阅读说明：本技术 一种多功能埃洛石杂化粒子及其制备方法 (Multifunctional halloysite hybrid particle and preparation method thereof ) 是由 张焱 吴雨欣 汤琳 唐群 于 2021-09-13 设计创作，主要内容包括：本发明属于纳米材料技术领域,涉及一种多功能埃洛石杂化粒子及其制备方法。本发明先将埃洛石纳米管、硝酸钴、氨基三亚甲基磷酸均匀分散于去离子水和DMF的复合溶剂中,然后将其置于反应釜中,加热进行溶剂热反应,随后冷却至室温、离心分离、洗涤、干燥,得到多功能埃洛石杂化粒子。所制备得到的多功能埃洛石杂化粒子具有优异的抗菌性能、氨气响应性能和紫外线吸收性能,且制备工艺简单、环保、成本低廉,且适于放大生产,在气体传感、生物医疗、环境安全等领域具有广泛的应用前景。(The invention belongs to the technical field of nano materials, and relates to a multifunctional halloysite hybrid particle and a preparation method thereof. The preparation method comprises the steps of uniformly dispersing the halloysite nanotube, cobalt nitrate and aminotrimethylene phosphoric acid in a composite solvent of deionized water and DMF, then placing the mixture in a reaction kettle, heating the mixture to carry out solvothermal reaction, then cooling the mixture to room temperature, carrying out centrifugal separation, washing and drying to obtain the multifunctional halloysite hybrid particles. The prepared multifunctional halloysite hybrid particles have excellent antibacterial performance, ammonia response performance and ultraviolet absorption performance, are simple in preparation process, environment-friendly and low in cost, are suitable for amplification production, and have wide application prospects in the fields of gas sensing, biomedical treatment, environmental safety and the like.)

1. A preparation method of multifunctional halloysite hybrid particles is characterized by comprising the following steps:

(1) preparation of a reaction mixture: dispersing halloysite nanotubes in a composite solvent of deionized water and DMF, adding cobalt nitrate, stirring for 3 hours, uniformly mixing, adding aminotrimethylene phosphoric acid, stirring for 1 hour, and uniformly mixing to obtain a reaction mixed solution;

(2) preparation of multifunctional halloysite hybrid particles: and (2) placing the reaction mixed solution obtained in the step (1) into a reaction kettle, heating to perform solvothermal reaction, then cooling to room temperature, centrifugally separating, washing and drying to obtain the multifunctional halloysite hybrid particles.

2. The method for preparing multifunctional halloysite hybrid particles according to claim 1, wherein the mass ratio of halloysite nanotubes, cobalt nitrate, aminotrimethylene phosphoric acid, deionized water and DMF in the step (1) is 6.25: 3: 4: 400: 1900.

3. the method for preparing functionalized modified cellulose nanocrystal according to claim 1, wherein the solvothermal reaction temperature in the step (2) is 140 ℃ and the reaction time is 18 h.

4. The multifunctional halloysite hybrid particles obtained by the preparation method of any one of claims 1 to 3.

Technical Field

The invention belongs to the technical field of nano materials, and particularly relates to a multifunctional halloysite hybrid particle and a preparation method thereof.

Background

Halloysite Nanotubes (HNTs) are natural one-dimensional nanomaterials with hollow tubular structures, have the advantages of abundant reserves, low price, good adsorbability, biocompatibility, environmental friendliness, unique crystal structures and the like, and are widely used in the fields of catalyst carriers, templates, adsorbents, reinforcing agents, drug carriers, biological detection and the like. In addition, the halloysite nanotube contains a large amount of hydroxyl and siloxy on the surface and hydroxyl on the edge, and the characteristics enable the halloysite nanotube to be easily subjected to functional modification, so that the halloysite nanotube is expected to be used for producing various advanced functional materials with high added values. Materials with multiple functions (such as antibacterial function, ammonia response, ultraviolet absorption and the like) have wide application prospects in the fields of gas sensing, biological medical treatment, environmental safety and the like, and become a current research hotspot. Therefore, the method for preparing the multifunctional (such as antibacterial function, ammonia response, ultraviolet absorption and the like) halloysite hybrid particles by a simple and economic method has wide application prospect.

Disclosure of Invention

Based on the background, the invention provides a multifunctional halloysite hybrid particle and a preparation method thereof. The multifunctional halloysite hybrid particle provided by the invention has excellent antibacterial performance, ammonia response performance and ultraviolet absorption performance, is simple in preparation process, environment-friendly and low in cost, and is suitable for large-scale production.

The technical scheme of the invention is as follows:

a preparation method of multifunctional halloysite hybrid particles comprises the following steps:

(1) preparation of a reaction mixture: dispersing halloysite nanotubes in a composite solvent of deionized water and DMF, adding cobalt nitrate, stirring for 3 hours, uniformly mixing, adding aminotrimethylene phosphoric acid, stirring for 1 hour, and uniformly mixing to obtain a reaction mixed solution;

(2) preparation of multifunctional halloysite hybrid particles: and (2) placing the reaction mixed solution obtained in the step (1) into a reaction kettle, heating to perform solvothermal reaction, then cooling to room temperature, centrifugally separating, washing and drying to obtain the multifunctional halloysite hybrid particles.

Preferably, the mass ratio of the halloysite nanotubes to the cobalt nitrate to the aminotrimethylene phosphoric acid to the deionized water to the DMF in the step (1) is 6.25: 3: 4: 400: 1900.

preferably, the solvothermal reaction temperature in the step (2) is 140 ℃ and the reaction time is 18 h.

The multifunctional halloysite hybrid particles prepared by the method.

The invention has the following beneficial effects:

the multifunctional halloysite hybrid particle prepared by the invention has excellent antibacterial property, ammonia response property and ultraviolet absorption property, is simple in preparation process, environment-friendly and low in cost, is suitable for amplification production, and has wide application prospects in the fields of gas sensing, biological medical treatment, environmental safety and the like.

Drawings

FIG. 1 is a scanning electron micrograph of a multifunctional halloysite hybrid particle prepared according to the present invention;

FIG. 2 is a graph of the infrared spectra of unmodified halloysite and multifunctional halloysite hybrid particles prepared according to the invention;

FIG. 3 is a photograph showing the antibacterial activity of the antibacterial zone of Escherichia coli by using unmodified halloysite and the multifunctional halloysite hybrid particles prepared by the method;

FIG. 4 is a photograph of the antibacterial activity test of the antibacterial zone of the unmodified halloysite and the multifunctional halloysite hybrid particles prepared by the invention on Staphylococcus aureus;

FIG. 5 is a UV-Vis spectrum of unmodified halloysite and aqueous dispersions of multifunctional halloysite hybrid particles prepared according to the invention;

FIG. 6 is a thermogravimetric analysis plot of unmodified halloysite and multifunctional halloysite hybrid particles made according to the invention.

Detailed Description

The present invention is described in detail below by way of examples, it should be noted that these examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make insubstantial modifications and adjustments to the above-described invention, wherein the raw material parts are in parts by weight unless otherwise specified.

In a specific embodiment, the halloysite nanotube (i.e., the unmodified halloysite in the invention) is a high-purity product provided by Guangzhou Runwo materials science and technology Limited, and has a diameter of 40-80 nm and a length of 200-1000 nm; cobalt nitrate is an analytical pure-grade reagent provided by chemical corporation of Shirong; DMF (N, N-dimethylformamide) is an analytical pure grade reagent provided by chemical corporation, julong; aminotrimethylene phosphate was used as a product provided by Shanghai Michelin Biochemical technology Ltd.

Example (b):

a preparation method of multifunctional halloysite hybrid particles comprises the following steps:

(1) preparation of a reaction mixture: dispersing 6.25 parts of halloysite nanotubes in 2300 parts by mass of a mixture of the following components in percentage by mass: 1900, adding 3 parts of cobalt nitrate into a composite solvent of deionized water and DMF, stirring for 3 hours, uniformly mixing, adding 4 parts of aminotrimethylene phosphoric acid, stirring for 1 hour, and uniformly mixing to obtain a reaction mixed solution;

(2) preparation of multifunctional halloysite hybrid particles: and (2) placing the reaction mixed solution obtained in the step (1) into a reaction kettle, heating to carry out a solvothermal reaction at the temperature of 140 ℃ for 18 hours, then cooling to room temperature, carrying out centrifugal separation, washing and drying to obtain the multifunctional halloysite hybrid particles.

The unmodified halloysite has the diameter of 40-80 nm, the length of 200-1000 nm and a smooth surface; the surface of the modified halloysite, namely the multifunctional halloysite hybrid particle prepared by the invention is covered with a layer of particles, and the surface becomes rougher (see figure 1); FIG. 2 is an infrared spectrum of a multifunctional halloysite hybrid particle prepared according to the invention; the results show that the multifunctional halloysite hybrid particles prepared by the invention have different structures compared with unmodified halloysite.

The color of the unmodified halloysite is white, and the color is not changed after the unmodified halloysite is exposed in an ammonia environment; the color of the modified halloysite, namely the multifunctional halloysite hybrid particle prepared by the method, is bluish purple, and the color of the modified halloysite is quickly changed into tan within 1min after the modified halloysite is exposed to an ammonia gas environment, so that the multifunctional halloysite hybrid particle product has excellent ammonia gas response performance.

Evaluating the antibacterial performance of the product by adopting an antibacterial activity experimental method of a bacteriostatic zone; the inhibition zones of unmodified halloysite to escherichia coli and staphylococcus aureus are both 0mm, and the diameters of the inhibition zones of the modified halloysite, namely the multifunctional halloysite hybrid particle product prepared by the method to escherichia coli and staphylococcus aureus can reach 16.5mm and 33mm respectively, so that the multifunctional halloysite hybrid particle product is excellent in antibacterial effect.

Evaluating the ultraviolet-visible performance of the product by adopting an ultraviolet-visible spectrometer (Lamdba365, platinum Elmer instruments Co.); FIG. 5 is a UV-Vis spectrum of unmodified halloysite and aqueous dispersions of multifunctional halloysite hybrid particles prepared according to the invention; the result shows that compared with unmodified halloysite, the multifunctional halloysite hybrid particle product prepared by the method has obviously improved ultraviolet absorption performance.

The thermal stability of the product was evaluated using a thermogravimetric analyzer (SDT-Q600, TA corporation, usa); the results show that the multifunctional halloysite hybrid particles prepared by the invention have somewhat reduced thermal stability but still maintain higher thermal stability compared with unmodified halloysite (see fig. 6).

In conclusion, the multifunctional halloysite hybrid particle prepared by the invention has excellent antibacterial property, ammonia response property and ultraviolet absorption property, is simple in preparation process, environment-friendly and low in cost, is suitable for amplification production, and has wide application prospects in the fields of gas sensing, biomedical treatment, environmental safety and the like.

The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.