, _{sorbic acid} , polypropylene glycol, potassium _borohydride , _{sodium borohydride} , _N2H4.H2O , _N2H4.HCl , _N2H4.H2SO4 one or a mixture thereof; the solvent is one or more of deionized water, ethanol, isopropanol, ethylene glycol methyl ether, ethylene glycol ethyl ether; the organic acid is oxalic acid, tartaric acid, acetic acid, benzene One or more of formic acid, lactic acid, citric acid, ascorbic acid, sorbic acid, malic acid, etc.; The nRe-M _x WO ₃ F _y , wherein, M is Li, Na, K, Rb, Cs, NH ₄ , x=0.2～0.35, n=0.001～0.9, y=0～1.0; Re is Tm and Yb, the main crystal phase of the nRe-M _x WO ₃ F _y particles is a hexagonal M _x WO ₃ crystal structure. 2 . The method according to claim 1 , wherein: in the nRe-M _x WO ₃ F _y , y=0.01-0.95. 3 . 3. method according to claim 1 is characterized in that: described M salt is sulfate, nitrate, chloride. 4 . The method according to claim 1 , wherein the concentration of the HF solution is 0.05-0.85 mol/L; the molar ratio of the inducer to the W atom is 1-10:1. 5 . 5 . The method according to claim 1 , wherein the method further comprises the step of heat treatment, specifically: subjecting the rare earth modified nRe-M _x WO ₃ F _y particles to a reducing atmosphere or Heat treatment in an inert atmosphere for 10min-3h. The method according to claim 1, characterized in that: the concentration of M _x WO ₃ F _y in the reaction solution is 0.05-3 mol/L, and the molar ratio of rare earth Re ³⁺ to M _x WO ₃ F _y is Re ³⁺ : M _x WO ₃ F _y =0.001 to 0.9:1. 7. The method according to claim 1, wherein: the rare earth salt is one or more of the nitrate, chloride, sulfate or acetate of Tm and Yb; Salts formed by acid dissolution of Yb oxides. 8. The rare earth modified nRe-M _x WO ₃ F _y particles prepared by the method according to any one of claims 1 to 7, characterized in that: the nRe-M _x WO ₃ F _y , wherein M is Li, Na, K, Rb, Cs, NH ₄ , x=0.2-0.35, n=0.001-0.9, y=0-1.0; Re is Tm and Yb, the main crystal phase of the nRe-M _x WO ₃ F _y particles For the hexagonal M _x WO ₃ crystal structure. 9. nRe-M _x WO ₃ F _y particles according to claim 8, characterized in that: the particles have the functions of visible light transmission, near-infrared shielding and transparent heat insulation; the particles have photocatalytic degradation of organic pollutants function.

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