阅读说明：本技术 一种缺氧型氧化钨的制备方法 (Preparation method of oxygen-deficient tungsten oxide ) 是由 汪建新 劳成文 陈太军 王莹莹 徐啟真 魏冉 吴佳杭 翁杰 段可 冯波 于 2019-09-17 设计创作，主要内容包括：本发明公开了一种缺氧型氧化钨的制备方法,包括以下步骤：S1.将钨盐加入到有机溶剂中,配制得到溶液A；S2.向所述溶液A中加入TaCl<Sub>5</Sub>或NbCl<Sub>5</Sub>,并且搅拌均匀得到溶液B；S3.将所述溶液B加入到高压反应釜中,反应后冷却至室温,得到中间物；S4.对所述中间物依次进行离心、洗涤和干燥处理后,即可得到所述缺氧型氧化钨。其中,所述钨盐为WCl<Sub>6</Sub>,所述有机溶剂为乙二醇、二甘醇或三甘醇。本发明采用溶剂热的方法,通过掺杂TaCl<Sub>5</Sub>或NbCl<Sub>5</Sub>的方式,使Ta<Sup>5+</Sup>或Nb<Sup>5+</Sup>进入到氧化钨的晶格中,形成了氧空位,达到了合成高纯度的W<Sub>18</Sub>O<Sub>49</Sub>材料的效果。本发明操作简单,具有合成温度低、反应时间短、能耗低和重复性高等优点。(The invention discloses a preparation method of oxygen-deficient tungsten oxide, which comprises the following steps: s1, adding a tungsten salt into an organic solvent to prepare a solution A; s2, adding TaCl into the solution A 5 Or NbCl 5 and uniformly stirring to obtain a solution B; s3, adding the solution B into a high-pressure reaction kettle, and cooling to room temperature after reaction to obtain an intermediate; and S4, sequentially centrifuging, washing and drying the intermediate to obtain the oxygen-deficient tungsten oxide. Wherein the tungsten salt is WCl 6 The organic solvent is ethylene glycol, diethylene glycol or triethylene glycol. The invention adopts a solvothermal method and adopts TaCl doping 5 Or NbCl 5 A mode of (1) to Ta 5+ or Nb 5+ Enters into the crystal lattice of the tungsten oxide to form oxygen vacancy, thereby achieving the purpose of synthesizing high-purity W 18 O 49 The effect of the material. The invention has simple operation, low synthesis temperature, short reaction time and energy consumptionLow cost and high repeatability.)

1. A preparation method of oxygen-deficient tungsten oxide is characterized by comprising the following steps: the method comprises the following steps:

S1, adding a tungsten salt into an organic solvent to prepare a solution A;

S2, adding TaCl into the solution A₅Or NbCl₅And uniformly stirring to obtain a solution B;

S3, adding the solution B into a high-pressure reaction kettle, and cooling to room temperature after reaction to obtain an intermediate;

And S4, sequentially centrifuging, washing and drying the intermediate to obtain the oxygen-deficient tungsten oxide.

2. The method for preparing oxygen-deficient tungsten oxide according to claim 1, wherein: the oxygen-deficient tungsten oxide is W₁₈O₄₉。

3. The method for preparing oxygen-deficient tungsten oxide according to claim 1, wherein: in S1, the tungsten salt is WCl₆WCl in said solution A₆the concentration of (b) is 0.03-0.05 mol/L.

4. The method for preparing oxygen-deficient tungsten oxide according to claim 3, wherein: the organic solvent is an alcohol solvent.

5. the method for preparing oxygen-deficient tungsten oxide according to claim 4, wherein: the alcohol solvent is ethylene glycol, diethylene glycol or triethylene glycol.

6. The method for producing an oxygen-deficient tungsten oxide according to claim 1 or 5, wherein: when the organic solvent is ethylene glycol or triethylene glycol, the tungsten salt and TaCl₅Or NbCl₅The amount ratio of the substances is 1: 0.1-0.2; when the organic solvent is diethylene glycol, the tungsten salt and TaCl₅Or NbCl₅The amount ratio of the substances (c) is 1:0.

7. The method for preparing oxygen-deficient tungsten oxide according to claim 1The method is characterized in that: s2, adding TaCl into the solution A₅Or NbCl₅And stirring for 4-8 h at the temperature of 45-80 ℃ to obtain a solution B.

8. The method for preparing oxygen-deficient tungsten oxide according to claim 1, wherein: in S3, adding the solution B into a high-pressure reaction kettle, then putting the high-pressure reaction kettle into a homogeneous reaction kettle, reacting at 160-200 ℃ for 16-26 h, and cooling to room temperature to obtain an intermediate; wherein the volume of the solution B is 60-75% of the volume of the high-pressure reaction kettle.

9. The method for preparing oxygen-deficient tungsten oxide according to claim 1, wherein: s4, the drying method is that the intermediate after centrifugation and washing is placed in a vacuum drying box and dried for 8-12 hours at the temperature of 40-60 ℃.

Technical Field

the invention relates to the technical field of nano material preparation, in particular to a preparation method of oxygen-deficient tungsten oxide.

Background

The rapid development of modern industry leads to the increasing exhaustion of energy and serious pollution of the environment, and thus, the protection of the environment and the improvement of energy utilization have been the focus of attention. And a semiconductor oxide such as TiO₂and zinc oxide, tungsten oxide, etc. have attracted attention of researchers as photocatalytic materials in the fields of environmental protection, etc.

Wherein the nano-structured tungsten trioxide (WO)₃) And tungsten sub-oxide (WO)_3-X，X>0) it is widely used in the fields of gas sensors, photocatalysts, electrochromic devices, field emission devices, solar devices, etc. due to its unique physical and chemical properties. Especially monoclinic phase W₁₈O₄₉The material, the most oxygen deficient of the non-stoichiometric materials studied, is the only tungsten oxide known to exist in pure form. W₁₈O₄₉The infrared absorption material has stable property, is easy to prepare and separate, has good infrared absorption performance and photo-induced heating performance, and can absorb infrared light in the whole near-infrared spectrum region.

At present, the method for preparing the nano tungsten oxide mainly comprises the following steps: chemical vapor deposition, sputtering, etc., but these methods have high requirements for conditions, and are difficult and costly to synthesize.

Chinese patent document cn201710313210.x, application date 20170505, patent name: a preparation method of tungsten oxide nanoparticles with ultra-small defects adopts the technical scheme that: dopamine is used as a stabilizer and a reducing agent, tungsten chloride is used as a precursor, and the mixture is uniformly stirred in an organic solution and then subjected to hydrothermal reaction to obtain uniformly distributed tungsten oxide nanoparticles with ultra-small defects; the molar ratio of tungsten chloride to dopamine is 1: 1-8; the organic solvent comprises one or more of triethylene glycol, ethylene glycol and propylene glycol.

The above patent documents utilize dopamine as a stabilizer and a reducing agent, and tungsten chloride as a precursor, and the purpose of preparing tungsten oxide with ultra-small defects is achieved by performing hydrothermal reaction after uniformly stirring in an organic solution. But for one-step synthesis of W of high purity₁₈O₄₉The material and the preparation method with high reaction safety are not proposed yet.

disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a preparation method of oxygen-deficient tungsten oxide, so that high-purity W is synthesized in one step₁₈O₄₉Material and high reaction safety.

the purpose of the invention is realized by the following technical scheme: a preparation method of oxygen-deficient tungsten oxide comprises the following steps:

S1, adding a tungsten salt into an organic solvent to prepare a solution A;

S2, adding TaCl into the solution A₅Or NbCl₅And uniformly stirring to obtain a solution B; by adding TaCl to the solution A₅Or NbCl₅Elements with the atomic radius similar to that of the tungsten element are introduced and enter the crystal lattice of the tungsten oxide to form oxygen vacancies, so that the effect of improving the purity of the product is achieved;

S3, adding the solution B into a high-pressure reaction kettle, and cooling to room temperature after reaction to obtain an intermediate; the high-pressure reaction kettle provides high-temperature and high-pressure conditions for reaction;

And S4, sequentially centrifuging, washing and drying the intermediate to obtain the oxygen-deficient tungsten oxide.

Preferably, the first and second liquid crystal materials are,The oxygen-deficient tungsten oxide is W₁₈O₄₉。

Preferably, in S1, the tungsten salt is WCl₆WCl in said solution A₆The concentration of (b) is 0.03-0.05 mol/L.

Through the technical scheme, WCl is selected₆the tungsten salt can improve the dissolution rate of the tungsten salt in the alcohol solution, and achieves the effect of improving the yield.

Preferably, the organic solvent is an alcohol solvent.

Preferably, the WCl₆、TaCl₅and NbCl₅The purity of (A) should be analytically pure and above.

Preferably, the alcoholic solvent is ethylene glycol, diethylene glycol or triethylene glycol.

According to the technical scheme, ethylene glycol, diethylene glycol or triethylene glycol which are not inflammable and explosive is used as an organic solvent to replace absolute ethyl alcohol with inflammable and explosive properties, so that the effect of improving the reaction safety is achieved; in addition to this, WCl₆、TaCl₅and NbCl₅The solvent has higher solubility, and the reaction effect is ensured.

Preferably, when the organic solvent is ethylene glycol or triethylene glycol, the tungsten salt is reacted with TaCl₅Or NbCl₅The amount ratio of the substances is 1: 0.1-0.2; when the organic solvent is diethylene glycol, the tungsten salt and TaCl₅or NbCl₅The amount ratio of the substances (c) is 1:0.

According to the technical scheme, ethylene glycol, diethylene glycol or triethylene glycol is selected as an organic solvent; wherein the diglycol has the strongest reducibility, and is not doped with TaCl in a reaction system₅Or NbCl₅High purity W can also be obtained₁₈O₄₉(ii) a In the system using ethylene glycol or triethylene glycol as a solvent, the reducibility of the ethylene glycol or triethylene glycol is not strong enough, so that TaCl needs to be doped₅Or NbCl₅To create oxygen vacancies to achieve the synthesis of W of high purity₁₈O₄₉Effect of the Material

Preferably, in S2, TaCl is added to the solution A₅Or NbCl₅Stirring for 4-8 h to obtain a solution B; the stirring is carried out at a temperature of 45-80 deg.C, preferably 60 deg.C.

Through the technical scheme, the stirring temperature is controlled at 60 ℃, and the effect of improving the reaction speed while ensuring the reaction efficiency is achieved.

Preferably, in S3, adding the solution B into a high-pressure reaction kettle, then putting the high-pressure reaction kettle into a homogeneous reaction kettle, reacting at 160-200 ℃ for 16-26 h, and cooling to room temperature to obtain an intermediate; wherein the volume of the solution B is 60-75% of the volume of the high-pressure reaction kettle.

through the technical scheme, a reaction environment is provided for the solvothermal reaction in the invention.

Preferably, in S4, the drying method is to place the intermediate after centrifugation and washing in a vacuum drying oven and dry the intermediate at 40-60 ℃ for 8-12 h.

Through the technical scheme, the intermediate is dried in vacuum, so that oxygen in a drying environment can be avoided, and the purpose of preventing generated W is achieved₁₈O₄₉Is oxidized into WO₃The effect of (1).

The invention has the beneficial effects that:

1. the invention relates to a preparation method of oxygen-deficient tungsten oxide, which adopts a solvothermal method and adopts WCl₆Adding into alcohol solvent, and doping TaCl₅or NbCl₅Thereby making Ta⁵⁺Or Nb⁵⁺Enters into the crystal lattice of the tungsten oxide to cause oxygen vacancy, thereby achieving the synthesis of high-purity W₁₈O₄₉the effect of (1).

2. According to the preparation method of the oxygen-deficient tungsten oxide, the ethylene glycol, the diethylene glycol or the triethylene glycol is used as an organic solvent to replace anhydrous ethanol with flammable and explosive properties, so that the effects of improving the reaction safety and enabling the reaction to be suitable for industrial production are achieved.

3. The preparation method of the oxygen-deficient tungsten oxide is simple, has few raw material components and lower cost, does not need later crystallization treatment, and achieves the effect of improving the reaction efficiency.

4. The invention relates to a preparation method of oxygen-deficient tungsten oxide, and W prepared by the method₁₈O₄₉has good near infrared absorption performance.

drawings

FIG. 1 shows W prepared in example 1 of the present invention₁₈O₄₉An XRD pattern of (a);

FIG. 2 shows W prepared in example 1 of the present invention₁₈O₄₉(ii) solid absorption spectrum of (d);

FIG. 3 is an XRD pattern of the product obtained from the control group in example 1 of the present invention;

FIG. 4 shows W prepared in example 2 of the present invention₁₈O₄₉An XRD pattern of (a);

FIG. 5 shows W prepared in example 2 of the present invention₁₈O₄₉(ii) solid absorption spectrum of (d);

FIG. 6 is an XRD pattern of the product obtained from the control group in example 2 of the present invention;

FIG. 7 shows W prepared in example 3 of the present invention₁₈O₄₉an XRD pattern of (a);

FIG. 8 is W prepared according to example 3 of the present invention₁₈O₄₉(ii) solid absorption spectrum of (d);

Detailed Description

The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the following.