阅读说明：本技术 一种二维材料掺杂多元组凝胶玻璃的制备方法 (Preparation method of two-dimensional material doped multicomponent gel glass ) 是由 郑婵 王亭亭 李巍 陈文哲 于 2019-11-28 设计创作，主要内容包括：本发明公开了一种二维材料掺杂多元组玻璃的制备方法,其以正硅酸乙酯、钛酸丁酯、醋酸铅为先驱体,乙醇作为溶剂,采用溶胶-凝胶湿化学工艺将Pb<Sup>2+</Sup>、Ti<Sup>4+</Sup>、Zr<Sup>3+</Sup>等第二或第三组分引入二氧化硅凝胶基质中,并且将二维材料掺杂入其中,从而制备出一种二维材料掺杂的Si-Pb、Si-Ti、Si-Ti-Pb等凝胶体系的无机凝胶玻璃。其具有良好的化学稳定性,微孔散射少,在可见光区透明性良好,且工艺简单、成本低,为凝胶玻璃带来一些新的光学特性,拓展了其在非线性光学领域的应用。(The invention discloses a preparation method of two-dimensional material doped multi-element glass, which takes tetraethoxysilane, tetrabutyl titanate and lead acetate as precursors, ethanol as a solvent and adopts a sol-gel wet chemical process to lead (Pb) to 2+ 、Ti 4+ 、Zr 3+ And introducing the second or third components into the silica gel matrix, and doping the two-dimensional material into the silica gel matrix, thereby preparing the inorganic gel glass of the two-dimensional material doped Si-Pb, Si-Ti-Pb and other gel systems. The preparation method has the advantages of good chemical stability, less micropore scattering, good transparency in a visible light region, simple process and low cost, brings some new optical characteristics for the gel glass, and expands the application of the gel glass in the field of nonlinear optics.)

1. The preparation method of the two-dimensional material doped multi-element glass is characterized by comprising the following steps of: the method comprises the following steps:

(1) preparing precursor liquid: weighing tetraethyl orthosilicate, absolute ethyl alcohol and deionized water, and pouring the tetraethyl orthosilicate, the absolute ethyl alcohol and the deionized water into a clean beaker in sequence to be mixed and stirred uniformly to obtain precursor solution;

(2) introduction of two-dimensional material: uniformly mixing and stirring the two-dimensional material and N, N-dimethylformamide to obtain a dispersion liquid of the two-dimensional material in the N, N-dimethylformamide;

(3) introduction of heavy metal ions: dissolving heavy metal alkoxide in an organic solvent, and uniformly stirring;

(4) preparing two-dimensional material doped multi-component glass: and (3) mixing a proper amount of precursor liquid obtained in the step (1) with the solution obtained in the step (2) and the step (3), dropwise adding a catalyst, magnetically stirring, fully hydrolyzing and polycondensing tetraethyl orthosilicate, standing to form gel, and standing, aging and drying to obtain the two-dimensional material doped multicomponent glass.

2. The method of claim 1, wherein the two-dimensional material is doped with multiple glass elements, and the method comprises the following steps: the molar ratio of ethyl orthosilicate, absolute ethyl alcohol and water in the step (1) is 1: 5: 5.

3. the method of claim 1, wherein the two-dimensional material is doped with multiple glass elements, and the method comprises the following steps: the two-dimensional material introduced in the step (2) can be graphene, molybdenum disulfide or black phosphorus.

4. The method of claim 1, wherein the two-dimensional material is doped with multiple glass elements, and the method comprises the following steps: the heavy metal ion in the heavy metal alkoxide in the step (3) can be Pb²⁺、Ti⁴⁺、Zr³⁺And the like.

5. The method of claim 1, wherein the two-dimensional material is doped with multiple glass elements, and the method comprises the following steps: in the step (3), the organic solvent is one or a mixture of more of ethylene glycol monomethyl ether, glacial acetic acid and acetylacetone.

6. The method of claim 1, wherein the two-dimensional material is doped with multiple glass elements, and the method comprises the following steps: the catalyst dripped in the step (4) is nitric acid.

7. A two-dimensional material doped multi-component glass prepared by the preparation method of any one of claims 1 to 6.

Technical Field

The invention belongs to the technical field of sol-gel glass, and particularly relates to a preparation method of two-dimensional material doped multicomponent glass.

Background

In recent years, two-dimensional materials having a unique layered structure, such as graphene, have been found to be drawing attention from researchers in a variety of fields, such as physics, chemistry, materials, and electronics. The two-dimensional material has excellent optical, electrical, thermal and mechanical properties, so that the two-dimensional material has wide application in the fields of high-performance micro-nano electronic devices, composite materials, field effect transistors, sensors, energy storage, biological medicines and the like. The two-dimensional material also has excellent nonlinear optical amplitude limiting performance, and can effectively prevent optical devices or human eyes from being damaged under broadband high-energy pulse laser. With the continuous development of laser technology, the research on the properties and the practical application of two-dimensional materials with good nonlinear optical limiting performance are increasingly shown in people, and the research on the nonlinear optical performance of two-dimensional materials has become one of the hottest directions of nanotechnology research. However, its research in the field of nonlinear optics has mainly focused on liquid matrices, which, although they allow the composite material to recover rapidly from laser irradiation and provide considerable convenience for studying its properties and mechanism, solution testing environments generally do not represent practical environments in device integration and other applications, and furthermore the effects of organic solvent volatilization on human body and environment cannot be ignored. In contrast, solid state testing has greater practical value for fabricating device components and for studying basic optoelectronic mechanisms. Therefore, the research hot spot of nonlinear optics is gradually transferred to the solid phase matrix, and lays a foundation for the practical application of the material.

The silica gel glass has excellent physical and chemical properties, excellent optical stability and high transparency, and can be used as an ideal substrate for the solid phase of a nonlinear optical amplitude limiting material. If Pb is introduced into the silica gel system²⁺、Ti^4+、Zr³⁺The heavy metal ions may bring some new optical characteristics to the gel glass so as to expand the application of the gel glass in the field of nonlinear optics. Therefore, the prepared two-dimensional material-doped gel glass has the advantages of simple process, low cost and good nonlinear optical performance, can provide a high-quality solid-state composite light amplitude limiting material, and provides a new idea for materialization and device formation.

Disclosure of Invention

The invention aims to provide a preparation method of two-dimensional material doped multi-element glass, which takes tetraethoxysilane as a precursor and ethanol as a solvent and adopts sol-gel wet chemical technologyProcess for preparing Pb from²⁺、Ti⁴⁺、Zr³⁺And introducing the second or third components into the silica gel matrix, and doping the two-dimensional material into the silica gel matrix, thereby preparing the inorganic gel glass of the two-dimensional material doped Si-Pb, Si-Ti-Pb and other gel systems.

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

a preparation method of two-dimensional material doped multi-element glass comprises the following steps:

(1) preparing precursor liquid: pouring a proper amount of tetraethyl orthosilicate, absolute ethyl alcohol and deionized water into a clean beaker in sequence, and uniformly mixing and stirring to obtain a precursor solution;

(2) introduction of two-dimensional material: uniformly mixing and stirring the two-dimensional material and a proper amount of N, N-dimethylformamide to obtain a dispersion liquid of the two-dimensional material in the N, N-dimethylformamide;

(3) introduction of heavy metal ions: mixing and stirring a proper amount of heavy metal alkoxide uniformly;

(4) preparing two-dimensional material doped multi-component glass: and (3) mixing a proper amount of precursor liquid obtained in the step (1) with the solution obtained in the step (2) and the step (3), dropwise adding a catalyst, magnetically stirring for several hours, standing for gelling after the tetraethyl orthosilicate is fully hydrolyzed and condensed, and standing, aging and drying to obtain the two-dimensional material doped multicomponent glass.

Further, in the precursor solution in the step (1), ethyl orthosilicate: anhydrous ethanol: the molar ratio of water is 1: 5: 5.

Further, the DMF in step (2) was taken in an amount of 1/2 volumes of anhydrous ethanol.

Further, nitric acid in step (4) is used as a catalyst to control the pH value.

The two-dimensional material doped multicomponent glass prepared by the preparation method has good optical transparency, photochemical stability and thermal stability, and Pb is introduced into a silicon dioxide gel system²⁺、Ti⁴⁺The two-dimensional material is doped with the same heavy metal ions, so that the two-dimensional material can be subjected to solid phase formation on the one hand and the gel glass belt on the other handAnd the application of the optical fiber in the field of nonlinear optics is expanded due to some new optical characteristics.

Drawings

FIG. 1 is a FESEM image of graphene doped Si-Pb binary composite gel glass;

FIG. 2 is a diagram of UV-Vis transmission spectra of Si-Pb, Si-Ti and Si-Ti-Pb gel system glasses;

FIG. 3 is a TGA graph of two-dimensional material doped Si-Pb, Si-Ti and Si-Ti-Pb gel system glass;

FIG. 4 is a FT-IR spectrum of two-dimensional material doped Si-Pb, Si-Ti and Si-Ti-Pb gel system glass.

Detailed Description

In order to facilitate an understanding of the present invention, the following examples are provided to further illustrate the present invention, but are not intended to limit the scope of the present invention.