CN114014364A - 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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- CN114014364A CN114014364A CN202111572797.9A CN202111572797A CN114014364A CN 114014364 A CN114014364 A CN 114014364A CN 202111572797 A CN202111572797 A CN 202111572797A CN 114014364 A CN114014364 A CN 114014364A
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- tungsten bronze
- tungstate
- tartrate
- ammonium
- alkali metal
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- 229910000906 Bronze Inorganic materials 0.000 title claims abstract description 44
- 239000010974 bronze Substances 0.000 title claims abstract description 44
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 32
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 24
- 239000010937 tungsten Substances 0.000 title claims abstract description 24
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 12
- 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 30
- 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 19
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 19
- 239000011975 tartaric acid Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 12
- 229940095064 tartrate Drugs 0.000 claims abstract description 11
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 9
- 239000012265 solid product Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- -1 ammonium ions Chemical class 0.000 claims description 9
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 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 7
- 239000001472 potassium tartrate Substances 0.000 claims description 7
- 229940111695 potassium tartrate Drugs 0.000 claims description 7
- 235000011005 potassium tartrates Nutrition 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 claims description 4
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 4
- 229910016327 MxWO3 Inorganic materials 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 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
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 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 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims description 2
- 229940102127 rubidium chloride Drugs 0.000 claims description 2
- 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 claims description 2
- 239000001433 sodium tartrate Substances 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000001476 sodium potassium tartrate Substances 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 6
- 230000003321 amplification Effects 0.000 abstract description 3
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- OHUPZDRTZNMIJI-UHFFFAOYSA-N [Cs].[W] Chemical compound [Cs].[W] OHUPZDRTZNMIJI-UHFFFAOYSA-N 0.000 description 13
- 230000008033 biological extinction Effects 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- ZGRBQKWGELDHSV-UHFFFAOYSA-N N.[W+4] Chemical compound N.[W+4] ZGRBQKWGELDHSV-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 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
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 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
- LIHHHYMOABTJCZ-UHFFFAOYSA-N [Rb].[W] Chemical compound [Rb].[W] LIHHHYMOABTJCZ-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 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
- 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
- 238000004321 preservation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012074 organic phase 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
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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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
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- 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
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- 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
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- 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
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- 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)
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- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic 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 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, tungstate, tartaric acid and/or tartrate, alkali metal compound and/or ammonium source are sequentially dissolved in water, the mixture is fully mixed and then placed in a hydrothermal reaction kettle, a homogeneous reactor is used for controlling the reaction temperature to be 120 ℃ and 200 ℃, the reaction lasts for 12-24h, and the obtained solid product is cleaned and dried to prepare the tungsten bronze nano material. The method has the advantages that the used raw materials are low in price and environment-friendly, industrial amplification and large-scale production are facilitated, the size of the produced tungsten bronze nano material is about 50-200nm, the crystallinity is good, and the tungsten bronze nano material shows excellent 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 a tungsten bronze nano material by using environment-friendly and cheap tartaric acid (salt) as a reducing agent in a low-temperature water phase.
Background
The tungsten bronze material is a non-stoichiometric compound with a molecular formula of MxWO3(0<x<1) M is an alkaline earth metal, alkali metal, rare earth metal, ammonium ion or the like, and it is essential that the above ion is intercalated into WO3A solid solution formed by crystal lattice, wherein the valence of tungsten is +5 and + 6. The tungsten bronze is widely applied to photo-thermal treatment, infrared shielding and heat preservation coatings due to good mechanical, optical and thermal properties, and is also used as a catalyst due to chemical inertness.
The preparation method of tungsten bronze mainly comprises a chemical vapor transport 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-: 1. the process needs to be carried out at high or ultra-high temperature; 2. the reaction adopts an organic phase or introduces oleylamine and oleic acid, so that the environment is easily polluted, the product belongs to flammable and explosive dangerous goods, and great trouble is brought to chemical production; 3. the tungsten source selected in the process is WCl which is expensive and corrosive6Or WCl4(ii) a 4. The crystallinity is not good (low temperature molten salt synthesis).
Disclosure of Invention
Aiming at the problems existing at present, the invention aims to provide a water phase synthesis method of a tungsten bronze nano material, which uses low-cost and environment-friendly raw materials to synthesize the nano-scale tungsten bronze material in a low-temperature water phase so as to realize the amplification production and safety management of tungsten bronze.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing tungsten bronze nanometer material comprises the following steps:
the method comprises the following steps: sequentially dissolving tungstate, tartaric acid and/or tartrate, and alkali metal compound and/or ammonium source in water, and fully mixing;
step two: placing the mixed solution in a hydrothermal reaction kettle, using a homogeneous reactor, controlling the reaction temperature to be 120-200 ℃, and reacting for 12-24h to obtain a solid product;
step three: and washing the solid product with deionized water for multiple times, and drying to obtain the dark blue nano tungsten bronze.
The molecular formula of the tungsten bronze nano material is MxWO3Wherein 0 is<x<1, M is alkali metal 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 reducing agent, and specifically, one or more of tartaric acid, potassium tartrate, sodium tartrate and potassium sodium tartrate can be used.
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 the first step, preferably, the time interval between dissolving each substance in water is 5-10 min.
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 used as a 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 0.33 mol/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 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 meanwhile, the reaction temperature is low (120-200 ℃), so that the method is beneficial to energy conservation and emission reduction;
the reaction system adopted by the invention is a water phase, and reactants are all solid, and meanwhile, the price is low, the environment is friendly, and the industrial amplification and large-scale production are easy;
the tungsten source adopted by the method is tungstate, so that the corrosivity of tungsten chloride adopted in the prior art is overcome, and meanwhile, tungstate ions in the tungstate are beneficial to reaction;
the tartaric acid or tartrate adopted by the method is a reducing agent, the reducibility of alcoholic hydroxyl in the tartaric acid or tartrate is fully utilized, and the tartaric acid or tartrate is a solid non-dangerous chemical, is more friendly than traditional reducing agents such as oleylamine and oleic acid, and is beneficial to safety management;
the nano-size of the cesium tungsten bronze, the rubidium tungsten bronze and the ammonium tungsten bronze produced by the method is about 50-200nm, the crystallinity is good, and the optical characteristics are better.
Drawings
Fig. 1 is a scanning electron micrograph of cesium tungsten bronze prepared in example 2.
Figure 2 is an XRD pattern of cesium tungsten bronze prepared in example 2.
FIG. 3 is a spectrum of extinction coefficients at different wavelength bands for cesium tungsten bronze prepared in example 2.
FIG. 4 is an XRD pattern of ammonium tungsten bronze prepared according to example 4.
FIG. 5 is a graph of extinction coefficients at different wavelength bands for the ammonium tungsten bronze prepared in example 4.
Detailed Description
Example 1:
the method comprises the following steps: adding 2g of sodium tungstate dihydrate into 30mL of deionized water, and stirring and dissolving for 5 min; then adding potassium tartrate (according to the amount of 0.6mol/L after the potassium tartrate is dissolved), stirring and dissolving for 5 min; adding cesium carbonate (according to the amount of 0.1mol/L after the cesium carbonate is dissolved), stirring, dissolving and standing for 10 min;
step two: placing the mixed solution into a 50mL polytetrafluoroethylene lining, placing the mixed solution into a hydrothermal reaction kettle, using a homogeneous reactor, controlling the reaction temperature to be 140 ℃, setting the rotating speed to be 10r/min, and reacting for 15 hours to obtain a solid product;
step three: and (3) washing the reaction solid with deionized water for three times, and drying in an oven at 60 ℃ for 6h to obtain the nano cesium tungsten bronze.
Example 2:
the method comprises the following steps: adding 1g of potassium tungstate dihydrate into 30mL of deionized water, and stirring and dissolving for 5 min; then adding tartaric acid and potassium tartrate (the molar ratio of the tartaric acid to the potassium tartrate is 1:1, and the amount of the dissolved tartaric acid and the potassium tartrate is 0.4mol/L respectively), and stirring for dissolving for 5 min; then adding rubidium hydroxide (according to the amount of 0.033mol/L after the rubidium hydroxide is dissolved), stirring, dissolving and standing for 10 min;
step two: placing the mixed solution into a 50mL polytetrafluoroethylene lining, placing the mixed solution into a hydrothermal reaction kettle, using a homogeneous reactor, controlling the reaction temperature to be 150 ℃, setting the rotating speed to be 10r/min, and reacting for 20 hours to obtain a solid product;
step three: and (3) washing the reaction solid with deionized water for three times, and drying in an oven at 60 ℃ for 6h to obtain the nano rubidium tungsten bronze.
The scanning electron microscope image of the cesium tungsten bronze particles obtained in the example is shown in fig. 1, the length of the cesium tungsten bronze particles is 50-150nm, the thickness of the cesium tungsten bronze 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 thereof0.32WO3The standard card diffraction peaks of PDF #83-1334 completely correspond to each other and belong to the hexagonal crystal phase, and the peak type and the peak value of XRD show that the crystallinity is better.
The extinction coefficient of the cesium tungsten bronze obtained in the example is measured by grinding and tabletting cesium tungsten bronze particles and KBr, measuring and calculating the extinction coefficient, and generating a wave trough at the wavelength of 400-1000nm, namely the optical absorption effect of a visible region is poor; a peak appears at a wavelength of 1150-3000nm, and the mass extinction coefficient of the region exceeds 0.8m2A strong absorption in the near-infrared and mid-infrared range, wherein the mass extinction coefficient is up to 1.14m at 1800nm2(ii) in terms of/g. As the wavelength continues to increase, the quality extinction coefficient gradually decreases. The series of optical properties can be applied to the heat preservation coating with good light transmission.
Example 3:
the method comprises the following steps: adding 1g of sodium tungstate dihydrate and 1g of potassium tungstate dihydrate into 25mL of deionized water, and stirring and dissolving for 5 min; then adding tartaric acid (the amount of dissolved tartaric acid is 0.5mol/L respectively), stirring and dissolving for 5 min; then adding ammonium chloride (according to the amount of 0.1mol/L after the ammonium chloride is dissolved), stirring, dissolving and standing for 10 min;
step two: placing the mixed solution into a 50mL polytetrafluoroethylene lining, placing the mixed solution into a hydrothermal reaction kettle, using a homogeneous reactor, controlling the reaction temperature to be 160 ℃, setting the rotating speed to be 10r/min, and reacting for 24 hours to obtain a solid product;
step three: and (3) washing the reaction solid with deionized water for three times, and drying in an oven at 60 ℃ for 6h to obtain the nano ammonium tungsten bronze.
Example 4:
the method comprises the following steps: adding 1g of sodium tungstate dihydrate and 1g of potassium tungstate dihydrate into 25mL of deionized water, and stirring and dissolving for 5 min; then adding tartaric acid (the amount of dissolved tartaric acid is 0.5mol/L respectively), stirring and dissolving for 5 min; then adding ammonium chloride (according to the amount of 0.1mol/L after the ammonium chloride is dissolved), stirring, dissolving and standing for 10 min;
step two: placing the mixed solution into a 50mL polytetrafluoroethylene lining, placing the mixed solution into a hydrothermal reaction kettle, using a homogeneous reactor, controlling the reaction temperature to be 160 ℃, setting the rotating speed to be 10r/min, and reacting for 24 hours to obtain a solid product;
step three: and (3) washing the reaction solid with deionized water for three times, and drying in an oven at 60 ℃ for 6h 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)0.33WO3The standard card diffraction peaks of PDF #42-0452 completely correspond to each other and belong to the hexagonal crystal phase, and the peak type and the peak value of XRD show that the crystallinity is better.
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 calculating the extinction coefficient, wherein a wave trough appears at the wavelength of 400-class 1000nm, namely the optical absorption effect of a visible region is poor, but the extinction coefficient of the value at the wavelength of 400-class 930nm is higher than that of the cesium tungsten bronze at the same wave band. The peak appears at the wavelength of 1150-type 3000nm, that is, the near-infrared and mid-infrared partial regions have strong absorption effect, the extinction coefficient of the wave band is lower than that of the cesium tungsten bronze in the same wave bandMedium at 1880nm, mass extinction coefficient can reach 0.88m2(ii) in terms of/g. As the wavelength continues to increase, the quality extinction coefficient gradually decreases.
Claims (8)
1. A method for preparing tungsten bronze nanometer material comprises the following steps:
1) sequentially dissolving tungstate, tartaric acid and/or tartrate, and alkali metal compound and/or ammonium source in water, and fully mixing;
2) placing the mixed solution obtained in the step 1) in a hydrothermal reaction kettle, using a homogeneous reactor, controlling the reaction temperature to be 120-200 ℃, and reacting for 12-24 hours to obtain a solid product;
3) and washing 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 formula of MxWO3Wherein 0 is<x<1, M represents alkali metal cesium and/or rubidium or ammonium ions.
3. The method of claim 2, wherein the alkali metal compound in step 1) is selected from one or more of cesium chloride, cesium carbonate, cesium hydroxide, rubidium chloride, rubidium carbonate, and rubidium hydroxide; the ammonium source is selected from ammonium chloride and ammonium carbonate.
4. The method of claim 1, wherein the tungstate in step 1) is sodium tungstate and/or potassium tungstate, and the tartrate is one or more selected from potassium tartrate, sodium tartrate and sodium potassium tartrate.
5. The method of claim 1, wherein the time interval for dissolving each substance in the water in step 1) is 5 to 10 min.
6. The method according to claim 1, wherein the mixed solution obtained in step 1) has a tungstate concentration of 0.1 to 1.0mol/L, a total tartaric acid and/or tartrate concentration of 0.2 to 2.0mol/L, and an alkali metal compound and/or ammonium source concentration of 0.033 to 0.33 mol/L.
7. The method of claim 1, wherein the molar ratio of tartaric acid and/or tartrate to tungstate in step 1) is 1:1 to 10: 1; the molar ratio of the alkali metal compound and/or the ammonium source to the tungstate is 0.1-1.0.
8. The method of claim 1, wherein the drying in step 3) is performed in an oven at 60 ℃.
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