# US 10,120,106 B2 · Preparation methods and uses of doped VIB group metal oxide nanoparticles or dispersions thereof

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- Number: US 10,120,106 B2
- Document ID: US10120106B2
- Status: Granted
- Kind: B2
- Application number: 14/910,476
- Filed: 2014-08-05
- Published: 2016-06-23
- Granted: 2018-11-06
- Earliest claimed: 2013-08-05
- Assignees: Beijing University of Chemical Technology; Changzhou Institute of Advanced Material of Beijing University of Chemical Technology
- Applicants: Beijing University of Chemical Technology; Changzhou Institute of Advanced Material of Beijing University of Chemical Technology
- Inventors: Zhigang Shen; Jimmy Sung Lai Yun; Jianfeng Chen; Xiaofei Zeng
- Web page: https://patentgrep.com/patent/US10120106B2

## CPC

- G02B 1/10: Optical coatings produced by application to, or surface treatment of, optical elements (G02B1/08 takes precedence)
- C01G 39/02: Oxides; Hydroxides
- C01G 41/00: Compounds of tungsten
- C01G 41/02: Oxides; Hydroxides
- C09C 1/00: Treatment of specific inorganic materials other than fibrous fillers (tenebrescent materials C09K9/00; luminescent materials C09K11/00); Preparation of carbon black
- C09C 1/0003: {Compounds of molybdenum (C09C1/0015 takes precedence)}
- C09D 5/32: Radiation-absorbing paints {(protection against X-, gamma- or corpuscular radiation G21F)}
- G02B 5/208: {for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation}
- C01P 2002/30: Three-dimensional structures
- C01P 2002/34: perovskite-type (ABO3)
- C01P 2002/54: one element only
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2002/77: by unit-cell parameters, atom positions or structure diagrams
- C01P 2004/03: obtained by SEM
- C01P 2004/51: Particles with a specific particle size distribution
- C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer
- C01P 2004/62: Submicrometer sized, i.e. from 0.1-1 micrometer
- C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer
- C01P 2006/12: Surface area
- C01P 2006/60: Optical properties, e.g. expressed in CIELAB-values
- Y02P 20/54: using solvents, e.g. supercritical solvents or ionic liquids
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C09C: TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES (treatment of materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone C04B14/00, C04B18/00, C04B20/00); PREPARATION OF CARBON BLACK {; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS}
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The present invention is related to a method for preparing VIB Group metal oxide particles or dispersions, wherein the VIB Group metal is tungsten or molybdenum. The methods include: 1) providing precursors of VIB Group metal oxide, reductants and supercritical fluids. 2) said VIB Group metal oxide particles, or dispersions are obtained by the reaction between said metal oxide precursors, and reductants are under supercritical state in said supercritical fluids. Especially, said VIB Group metal oxide can be tungsten bronze, molybdenum bronze, or tungsten and molybdenum bronze which can be present by the formula AxByMOz. Wherein, A represents element exists in the form of dopant cation; and B represents element exists in the form of dopant anion; O represents oxygen; 0≤x≤1, 0≤y≤1, 0<x+y≤1, and 2≤z≤3. The said VIB Group metal oxide particles and dispersions can be applied to the glasses of houses, buildings, automobiles, ships etc, with high transparency and NIR and UV lights shielding properties, by which the control of sunlight and heat radiation can be achieved.

## Claims

### Claim 1

A method for preparing VIB Group metal oxide particles or a dispersion thereof, the method comprising:
1) reacting a salt solution of the VIB Group metal with a precipitating agent solution to produce colloid particles of an acid of the VIB Group metal;
2) removing impurities from the colloid particles to obtain purified colloid particles; and
3) reacting the purified colloid particles with a reductant in a supercritical fluid under a supercritical state to obtain the VIB Group metal oxide particles or the dispersion thereof, wherein the supercritical fluid under the supercritical state is substantially free of a solvent that is not a supercritical fluid under the supercritical state, wherein the VIB Group metal is molybdenum, tungsten, or both, and the acid of the VIB Group metal is tungstic acid, molybdic acid, or both,
wherein a concentration of the VIB Group metal oxide particles or the dispersion thereof in the supercritical fluid is in the range of 0.25 mol/L to 0.33 mol/L, and wherein the supercritical state has a temperature ranging from 150-400° C. and a pressure ranging from 1-30 atm.

### Claim 2 (depends on 1)

The method for preparing the VIB Group metal oxide particles or dispersion thereof according to claim 1, wherein the VIB Group metal oxide is selected from the group consisting of tungsten bronze, molybdenum bronze, and tungsten-molybdenum bronze, wherein the VIB Group metal oxide has an empirical formula: AxByMOz, wherein M is tungsten atom, molybdenum atom, or combinations thereof; A is a dopant element in form of cation; B is a dopant element in form of anion; O is oxygen; 0≤x≤1, 0≤y≤1, 0<x+y≤1, 2≤z≤3; wherein A is ammonium or one or more elements selected from elements of main-groups and sub-groups, and B is one or more elements selected from elements of main-groups and sub-groups.

### Claim 3 (depends on 2)

The method for preparing the VIB Group metal oxide particles or dispersion thereof according to claim 2, wherein a portion of said M has a valence of +6 and the rest of said M has a valence of lower than +6.

### Claim 4 (depends on 1)

The method for preparing the VIB Group metal oxide particles or dispersion thereof according to claim 1, wherein one or more of the precursor of VIB Group metal oxide, the reductant, and the supercritical fluid contains a VIIIB Group metal or a compound thereof as a catalyst to catalyze the reaction.

### Claim 5 (depends on 4)

The method for preparing the VIB Group metal oxide particles or dispersion thereof according to claim 4, wherein the one or more of the precursor of VIB Group metal oxide, the reductant and the supercritical fluid contains a pH regulator, and the pH regulator is selected from the group consisting of inorganic acids, inorganic bases, organic acids, organic bases, and combinations thereof.

### Claim 6 (depends on 5)

The method for preparing the VIB Group metal oxide particles or dispersion thereof according to claim 5, wherein the reductant, the catalyst, and the pH regulator is of the supercritical state and used as at least a part or all of the supercritical fluid in the reaction.

### Claim 7 (depends on 1)

The method for preparing the VIB Group metal oxide particles or dispersion thereof according to claim 1, wherein the VIB Group metal oxide particles have an average particle size of less than or equal to 10 μm.

### Claim 8 (depends on 1)

The method for preparing the VIB Group metal oxide particles or dispersion thereof according to claim 1, wherein the VIB Group metal oxide particles have a steepness ratio of less than or equal to 3 for particle size distribution.

### Claim 9 (depends on 1)

The method for preparing the VIB Group metal oxide particles or dispersion thereof according to claim 1, wherein the supercritical fluid is a supercritical fluid with a critical temperature of below 650° C.

### Claim 10 (depends on 1)

The method for preparing the VIB Group metal oxide particles or dispersion thereof according to claim 1, wherein the supercritical fluid is selected from a group consisting of water, ammonia, alcohols, ketones, esters, aldehydes, amines, hydrocarbons, ethers, heterocycles, organic acids and combinations thereof.

### Claim 11 (depends on 1)

The method for preparing the VIB Group metal oxide particles or dispersion thereof according to claim 1, wherein the reaction in step 3) is performed under a condition that the supercritical fluid has a Reynolds number of 2000-200000.

### Claim 12 (depends on 1)

The method for preparing the VIB Group metal oxide particles or dispersion thereof according to claim 1, further comprising: 4) adding a surfactant to the one or more of the precursor of VIB Group metal oxide, the reductant and the supercritical fluid in step 2) or to the VIB Group metal oxide particles or dispersions as obtained in step 3).

### Claim 13 (depends on 12)

The method for preparing the VIB Group metal oxide particles or dispersion thereof according to claim 12, wherein the surfactant is selected from the group consisting of non-silane surfactants, silane coupling agents, titanate coupling agents, and combinations thereof.

### Claim 14 (depends on 1)

The method for preparing the VIB Group metal oxide particles or dispersion thereof according to claim 1, further comprising: 5) separating the VIB Group metal oxide particles or dispersion thereof of step 3) from an impurity in the supercritical fluid, wherein the separation is performed in manner of liquid-liquid phase transfer, precipitation and/or filtration.

### Claim 15 (depends on 14)

The method for preparing the VIB Group metal oxide particles or dispersion thereof according to claim 14, further comprising: 6) redispersing the separated VIB Group metal oxide particles in a medium to form a dispersion of the VIB Group metal oxide particles.