CN112707434B - Preparation method of nano tin dioxide with large specific surface area - Google Patents
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Abstract
The invention relates to a preparation method of nano tin dioxide with large specific surface area, which comprises the following steps: dissolving analytically pure tin tetrachloride pentahydrate in pure water to obtain a tin tetrachloride solution with the concentration of 3-5 mol/L; adding a precipitator, controlling the reaction temperature to be 60-80 ℃, and controlling the pH value of the reaction liquid to be 6.5-7.5; adding a conversion agent, controlling the pH value of the feed liquid to be 9.0-10.0, heating to near boiling, and preserving heat for 20-30 min; adding a neutralizing agent, and controlling the pH value of the feed liquid to be 6.5-7.5; cleaning, filtering and drying; decomposing, cooling, pulverizing, and sieving. The preparation method disclosed by the invention is wide in raw material source, simple in process, mild in reaction condition, safe and pollution-free, and the prepared nano tin dioxide has the purity of over 99.995%, the particle size of 8-10 nm, the specific surface area of over 65 square meters per gram and the highest specific surface area of up to 100 square meters per gram, so that the requirement of a gas sensitive material with higher sensitivity can be met.
Description
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a preparation method of nano tin dioxide with large specific surface area.
Background
Tin dioxide (SnO) 2 ) The n-type metal oxide semiconductor is rich in raw materials, low in price, non-toxic and wide in forbidden band (Eg ═ 3.60 eV). Due to the potential application prospect in many fields, such as optical waveguide, solar cell, transistor and gas sensor, tin dioxide is attracting the attention of scientists, and one of the most important applications is to manufacture the gas sensor of the gas sensor. SnO 2 As a common oxide semiconductor, the microscopic action mechanism is mainly caused by the surface desorption of particles in the ambient atmosphere, the larger the specific surface of the particles is, the higher the sensitivity is, so that the nano SnO with the large specific surface is prepared 2 Becomes an effective way for improving the gas sensitivity.
At present, various synthetic routes are available for preparing nano tin dioxide, however, many synthetic methods have defects and shortcomings. In hydrothermal synthesis, the concentration of the precursor is low enough to obtain the nanostructure, but this in turn limits the application of these materials. Therefore, obtaining good morphology and high yield, high quality nano tin dioxide material remains a challenge in the field of material science. The traditional tin dioxide preparation process can not meet the requirement of grain size, and the purity is difficult to ensure. In recent years, various methods for producing nano tin dioxide have been developed, and the methods can be classified into a solid phase method, a liquid phase method, and a gas phase method according to the state of raw materials. The common methods include sol-gel method, micro-emulsion method, supercritical fluid drying method, arc gasification synthesis method, chemical precipitation method, hydrothermal method, etc. The existing tin dioxide has a plurality of related patents, but the existing method has the problems of complex process, high energy consumption, high cost, use of organic solvent and the like. For example: chinese patent CN102267718A discloses a synthesis method of a stannic oxide nano material, which takes stannous sulfate as a tin source and trisodium citrate dihydrate as a chelating agent to prepare the monodisperse stannic oxide nano material by a hydrothermal method. Chinese patent CN100354208C discloses a method for preparing stannic oxide nano-rod, which takes stannic chloride as a tin source and mixes hydrogen and airThe synthesis gas is used as a medium, and the stannic oxide nano-rods are generated in the combustion reactor. Chinese patent CN1297484C discloses a method for preparing a one-dimensional nano tin dioxide material, which comprises using tin tetrachloride as a tin source, using ammonia water as a precipitant, adding oxalic acid to form a sol, aging to form a gel, drying and sintering to obtain a target product. Chinese patent CN1260133C discloses a method for preparing nano SnO by precipitation method by using metallic tin powder/particles as raw material 2 The method has the advantages of relatively simple process, short production period and suitability for large-scale production. However, because the method adopts tin powder/particles as raw materials, the production cost is still higher; in addition, because the method cannot solve the problem of particle agglomeration in the chemical precipitation process, the generated precursor is washed, dried and then ground and sieved to obtain the nano SnO with fine particle size 2 The powder has unsatisfactory product yield and still complex operation. Chinese patent CN100537431 discloses a method for preparing nano tin dioxide, which adopts soluble tin salt as a tin source to prepare a tin salt solution with the concentration of 0.1-0.5 mol/L, adds a dilute acid solution, then adds 0-10 g/L of surfactant, drops a precipitator solution, adjusts the pH value to 2.5-10, and reacts with the constant temperature of 20-80 ℃ under magnetic stirring to generate a precursor; filtering, washing with deionized water, ultrasonic washing with absolute ethyl alcohol, drying, and roasting the obtained product to obtain nano SnO 2 And (5) finishing. The invention has the advantages that the soluble tin salt is adopted as the raw material, the price is low, and the cost is low; the precursor does not need to be ground and sieved, the product yield is high, the process is simpler, and the obtained nano SnO 2 The particle size of the particles is more uniform; the method has the disadvantages that the surfactant is required to be added, the organic solvent is adopted, the purity of the product is influenced, and the method is not environment-friendly; the particle size of the prepared powder particles is 10-30 nm, but the specific surface area is small, so that the requirement of a gas-sensitive material with higher sensitivity is difficult to meet.
Disclosure of Invention
The invention aims to provide a preparation method of nano tin dioxide with large specific surface area, which has the advantages of low cost, simple production process, convenient operation, safety and no pollution, and solves the problems of complex process, generally low specific surface area and the like in the prior art of common tin dioxide.
The technical scheme adopted by the invention is as follows:
a preparation method of nano tin dioxide with large specific surface area comprises the following steps:
s1: dissolving: dissolving analytically pure tin tetrachloride pentahydrate in pure water to obtain a tin tetrachloride solution with the concentration of 3-5 mol/L;
s2: and (3) precipitation: adding a precipitator into the solution, controlling the reaction temperature to be 60-80 ℃, the reaction time to be 30-50 min, continuously stirring until the precipitation is complete, and controlling the pH value of the feed liquid to be 6.5-7.5;
s3: and (3) transformation: adding a conversion agent into the feed liquid, controlling the pH value of the feed liquid to be 9.0-10.0, heating to be close to boiling, and then preserving heat for 20-40 min;
s4: neutralizing: adding a neutralizing agent into the feed liquid, and controlling the pH of the feed liquid to be 6.5-7.5;
s5: cleaning, filtering and drying: carrying out liquid-solid separation on the feed liquid after the neutralization reaction is finished, washing filter residues until no chloride ions exist, and then drying to obtain dry powder;
s6: and (3) decomposition and crushing: calcining and decomposing the dried powder at 300-600 ℃, and preserving heat for 50-70 min; and cooling the completely decomposed material to room temperature, and then crushing and screening to obtain the nano tin dioxide powder.
Further, in the step S1, the saturated solution of tin tetrachloride is prepared from analytically pure tin tetrachloride pentahydrate crystals.
Further, in step S2, the precipitant is one of ammonium bicarbonate, sodium bicarbonate or potassium bicarbonate.
Further, the precipitant is ammonium bicarbonate.
Further, in the step S2, the stirring speed is 50-100 r/min.
Further, in step S3, the converting agent is ammonia water.
Further, in the step S3, the temperature rise rate is 5-10 ℃/min.
Further, in step S4, the neutralizing agent is acetic acid.
Further, in the step S5, the drying temperature is 50-150 ℃.
Further, in the step S5, the drying is performed under a pressure of-0.1 to 1.0 MPa.
Further, in the step S6, the particle size of the nano tin dioxide powder is 8 to 10 nm.
The invention has the beneficial effects that:
1. the initial concentration of the tin ion concentration has certain influence on the quality of the nano ITO product, the tin ion concentration is too low, the reaction rate and the conversion rate are low, impurities are easy to adsorb, the tin ion concentration is too high, and agglomeration is easy to generate.
2. The method adopts a weakly alkaline substance as a precipitator, the reaction is carried out under a near-neutral condition, the reaction condition is mild, the particle size of the product basic carbonate is relatively uniform, but the basic carbonate contains much crystal water and is difficult to clarify and difficult to filter; the invention adds ammonia water to convert the precipitate, and has three advantages, firstly, under the condition of adding ammonia water and heating to be close to boiling, the invention can promote the produced basic carbonate precipitate to be completely converted into hydroxide precipitate, the conversion is carried out between solid phases, and the generated hydroxide has fine particle size, is loose and porous, thereby increasing the specific surface area; secondly, a buffer solution can be formed by the buffer solution and the ammonium chloride in the solution, and the pH value of the solution is controlled to be 9-10.0, so that metal impurities such as zinc, copper, cobalt, nickel and the like can be effectively separated, and the purity of the product is improved; thirdly, adding ammonia water can further convert the unreacted tin ions into tin hydroxide precipitates, thereby improving the product yield. The hydroxide precipitate does not contain crystal water, and the solution is adjusted to be neutral by acid, so that the problems that the product is not easy to filter and the impurities are not easy to clean can be well solved.
3. The invention reasonably designs a process combining precipitation and conversion, wherein the precipitation step adopts a low-temperature high-rotation-speed process, and regular fine-particle carbonate crystal seeds can be prepared; the nucleation speed of the hydroxide can be accelerated and promoted by the action of the crystal seeds and the reasonable control of the temperature rise rate in the conversion process, and the problem of uneven particle size distribution is effectively avoided.
4. The method has the advantages of mild reaction conditions, smooth operation process, good continuity, low cost, simple production process and convenient operation, can prepare the high-performance nano tin dioxide with the purity of more than 99.995 percent, the particle size of less than 10nm, the minimum size of 8nm, the specific surface area of more than 65 square meters per gram and the maximum size of 100 square meters per gram as described in the embodiment 4, can meet the requirements of gas-sensitive materials with higher sensitivity, has a larger prospect and is suitable for popularization and application.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
A preparation method of nano tin dioxide with large specific surface area comprises the following steps:
s1: dissolving: dissolving analytically pure tin tetrachloride pentahydrate in pure water to obtain a tin tetrachloride solution with the concentration of 3 mol/L;
s2: and (3) precipitation: adding sodium bicarbonate into the solution, controlling the reaction temperature at 60 ℃, the reaction time at 30min, continuously stirring at the stirring speed of 50r/min until the precipitation is complete, and controlling the pH value of the feed liquid at 6.5;
s3: and (3) transformation: adding ammonia water into the feed liquid, controlling the pH value of the feed liquid to be 9.0, heating to be close to boiling, wherein the heating rate is 5 ℃/min, and then keeping the temperature for 20 min;
s4: neutralizing: adding acetic acid into the feed liquid, and controlling the pH of the feed liquid to be 6.5;
s5: cleaning, filtering and drying: carrying out liquid-solid separation on the feed liquid after the neutralization reaction is finished, washing filter residues by deionized water until no chloride ion exists, and then drying at 50 ℃ and-0.1 MPa to obtain dry powder;
s6: and (3) decomposition and crushing: calcining the dried powder at 300 deg.C for decomposition, and maintaining the temperature for 50 min; cooling the completely decomposed materials to room temperature, and then crushing and screening to obtain the nano tin dioxide powder with the particle size of 10nm and the specific surface area of 100 square meters per gram.
Example 2
A preparation method of nano tin dioxide with large specific surface area comprises the following steps:
s1: dissolving: dissolving analytically pure tin tetrachloride pentahydrate in pure water to obtain a tin tetrachloride solution with the concentration of 4 mol/L;
s2: and (3) precipitation: adding ammonium bicarbonate into the solution, controlling the reaction temperature at 70 ℃, the reaction time at 40min, continuously stirring at the stirring speed of 80r/min until the precipitation is complete, and controlling the pH value of the feed liquid at 7.0;
s3: and (3) transformation: adding ammonia water into the feed liquid, controlling the pH value of the feed liquid to be 9.5, heating to be close to boiling, wherein the heating rate is 8 ℃/min, and then preserving heat for 30 min;
s4: neutralizing: adding acetic acid into the feed liquid, and controlling the pH value to be 7.0;
s5: cleaning, filtering and drying: carrying out liquid-solid separation on the feed liquid after the neutralization reaction is finished, washing filter residues by deionized water until no chloride ion exists, and then drying at 100 ℃ and-0.05 MPa to obtain dry powder;
s6: and (3) decomposition and crushing: calcining the dried powder at 450 deg.C for decomposition, and maintaining the temperature for 60 min; cooling the completely decomposed materials to room temperature, and then crushing and screening to obtain the nano tin dioxide powder with the particle size of 8nm and the specific surface area of 78 square meters per gram.
Example 3
A preparation method of nano tin dioxide with large specific surface area comprises the following steps:
s1: dissolving: dissolving analytically pure tin tetrachloride pentahydrate in pure water to obtain a tin tetrachloride solution with the concentration of 5 mol/L;
s2: and (3) precipitation: adding potassium bicarbonate into the solution, controlling the reaction temperature at 80 ℃, the reaction time at 50min, continuously stirring at the stirring speed of 100r/min until the precipitation is complete, and controlling the pH value of the feed liquid at 7.5;
s3: and (3) transformation: adding ammonia water into the feed liquid, controlling the pH value of the feed liquid to be 10.0, heating to be close to boiling, wherein the heating rate is 10 ℃/min, and then preserving heat for 30 min;
s4: neutralizing: adding acetic acid into the feed liquid, and controlling the pH value to be 7.5;
s5: cleaning, filtering and drying: carrying out liquid-solid separation on the feed liquid after the neutralization reaction is finished, washing filter residues by using deionized water until no chloride ion exists, and then drying at 150 ℃ under 1.0MPa to obtain dry powder;
s6: and (3) decomposition and crushing: calcining the dried powder at 600 deg.C for decomposition, and maintaining the temperature for 70 min; cooling the completely decomposed materials to room temperature, and then crushing and screening to obtain the nano tin dioxide powder with the particle size of 9nm and the specific surface area of 65 square meters per gram.
Comparative example 1
Essentially the same as example 2, except that no conversion and neutralization steps were included.
Comparative example 2
The method of example 8 in the Chinese patent application document "a method for preparing nano tin dioxide (publication number: CN 100537431)" is adopted to prepare the nano tin dioxide.
Example 4 comparative experiment
ICP-MS is adopted to carry out powder chemical element analysis detection and calculation, TEM is adopted to measure the particle size of the powder, a specific surface area tester is adopted to measure the specific surface area of the powder, and the purity, the particle size and the specific surface area of the nano tin dioxide powder prepared in the examples 1-3 and the comparative examples 1-2 are obtained, and the results are shown in Table 1.
TABLE 1 comparison of Properties of products prepared in examples 1 to 3 and comparative examples 1 to 2
| Group of | Purity/%) | Particle size/nm | Sintering temperature/. degree.C | Specific surface area per square meter per gram |
| Comparative example 1 | 99.99 | 12 | 450 | 15 |
| Comparative example 2 | 99.99 | 15 | 600 | 10 |
| Example 1 | 99.995 | 10 | 300 | 100 |
| Example 2 | 99.996 | 8 | 450 | 78 |
| Example 3 | 99.996 | 9 | 600 | 65 |
As can be seen from Table 1, compared with comparative examples 1 and 2, the nano tin dioxide powder prepared in the embodiments 1 to 3 of the present invention has greatly improved purity, specific surface area and target relative density, and is superior to comparative examples 1 and 2. The method converts the basic carbonate precipitate into hydroxide precipitate through the steps of conversion and neutralization, the converted substance is carried out between solid phases, the conversion rate is high, the particle size is fine, the particles are loose and porous, and the filtration is easy, so that the purity and the specific surface area are improved, the purity is over 99.995 percent, the specific surface area is over 65 square meters per gram, and the maximum is up to 100 square meters per gram.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. A preparation method of nano tin dioxide with large specific surface area is characterized by comprising the following steps:
s1: dissolving: dissolving analytically pure tin tetrachloride pentahydrate into pure water to obtain a tin tetrachloride solution with the concentration of 3-5 mol/L;
s2: and (3) precipitation: adding a precipitator into the solution, controlling the reaction temperature to be 60-80 ℃, the reaction time to be 30-50 min, continuously stirring until the precipitation is complete, and controlling the pH value of the feed liquid to be 6.5-7.5;
s3: and (3) transformation: adding a conversion agent into the feed liquid, controlling the pH value of the feed liquid to be 9.0-10.0, heating to be close to boiling, and then preserving heat for 20-40 min;
s4: neutralizing: adding a neutralizing agent into the feed liquid, and controlling the pH of the feed liquid to be 6.5-7.5;
s5: cleaning, filtering and drying: carrying out liquid-solid separation on the feed liquid after the neutralization reaction is finished, washing filter residues until no chloride ions exist, and then drying to obtain dry powder;
s6: and (3) decomposition and crushing: calcining and decomposing the dried powder at 300-600 ℃, and preserving heat for 50-70 min; cooling the completely decomposed materials to room temperature, and then crushing and screening to obtain nano tin dioxide powder;
in step S2, the precipitant is one of ammonium bicarbonate, sodium bicarbonate or potassium bicarbonate; the stirring speed is 50-100 r/min;
in the step S3, the transforming agent is ammonia water; the temperature rise rate is 5-10 ℃/min.
2. The method for preparing nano tin dioxide with large specific surface area according to claim 1, wherein the method comprises the following steps: the precipitant is ammonium bicarbonate.
3. The method for preparing nano tin dioxide with large specific surface area according to claim 1, wherein the method comprises the following steps: in step S4, the neutralizing agent is acetic acid.
4. The method for preparing nano tin dioxide with large specific surface area according to claim 1, wherein the method comprises the following steps: in the step S5, the drying temperature is 50-150 ℃.
5. The preparation method of the nano tin dioxide with large specific surface area according to claim 1, characterized in that: in the step S5, the drying is performed under a pressure of-0.1 to 1.0 MPa.
6. The method for preparing nano tin dioxide with large specific surface area according to claim 1, wherein in step S6, the particle size of nano tin dioxide powder is 8-10 nm.
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