CN1297484C

CN1297484C - Process for preparing one-dimensional nano tin dioxide material

Info

Publication number: CN1297484C
Application number: CNB2005100211198A
Authority: CN
Inventors: 刘春明; 祖小涛
Original assignee: University of Electronic Science and Technology of China
Current assignee: University of Electronic Science and Technology of China
Priority date: 2005-06-21
Filing date: 2005-06-21
Publication date: 2007-01-31
Anticipated expiration: 2025-06-21
Also published as: CN1724383A

Abstract

The present invention discloses a method for preparing nanometer SnO2 materials with a one-dimensional structure. The present invention has the preparation process flow that SnC1<4>*5H2O is prepared into solution and is added with ammonia water for forming deposition; chloride ions are removed by washing in a centrifugal mode; oxalic acid is added to the solution so as to form sol which forms gel by aging; a target product is finally obtained by drying and sintering the gel. The present invention has the technical scheme that nanometer SnO2 materials with a one-dimensional structure and high purity are prepared by controlling kinetics factors of chemical reaction. The invention has the advantages of simple preparing technology, mild reaction condition, low cost of raw materials and equipment, etc. The nanometer SnO2 materials with a one-dimensional structure prepared by the method of the present invention have an application prospect in the aspects of gas sensors with high sensitivity, transparent electrodes, etc.

Description

Method for preparing one-dimensional nano tin dioxide material

Technical Field

The invention belongs to the technical field of nano oxide semiconductor materials, and particularly relates to a method for preparing one-dimensional SnO₂The method of (1).

Background

SnO₂The semiconductor material is a wide-bandgap semiconductor material, is widely used as a gas sensor, and has some unique properties, such as high conductivity, high transmittance, good chemical and thermal stability, etc., which can be applied to many technical fields, including solar cells, liquid crystal displays, photodetectors, protective coatings, etc. Due to the nano SnO₂Because of having larger specific surface area and higher activity, the nano-silver particles have wide application prospect in the aspects of gas sensitivity, electric conduction and photosensitive absorption. Recently, SnO with one-dimensional structure is concerned due to unique physical properties and potential application prospect₂(nanowires or nanobelts) are favored. It has been shown that SnO has a one-dimensional structure₂Has extremely high gas-sensitive property and good thermal stability, and not only has high gas-sensitive property to CO and NO as environmental pollution gases₂The method has very high sensitivity, can analyze ethanol, and can be used for food control and breath atmosphere detection. For example, with a single SnO under UV irradiation₂The sensor made of the nanobelt can detect NO with ppm level at room temperature₂And has the advantages of small volume, rapidness, sensitivity and the like.

Reported preparation of SnO₂Methods for nanomaterials are numerous, but mainly involve molten salt methods and gas phase evaporation methods.

Molten salt method with nano SnO₂The powder is used as a precursor, KCl is used as a molten salt medium, and the nano wire rod can be obtained by annealing treatment at 800 ℃. The limitation of this approach is that the precursor particles must be small enough that nanowires are not available if the particle size exceeds 100 nm.

The vapor phase evaporation method uses Sn, SnO and SnO₂Or their mixture as starting material, the tube furnace is first evacuated to 1X 10^-3About torr, argon and oxygen are filled according to a certain proportion, and thenThe raw material is vaporized at high temperature in a tube furnace, the vaporization temperature is different according to the raw material, if pure SnO is used₂As raw material, the evaporation temperature is above 1300 ℃. The raw material vapor is carried by argon gas and deposited on the single crystal Al₂O₃Single crystal LaAlO₃Or a single crystal Si substrate, the substrate temperature being maintained at 900 deg.C-950 deg.C. The method can obtain nano SnO with various structures such as nano wires, nano belts, nano particles and the like₂A material. The vapor phase evaporation method requires high temperature, vacuum and other process conditions, requires a raw material with a purity of 99.9% or more, and requires a single crystal substrate, so that the equipment and production costs are expensive.

Therefore, how to develop a method for preparing nano SnO with one-dimensional structure, which has the advantages of simple equipment requirement, mild reaction condition,cheap and easily-obtained raw materials and capability of realizing large-scale production₂The method of material is an urgent problem to be solved.

The sol-gel method is a wet chemical method, and compared with other methods, the method has the advantages of simple equipment, good chemical uniformity of the product, high purity, convenient doping or co-doping, and capability of preparing large-area films.

So far, the sol-gel method for preparing nano SnO with one-dimensional structure is not seen₂And (5) research reports of materials.

Disclosure of Invention

The invention aims to provide a method for preparing one-dimensional nano SnO, which has the advantages of simple equipment requirement, mild reaction condition, cheap and easily obtained raw materials and capability of realizing large-scale production₂A method of making a material.

The specific technical scheme of the invention is to prepare high-purity nano SnO with a one-dimensional structure by controlling the kinetic factors of chemical reaction₂A material.

The specific preparation steps are shown in figure 1:

first, prepare SnCl₄An aqueous solution. Using SnCl₄·5H₂Dissolving O as raw material in distilled water to obtain SnCl with certain concentration₄Solution and adjusting the P of the solution with a weak acidH value, and the PH value of the mixture is controlled to be between 1 and 2. In order to obtain high purity SnO₂High purity SnCl should be used₄·5H₂O starting material, preferably analytically pure SnCl₄·5H₂O; the purpose of adjusting pH with weak acid is to prevent SnCl₄And (4) hydrolyzing.

Secondly, adding ammonia water until the pH value of the solution is between 7 and 8, and reacting to generate Sn (OH)₄And (4) precipitating. The ammonia water is preferably added in a slow dropwise manner while stirring, and the whole reaction process is preferably carried out at a temperature of about 50 ℃.

Third, take out Sn (OH)₄The precipitate was washed by centrifugation. Using a centrifugal device, mixing Sn (OH)₄The precipitate was washed centrifugally to remove Sn (OH)₄The chloride ions adsorbed on the precipitate can be washed with AgNO₃The solution was checked and no new precipitate (AgCl) was produced, and the centrifugation wash process could be terminated.

The three steps can be summarized as preparing Sn (OH)₄Raw materials, in the actual production process, other direct or indirect methods can also be adopted to prepare Sn (OH)₄。

Fourthly, preparation of Sn (OH)₄And (3) sol. A reaction product of Sn (OH)₄Adding into oxalic acid solution, controlling pH value at 1-2, controlling temperature at about 50 deg.C, ultrasonically dispersing, and stirring to form Sn (OH)₄And (3) sol.

And fifthly, forming gel. And aging the sol prepared in the fourth step for 24-48h to form gel.

Sixthly, drying and grinding. And (4) drying the gel obtained in the fifth step for 5-8h at the temperature of more than 100 ℃, removing adsorbed water, and grinding the obtained product into powder.

And seventhly, drying and sintering. Mixing the powder obtained in the sixth step (Sn (OH)₁) Sintering at 250-500 deg.C to make it lose water content, recrystallizing to obtain target product (SnO)₂). The chemical reaction that takes placetherein is:

the essence of the invention is thatPreparing nano SnO with one-dimensional structure by sol-gel method under environment₂A material.

The invention has the beneficial effects that:

the rutile type SnO can be successfully prepared by a sol-gel method₂One-dimensional structure, fig. 2 is the X-ray diffraction pattern of the sample obtained through the above steps, all the diffraction peaks correspond to the rutile phase, no diffraction peak of the hetero-phase is found, which shows that the purity of the sample obtained by the present invention is very high. Nano SnO prepared by the invention₂Has abundant morphological structure, which is similar to the structure obtained by a gas phase evaporation method. It not only contains nano-rods and spherical nano-particles (as shown in FIG. 3), but also contains SnO with one-dimensional structure₂(as shown in fig. 4). The nano-rod has a diameter of about 40nm, a length of about 400nm, a nano-particle size of about 10nm, and a one-dimensional structure of SnO₂The width is about 40 nanometers and the length is at least in the micrometer range.

The sol-gel method provided by the invention is used for preparing SnO with one-dimensional structure₂The method has the advantages of simple preparation process, mild reaction conditions and low cost of raw materials and equipment, so the method has great popularization and application values.

Drawings

FIG. 1 is a schematic view of the process of the present invention;

FIG. 2 shows nano SnO₂X-ray diffraction patterns of (a);

FIG. 3 is SnO₂Transmission electron microscope photographs of nanorods and nanoparticles;

FIG. 4 is SnO₂Transmission electron microscope photographs of one-dimensional structures;

Detailed Description

Will analyze pure SnCl₄·5H₂Dissolving O in distilled water (pH value is adjusted to 1-2 with hydrochloric acid or citric acid to prevent hydrolysis) to obtain 0.5mol/l solution, heating to about 50 deg.C, maintaining constant temperature, adding 28% ammonia water under vigorous stirringAnd controlling the dropping speed to be about 1ml/min until the pH of the solution is about 7-8 to form a precipitate. The precipitate was washed centrifugally to remove chloride ions (with 0.5mol/l AgNO)₃Solution inspection), adding oxalic acid solution to adjust the pH value to 1-2, performing ultrasonic dispersion, heating to about 50 ℃ under vigorous stirring to form sol, aging the sol for 24-48h to form gel, drying the gel at 100 ℃ for 5-8h, and sintering the gel in a resistance furnace at 250-500 ℃ for 0.5-1h to obtain the target product. XRD is used for analyzing the phase of a sample, Transmission Electron Microscopy (TEM) is used for analyzing the appearance of the sample, X-ray photoelectron spectroscopy (XPS) is used for analyzing the chemical components of the sample, and ultraviolet-visible light absorption spectrum is used for measuring the forbidden bandwidth of the sample.

Claims

1. A method for preparing a one-dimensional nano tin dioxide material is characterized by comprising the following steps:

1) preparing SnCl₄Aqueoussolution

Using SnCl₄·5H₂Dissolving O as raw material in distilled water to obtain SnCl with certain concentration₄Adjusting the pH value of the solution to be between 1 and 2 by weak acid;

2) adding ammonia water until the pH value of the solution is between 7 and 8, and reacting to generate Sn (OH)₄Precipitating;

3) taking out Sn (OH)₄Precipitating, and centrifugally washing the precipitate

Using a centrifugal device, mixing Sn (OH)₄The precipitate was washed centrifugally to remove Sn (OH)₄Precipitating the adsorbed chloride ions;

4) preparation of Sn (OH)₄Sol gel

A reaction product of Sn (OH)₄Adding into oxalic acid solution, controlling pH value between 1-2, controlling temperature at 50 deg.C, ultrasonically dispersing, and stirring to form Sn (OH)₄Sol;

5) forming a gel

Aging the sol prepared in the step four for 24-48h to form gel;

6) drying and grinding

Drying the gel obtained in the fifth step for 5-8h at the temperature of more than 100 ℃, removing the adsorbed water, and grinding the obtained product into powder;

7) drying and sintering

The Sn (OH) obtained in the sixth step₄Sintering the powder at 250-500 ℃, and obtaining the nano SnO with a one-dimensional structure through thermal decomposition and recrystallization₂A material.

2. The method for preparing one-dimensional nano tin dioxide material according to claim 1, wherein analytically pure SnCl is adopted in the step 1)₄·5H₂O; the weak acid is dilute hydrochloric acid or citric acid; the concentration of the solution was 0.5 mol/l.

3. The method for preparing one-dimensional nano tin dioxide material according to claim 1, wherein in the reaction process of the step 2), the reaction temperature is controlled at 50 ℃, and stirring measures are taken; the ammonia water is added in a slow dropping mode, and the concentration of the ammonia water is 28 percent.