阅读说明：本技术 负载铂和钌双金属的氧化锆纳米管复合材料及其制备方法与在低温热催化处理甲苯中的应用 (Platinum and ruthenium bimetal loaded zirconium oxide nanotube composite material, preparation method thereof and application thereof in low-temperature thermal catalytic treatment of toluene ) 是由 路建美 陈冬赟 蒋军 于 2019-10-18 设计创作，主要内容包括：本发明公开了一种负载铂和钌双金属的氧化锆纳米管复合材料及其制备方法与在甲苯热催化处理中的应用；以SBA-15-OH分子筛作为模板,以八水合氧氯化锆作为金属前驱体,通过陈化、煅烧、刻蚀制备得到氧化锆纳米管材料；取定量制得的氧化锆作为载体,加入一定量氯铂酸、三氯化钌等金属前驱体,通过超声搅拌,搅拌溶剂热蒸发以及氢气还原煅烧得到负载一定比例铂钌双金属的氧化锆纳米管复合材料。本发明通过一系列步骤合成的负载铂和钌双金属纳米粒子的氧化锆纳米管复合材料对甲苯气体有着很好的热催化效果,并且能够实现在较低温度下对低浓度甲苯的完全催化,对解决空气环境中甲苯污染气体有着很大研究意义及一定的应用前景。(The invention discloses a platinum and ruthenium loaded zirconium oxide nanotube composite material, a preparation method thereof and application thereof in toluene thermocatalytic treatment; preparing a zirconium oxide nanotube material by aging, calcining and etching by taking an SBA-15-OH molecular sieve as a template and zirconium oxychloride octahydrate as a metal precursor; taking the zirconium oxide which is prepared quantitatively as a carrier, adding a certain amount of metal precursors such as chloroplatinic acid, ruthenium trichloride and the like, and obtaining the zirconium oxide nanotube composite material loaded with a certain proportion of platinum-ruthenium bimetal through ultrasonic stirring, stirring solvent thermal evaporation and hydrogen reduction calcination. The platinum and ruthenium bimetallic nanoparticle-loaded zirconia nanotube composite material synthesized by a series of steps has a good thermal catalysis effect on toluene gas, can realize complete catalysis on low-concentration toluene at a lower temperature, and has great research significance and certain application prospect on solving toluene pollution gas in an air environment.)

1. The preparation method of the zirconium oxide nanotube composite material loaded with the platinum and ruthenium bimetallic nanoparticles is characterized by comprising the following steps of:

(1) adding zirconium salt into an SBA-15-OH acid solution, and performing aging, calcination and alkali liquor etching to obtain a zirconium oxide nanotube;

(2) soaking the zirconia nano tube in a solution containing platinum salt and ruthenium salt, stirring, removing the solvent, and then carrying out reduction treatment to obtain the zirconia nano tube composite material loaded with the platinum and ruthenium bimetallic nano particles.

2. The platinum and ruthenium bimetallic nanoparticle-loaded zirconia nanotube composite of claim 1, characterized in that: in the step (1), the dosage ratio of SBA-15-OH, zirconium salt and acid is 0.5g (0.4-0.5 g) to 2.5-3.5 ml.

3. The platinum and ruthenium bimetallic nanoparticle-loaded zirconia nanotube composite of claim 1, characterized in that: in the step (1), the aging temperature is 50-90 ℃ and the aging time is 20-80 hours.

4. The platinum and ruthenium bimetallic nanoparticle-loaded zirconia nanotube composite of claim 1, characterized in that: in the step (1), the calcination is carried out in the air, the calcination temperature is 400-500 ℃, and the calcination time is 3-6 hours.

5. The platinum and ruthenium bimetallic nanoparticle-loaded zirconia nanotube composite of claim 1, characterized in that: in the step (1), the temperature of the alkali liquor etching is 65-75 ℃, and the time is 10-15 hours.

6. The platinum and ruthenium bimetallic nanoparticle-loaded zirconia nanotube composite of claim 1, characterized in that: in the step (2), the sum of the molar weight of the platinum salt and the molar weight of the ruthenium salt is 1 percent of the molar weight of the zirconia nanotube; the molar weight ratio of the platinum salt to the ruthenium salt is (1-9): 1.

7. The platinum and ruthenium bimetallic nanoparticle-loaded zirconia nanotube composite of claim 1, characterized in that: in the step (2), the stirring is ultrasonic treatment, the solvent is removed by adopting a stirring solvent thermal evaporation method, and the reduction treatment is carried out in hydrogen.

8. The platinum and ruthenium bimetallic nanoparticle-loaded zirconia nanotube composite of claim 1, characterized in that: zirconium salt is zirconium oxychloride, platinum salt is chloroplatinic acid, and ruthenium salt is ruthenium trichloride; in the SBA-15-OH acid solution, the acid is hydrochloric acid; the alkali liquor is sodium hydroxide solution; in the solution containing platinum salt and ruthenium salt, the solvent is water.

9. The use of the platinum and ruthenium bimetallic nanoparticle-loaded zirconia nanotube composite of claim 1 in the low temperature thermocatalytic treatment of toluene.

10. A preparation method of a zirconium oxide nanotube composite material loaded with platinum and ruthenium bimetallic nanoparticles is characterized by comprising the following steps:

(1) adding zirconium salt into an SBA-15-OH acid solution, and performing aging, calcination and alkali liquor etching to obtain a zirconium oxide nanotube;

(2) soaking the zirconia nano tube in a solution containing platinum salt and ruthenium salt, stirring, removing the solvent, and then carrying out reduction treatment to obtain the zirconia nano tube composite material loaded with the platinum and ruthenium bimetallic nano particles.

Technical Field

The invention relates to the technical field of nano composite materials, in particular to a zirconium oxide nano tube composite material loaded with platinum and ruthenium bimetallic nano particles, a preparation method thereof and application thereof in low-temperature thermocatalytic treatment of toluene.

Background

With the rapid development of the technology and the industrialization in recent years, the emission of toxic volatile organic gases such as benzene, toluene, formaldehyde and the like seriously exceeds the standard, and the indoor sources of the toxic volatile organic gases are wide, thus seriously harming the health of human beings. Toluene is one of common indoor volatile organic compounds, and the discharge of toluene gas mainly comes from building materials, indoor decorative materials and living and office supplies; incomplete combustion of household fuel and tobacco leaves, human waste; outdoor industrial waste gas, automobile exhaust, photochemical smog and the like are very serious in harm to human bodies. Therefore, the treatment of the pollution of toluene gas is very important, and the treatment of toluene by using metal nanoparticles for low-temperature catalytic oxidation is a promising gas treatment method, however, in practical application, the nanoparticles need to be a good carrier as a catalyst. In the related literature reports, the commonly used carrier is mainly Co₃O₄、CeO₂And the carrier with larger specific surface area is very key to the uniform distribution and the size control of the nano particles, and the bimetallic load is a good choice for improving the catalytic effect and the economy. Zirconia materials are a class of support materials; however, the preparation methods of uniformly loading the metal nanoparticles on the surfaces of the metal nanoparticles in the prior art are relatively complex, and how to realize the catalysis of the catalyst at low temperature is urgently needed to be solved. Therefore, in view of the current situation, it is necessary to develop an effective method and a supported catalyst.

Disclosure of Invention

The invention aims to provide a zirconium oxide nanotube composite material loaded with platinum and ruthenium bimetallic nanoparticles and a preparation method thereof.

In order to achieve the purpose, the invention adopts the following specific technical scheme:

a zirconium oxide nanotube composite material loaded with platinum and ruthenium bimetallic nanoparticles is prepared by the following steps:

(1) adding zirconium salt into an SBA-15-OH acid solution, and performing aging, calcination and alkali liquor etching to obtain a zirconium oxide nanotube;

(2) soaking the zirconia nano tube in a solution containing platinum salt and ruthenium salt, stirring, removing the solvent, and then carrying out reduction treatment to obtain the zirconia nano tube composite material loaded with the platinum and ruthenium bimetallic nano particles.

A method for low-temperature thermocatalytic treatment of toluene comprises the following steps:

(1) adding zirconium salt into an SBA-15-OH acid solution, and performing aging, calcination and alkali liquor etching to obtain a zirconium oxide nanotube;

(2) soaking a zirconium oxide nanotube in a solution containing platinum salt and ruthenium salt, stirring, removing the solvent, and performing reduction treatment to obtain a zirconium oxide nanotube composite material loaded with platinum and ruthenium bimetallic nanoparticles;

(3) and (3) placing the zirconium oxide nanotube composite material loaded with the platinum and ruthenium bimetallic nanoparticles into an environment containing toluene, and heating at a low temperature to finish the treatment of the toluene.

In the invention, zirconium salt is zirconium oxychloride, platinum salt is chloroplatinic acid, and ruthenium salt is ruthenium trichloride; in the SBA-15-OH acid solution, the acid is hydrochloric acid; the alkali liquor is sodium hydroxide solution; in the solution containing platinum salt and ruthenium salt, the solvent is water.

In the invention, the aging temperature is 50-90 ℃ and the aging time is 20-80 hours, preferably, the aging is aging at 50 ℃ for 24 hours and then aging at 90 ℃ for 48 hours; the calcining temperature is 400-500 ℃ and the calcining time is 3-6 hours, preferably, the calcining is carried out in the air, the heating rate is 1 ℃/min, the temperature is 450 ℃ and the calcining time is 5 hours; the temperature of the alkali liquor etching is 65-75 ℃, the time is 10-15 hours, and preferably, the temperature of the alkali liquor etching is 70 ℃, and the time is 12 hours.

In the invention, the stirring is ultrasonic treatment, the solvent is removed by adopting a stirring solvent thermal evaporation method, and the reduction treatment is carried out in hydrogen; preferably, the time of ultrasonic treatment is 1.8-2.3 hours, preferably 2 hours, and the temperature for removing the solvent is 80 ℃; the temperature during the reduction treatment is 380-420 ℃, the time is 4.5-5.5 h, preferably, the temperature during the reduction treatment is 400 ℃, the time is 5h, and the temperature rise rate is 1 ℃/min.

In the invention, in the step (1), the dosage ratio of SBA-15-OH, zirconium salt and acid is 0.5g (0.4-0.5 g) to 2.5-3.5 ml, preferably 0.5g:0.4695g:3 ml.

In the invention, in the step (2), the sum of the molar weight of the platinum salt and the molar weight of the ruthenium salt is 1 percent of the molar weight of the zirconia nanotube; the molar weight ratio of the platinum salt to the ruthenium salt is (1-9): 1, preferably 7: 3.

The invention firstly adopts SBA-15-OH as a template to prepare the zirconia nano-tube, has larger specific surface area, uniform aperture size, controllable structure and good repeatability, can be used as a good carrier to load platinum and ruthenium bimetallic nano-particles, and the larger specific surface area can promote the catalytic performance, thereby being a good carrier material. The reduction treatment is carried out in hydrogen, the platinum-ruthenium bimetallic nanoparticles are directly loaded into the zirconia nano-tube by adopting a simple in-situ reduction method during calcination, the formed bimetallic platinum-ruthenium nanoparticles are very small and are uniformly loaded into a carrier pore channel, and the low-temperature catalytic oxidation of toluene is facilitated.

After reduction and calcination treatment, the zirconium oxide nanotube composite material loaded with the platinum-ruthenium bimetallic nanoparticles quantitatively is placed in a toluene environment with a certain concentration, the zirconium oxide nanotube composite material is heated and catalyzed by using a fixed bed reactor, and the temperature for completely catalyzing and oxidizing the toluene is found by using a GC-MS test, so that the toluene is catalyzed and oxidized at a low temperature.

The invention further discloses an application of the zirconium oxide nanotube composite material loaded with the platinum and ruthenium bimetallic nanoparticles in low-temperature catalytic oxidation of toluene.

The method for treating toluene by low-temperature thermocatalysis disclosed by the invention comprises the steps of placing the zirconium oxide nanotube composite material loaded with the platinum and ruthenium bimetallic nanoparticles into an environment containing toluene, and finishing the treatment of the toluene by using a fixed bed reactor, wherein preferably, the temperature for heating and catalytically oxidizing toluene gas at low temperature is 140-160 ℃.

The invention has the advantages that:

1. the zirconium oxide nanotube composite material loaded with the platinum and ruthenium bimetallic nanoparticles disclosed by the invention has a larger specific surface area, uniform pore size and a controllable structure; the platinum and ruthenium bimetallic nanoparticles are uniformly loaded in the zirconia nano-tube, and the large specific surface area can promote the catalytic performance, so that the platinum and ruthenium bimetallic nanoparticles are a good loaded catalyst material.

2. According to the preparation method of the zirconium oxide nanotube composite material loaded with the platinum and ruthenium bimetallic nanoparticles, the platinum and ruthenium bimetallic nanoparticles are extremely small and are uniformly loaded in the carrier pore channel, the bimetallic catalytic performance is more excellent, the catalytic oxidation of toluene at a lower temperature can be realized, and the method has better economic practicability.

Drawings

FIG. 1 is a Transmission Electron Micrograph (TEM) of SBA-15-OH;

FIG. 2 is a Scanning Electron Micrograph (SEM) of SBA-15-OH;

FIG. 3 is a Transmission Electron Micrograph (TEM) of zirconia nanotubes;

FIG. 4 is a Scanning Electron Micrograph (SEM) of zirconia nanotubes;

FIG. 5 shows Pt_0.7Ru_0.3/ZrO₂Transmission Electron Microscopy (TEM) of the composite;

FIG. 6 shows Pt_0.7Ru_0.3/ZrO₂Scanning Electron Micrographs (SEM) of the composite;

FIG. 7 is a graph showing the thermal catalytic effect of the zirconium oxide nanotube composite loaded with platinum and ruthenium bimetallic nanoparticles on toluene gas.

Detailed Description

The preparation method of the zirconium oxide nanotube composite material loaded with the platinum and ruthenium bimetallic nanoparticles comprises the following steps:

(1) adding zirconium salt into an SBA-15-OH acid solution, and performing aging, calcination and alkali liquor etching to obtain a zirconium oxide nanotube;

(2) soaking the zirconia nano tube in a solution containing platinum salt and ruthenium salt, stirring, removing the solvent, and then carrying out reduction treatment to obtain the zirconia nano tube composite material loaded with the platinum and ruthenium bimetallic nano particles.