阅读说明：本技术 三明治结构空心纳米反应器光催化材料的制备方法及产品和应用 (Preparation method of sandwich structure hollow nano reactor photocatalytic material, product and application ) 是由 崔大祥 吴晓燕 林琳 王敬锋 陈超 于 2021-08-23 设计创作，主要内容包括：本发明提供一种三明治结构空心纳米反应器光催化材料的制备方法及其产品和应用,第一步：按摩尔比将钼酸盐水溶液加入到CTAB的醇溶液中磁力搅拌2～3 h；第二步：将乙二醇和盐酸按体积比依次加入上述混合溶液中,继续磁力搅拌3～5 h；第三步：再将硫脲加入继续搅拌1～2 h,钼酸盐、CTAB和硫脲的摩尔量比为1：15：10,转入反应釜160～180℃反应16～18 h,将沉淀物过滤、洗涤后,在60～80℃干燥18～24 h得黑色粉末,将该黑色粉末置于惰性气氛中600～750℃煅烧3～5 h得MoO-(2)/MoS-(2)/C。在紫外光催化条件下,对四环素的降解可达99.6%。该制备工艺简单,易操作。(The invention provides a preparation method of a hollow nano-reactor photocatalytic material with a sandwich structure, a product and an application thereof, wherein the first step is as follows: adding molybdate aqueous solution into CTAB alcoholic solution according to molar ratio, and magnetically stirring for 2-3 h; the second step is that: adding ethylene glycol and hydrochloric acid into the mixed solution in sequence according to the volume ratio, and continuing to magnetically stir for 3-5 hours; the third step: and adding thiourea into the mixture and continuously stirring for 1-2 h, wherein the molar weight ratio of molybdate to CTAB to thiourea is 1: 15: 10, transferring the mixture into a reaction kettle for reaction at 160-180 ℃ for 16-18 h, filtering and washing the precipitate, drying the precipitate at 60-80 ℃ for 18-24 h to obtain black powder, and calcining the black powder at 600-750 ℃ for 3-5 h in an inert atmosphere to obtain MoO 2 /MoS 2 and/C. Under the condition of ultraviolet light catalysis, the degradation of tetracycline can reach 99.6%. The preparation method is simple and easyAnd (5) operating.)

1. preparation method of sandwich-structure hollow nano-reactor photocatalytic material, wherein MoO is adopted as the sandwich-structure hollow nano-reactor photocatalytic material₂/MoS₂a/C, characterized in that it comprises the following steps,

the first step is as follows: adding a molybdate aqueous solution into an alcoholic solution of CTAB, and magnetically stirring for 2-3 h, wherein the molar weight ratio of molybdate to CTAB is 1: 15;

the second step is that: and (2) sequentially adding ethylene glycol and hydrochloric acid into the mixed solution, wherein the volume ratio of the ethylene glycol to the hydrochloric acid is 50: (1-3), continuing magnetic stirring for 3-5 h;

the third step: and adding thiourea into the mixture, and continuously stirring for 1-2 hours to ensure that the molar weight ratio of the molybdate to the CTAB to the thiourea is 1: 15: 10, transferring the mixture into a reaction kettle for reaction at 160-180 ℃ for 16-18 h, filtering the precipitate, washing the precipitate for 3-5 times by deionized water and ethanol, drying the precipitate for 18-24 h at 60-80 ℃ to obtain black powder, and placing the black powder in an inert atmosphere for 600-75 hCalcining for 3-5 h at 0 ℃ to obtain MoO₂/MoS₂/C。

2. The method for preparing the photocatalytic material for the sandwich-structured hollow nanoreactor according to claim 1, wherein in the first step, the molybdate is one or a combination of sodium molybdate, potassium molybdate and ammonium molybdate.

3. The method for preparing the photocatalytic material for the sandwich-structured hollow nanoreactor according to claim 1, wherein in the first step, the alcohol is one or a combination of n-butanol, ethanol or glycerol.

4. The method for preparing the photocatalytic material for the sandwich-structured hollow nano-reactor according to claim 1, wherein in the third step, the thiourea is one or a combination of dodecyl thiourea, lauryl thiourea and 1-docosyl thiourea.

5. The method for preparing the photocatalytic material for the sandwich-structured hollow nanoreactor according to claim 1, wherein the inert gas is one or a combination of nitrogen and argon.

6. A hollow nanoreactor photocatalytic material with a sandwich structure, characterized by being prepared according to the method of any one of claims 1 to 5.

7. Use of the sandwich structured hollow nanoreactor photocatalytic material according to claim 6 in wastewater treatment.

Technical Field

The invention relates to a photocatalytic material, and preparation and application thereof, in particular to a preparation method, a product and application of a photocatalytic material of a hollow nano-reactor with a sandwich structure.

Background

With the development of chemical industry, environmental pollution is becoming more serious. The discharge of printing and dyeing wastewater is one of the important causes of water pollution. Every year, a large amount of commercial dyes are discharged, and the dyes are stable in chemical property and cause great damage to the ecological environment. By utilizing the characteristic that the semiconductor oxide material can be activated under the irradiation of sunlight, organic matters can be effectively oxidized and degraded into carbon dioxide, water and other small molecules.

Compared with the traditional purification method, the semiconductor photocatalysis technology has the advantages of mild reaction conditions, no secondary pollution, simple operation, obvious degradation effect and the like. Titanium dioxide is one of the most interesting photocatalysts, which is low-toxic, low-cost, durable, superhydrophilic and has excellent photochemical stability.

Transition metal dichalcogenides are an important class of materials, and are receiving attention due to abundant physical and chemical properties. In particular MoS₂、WS₂And WSe₂As a typical transition metal dichalcogenide, a wide variety of phenomena are shown in the fields of optoelectronics, energy valley electronics, and spintronics, and a wide spectrum of research enthusiasm is excited.

Recent studies show that the application of molybdenum disulfide in transition metal dichalcogenide compounds in nano electronics, photonics, sensors, energy storage system electrodes and the like has attracted wide attention. Can be used in the field of photocatalysis.

Disclosure of Invention

The invention aims to provide a preparation method of a hollow nano-reactor photocatalytic material with a sandwich structure.

Yet another object of the present invention is to: provides the photocatalytic material product with the sandwich structure hollow nano reactor prepared by the method.

Yet another object of the present invention is to: applications of the above products are provided.

The invention aims to realize the preparation method of the photocatalytic material of the hollow nano-reactor with the sandwich structure, wherein the photocatalytic material of the hollow nano-reactor with the sandwich structure is MoO₂/MoS₂The method comprises the following specific steps:

the first step is as follows: adding a molybdate aqueous solution into an alcoholic solution of CTAB, and magnetically stirring for 2-3 h, wherein the molar weight ratio of molybdate to CTAB is 1: 15;

the second step is that: and (2) sequentially adding ethylene glycol and hydrochloric acid into the mixed solution, wherein the volume ratio of the ethylene glycol to the hydrochloric acid is 50: (1-3), continuing magnetic stirring for 3-5 h;

the third step: and adding thiourea into the mixture and continuously stirring for 1-2 h, wherein the molar weight ratio of molybdate, CTAB and thiourea is 1: 15: 10, transferring the mixture into a reaction kettle for reaction at 160-180 ℃ for 16-18 h, filtering the precipitate, washing the precipitate with deionized water and ethanol for 3-5 times, drying the precipitate at 60-80 ℃ for 18-24 h to obtain black powder, and calcining the black powder at 600-750 ℃ for 3-5 h in an inert atmosphere to obtain MoO₂/MoS₂/C。

In the first step, the molybdate is one or the combination of sodium molybdate, potassium molybdate or ammonium molybdate.

In the first step, the alcohol is one or the combination of n-butanol, ethanol or glycerol.

In the third step, the thiourea is one or the combination of dodecyl thiourea, lauryl thiourea and 1-docosyl thiourea.

In the third step, the inert gas is one or the combination of nitrogen or argon.

The invention provides a preparation method of a hollow nano-reactor photocatalytic material with a sandwich structure, which is prepared according to any one of the methods.

The invention provides an application of a hollow nano-reactor photocatalytic material with a sandwich structure in wastewater treatment.

Photocatalytic degradation of tetracycline: the concentration of the tetracycline solution is 10mgL^-1Firstly, 3mg of the powder sample is weighed by an electronic balance and transferred into a 100mL quartz round-bottom flask, 60mL of tetracycline solution is poured into the flask, a magnetic stirrer is placed into the flask, the flask mouth is sealed, the flask is placed in a dark room and stirred at a medium speed for 30min, so that the powder sample is uniformly dispersed in the solution, and the absorption and desorption of tetracycline are balanced. Thereafter, the flask was placed under simulated ultraviolet lightStarting irradiation and timing, taking out 2mL of mixed solution at fixed time intervals of 1h, centrifuging to remove powder samples, and then carrying out an absorbance test. The degradation rate reaches more than 98 percent.

Compared with the prior art, the invention has the following beneficial effects:

the invention provides a sandwich structure MoO₂/MoS₂Preparation method of/C hollow nano reactor photocatalytic material, MoO₂/MoS₂the/C hollow nano reactor photocatalytic material has a large specific surface area, and the oxygen-deficient defects play an important role in improving the photocatalytic performance of the material. Is favorable for improving the photocatalytic performance of the material. The preparation process is relatively simple and easy to operate.

Detailed Description

The present invention is described in detail by the following specific examples, but the scope of the present invention is not limited to these examples.

Example 1

A photocatalytic material with sandwich structure for the hollow nano-reactor is MoO₂/MoS₂The preparation method comprises the following steps:

the first step is as follows: adding a sodium molybdate aqueous solution into a glycerol solution of CTAB, and magnetically stirring for 2 h, wherein the molar weight ratio of sodium molybdate to CTAB is 1: 15;

the second step is that: and (2) sequentially adding ethylene glycol and hydrochloric acid into the mixed solution, wherein the volume ratio of the ethylene glycol to the hydrochloric acid is 50: 1, continuing magnetic stirring for 3 hours;

the third step: adding the lauryl thiourea into the mixture, and continuously stirring for 1h, wherein the molar weight ratio of the sodium molybdate to the CTAB to the lauryl thiourea is 1: 15: 10, transferring the mixture into a reaction kettle to react for 16 h at 180 ℃, filtering the precipitate, washing the precipitate for 3 times by deionized water and ethanol, drying the precipitate for 24 h at 80 ℃ to obtain black powder, and calcining the black powder for 4 h at 700 ℃ in an inert argon atmosphere to obtain MoO₂/MoS₂a/C hollow nano reactor photocatalysis material.

The resulting MoO₂/MoS₂The degradation rate of the/C photocatalytic degradation tetracycline reaches 99.6 percent, which is shown in Table 1.

Example 2

Three-componentThe hollow nano reactor photocatalysis material with a structure of Mingming is MoO₂/MoS₂Similar to example 1, the preparation method comprises the following steps:

the first step is as follows: adding a potassium molybdate aqueous solution into a CTAB (cetyl trimethyl ammonium bromide) n-butyl alcohol solution, and magnetically stirring for 2 hours, wherein the molar weight ratio of potassium molybdate to CTAB is 1: 15;

the second step is that: and (2) sequentially adding ethylene glycol and hydrochloric acid into the mixed solution, wherein the volume ratio of the ethylene glycol to the hydrochloric acid is 50: 3, continuing magnetic stirring for 3 hours;

the third step: and adding dodecyl thiourea into the mixture and continuously stirring the mixture for 1 hour, wherein the molar weight ratio of potassium molybdate to CTAB to dodecyl thiourea is 1: 15: 10, transferring the mixture into a reaction kettle to react for 18 h at 160 ℃, filtering the precipitate, washing the precipitate for 3 times by deionized water and ethanol, drying the precipitate for 24 h at 60 ℃ to obtain black powder, and calcining the black powder for 5 h at 600 ℃ in a nitrogen atmosphere to obtain MoO₂/MoS₂a/C hollow nano reactor photocatalysis material.

The resulting MoO₂/MoS₂The degradation rate of the/C photocatalytic degradation tetracycline reaches 98.9 percent, which is shown in Table 1.

Example 3

A photocatalytic material with sandwich structure for the hollow nano-reactor is MoO₂/MoS₂Similar to example 1, the preparation method comprises the following steps:

the first step is as follows: adding an ammonium molybdate aqueous solution into a glycerol solution of CTAB, and magnetically stirring for 3 h, wherein the molar weight ratio of ammonium molybdate to CTAB is 1: 15;

the second step is that: and (2) sequentially adding ethylene glycol and hydrochloric acid into the mixed solution, wherein the volume ratio of the ethylene glycol to the hydrochloric acid is 50: 3, continuing magnetic stirring for 3 hours;

the third step: adding the 1-docosyl thiourea into the mixture, and continuously stirring the mixture for 1 hour, wherein the molar weight ratio of the potassium molybdate to the CTAB to the 1-docosyl thiourea is 1: 15: 10, transferring the mixture into a reaction kettle to react for 18 h at 160 ℃, filtering the precipitate, washing the precipitate for 5 times by deionized water and ethanol, drying the precipitate for 24 h at 60 ℃ to obtain black powder, and calcining the black powder for 3 h at 750 ℃ in an inert atmosphere to obtain MoO₂/MoS₂a/C hollow nano reactor photocatalysis material.

The resulting MoO₂/MoS₂The degradation rate of the/C photocatalytic degradation tetracycline reaches 99.3 percent, which is shown in Table 1.

Photocatalytic degradation of tetracycline: the concentration of the tetracycline solution is 10mgL^-1Firstly, 3mg of the powder samples of examples 1-3 are respectively weighed by an electronic balance and respectively transferred into 100mL quartz round-bottom flasks, 60mL of tetracycline solution is poured into each flask, a magnetic stirrer is placed in each flask, the flask mouth is sealed, the flask is placed in a dark room and stirred at medium speed for 30min, so that the powder samples are uniformly dispersed in the solution, and the absorption and desorption of tetracycline are balanced. Then, the flask was placed in simulated ultraviolet light to start irradiation and time, 2mL of the mixed solution was taken out at regular time intervals of 1 hour, and the absorbance test was performed after the powder sample was removed by centrifugal separation.

TABLE 1 MoO₂/MoS₂The degradation rate of the photocatalytic material of the C hollow nano reactor to tetracycline after 1h under the ultraviolet photocatalysis condition is as follows:

。