CN114014364B - Environment-friendly method for preparing tungsten bronze nano material - Google Patents
Environment-friendly method for preparing tungsten bronze nano material Download PDFInfo
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- 229910000906 Bronze Inorganic materials 0.000 title claims abstract description 43
- 239000010974 bronze Substances 0.000 title claims abstract description 43
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 23
- 239000010937 tungsten Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 13
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 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 abstract description 17
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 17
- 239000011975 tartaric acid Substances 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000012265 solid product Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 claims description 9
- 239000001472 potassium tartrate Substances 0.000 claims description 9
- 229940111695 potassium tartrate Drugs 0.000 claims description 9
- 235000011005 potassium tartrates Nutrition 0.000 claims description 9
- -1 potassium tungstate dihydrate Chemical class 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 5
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 8
- 229940095064 tartrate Drugs 0.000 abstract description 8
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 abstract description 8
- 230000003287 optical effect Effects 0.000 abstract description 6
- 150000001339 alkali metal compounds Chemical class 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000003321 amplification Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- OHUPZDRTZNMIJI-UHFFFAOYSA-N [Cs].[W] Chemical compound [Cs].[W] OHUPZDRTZNMIJI-UHFFFAOYSA-N 0.000 description 14
- 230000008033 biological extinction Effects 0.000 description 13
- 239000007787 solid Substances 0.000 description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- ZGRBQKWGELDHSV-UHFFFAOYSA-N N.[W+4] Chemical compound N.[W+4] ZGRBQKWGELDHSV-UHFFFAOYSA-N 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- LIHHHYMOABTJCZ-UHFFFAOYSA-N [Rb].[W] Chemical compound [Rb].[W] LIHHHYMOABTJCZ-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 229940102127 rubidium chloride Drugs 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001476 sodium potassium tartrate Substances 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical group [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses an environment-friendly method for preparing a tungsten bronze nano material. The invention adopts a low-temperature hydrothermal synthesis method, sequentially dissolves tungstate, tartaric acid and/or tartrate, alkali metal compound and/or ammonium source in water, fully mixes, then places the mixture in a hydrothermal reaction kettle, uses a homogeneous reactor to control the reaction temperature to be 120-200 ℃ for 12-24 hours, and cleans and dries the obtained solid product to prepare the tungsten bronze nano material. The raw materials used by the method are low in price and environment-friendly, industrial amplification and large-scale production are easy, and the produced tungsten bronze nanomaterial is about 50-200nm in size, good in crystallinity and excellent in optical characteristics.
Description
Technical Field
The invention relates to an environment-friendly method for preparing a tungsten bronze nano material, belongs to the technical field of preparation of tungsten bronze materials, and particularly relates to a method for preparing the tungsten bronze nano material by using environment-friendly and low-cost tartaric acid (salt) as a reducing agent in a low-temperature water phase.
Background
Tungsten bronze materials are a non-stoichiometric class of compounds of the formula M x WO 3 (0<x<1) M is an alkaline earth metal, an alkali metal, a rare earth metal, an ammonium ion or the like, and is essentially the above ion intercalating WO 3 Lattice, wherein the valence states of tungsten are +5 and +6. Tungsten bronze is widely applied to photothermal treatment, infrared shielding and heat preservation coating due to good mechanical, optical and thermal properties, and is also used as a catalyst due to chemical inertness.
The preparation method of the tungsten bronze mainly comprises a chemical vapor transmission method (Journal of Solid State Chemistry,2008,181 (1): 90-100), a high-temperature solid phase reaction method (Journal of the American Ceramic Society,2018, (10): 4458-4462), a low-temperature molten salt synthesis method (CN 107601568A), a hydrothermal or solvothermal method (CN 103496744A) and the like, and the main problems of the methods are as follows: 1. the process needs to be carried out at high temperature or ultra-high temperature; 2. the reaction adopts an organic phase or introduces oleylamine and oleic acid, is easy to pollute the environment, belongs to inflammable and explosive dangerous goods, and brings great trouble to chemical production; 3. the tungsten source selected in the process is WCl which is expensive and corrosive 6 Or WCl 4 The method comprises the steps of carrying out a first treatment on the surface of the 4. Poor crystallinity (low temperature molten salt synthesis).
Disclosure of Invention
Aiming at the existing problems, the invention aims to provide a water phase synthesis method of tungsten bronze nano-materials, which uses low-cost and environment-friendly raw materials to synthesize nano-scale tungsten bronze materials in a low-temperature water phase so as to realize the enlarged production and the safety management of tungsten bronze.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method of preparing a tungsten bronze nanomaterial comprising the steps of:
step one: sequentially dissolving tungstate, tartaric acid and/or tartrate, alkali metal compound and/or ammonium source in water, and fully mixing;
step two: placing the mixed solution into a hydrothermal reaction kettle, and controlling the reaction temperature to be 120-200 ℃ by using a homogeneous reactor to react for 12-24 hours to obtain a solid product;
step three: and (3) washing the solid product with deionized water for a plurality of times, and drying to obtain the deep blue nano tungsten bronze.
The molecular formula of the tungsten bronze nano material is M x WO 3 Wherein 0 is<x<1, M is alkali cesium (Cs) + ) And/or rubidium (Rb) + ) Or ammonium ion (NH) 4 + )。
The tungstate is sodium tungstate and/or potassium tungstate.
In the above method, tartaric acid or tartrate is used as a reducing agent, and may be one or more of tartaric acid, potassium tartrate, sodium tartrate and sodium potassium tartrate.
The alkali metal compound is preferably one or more of cesium chloride, cesium carbonate, cesium hydroxide, rubidium chloride, rubidium carbonate and rubidium hydroxide; the ammonium source is preferably ammonium chloride, ammonium carbonate, or the like.
In step one, it is preferable that each substance is dissolved in water for an interval of 5 to 10 minutes.
In the mixed solution obtained in the first step, the concentration of tungstate is 0.1-1.0 mol/L; the total concentration of tartaric acid and/or tartrate as the reducing agent is 0.2-2.0 mol/L; the concentration of the alkali metal compound and/or the ammonium source is 0.033 to 0.33mol/L.
Further, the molar ratio of the reducing agent to the tungstate in the reaction is 1:1-10:1; the molar ratio of the alkali metal compound and/or the ammonium source to the tungstate is 0.1-1.0.
In the third step, the product can be dried by adopting an oven at 60 ℃ after being cleaned.
The method of the invention can achieve the following beneficial effects:
the method is simple to operate, and the reaction temperature is low (120-200 ℃), so that energy conservation and emission reduction are facilitated;
the reaction system adopted by the invention is water phase, the reactants are all solid, and the method is low in price, environment-friendly and easy for industrial scale-up and large-scale production;
the tungsten source adopted by the invention is tungstate, so that the corrosiveness of tungsten chloride adopted in the prior art is overcome, and tungstate ions in the tungstate are favorable for reaction;
the tartaric acid or tartrate is used as the reducing agent, the reducibility of the alcoholic hydroxyl in the tartaric acid or tartrate is fully utilized, and the tartaric acid or tartrate is a solid non-dangerous chemical, so that the tartaric acid or tartrate is more friendly compared with the traditional reducing agents such as oleylamine, oleic acid and the like, and is beneficial to safety management;
the nano-size of cesium tungsten bronze, rubidium tungsten bronze and ammonium tungsten bronze produced by the invention is about 50-200nm, the crystallinity is good, and the excellent optical characteristics are shown.
Drawings
FIG. 1 is a scanning electron microscope image of cesium tungsten bronze prepared in example 2.
Fig. 2 is an XRD pattern of cesium tungsten bronze prepared in example 2.
FIG. 3 is an extinction coefficient plot at different wavebands for cesium tungsten bronze prepared in example 2.
Fig. 4 is an XRD pattern of ammonium tungsten bronze prepared in example 4.
FIG. 5 is an extinction coefficient plot at different wavebands for the ammonium tungsten bronze prepared in example 4.
Detailed Description
Example 1:
step one: adding 2g of sodium tungstate dihydrate into 30mL of deionized water, and stirring and dissolving for 5min; then adding potassium tartrate (according to the amount of 0.6mol/L after the potassium tartrate is dissolved), and stirring and dissolving for 5min; then adding cesium carbonate (according to the amount of 0.1mol/L after dissolving cesium carbonate), stirring and dissolving, and standing for 10min;
step two: placing the mixed solution into a 50mL polytetrafluoroethylene lining, placing the mixed solution into a hydrothermal reaction kettle, controlling the reaction temperature to 140 ℃ by using a homogeneous reactor, setting the rotating speed to 10r/min, and reacting for 15h to obtain a solid product;
step three: and (3) cleaning the reaction solid with deionized water for three times, and drying the reaction solid in an oven at 60 ℃ for 6 hours to obtain the nano cesium tungsten bronze.
Example 2:
step one: 1g of potassium tungstate dihydrate is added into 30mL of deionized water, and stirred and dissolved for 5min; then adding tartaric acid and potassium tartrate (the molar ratio of tartaric acid to potassium tartrate=1:1, and the amount of each of the tartaric acid and the potassium tartrate is 0.4mol/L after dissolution), and stirring and dissolving for 5 minutes; then adding cesium hydroxide (according to the amount of 0.033mol/L dissolved cesium hydroxide), stirring, dissolving and standing for 10min;
step two: placing the mixed solution into a 50mL polytetrafluoroethylene lining, placing the mixed solution into a hydrothermal reaction kettle, controlling the reaction temperature to be 150 ℃ by using a homogeneous reactor, setting the rotating speed to be 10r/min, and reacting for 20h to obtain a solid product;
step three: and (3) cleaning the reaction solid with deionized water for three times, and drying the reaction solid in an oven at 60 ℃ for 6 hours to obtain the nano cesium tungsten bronze.
The scanning electron microscope image of the cesium tungsten bronze particles obtained in the example is shown in figure 1, the length of the cesium tungsten bronze nano particles is 50-150nm, the thickness of the cesium tungsten bronze nano particles is 20-40nm, and the particles are uniform.
The XRD pattern of cesium tungsten bronze obtained in this example is shown in FIG. 2, and the diffraction peaks and Cs thereof 0.32 WO 3 The diffraction peaks of the standard cards of PDF #83-1334 completely correspond to each other, the diffraction peaks also belong to hexagonal crystal phases, and the crystallinity is good in the peak-to-peak view of XRD.
The extinction coefficient of cesium tungsten bronze obtained by the example is measured by grinding and tabletting cesium tungsten bronze particles and KBr, and the extinction coefficient is calculated by measurement, and the trough appears at the wavelength of 400-1000nm, namely the optical absorption effect in the visible region is poor; peaks appear at 1150-3000nm wavelength, and the area has a mass extinction coefficient exceeding 0.8m 2 The absorption of the component/g, that is to say the near infrared and mid infrared regions, is very strong, wherein the mass extinction coefficient can reach 1.14m at 1800nm 2 And/g. As the wavelength continues to increase, the mass extinction coefficient gradually decreases. The series of optical properties can enable the coating to be applied to heat-insulating coatings with good light transmittance.
Example 3:
step one: adding 1g of sodium tungstate dihydrate and 1g of potassium tungstate dihydrate into 25mL of deionized water, and stirring and dissolving for 5min; then adding tartaric acid (the amount of each 0.5mol/L after dissolution), stirring and dissolving for 5min; then adding ammonium chloride (according to the amount of 0.1mol/L after the ammonium chloride is dissolved), stirring, dissolving and standing for 10min;
step two: placing the mixed solution into a 50mL polytetrafluoroethylene lining, placing the mixed solution into a hydrothermal reaction kettle, controlling the reaction temperature to 160 ℃ by using a homogeneous reactor, setting the rotating speed to 10r/min, and reacting for 24 hours to obtain a solid product;
step three: and (3) cleaning the reaction solid for three times by adopting deionized water, and drying the reaction solid for 6 hours at the temperature of 60 ℃ by adopting an oven to obtain the nano ammonium tungsten bronze.
Example 4:
step one: adding 1g of sodium tungstate dihydrate and 1g of potassium tungstate dihydrate into 25mL of deionized water, and stirring and dissolving for 5min; then adding tartaric acid (the amount of each 0.5mol/L after dissolution), stirring and dissolving for 5min; then adding ammonium chloride (according to the amount of 0.1mol/L after the ammonium chloride is dissolved), stirring, dissolving and standing for 10min;
step two: placing the mixed solution into a 50mL polytetrafluoroethylene lining, placing the mixed solution into a hydrothermal reaction kettle, controlling the reaction temperature to 160 ℃ by using a homogeneous reactor, setting the rotating speed to 10r/min, and reacting for 24 hours to obtain a solid product;
step three: and (3) cleaning the reaction solid for three times by adopting deionized water, and drying the reaction solid for 6 hours at the temperature of 60 ℃ by adopting an oven to obtain the nano ammonium tungsten bronze.
The XRD pattern of the ammonium tungsten bronze obtained in this example is shown in FIG. 4, and the diffraction peaks and (NH) 4 ) 0.33 WO 3 The diffraction peaks of the standard cards of PDF #42-0452 completely correspond to each other, and also belong to hexagonal crystal phases, and the crystallinity is good in the peak and the peak of XRD.
The extinction coefficient of the ammonium tungsten bronze obtained in the example is measured by grinding and tabletting ammonium tungsten bronze particles and KBr, and the extinction coefficient is calculated by measurement, wherein the extinction coefficient is higher than that of cesium tungsten bronze in the same wave band at the position of 400-930nm when the trough appears at the wavelength of 400-1000nm, namely the optical absorption effect in the visible region is poor. The wave peak appears at 1150-3000nm, that is, near infrared and middle infrared part regions have strong absorption effect, the extinction coefficient of the wave band is lower than that of cesium tungsten bronze with the same wave band, wherein at 1880nm, the mass extinction coefficient can reach 0.88m 2 And/g. As the wavelength continues to increase, the mass extinction coefficient gradually decreases.
Claims (4)
1. A method of preparing a tungsten bronze nanomaterial comprising the steps of:
1) Adding 1g of potassium tungstate dihydrate into 30mL of deionized water, and stirring for dissolution; then adding tartaric acid and potassium tartrate according to the molar ratio of potassium tartrate=1:1, and stirring and dissolving the tartaric acid and the potassium tartrate in the concentration of 0.4mol/L respectively after dissolution;
adding cesium hydroxide according to the amount of 0.033mol/L after dissolving cesium hydroxide, stirring for dissolving, and fully mixing;
2) Placing the mixed solution obtained in the step 1) into a hydrothermal reaction kettle, and controlling the reaction temperature to be 150 ℃ by using a homogeneous reactor to react for 12-24 hours to obtain a solid product;
3) And cleaning the solid product with deionized water for multiple times, and drying to obtain the tungsten bronze nano material.
2. The method of claim 1, wherein the tungsten bronze nanomaterial has a molecular formula of M x WO 3 Wherein 0 is<x<1, M represents alkali cesium.
3. The method of claim 1, wherein each of the substances of step 1) is dissolved in water for an interval of 5 to 10 minutes.
4. The method of claim 1, wherein the drying is performed in step 3) using an oven at 60 ℃.
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