阅读说明：本技术 一种短流程制备W0.4Mo0.6O3的方法及其应用 (Short-process preparation of W0.4Mo0.6O3And applications thereof ) 是由 马立文 刘亚男 刘阳思 席晓丽 聂祚仁 于 2021-10-14 设计创作，主要内容包括：本发明提供一种短流程制备W-(0.4)Mo-(0.6)O-(3)的方法及其应用,所述方法包括：采用树脂吸附溶液中以离子形式存在的钨和钼元素,将吸附后的树脂进行煅烧。本发明通过树脂吸附钨钼的离子,无需对钨钼进行分离,再经过煅烧即可获得钨钼氧化物,具有流程短、简便可行、绿色环保等优点,所得到的钨钼氧化物产物光催化性能好,可广泛应用于污染物染料降解及其他半导体光催化领域,并且此制备过程可以实现资源循环,减小环境的负担,对钨钼废弃物的回收再利用提供了一种新思路。(The invention provides a short-process preparation method of W 0.4 Mo 0.6 O 3 The method of (1) and applications thereof, the method comprising: tungsten and molybdenum elements existing in the form of ions in the resin adsorption solution are adopted, and the resin after adsorption is calcined. The method adsorbs tungsten and molybdenum ions through the resin, does not need to separate tungsten and molybdenum, can obtain tungsten and molybdenum oxide through calcination, has the advantages of short flow, simplicity, convenience, feasibility, environmental friendliness and the like, and the obtained tungsten and molybdenum oxide product has good photocatalytic performance and can be widely applied to the fields of pollutant dye degradation and other semiconductor photocatalysis.)

1. Short-process preparation of W_0.4Mo_0.6O₃The method of (2), comprising: tungsten and molybdenum elements existing in the form of ions in the resin adsorption solution are adopted, and the resin after adsorption is calcined.

2. The short run preparation of W of claim 1_0.4Mo_0.6O₃The method of (1), wherein tungsten is present as tungstate ions and molybdenum is present as molybdate ions.

3. The short run preparation of W according to claim 1 or 2_0.4Mo_0.6O₃The method is characterized in that the molar concentration ratio of the tungsten element to the molybdenum element in the solution is (0.5-1.75): 1.

4. The short run preparation of W of claim 3_0.4Mo_0.6O₃The method of (A), characterized in thatThe resin is D201 resin, and the dosage of the D201 resin is 6-9g of the resin added in every 50mL of the solution.

5. The short run preparation of W of claim 4_0.4Mo_0.6O₃Characterized in that the resin is pretreated by alkali washing and acid washing.

6. The short run preparation of W according to any one of claims 1 to 5_0.4Mo_0.6O₃The method is characterized in that the calcination is two-stage calcination, the temperature of the primary calcination is 0-10 ℃ higher than the decomposition temperature of the functional group of the resin, and the temperature of the secondary calcination is 50-300 ℃ higher than the temperature of the primary calcination.

7. The short run preparation of W of claim 6_0.4Mo_0.6O₃The method is characterized in that in the primary calcining process, a container for containing the resin also contains water, and after the primary calcining, the obtained material is dried and then is subjected to secondary calcining.

8. The short run preparation of W according to any one of claims 1 to 7_0.4Mo_0.6O₃The method is characterized by comprising the following steps:

s1, preprocessing the resin;

s2, mixing the pretreated resin with a solution containing tungsten and molybdenum elements existing in an ion form, and adjusting the pH value to promote adsorption;

s3, carrying out primary calcination on the resin after adsorption;

and S4, drying the primary calcined product, and then carrying out secondary calcination.

9. Mesoporous oxide W_0.4Mo_0.6O₃The compound is characterized by being prepared by the method of any one of claims 1 to 8.

10. The mesoporous oxide W according to claim 9_0.4Mo_0.6O₃The application in the field of dye pollutant degradation or other semiconductor photocatalysts.

Technical Field

The invention relates to the technical field of micro-nano materials, in particular to a short-process W preparation method_0.4Mo_0.6O₃And applications thereof.

Background

Tungsten and molybdenum are two high-temperature-resistant metals, have the characteristics of good heat conduction, electric conduction, low thermal expansion coefficient, high-temperature strength, low vapor pressure, wear resistance and the like, and are important materials for the application in the electronic and electric equipment manufacturing industry, the metal material processing industry, the glass manufacturing industry, the high-temperature furnace part structure component manufacturing industry, aerospace and national defense industry. However, with the development of industry, tungsten and molybdenum wastes are more and more, and if the tungsten and molybdenum wastes cannot be fully recycled, great resource waste can be caused.

Molybdenum tungsten oxide W_xMo_1-xO₃The (0 < x < 1) system exhibits "displacive" and "reconstructive" phase transitions due to hydrogen intercalation and high temperatures, leading to rearrangement of the electronic and atomic structures. Conventional methods for synthesizing molybdenum tungsten oxide include high temperature synthesis, wet impregnation, sputter deposition, and electrodeposition, but all suffer from certain drawbacks. For example, direct reaction between molybdenum oxide and tungsten oxide requires a long time (5 days) for sintering, and wet impregnation, electrodeposition and sputter deposition methods cannot control the physicochemical characteristics of the mixed oxide, such as pore size and surface area.

Therefore, the invention aims to develop a method for preparing molybdenum-tungsten oxide in a short process, and the method can be used for recovering tungsten-molybdenum waste materials and reducing the environmental burden.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a short-process preparation method of W_0.4Mo_0.6O₃And applications thereof.

The invention provides a short-process preparation method of W_0.4Mo_0.6O₃The method of (1), comprising: tungsten and molybdenum elements existing in the form of ions in the resin adsorption solution are adopted, and the resin after adsorption is calcined.

The traditional preparation method generally prepares the tungsten-molybdenum bimetallic oxide W by taking molybdenum oxide and tungsten oxide as raw materials_0.4Mo_0.6O₃This process is both time and energy consuming. The research of the invention finds that tungsten and molybdenum oxide can be directly prepared by reacting tungsten and molybdenum together in an ionic form without extracting and separating tungsten and molybdenum simple substances or tungsten oxide and molybdenum oxide respectively, thereby greatly shortening the timeThe preparation process is convenient and quick, and can also be used for recovering tungsten-molybdenum-containing waste liquid. The resin is used as an adsorption carrier, can adsorb tungsten and molybdenum, and is easy to remove in the subsequent treatment process.

Further, tungsten is present in the form of tungstate ions and molybdenum is present in the form of molybdate ions.

The research of the invention finds that tungstate ions and molybdate ions are more easily absorbed by resin.

Furthermore, the molar concentration ratio of the tungsten element to the molybdenum element in the solution is (0.5-1.75): 1.

In one embodiment of the invention, the concentration of tungstate ions in the solution is 0.3mol/L, and the concentration of molybdate ions in the solution is 0.3 mol/L.

The concentration of tungstate ions and molybdate ions is controlled within the range, so that the finally obtained tungsten-molybdenum oxide is ensured to be W_0.4Mo_0.6O₃And the adsorption rate and the adsorption quantity of the resin can be matched.

Further, the resin is a D201 resin, which is added in an amount of 6 to 9g per 50mL of the solution.

When the resin with the dosage ratio is selected, the adsorption effect is excellent, the economic benefit is considered, the resin cannot be wasted, and excessive tungsten and molybdenum elements cannot be remained in the solution.

Further, the resin was pretreated with alkali washing and acid washing. The resin is pretreated, so that the situation that substances such as excessive raw materials and new impurities contained in the new resin, incomplete reaction products and the like enter the solution to pollute the test solution can be prevented; and is also beneficial to prolonging the service life of the resin.

Further, the calcination is two-stage calcination, the temperature of the primary calcination is 0-10 ℃ higher than the decomposition temperature of the functional group of the resin, and the temperature of the secondary calcination is 50-300 ℃ higher than the temperature of the primary calcination.

Further, in the primary calcining process, a container for containing the resin also contains water, and after the primary calcining, the obtained material is dried and then is subjected to the secondary calcining.

In order to avoid the release of harmful substances in the resin calcination process, the safety is improved by adopting two-stage calcination, so that the harmful substances after the resin calcination are dissolved in water in a container (generally a reaction kettle), and the materials are taken out after primary calcination and then washed for secondary calcination, thereby ensuring that the final product only contains a small amount of carbon.

In a preferred embodiment of the invention, the resin is D201 resin, and preferably, the primary calcination temperature is 232 +/-2 ℃, and the secondary calcination temperature is 300-400 ℃.

In a preferred embodiment of the invention, the short run produces W_0.4Mo_0.6O₃The method specifically comprises the following steps:

s1, preprocessing the resin;

s2, mixing the pretreated resin with a solution containing tungsten and molybdenum elements existing in an ion form, and adjusting the pH value to promote adsorption;

s3, carrying out primary calcination on the resin after adsorption;

and S4, drying the primary calcined product, and then carrying out secondary calcination.

Further, the secondary calcination can be followed by carbon removal treatment, so that a small amount of carbon contained in the product is removed, the product purity is improved, and the application effect is improved.

The invention also provides a mesoporous oxide W prepared by any one of the methods_0.4Mo_0.6O₃。

The present invention also provides the mesoporous oxide W_0.4Mo_0.6O₃The application in the field of dye pollutant degradation or other semiconductor photocatalysts.

W obtained by the invention_0.4Mo_0.6O₃Has good effect on the degradation of dye pollutants and can be used as a semiconductor photocatalyst.

The invention provides a short-process preparation method of W_0.4Mo_0.6O₃The method and the application thereof can adsorb tungsten and molybdenum ions through the resin, do not need to separate the tungsten and the molybdenum, and can obtain tungsten and molybdenum oxides through calcination, and have the advantages of short flow and simplicityThe method has the advantages of feasibility, environmental protection and the like, the obtained tungsten-molybdenum oxide product has good photocatalytic performance, can be widely applied to the fields of pollutant dye degradation and other semiconductor photocatalysis, can realize resource circulation in the preparation process, reduces the burden of the environment, and provides a new idea for recycling tungsten-molybdenum wastes.

Drawings

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

FIG. 2 is an SEM photograph of the product obtained in example 1 of the present invention;

FIG. 3 is an SEM photograph of the product obtained in example 2 of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Unless otherwise specified, the test reagents and materials used in the examples of the present invention are commercially available.

Unless otherwise specified, the technical means used in the examples of the present invention are conventional means well known to those skilled in the art.

Example 1

This example provides a short run preparation of W_0.4Mo_0.6O₃The method comprises the following specific steps:

weighing 8g of D201 resin (D201 macroporous strongly basic styrene anion exchange resin, brand: Meclin), and performing alkali washing and acid washing to complete pretreatment;

preparing a mixed solution of sodium tungstate and sodium molybdate, wherein the concentrations of the sodium tungstate and the sodium molybdate are both 0.30 mol/L; adjusting the pH value to 3.5 by using hydrochloric acid, standing for 2 hours to ensure that the substance to be adsorbed exists in a specific form and stably exists so as to improve the adsorption efficiency;

adding the pretreated resin into 50ml of the mixed solution, adding magnetons, and magnetically stirring for 4 hours;

transferring the resin after adsorption to a reaction kettle, adding deionized water, and calcining for 1 hour at 232 ℃;

washing the resin after the primary calcination with deionized water for several times, and drying in a drying oven;

taking 0.5g of dried resin, placing the resin in a crucible, and placing the crucible in a muffle furnace for secondary calcination at the calcination temperature of 400 ℃ for 1 hour to obtain W containing a small amount of carbon_0.4Mo_0.6O₃。

FIG. 1 is an XRD pattern of the tungsten molybdenum oxide product obtained in example 1, with its peak value and orthorhombic phase W_0.4Mo_0.6O₃Correspondingly, the obtained product is single in crystal phase and free of other impurities.

FIG. 2 is an SEM image of the tungsten-molybdenum oxide product obtained in example 1, and it is clear that the prepared product has a relatively uniform size distribution and is a micro-nano granular structure.

Weighing 0.01g of the tungsten-molybdenum oxide product, dissolving the tungsten-molybdenum oxide product in 100ml of methylene blue solution with the concentration of 50mg/L, uniformly stirring for 30min under the condition of keeping out of the sun to achieve adsorption balance, placing the mixed solution under a xenon lamp light source with a filter (lambda is greater than 420nm), simulating the process of photocatalytic degradation of the methylene blue by the semiconductor oxide under visible light, ensuring continuous magnetic stirring and light source irradiation in the reaction process, and taking supernatant for detection at a certain time. The result shows that the obtained product has better photocatalytic degradation effect, and the degradation efficiency can reach 92% in 180 min.

Example 2

This example provides a short run preparation of W_0.4Mo_0.6O₃The method comprises the following specific steps:

weighing 8g of D201 resin, and completing pretreatment through alkali washing and acid washing;

preparing a mixed solution of sodium tungstate and sodium molybdate, wherein the concentrations of the sodium tungstate and the sodium molybdate are both 0.30 mol/L; adjusting the pH value to 3.5 by using hydrochloric acid, standing for 2 hours to ensure that the substance to be adsorbed exists in a specific form and stably exists so as to improve the adsorption efficiency;

adding the pretreated resin into 50ml of the mixed solution, adding magnetons, and magnetically stirring for 4 hours;

transferring the resin after adsorption to a reaction kettle, adding deionized water, and calcining for 1 hour at 232 ℃;

washing the resin subjected to primary calcination with deionized water, and drying in a drying oven;

taking 0.5g of dried resin, placing the dried resin in a crucible, placing the crucible in a muffle furnace for secondary calcination at the calcination temperature of 300 ℃ for 1 hour, then standing for decarbonization, and drying the resin after decarbonization to obtain W_0.4Mo_0.6O₃。

FIG. 3 is an SEM photograph of the tungsten molybdenum oxide product obtained in example 2.

Weighing 0.01g of the tungsten-molybdenum oxide product, dissolving the tungsten-molybdenum oxide product in 100ml of methylene blue solution with the concentration of 50mg/L, uniformly stirring for 30min under the condition of keeping out of the sun to achieve adsorption balance, placing the mixed solution under a xenon lamp light source with a filter (lambda is greater than 420nm), simulating the process of photocatalytic degradation of the methylene blue by the semiconductor oxide under visible light, ensuring continuous magnetic stirring and light source irradiation in the reaction process, and taking supernatant for detection at a certain time. The result shows that the prepared product has better photocatalytic degradation effect, and the degradation efficiency can reach 98% in 180 min.

Example 3

This example provides a short run preparation of W_0.4Mo_0.6O₃The method comprises the following specific steps:

weighing 8g of D201 resin, and completing pretreatment through alkali washing and acid washing;

preparing a mixed solution of sodium tungstate and sodium molybdate, wherein the concentrations of the sodium tungstate and the sodium molybdate are both 0.30 mol/L; adjusting the pH value to 3.5 by using hydrochloric acid, standing for 2 hours to ensure that the substance to be adsorbed exists in a specific form and stably exists so as to improve the adsorption efficiency;

adding the pretreated resin into 50ml of the mixed solution, adding magnetons, and magnetically stirring for 4 hours;

transferring the resin after adsorption to a reaction kettle, adding deionized water, and calcining for 1 hour at 232 ℃;

washing the resin subjected to primary calcination with deionized water, and drying in a drying oven;

taking 0.5g of dried resin, placing the resin in a crucible, and placing the crucible in a muffle furnace for secondary calcination at the calcination temperature of 300 ℃ for 1 hour to obtain W containing a small amount of carbon_0.4Mo_0.6O₃。

Weighing 0.01g of the tungsten-molybdenum oxide product, dissolving the tungsten-molybdenum oxide product in 100ml of methylene blue solution with the concentration of 50mg/L, uniformly stirring for 30min under the condition of keeping out of the sun to achieve adsorption balance, placing the mixed solution under a xenon lamp light source with a filter (lambda is greater than 420nm), simulating the process of photocatalytic degradation of the methylene blue by the semiconductor oxide under visible light, ensuring continuous magnetic stirring and light source irradiation in the reaction process, and taking supernatant for detection at a certain time. The prepared product has better photocatalytic degradation effect, and the degradation efficiency can reach 96% in 180 min.

Example 4

This example provides a short run preparation of W_0.4Mo_0.6O₃The method comprises the following specific steps:

weighing 8g of D201 resin, and completing pretreatment through alkali washing and acid washing;

preparing a mixed solution of sodium tungstate and sodium molybdate, wherein the concentrations of the sodium tungstate and the sodium molybdate are both 0.30 mol/L; adjusting the pH value to 3.5 by using hydrochloric acid, standing for 2 hours to ensure that the substance to be adsorbed exists in a specific form and stably exists so as to improve the adsorption efficiency;

adding the pretreated resin into 50ml of the mixed solution, adding magnetons, and magnetically stirring for 4 hours;

transferring the resin after adsorption to a reaction kettle, adding deionized water, and calcining for 1 hour at 232 ℃;

washing the resin subjected to primary calcination with deionized water, and drying in a drying oven;

taking 0.5g of dried resin, placing the resin in a crucible, and placing the crucible in a muffle furnace for secondary calcination at the calcination temperature of 350 ℃ for 1 hour to obtain the resinW containing a small amount of carbon_0.4Mo_0.6O₃。

Weighing 0.01g of the tungsten-molybdenum oxide product, dissolving the tungsten-molybdenum oxide product in 100ml of methylene blue solution with the concentration of 50mg/L, uniformly stirring for 30min under the condition of keeping out of the sun to achieve adsorption balance, placing the mixed solution under a xenon lamp light source with a filter (lambda is greater than 420nm), simulating the process of photocatalytic degradation of the methylene blue by the semiconductor oxide under visible light, ensuring continuous magnetic stirring and light source irradiation in the reaction process, and taking supernatant for detection at a certain time. The prepared product has better photocatalytic degradation effect, and the degradation efficiency can reach 96% in 180 min.

Example 5 (blank resin comparative experiment)

Weighing 8g of D201 resin, carrying out alkali washing and acid washing to finish pretreatment, transferring empty resin which does not adsorb any substance into a reaction kettle, adding deionized water, calcining for one hour at 232 ℃, washing the resin subjected to primary calcination for several times by using the deionized water, placing the resin in a drying oven for drying, placing 0.5g of the dried resin in a crucible, and placing the crucible in a muffle furnace for secondary calcination at 300 ℃ for 1 hour.

Weighing 0.01g of the resin calcined product, dissolving the resin calcined product in 100ml of methylene blue solution with the concentration of 50mg/L, uniformly stirring for 30min under the condition of keeping out of the sun to achieve adsorption balance, placing the mixed solution under a xenon lamp light source with a filter (lambda is greater than 420nm), simulating the process of photocatalytic degradation of the methylene blue by the semiconductor oxide under visible light, ensuring continuous magnetic stirring and light source irradiation in the reaction process, and taking supernatant for a certain time to detect. The prepared product has no remarkable photocatalytic degradation effect, and the degradation efficiency can be only 30% at 180 min.

Example 6

Weighing 8g of D201 resin, carrying out alkali washing and acid washing to complete pretreatment, preparing a mixed solution with the concentration of sodium tungstate and sodium molybdate being 2:1, adjusting the pH value to 3.5 by hydrochloric acid, standing for 2 hours, adding the pretreated resin into 50ml of the mixed solution, adding magnetons, and carrying out magnetic stirring for 4 hours. Transferring the resin after adsorption to a reaction kettle, adding deionized water, and reacting at 2Calcined at 32 ℃ for one hour. And (3) washing the resin subjected to primary calcination with deionized water for several times, placing the resin in a drying box for drying, placing 0.5g of the dried resin in a crucible, and placing the crucible in a muffle furnace for secondary calcination at the calcination temperature of 350 ℃ for 1 hour. XRD detection is carried out on the product, and the product is WO₃。

Weighing 0.01g of the tungsten resin calcined product, dissolving the tungsten resin calcined product in 100ml of methylene blue solution with the concentration of 50mg/L, uniformly stirring for 30min under the condition of keeping out of the sun to achieve adsorption balance, placing the mixed solution under a xenon lamp light source with a filter (lambda is greater than 420nm), simulating the process of photocatalytic degradation of the methylene blue by the semiconductor oxide under visible light, ensuring continuous magnetic stirring and light source irradiation in the reaction process, and taking supernatant for detection at a certain time. The prepared product has no remarkable photocatalytic degradation effect, and the degradation efficiency can be only 57.88% at 180 min.

Example 7

This example provides a short run preparation of W_0.4Mo_0.6O₃The method comprises the following specific steps:

weighing 8g of D201 resin, and completing pretreatment through alkali washing and acid washing;

taking a certain amount of tungsten-molybdenum-containing leachate generated by treating tungsten-molybdenum wastes in factories until the concentration of tungstate ions is 0.4mol/L and the concentration of molybdate ions is 0.3 mol/L;

adding the pretreated resin into 50ml of the solution, adjusting the pH to 3.5 by hydrochloric acid, standing for 2 hours, adding magnetons, and magnetically stirring for 4 hours;

transferring the resin after adsorption to a reaction kettle, adding deionized water, and calcining for 1 hour at 232 ℃;

washing the resin after the primary calcination with deionized water for several times, and drying in a drying oven;

taking 0.5g of dried resin, placing the resin in a crucible, and placing the crucible in a muffle furnace for secondary calcination at the calcination temperature of 400 ℃ for 1 hour to obtain W containing a small amount of carbon_0.4Mo_0.6O₃。

Weighing 0.01g of the tungsten-molybdenum oxide product, dissolving the tungsten-molybdenum oxide product in 100ml of methylene blue solution with the concentration of 50mg/L, uniformly stirring for 30min under the condition of keeping out of the sun to achieve adsorption balance, placing the mixed solution under a xenon lamp light source with a filter (lambda is greater than 420nm), simulating the process of photocatalytic degradation of the methylene blue by the semiconductor oxide under visible light, ensuring continuous magnetic stirring and light source irradiation in the reaction process, and taking supernatant for detection at a certain time. The result shows that the obtained product has better photocatalytic degradation effect, and the degradation efficiency can reach 91% in 180 min.

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.