CN110694611B - Rare earth modified nRe-M x WO 3 F y Particles and method for producing same - Google Patents
Rare earth modified nRe-M x WO 3 F y Particles and method for producing same Download PDFInfo
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- CN110694611B CN110694611B CN201910976495.4A CN201910976495A CN110694611B CN 110694611 B CN110694611 B CN 110694611B CN 201910976495 A CN201910976495 A CN 201910976495A CN 110694611 B CN110694611 B CN 110694611B
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- 239000002245 particle Substances 0.000 title claims abstract description 43
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 32
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 15
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000000411 inducer Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- -1 rare earth salt Chemical class 0.000 claims abstract description 9
- 150000007524 organic acids Chemical class 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 60
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 229910052775 Thulium Inorganic materials 0.000 claims description 20
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 235000015165 citric acid Nutrition 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 230000001699 photocatalysis Effects 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052701 rubidium Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
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- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
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- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000007146 photocatalysis Methods 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 11
- 238000004134 energy conservation Methods 0.000 abstract description 4
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- 238000002834 transmittance Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 23
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- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 6
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
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- 238000005265 energy consumption Methods 0.000 description 5
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- 229910052684 Cerium Inorganic materials 0.000 description 4
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- 229910052688 Gadolinium Inorganic materials 0.000 description 4
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
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- 229910052779 Neodymium Inorganic materials 0.000 description 4
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- 229910052772 Samarium Inorganic materials 0.000 description 4
- 229910052771 Terbium Inorganic materials 0.000 description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 description 4
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- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
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- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
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- 238000004433 infrared transmission spectrum Methods 0.000 description 1
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
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- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
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- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
-
- 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
-
- B01J35/39—
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to rare earth modified nRe-M x WO 3 F y Particles and a preparation method thereof, belonging to the field of new materials, energy conservation and environmental protection. Rare earth modified nRe-M x WO 3 F y Adding a tungstic acid solution into a reaction kettle, adding an M salt, an HF solution, an inducer and a solvent, and continuously stirring for 0.5-6 h to obtain a reaction precursor solution; reacting the precursor reaction solution at 150-400 ℃, washing the precipitate after reaction with water and alcohol in sequence, centrifuging, and drying to obtain M x WO 3 F y Particles; will M x WO 3 F y Adding the particles into a reaction kettle, adding a solvent, adding rare earth salt and organic acid during stirring, stirring to obtain a reaction solution, reacting at 150-350 ℃, washing the precipitate with water, washing with alcohol, centrifuging, and drying to obtain rare earth 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 ) The particles not only have higher visible light transmittance and near infrared shielding/transparent heat shielding functions, but also have excellent functions of photocatalytic degradation of organic pollutants.
Description
Technical Field
The invention relates to rare earth modified nRe-M x WO 3 F y Particles and a preparation method thereof, belonging to the field of new materials, energy conservation and environmental protection.
Background
With the development of society and the improvement of productivity, people have more and more demand for energy, and due to the fact that a large amount of polluted smoke and harmful gases are generated in the energy consumption process, various environmental problems caused by the pollution, such as greenhouse effect, acid rain and the like, are increasingly concerned by the whole society. Therefore, energy conservation and consumption reduction are the problems that need to be considered in the sustainable economic development of all countries. The near infrared light in the solar spectrum accounts for about 46%, the energy consumption of buildings accounts for about 30-40% of the energy consumption of the whole country in many countries, and the energy consumed by glass doors and windows accounts for more than 50% of the energy consumption of the buildings. The energy-saving and heat-insulating of the building window glass has important significance for energy conservation and emission reduction.
Meanwhile, along with the improvement of living conditions and the improvement of living quality requirements of people, the requirements of people on the living environment are correspondingly improved. Indoor air quality is becoming an important area of concern. The oil smoke generated by cooking in a kitchen and formaldehyde emitted by indoor furniture harms the health of people invisibly. The window glass of a building occupies most of the area of the building, which is in close contact with indoor air. If the transparent heat insulation film coated on the window glass of the building has the function of photocatalytic degradation of harmful pollutants, the indoor air quality is greatly improved.
It has been reported that the addition of M having transparent heat-insulating properties to a coating x WO 3 F y The particles can obtain a transparent heat insulating film capable of transmitting visible light and shielding near infrared light. The transparent heat insulation film can be widely applied to automobile films and building door and window films. However, M x WO 3 F y The photocatalytic properties of the particles are not very desirable. Therefore, research on preparation of M with excellent functions of transparency, heat insulation and photocatalytic degradation of organic pollutants x WO 3 Particles are necessary.
Disclosure of Invention
The invention aims to provide a rare earth modified M with transparent heat shielding performance and a function of photocatalytic degradation of organic pollutants x WO 3 F y (nRe-M x WO 3 F y ) Particles and methods of making the same, wherein M can be lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), or ammonia (NH) 4 ) X is 0.2-0.35; the rare earth element Re can be one or more of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu), and n is 0.001-0.9; y is 0 to 1.0, preferably 0.01 to 0.95, and most preferably 0.20 to E0.75。
Rare earth modified nRe-M x WO 3 F y Adding a tungstic acid solution into a reaction kettle, adding an M salt or an M salt solution, stirring, adding an HF solution, an inducer or an inducer solution and a solvent, and continuously stirring for 0.5-6 hours to obtain a reaction precursor solution; reacting the precursor reaction solution at 150-400 ℃ for 5-72 hours, washing the reacted precipitate with water and alcohol in sequence, centrifugally separating, and drying at 50-100 ℃ to obtain M x WO 3 F y Particles; will M x WO 3 F y Adding the particles into a reaction kettle, adding a solvent, adding rare earth salt or a rare earth salt solution and an organic acid in the stirring process, stirring for 0.5-3 h to obtain a reaction solution, reacting at 150-350 ℃ for 12-72 h, washing the precipitate with water, washing with alcohol, centrifuging, and drying at 50-120 ℃ to obtain rare earth modified nRe-M x WO 3 F y Particles of a polymeric material, wherein,
the molar ratio of the inducer to the W atom in the reaction precursor liquid is 0.05-15: 1; f: the atomic molar ratio of M to W is 0-1: 0.1-0.5: 1; the concentration of the tungstic acid in the reaction precursor liquid 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 or NH 4 The salt of (1) wherein x is 0.2 to 0.35, n is 0.001 to 0.9, and y is 0 to 1.0.
In the above technical solution, the nRe-M x WO 3 F y Of these, y is preferably 0.01 to 0.95, and most preferably 0.20 to 0.75.
In the technical scheme, the tungstic acid solution is prepared by the following method: tungstate is dissolved in water to prepare a tungstate solution with the concentration of 0.1-2 mol/L, and the tungstate solution is converted into a tungstic acid solution by using cation exchange resin. Further, the tungstate is one of sodium tungstate, potassium tungstate, ammonium metatungstate, ammonium ortho-tungstate, ammonium para-tungstate or a mixture thereof.
In the technical scheme, the rare earth salt is one or more of nitrate, chloride, sulfate, carbonate or acetate of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; or salts formed by acid dissolution of oxides containing La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
Further, the rare earth salt is most preferably one or more of nitrate, chloride, carbonate, sulfate or acetate of ytterbium (Yb) or thulium (Tm); or salts formed by acid dissolution of Yb and Tm containing oxides.
Further, the rare earth Yb, Tm is commonly paired with M x WO 3 F y During modification, Yb is contained in the reaction solution 3+ 、Tm 3+ And M x WO 3 F y The molar ratio of (A) to (B) is: yb of 3+ :Tm 3+ :M x WO 3 F y =0.001~0.6:0.0001~0.1:1。
Further, the M salt is sulfate, nitrate, carbonate or chloride.
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 O、N 2 H 4 ·HCl、 N 2 H 4 ·H 2 SO 4 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 the W atom is 1-10: 1.
Further, the solvent is one or more of deionized water, ethanol, isopropanol, ethylene glycol monomethyl 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, M in the reaction solution x WO 3 F y The concentration of (A) is 0.05-3 mol/L, and the rare earth Re 3+ And M x WO 3 F y In a molar ratio of Re 3+ :M x WO 3 F y =0.001~0.9:1。
The rare earth modified nRe-M of the invention x WO 3 F y The preparation method of the particles also comprises a heat treatment step, which specifically comprises the following steps: modifying rare earth with M x WO 3 F y The particles are subjected to heat treatment in a reducing atmosphere or an inert atmosphere at the temperature of 350-800 ℃ for 10 min-3 h.
Further, the reducing atmosphere comprises a single H 2 、NH 3 A gas mixture of gases or a combination thereof; the inert atmosphere comprises N 2 Ar, or a combination thereof, and may also be N 2 /H 2 Or N 2 /HH 3 And the like.
Further, the reducing atmosphere may be added to the reaction furnace for heat treatment while introducing an inert atmosphere capable of generating H 2 、NH 3 And organic acids or organic compounds of reducing gases such as CO.
The invention also aims to provide the rare earth modified nRe-M prepared by the method x WO 3 F y Particles of said nRe-M x WO 3 F y Wherein M is Li, Na, K, Rb, Cs, NH 4 X is 0.2 to 0.35, n is 0.001 to 0.9, and y is 0 to 1.0, preferably 0.01 to 0.95, and most preferably 0.20 to 0.75; re is one or more of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu salts, and the nRe-M x WO 3 F y The main crystal phase of the particles is hexagonal M x WO 3 A crystal structure.
nRe-M prepared by the method x WO 3 F y The particles have visible light transmission, near infrared shielding and transparent heat insulation functions.
nRe-M prepared by the method x WO 3 F y The particles have the function of degrading organic pollutants by photocatalysis.
The invention has the beneficial effects that: the invention has the advantages and creativity that the rare earth modified M x WO 3 F y (nRe-M x WO 3 F y ) The particles not only have higher visible light transmittance and near infrared shielding/transparent heat shielding functions, but also have excellent functions of photocatalytic degradation of organic pollutants. This is due to the doping modification of rare earth ions to expand M x WO 3 F y The light absorption range of the compound increases the number of photo-generated electrons, inhibits the recombination of the photo-generated electrons and holes, and improves the M x WO 3 F y Photocatalytic properties of tungsten bronze particles. Therefore, the rare earth modified M of the invention x WO 3 F y (nRe-M x WO 3 F y ) The particles are particularly suitable for preparing coatings, films and the like which have the functions of self-cleaning, air purification, sterilization and transparent heat insulation.
Drawings
FIG. 1 shows Yb, Tm modified Cs synthesized in examples 1 to 4 and comparative example 1 x WO 3 (Yb,Tm-Cs x WO 3 ) XRD patterns of the particles, as can be seen from FIG. 1, Yb, Tm modified Cs synthesized in examples 1 to 4 x WO 3 The main crystal phase in the particles is hexagonal Cs 0.2 WO 3 。
FIG. 2 is a time-dependent change curve of absorbance of solutions obtained by subjecting products of examples 1-4 and comparative example 1 to photocatalytic degradation of RhB under xenon lamp irradiation, and it can be seen that the full-spectrum photocatalytic performance of the products synthesized in examples 1-4 is improved to some extent compared with that of the comparative example.
Fig. 3 is a graph showing the absorbance of the products of examples 1 to 4 and comparative example 1 in the form of a change with time of the absorbance of the solution for photocatalytic degradation of RhB under a UV lamp, and it can be seen that the UV catalytic performance of the products of examples 1 to 4 is further enhanced compared to that of the comparative example.
Fig. 4 shows the uv-vis-nir transmission spectra of the product particles of examples 1 to 4 and comparative example 1 after being dispersed and then coated with a thin film on the glass surface, and it can be seen that the product particles of examples 1 to 4 all have good visible light transmission and nir shielding properties.
FIG. 5 is a graph showing the change of absorbance of the solution of the products of examples 5 to 7 in which RhB is photocatalytic-degraded under a UV lamp with time, and it can be seen that the products of examples 5 to 7 have very strong ultraviolet photocatalytic degradation performance.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Cs x WO 3 Preparation of particles: preparing sodium tungstate solution by taking sodium tungstate as a raw material, obtaining 0.5mol/L tungstic acid solution through ion exchange, measuring 38.5mL of tungstic acid solution, adding into a reaction kettle, adding 49.5mL of deionized water, adding 1.4186g of cesium sulfate, stirring at a high speed for 1h, reacting for 72h at 190 ℃, taking out reactants after the reaction kettle is cooled, washing the reactants by ultrasonic water and alcohol for three times respectively, centrifuging and drying to obtain Cs 0.33 WO 3 And (3) powder.
Cs x WO 3 F y Preparation of particles: taking sodium tungstate as a raw material, obtaining a 0.5mol/L tungstic acid solution through ion exchange, measuring 50mL of the tungstic acid solution, adding the tungstic acid solution into a reaction kettle, adding 50mL of an HF solution with the concentration of 0.25mol/L, stirring for 30min, adding 30mL of deionized water, and continuing stirring; and adding 1.074g of cesium carbonate into 20mL of deionized water to prepare a cesium carbonate solution, measuring 5mL of the cesium carbonate solution, adding the cesium carbonate solution into the reaction kettle, continuously stirring for 2 hours, and then reacting in an oven at 190 ℃ for 72 hours. Washing with water and alcohol for three times, and drying at 60 deg.C to obtain Cs 0.33 WO 3 F 0.5 And (3) powder. The preparation process is similar, 25mL of HF solution with the concentration of 0.25mol/L is added, and Cs is obtained through the similar preparation process 0.33 WO 3 F 0.25 And (3) powder.
Upper surface Cs x WO 3 And Cs x WO 3 F y The particles can also be prepared by other similar processes, and the Cs can be obtained x WO 3 And Cs x WO 3 F y The description of the preparation of the particles is not intended to be limiting in any wayMaking the subject matter of the invention, however, Cs x WO 3 And Cs x WO 3 F y The type of (b), the preparation method and the process of (c) will influence the final properties of the product to a certain extent.
In the following examples, the obtained rare earth-modified Cs was subjected to x WO 3 F y In the measurement of the performance parameters of the nano-particle products:
(1) the phase structure of the product is tested by an X-ray diffractometer, the model of the X-ray diffractometer is Shimadzu XRD-7000S, Shimadzu corporation in Japan, Cu Ka rays are adopted, lambda is 0.15406nm, the scanning speed is 5 degrees/min, the scanning step is 0.01 degrees, and the scanning range 2 theta is 10 degrees to 70 degrees.
(2) Testing the photocatalytic performance: 0.2g of sample powder was added to 300mL of 1 × 10 molar solution -5 And (3) in mol/L RhB solution, transferring the obtained liquid into a dark room, carrying out magnetic stirring for 30min for dark room adsorption, sampling and centrifuging at the beginning of the dark room adsorption process, and measuring the absorbance as a first data point, wherein the measured wavelength is 553 nm. And after the adsorption process of the darkroom is finished, sampling to serve as a second data point, then turning on a xenon lamp light source to perform a photocatalytic reaction, sampling once every 10min to test the absorbance of the supernatant, putting the sample back into the sample cell to continuously participate in the photocatalytic reaction after the absorbance is measured, and repeating the steps until the step is finished after 120 min.
The ultraviolet light catalysis process is similar to the steps of photocatalysis experiments under the irradiation of a xenon lamp, and the difference is that the ultraviolet light catalysis reaction is finished until 1 hour later.
(3) The UV-visible-near infrared transmission spectrum of the powder dispersion after coating on the glass surface was tested using a UV-VIS-NIR spectrometer (Perkin Elmer, Lambda 950, USA).
Example 1
Taking the prepared Cs 0.33 WO 3 5.5g of the powder was added to a reaction vessel, 110mL of deionized water was added and 0.8982g of Yb (NO) was added while stirring 3 ) 3 ·5H 2 O and 0.0185g Tm (NO) 3 ) 3 ·6H 2 O, then 21g of citric acid monohydrate is added and stirred for 1h, the mixture reacts at 190 ℃ for 24h, after cooling, the water washing and the alcohol washing are repeated for three times respectively, and the mixture is centrifugedDrying, heat treating at 450 deg.C in hydrogen atmosphere for 30min, cooling, grinding to obtain Yb and Tm modified Cs x WO 3 The final product of the powder is 0.10Yb,0.002Tm-Cs 0.33 WO 3 。
Example 2
Taking the prepared Cs x WO 3 5.5g of powder was added to the autoclave, 110mL of deionized water was added and 0.8982g of Yb (NO) was added while stirring 3 ) 3 ·5H 2 O and 0.0463g Tm (NO) 3 ) 3 ·6H 2 O, then adding 21g of citric acid monohydrate, stirring for 1h, reacting for 24h at 190 ℃, cooling, repeatedly washing with water and alcohol for three times, centrifugally drying, performing heat treatment for 30min at 450 ℃ in a hydrogen atmosphere, cooling, taking out and grinding to obtain Yb and Tm modified Cs x WO 3 The final product of the powder is 0.10Yb,0.005Tm-Cs 0.33 WO 3 。
Example 3
Taking the prepared Cs x WO 3 5.5g of the powder was added to a reaction vessel, 110mL of deionized water was added and 0.8982g of Yb (NO) was added while stirring 3 ) 3 ·5H 2 O and 0.0925g Tm (NO) 3 ) 3 ·6H 2 O, then adding 21g of citric acid monohydrate, stirring for 1h, reacting for 24h at 190 ℃, cooling, repeatedly washing with water and alcohol for three times, centrifugally drying, performing heat treatment for 30min at 450 ℃ in a hydrogen atmosphere, cooling, taking out and grinding to obtain Yb and Tm modified Cs x WO 3 The final product of the powder is 0.10Yb,0.01Tm-Cs 0.33 WO 3 。
Example 4
Taking the prepared Cs x WO 3 5.5g of the powder was added to a reaction vessel, 110mL of deionized water was added and 0.8982g of Yb (NO) was added while stirring 3 ) 3 ·5H 2 O and 0.1388g Tm (NO) 3 ) 3 ·6H 2 O, then adding 21g of citric acid monohydrate, stirring for 1h, reacting for 24h at 190 ℃, cooling, repeatedly washing with water and alcohol for three times, centrifugally drying, performing heat treatment for 30min at 450 ℃ in a hydrogen atmosphere, cooling, taking out and grinding to obtain Yb and Tm modified Cs x WO 3 The final product of the powder is 0.10Yb,0.015Tm-Cs 0.33 WO 3 。
Example 5
Weigh a defined amount of YbCl 3 ·6H 2 O, preparing YbCl of 0.109mol/L 3 ·6H 2 O solution; weigh a defined amount of TmCl 3 ·6H 2 O, preparing TmCl of 0.052mol/L 3 ·6H 2 O solution; taking the prepared Cs 0.33 WO 3 F 0.5 Adding powder 2.0g into deionized water 40mL, adding into reaction kettle, adding 3.3mLYbCl 3 ·6H 2 Adding TmCl into the O solution 3 ·6H 2 2.02mL of O solution, adding 70mL of citric acid solution with the concentration of 1mol/L, stirring for 2h, and placing in an oven for reacting for 24h at 180 ℃; centrifugally washing after the reaction is finished, and drying for 2h at 80 ℃ to obtain Yb and Tm modified Cs 0.33 WO 3 F 0.5 And (3) powder. Ultraviolet light catalysis test shows that the prepared 0.05Yb,0.015Tm-Cs 0.33 WO 3 F 0.5 The photocatalytic degradation rate of the powder is close to 100% in 100 min.
Example 6
Weigh a defined amount of YbCl 3 ·6H 2 O, preparing YbCl of 0.109mol/L 3 ·6H 2 O solution; weigh a defined amount of TmCl 3 ·6H 2 O, preparing TmCl of 0.052mol/L 3 ·6H 2 O solution; taking the prepared Cs 0.33 WO 3 F 0.25 Adding powder 2.0g into deionized water 40mL, adding into reaction kettle, adding 3.3mLYbCl 3 ·6H 2 Adding TmCl into the O solution 3 ·6H 2 2.02mL of O solution, adding 70mL of citric acid solution with the concentration of 1mol/L, stirring for 2h, and putting into an oven for reacting for 24h at 180 ℃; centrifugally washing after the reaction is finished, and drying for 2h at 80 ℃ to obtain Yb and Tm modified Cs 0.33 WO 3 F 0.25 And (3) powder. Ultraviolet light catalysis test shows that the prepared 0.05Yb,0.015Tm-Cs 0.33 WO 3 F 0.25 The photocatalytic degradation rate of the powder is close to 99.5 percent at 100 min.
Example 7
Weighing a certain amount of YbCl 3 ·6H 2 O, preparation of 0.109mol/L YbCl 3 ·6H 2 O solution; weigh a defined amount of TmCl 3 ·6H 2 O, preparing 0.052mol/l of TmCl 3 ·6H 2 O solution; taking the prepared Cs 0.33 WO 3 Adding powder 2.0g into deionized water 40mL, adding into reaction kettle, adding 3.3mLYbCl 3 ·6H 2 Adding TmCl into the O solution 3 ·6H 2 2.02mL of O solution, adding 65mL of citric acid solution with the concentration of 1mol/L, stirring for 2h, and placing in an oven for reacting for 24h at 180 ℃; centrifugally washing after the reaction is finished, and drying for 2h at 80 ℃ to obtain Yb and Tm modified Cs 0.33 WO 3 And (3) powder. Ultraviolet light catalysis test shows that the prepared 0.05Yb,0.015Tm-Cs 0.33 WO 3 The photocatalytic degradation rate of the powder is close to 99% in 100 min.
Comparative example 1
Preparing sodium tungstate solution by taking sodium tungstate as a raw material, obtaining 0.5mol/L tungstic acid solution through ion exchange, measuring 38.5mL of tungstic acid solution, adding into a reaction kettle, adding 49.5mL of deionized water, adding 1.4186g of cesium sulfate, stirring, adding 25.427g of citric acid monohydrate, stirring at a high speed for 1h, reacting at 190 ℃ for 72h, taking out a reactant after the reaction kettle is cooled, washing the reactant with ultrasonic water and alcohol for three times respectively, and centrifugally drying to obtain Cs x WO 3 And (3) powder.
Claims (9)
1. Rare earth modified nRe-M x WO 3 F y A method for producing particles, characterized by: adding a tungstic acid solution into a reaction kettle, adding an M salt or an M salt solution, stirring, adding an HF solution, an inducer or an inducer solution and a solvent, and continuously stirring for 0.5-6 h to obtain a reaction precursor solution; reacting the precursor reaction solution at 150-400 ℃ for 5-72 hours, washing the reacted precipitate with water and alcohol in sequence, centrifugally separating, and drying at 50-100 ℃ to obtain M x WO 3 F y Particles; will M x WO 3 F y Adding the particles into a reaction kettle, adding a solvent, adding rare earth salt or a rare earth salt solution and an organic acid in the stirring process, stirring for 0.5-3 h to obtain a reaction solution, reacting at 150-350 ℃ for 12-72 h, and then carrying out precipitationWashing with water, washing with alcohol, centrifuging, and drying at 50-120 ℃ to obtain the rare earth modified nRe-M x WO 3 F y Particles of a polymeric material, wherein,
the molar ratio of the inducer to the W atom in the reaction precursor liquid is 0.05-15: 1; the atomic molar ratio of F to M to W is 0-1: 0.1-0.5: 1; the concentration of the tungstic acid in the reaction precursor liquid 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 or NH 4 0.2 to 0.35, 0.001 to 0.9 and 0 to 1.0; 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 O、N 2 H 4 ·HCl、N 2 H 4 ·H 2 SO 4 One or a mixture thereof; the solvent is one or more of deionized water, ethanol, isopropanol, ethylene glycol monomethyl ether and ethylene glycol ethyl ether; 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;
the nRe-M x WO 3 F y Wherein M is Li, Na, K, Rb, Cs, NH 4 X is 0.2 to 0.35, n is 0.001 to 0.9, and y is 0 to 1.0; re is Tm and Yb, the nRe-M x WO 3 F y The main crystal phase of the particles is hexagonal M x WO 3 A crystal structure.
2. The method of claim 1, wherein: the nRe-M x WO 3 F y Wherein y is 0.01 to 0.95.
3. The method of claim 1, wherein: the M salt is sulfate, nitrate or chloride.
4. The method of 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. The method of claim 1, wherein: the method also comprises a heat treatment step, which specifically comprises the following steps: rare earth is modified with nRe-M x WO 3 F y The particles are subjected to heat treatment in a reducing atmosphere or an inert atmosphere at the temperature of 350-800 ℃ for 10 min-3 h.
6. The method of claim 1, wherein: m in the reaction solution x WO 3 F y The concentration of (A) is 0.05-3 mol/L, and the rare earth Re 3+ And M x WO 3 F y In a molar ratio of Re 3+ :M x WO 3 F y =0.001~0.9:1。
7. The method of claim 1, wherein: the rare earth salt is one or more of nitrate, chloride, sulfate or acetate of Tm and Yb; or salts formed by acid dissolution of oxides containing Tm and Yb.
8. Rare earth modified nRe-M prepared by the method of any one of claims 1 to 7 x WO 3 F y A particle, characterized in that: the nRe-M x WO 3 F y Wherein M is Li, Na, K, Rb, Cs, NH 4 X is 0.2 to 0.35, n is 0.001 to 0.9, and y is 0 to 1.0; re is Tm and Yb, the nRe-M x WO 3 F y The main crystal phase of the particles is hexagonal M x WO 3 A crystal structure.
9. The nRe-M of claim 8 x WO 3 F y A particle, characterized in that: the particles have visible light transmission, near infrared shielding and transparent heat insulation functions; the particles have the function of degrading organic pollutants by photocatalysis.
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