阅读说明：本技术 一种室内抗菌纳米催化材料及其制备方法 (Indoor antibacterial nano catalytic material and preparation method thereof ) 是由 张宏强 于 2019-08-07 设计创作，主要内容包括：本发明涉及一种室内抗菌纳米催化材料及其制备方法,在以高锰酸钾和锰盐为原料合成二氧化锰的整个过程中,采用超声纳米化装置处理反应体系,并在反应3～6min时向反应体系中添加盐酸胍和马来酸酐,同时在反应10～15min后以9℃/min以上的速率快速降温至-10℃以下制得室内抗菌纳米催化材料；最终制得的室内抗菌纳米催化材料为负载有抗菌功能化马来酸酐的多孔颗粒；抗菌功能化马来酸酐由盐酸胍与马来酸酐反应生成；多孔颗粒的材质为二氧化锰,平均粒径≤30nm,比表面积≥300g/m<Sup>2</Sup>,孔隙率≥40％,多孔的孔径≤5nm。本发明的制备方法简单易行,采用本发明的方法制得的室内抗菌纳米催化材料具有优异的抗菌性能。(The invention relates to an indoor antibacterial nano catalytic material and a preparation method thereof, wherein in the whole process of synthesizing manganese dioxide by taking potassium permanganate and manganese salt as raw materials, an ultrasonic nano device is adopted to treat a reaction system, guanidine hydrochloride and maleic anhydride are added into the reaction system when the reaction is carried out for 3-6 min, and the temperature is rapidly reduced to above 9 ℃/min after the reaction is carried out for 10-15 minPreparing an indoor antibacterial nano catalytic material at the temperature of below-10 ℃; the finally prepared indoor antibacterial nano catalytic material is porous particles loaded with antibacterial functional maleic anhydride; the antibacterial functional maleic anhydride is generated by the reaction of guanidine hydrochloride and maleic anhydride; the porous particles are made of manganese dioxide, the average particle size is less than or equal to 30nm, and the specific surface area is more than or equal to 300g/m 2 The porosity is more than or equal to 40 percent, and the pore diameter of the porous material is less than or equal to 5 nm. The preparation method is simple and feasible, and the indoor antibacterial nano catalytic material prepared by the method has excellent antibacterial performance.)

1. A preparation method of an indoor antibacterial nano catalytic material is characterized by comprising the following steps: in the whole process of synthesizing manganese dioxide by taking potassium permanganate and manganese salt as raw materials, an ultrasonic nano device is adopted to treat a reaction system, guanidine hydrochloride and maleic anhydride are added into the reaction system when the reaction is carried out for 3-6 min, and the indoor antibacterial nano catalytic material is prepared by rapidly cooling to below-10 ℃ at a speed of more than 9 ℃/min after the reaction is carried out for 10-15 min.

2. The method for preparing indoor antibacterial nanocatalysis material as claimed in claim 1, wherein before the reaction, the reaction system consists of potassium permanganate, manganese salt and water.

3. The preparation method of the indoor antibacterial nano catalytic material according to claim 2, characterized in that before the reaction starts, the molar ratio of potassium permanganate, manganese salt and water in the reaction system is 1: 2-4: 6-7; the molar ratio of guanidine hydrochloride to maleic anhydride is 2-4: 1, and the mass addition amount of the maleic anhydride is 1.2-2 times of that of the potassium permanganate.

4. The method as claimed in claim 2, wherein the manganese salt is one or more of manganese sulfate, manganese chloride, manganese oxalate, manganese carbonate and manganese acetate.

5. The preparation method of the indoor antibacterial nano catalytic material according to claim 2, characterized by comprising the following specific steps: firstly, heating a reaction system consisting of potassium permanganate, manganese salt and water to 80-100 ℃ for reaction for A min, treating the reaction system with an ultrasonic nano device, then adding guanidine hydrochloride and maleic anhydride into the reaction system, continuing to react for B min, treating the reaction system with the ultrasonic nano device, and finally rapidly cooling to-10-30 ℃ at the speed of 9-20 ℃/min, and treating the reaction system with the ultrasonic nano device; a is 3-6, and the sum of A and B is 10-15.

6. The preparation method of the indoor antibacterial nano catalytic material as claimed in claim 5, wherein the working frequency range of the ultrasonic nano device is 20-25 KHz.

7. The indoor antibacterial nano catalytic material prepared by the preparation method of the indoor antibacterial nano catalytic material as claimed in any one of claims 1 to 6, is characterized in that: the antibacterial functional maleic anhydride-loaded porous particles are prepared by the following steps; the antibacterial functional maleic anhydride is generated by the reaction of guanidine hydrochloride and maleic anhydride; the porous particles are made of manganese dioxide, the average particle size is less than or equal to 30nm, and the specific surface area is more than or equal to 300g/m²The porosity is more than or equal to 40 percent, and the pore diameter of the porous material is less than or equal to 5 nm.

8. The indoor antibacterial nanocatalysis material as claimed in claim 7, wherein the porous particles have an average particle size of 10-30 nm and a specific surface area of 300-600 g/m²The porosity is 40-70%, and the pore diameter of the porous material is 3-5 nm.

9. The indoor antibacterial nanocatalysis material of claim 7 or 8, wherein the antibacterial rate of the indoor antibacterial nanocatalysis material is 99-99.999%.

Technical Field

The invention belongs to the technical field of catalytic materials, and relates to an indoor antibacterial nano catalytic material and a preparation method thereof.

Background

In recent years, with the improvement of living standard and the enhancement of health consciousness of people, people pay more attention to indoor air quality of buildings. According to the research of the united states Environmental Protection Agency (EPA), it is shown that indoor air of homes and office buildings is more seriously polluted than air of industrialized cities. Meanwhile, people stay indoors for 90% of the time, so that the pollution of indoor air is more harmful to the health of human bodies than the pollution of outdoor air. Deterioration of indoor air quality directly leads to sick building syndrome and building morbidity. The microorganisms such as bacteria and fungi propagate indoors to pollute the air, which is an important public environmental sanitation problem at present. The case that the indoor air microbial pollution causes human health influence happens occasionally, and even the case that the indoor air microbial pollution causes life threatening influence is not rare. Indoor sterilization becomes an important concern.

There are generally three ways to sterilize indoors: sterilizing with a sterilizing lamp, sterilizing with a liquid bactericide, and sterilizing with ozone. Wherein, the disinfection lamp has the defects of limited action distance, incapability of sterilizing dead corners and the like; the liquid bactericide mainly comprises chemical components which are possibly harmful to human bodies, and when the liquid components are volatilized into the air, the liquid bactericide is easy to absorb into the human bodies to cause potential harm; ozone is a strong oxidant, which is harmful to human body and is not approved for final use.

Therefore, the research of a new material for indoor sterilization is of great significance.

Disclosure of Invention

The invention aims to solve the problem of poor sterilization effect of indoor sterilization materials in the prior art, and provides an indoor antibacterial nano catalytic material and a preparation method thereof.

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

a preparation method of an indoor antibacterial nano catalytic material comprises the steps of treating a reaction system by using an ultrasonic nano device in the whole process of synthesizing manganese dioxide by taking potassium permanganate and manganese salt as raw materials, adding guanidine hydrochloride and maleic anhydride into the reaction system when the reaction is carried out for 3-6 min, and rapidly cooling to the temperature below-10 ℃ at the speed of more than 9 ℃/min after the reaction is carried out for 10-15 min to obtain the indoor antibacterial nano catalytic material.

In the invention, guanidine hydrochloride and maleic anhydride are added in the synthesis process of manganese dioxide, and react to generate the antibacterial functional maleic anhydride, and the antibacterial functional maleic anhydride is uniformly loaded on the surface of the manganese dioxide through hydrogen bonds because the guanidine hydrochloride and the maleic anhydride are added at a specific stage (reacting for 3-6 min), and the manganese dioxide has a sterilization effect, and the sterilization mechanism is as follows: manganese dioxide has strong oxidizing property, can oxidize and damage cells, and gradually leads to cell inactivation, and the antibacterial functional maleic anhydride also has a sterilization effect, after the antibacterial functional maleic anhydride is loaded on the surface of the manganese dioxide, the antibacterial functional maleic anhydride enhances the sterilization effect of the manganese dioxide, and simultaneously, the manganese dioxide can oxidize sulfydryl in bacterial metabolic enzyme by virtue of the strong oxidizing property of the manganese dioxide per se so as to inactivate the enzyme, so that bacteria die due to incapability of metabolism, cations of organic guanidine in the antibacterial functional maleic anhydride can generate electrostatic adsorption with anions on the surfaces of the bacterial cells, and the surface structure of the bacteria is damaged, so that the high-efficiency sterilization can be realized, a certain synergistic effect can be realized, and the sterilization effect of the material is further enhanced;

in addition, compared with the prior art, the method for synthesizing manganese dioxide of the present invention has the following differences:

1) the reaction system is treated by the ultrasonic nanocrystallization device, so that the particle size of the nano manganese dioxide particles is smaller than that of manganese dioxide nano particles prepared by the reaction system without the ultrasonic nanocrystallization device, the specific surface area of the manganese dioxide nano particles is favorably improved, the contact surface of manganese dioxide and bacteria can be enhanced after the specific surface area is improved, the sulfydryl in manganese dioxide oxidizing bacteria metabolic enzyme is further enhanced, the enzyme is inactivated, and the bacteria can die quickly due to the incapability of metabolism;

2) after reacting for a period of time, rapidly cooling to below-10 ℃, the temperature is slowly reduced after the reaction is finished in the existing reaction, the rapid cooling is favorable for rapidly terminating the reaction, and preventing the generated manganese dioxide particles from further growing, because the manganese dioxide powder can grow gradually along with the reaction in the reaction process, the temperature is a necessary condition for promoting the reaction, the reaction can be inhibited by instantly reducing the temperature, the further growth of the powder is prevented, a large amount of water molecules are remained in the formed manganese dioxide powder after the rapid cooling, a porous structure can be formed after the prepared manganese dioxide is put into a liquid water evaporation under a normal temperature environment, and the specific surface area of the manganese dioxide is improved; if the temperature does not reach below-10 ℃, the reaction still proceeds slowly, resulting in a larger final particle size.

As a preferable scheme:

according to the preparation method of the indoor antibacterial nano catalytic material, before the reaction starts, the reaction system consists of potassium permanganate, manganese salt and water.

According to the preparation method of the indoor antibacterial nano catalytic material, before the reaction starts, the molar ratio of potassium permanganate, manganese salt and water in a reaction system is 1: 2-4: 6-7, the range is the most suitable molar ratio, and the reaction is insufficient when the ratio is too large or too small; the molar ratio of guanidine hydrochloride to maleic anhydride is 2-4: 1, and guanidine hydrochloride is used for carrying out antibacterial functional treatment on maleic anhydride, so that the content of guanidine hydrochloride is higher, the mass addition amount of maleic anhydride is 1.2-2 times of that of potassium permanganate, the effect of manganese dioxide is weakened when the mass addition amount of maleic anhydride is too large, and the comprehensive antibacterial performance is deteriorated when the mass addition amount of maleic anhydride is too small.

In the preparation method of the indoor antibacterial nano catalytic material, the manganese salt is more than one of manganese sulfate, manganese chloride, manganese oxalate, manganese carbonate and manganese acetate.

The preparation method of the indoor antibacterial nano catalytic material comprises the following specific steps: firstly, heating a reaction system consisting of potassium permanganate, manganese salt and water to 80-100 ℃ for reaction for A min, treating the reaction system with an ultrasonic nano device, then adding guanidine hydrochloride and maleic anhydride into the reaction system, continuing to react for B min, treating the reaction system with the ultrasonic nano device, and finally rapidly cooling to-10-30 ℃ at the speed of 9-20 ℃/min, and treating the reaction system with the ultrasonic nano device; a is 3-6, and the sum of A and B is 10-15.

According to the preparation method of the indoor antibacterial nano catalytic material, the working frequency range of the ultrasonic nano device is 20-25 KHz, the ultrasonic wave is in the range, the ultrasonic wave has obvious influence on the synthesis of the material, the particles can be uniformly distributed, the size reaches the nanometer level, the ultrasonic crushing effect is optimal at the frequency, and the crushing effect can be reduced when the frequency is higher or lower than the frequency.

The invention also provides an indoor antibacterial nano catalytic material prepared by the preparation method of the indoor antibacterial nano catalytic material, which is porous particles loaded with antibacterial functional maleic anhydride; the antibacterial functional maleic anhydride is generated by the reaction of guanidine hydrochloride and maleic anhydride; the porous particles are made of manganese dioxide, the average particle size is less than or equal to 30nm, and the specific surface area is more than or equal to 300g/m²The porosity is more than or equal to 40 percent, and the pore diameter of the porous material is less than or equal to 5 nm.

As a preferable scheme:

the indoor antibacterial nano catalytic material has the average particle size of the porous particles of 10-30 nm and the specific surface area of 300-600 g/m²The porosity is 40-70%, and the pore diameter of the porous material is 3-5 nm.

According to the indoor antibacterial nano catalytic material, the antibacterial rate of the indoor antibacterial nano catalytic material is 99-99.999%.

Has the advantages that:

(1) according to the preparation method of the indoor antibacterial nano catalytic material, guanidine hydrochloride and maleic anhydride are added in the process of synthesizing manganese dioxide, and antibacterial functional maleic anhydride generated by the reaction of the guanidine hydrochloride and the maleic anhydride is uniformly loaded on the surface of the manganese dioxide through hydrogen bonds, so that the antibacterial performance of the manganese dioxide is greatly improved;

(2) the indoor antibacterial nano catalytic material prepared by the preparation method of the indoor antibacterial nano catalytic material has excellent antibacterial performance and better application prospect.

Detailed Description

The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.