CN107607588B - Modified SnO for gas sensors2Nano material - Google Patents
Modified SnO for gas sensors2Nano material Download PDFInfo
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- CN107607588B CN107607588B CN201710611962.4A CN201710611962A CN107607588B CN 107607588 B CN107607588 B CN 107607588B CN 201710611962 A CN201710611962 A CN 201710611962A CN 107607588 B CN107607588 B CN 107607588B
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Abstract
The invention discloses modified SnO for a gas sensor2The preparation method of the nano material comprises the following steps: taking anhydrous stannic chloride as a raw material, taking deionized water and N, N-dimethylformamide as solvents, premixing the solvents with an auxiliary agent, heating the solution, and reacting to obtain SnO2Nano material prepared from SnO2Mixing the nanometer material with urea, and heat treating to obtain g-C3N4Modified SnO2And (3) nano materials. The method is characterized by realizing g-C3N4With SnO2In-situ compounding of nano material while maintaining SnO2Simultaneous achievement of g-C of structural integrity3N4The surface modification of the composite material realizes the construction of the high-sensitivity gas-sensitive material by utilizing the advantages of large specific surface area of the nano material and fast electronic transmission of the composite material. The nano material prepared by the invention can greatly improve SnO2Sensitivity of gas sensitive materials. The preparation method has the characteristics of simple preparation process, low cost, stable product performance and high gas sensitivity.
Description
Technical Field
The invention belongs to qiThe technical field of a gas sensor, in particular to modified SnO for the gas sensor2Nanomaterials, especially g-C for gas sensors3N4Modified SnO2Nano material, and its preparation method and application.
Background
Metal oxides, e.g. ZnO, SnO2、WO3And the gas sensitive material is widely researched due to the advantages of excellent performance, environmental friendliness, rich resources, low price and the like. The gas-sensitive performance of the material can be improved by the processes of metal oxide surface modification, metal/precious metal doping and the like, and the method is widely applied to the field of gas-sensitive sensors.
Key factors determining the sensitivity of semiconductor gas sensitive materials include: the specific surface area is formed by constructing the nano material by a chemical method, so that the material has larger specific surface area, the contact between the material and target gas can be increased, and the sensitivity of the material is further improved; vacancy/defect regulation, the reactivity of the target gas and the sensitive material can be improved by controlling the oxygen vacancy of the system, and the sensitivity of the material can be improved; the composite material is constructed, and the construction of the high-sensitivity gas-sensitive material can be realized by utilizing the advantages of large specific surface area of the nano material and fast electronic transmission of the composite material.
g-C3N4As a new two-dimensional material, the composite material has a very wide application prospect in various fields, and particularly, the composite material is compounded with metal oxide to improve the gas-sensitive property of the material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides modified SnO for a gas sensor2Nanomaterials, i.e. g-C for gas-sensitive sensors3N4Modified SnO2And (3) nano materials.
Yet another object of the present invention is to: providing the modified SnO for gas sensor2Application of nanometer material is provided.
The modified SnO for the gas sensor2The preparation method of the nano material comprises the following steps:
the inventionThe purpose is realized by the following scheme: g-C for gas sensor3N4Modified SnO2The nano material is obtained by the following preparation method, and comprises the following steps:
(1) dissolving anhydrous stannic chloride into 30 mL of premixed solvent by using the anhydrous stannic chloride as a raw material, wherein the concentration of the anhydrous stannic chloride solution is between 0.05M ~ 0.2.2M;
(2) premixing the adjuvant with 30 mLN, N-dimethylformamide, and stirring for 10 ~ 20min to obtain adjuvant solution;
(3) mixing anhydrous tin tetrachloride solution and adjuvant solution, stirring at room temperature for 20 ~ 30 min, transferring the solution into water bath heated to 60 ~ 95 deg.C, stirring for 2 ~ 5 h, and drying centrifugally precipitated sample at 60 ~ 70 deg.C for 4 ~ 12 hr;
(4) premixing the dried sample and urea according to the mass ratio of 1:3 ~ 10, and then carrying out heat treatment to obtain g-C3N4Modified SnO2The nanometer material has the heat treatment condition of air atmosphere, temperature of 200 ~ 250 deg.c, 1 ~ 3 hr, 300 ~ 350 deg.c, 1.5 ~ 2.5.5 hr, 500 ~ 600 deg.c, 1.5 ~ 5 hr, and temperature raising rate of 1 ~ 4 deg.c/min.
On the basis of the scheme, the premixed solvent is a mixed solvent of N, N-dimethylformamide and deionized water, and the volume ratio of the N, N-dimethylformamide to the deionized water is 5 ~ 20: 100.
The auxiliary agent is one or the combination of 1-methylimidazole, 2-methylimidazole and 1, 2-methylimidazole.
Based on the scheme, the molar ratio of the anhydrous stannic chloride to the auxiliary agent is 1:3 ~ 5.
The invention directly synthesizes SnO by premixing the precursor and the auxiliary agent at low temperature and through the temperature change of the system and the proportion of the raw materials2Nano material and realizes vacancy regulation, and then realizes g-C by heat treatment3N4Modifying SnO2 nano-materials. Test results show that the method can improve SnO2The sensitivity of the nanomaterial. To provide a g-C obtained by a simple method3N4Modified SnO2Nano materials, not only greatly increasingHigh SnO2The nano material has the gas-sensitive performance, simple preparation process and low cost, and has practical application value for further promoting the development of semiconductor gas-sensitive devices.
The invention provides the g-C for the gas sensor3N4Modified SnO2Use of nanomaterials for g-C of gas sensors3N4Modified SnO2The application of the nano material in a gas sensor.
The invention has the advantages that: realize g-C3N4With SnO2In-situ compounding of nano material while maintaining SnO2Simultaneous achievement of g-C of structural integrity3N4The surface modification of the composite material realizes the construction of the high-sensitivity gas-sensitive material by utilizing the advantages of large specific surface area of the nano material and fast electronic transmission of the composite material. The nano material prepared by the invention can greatly improve SnO2Sensitivity of gas sensitive materials. The preparation method has the characteristics of simple preparation process, low cost, stable product performance and high gas sensitivity.
Drawings
FIG. 1 is a SnO of the present invention2Nanomaterial and g-C3N4A composite electron scanning micrograph (SEM);
FIG. 2 is SnO of the present invention2Graph comparing the sensitivity of the nano material and the composite material to acetone at the working temperature of 130 ℃.
Detailed Description
Example 1
g-C for gas sensor3N4Modified SnO2The nano material is obtained by the following preparation method, and comprises the following steps:
(1) taking anhydrous stannic chloride as a raw material, mixing 5mL of N, N-dimethylformamide with 25mL of deionized water, and then adding 1.5 mmol of stannic chloride pentahydrate to prepare a solution A;
(2) placing 4.5 mmol of 1-methylimidazole in 30 mLN, N-dimethylformamide for premixing, and stirring for 20min to obtain a solution B;
(3) mixing the solution A and the solution B, stirring at room temperature for 20min, transferring the solution into a water bath kettle heated to 65 ℃, stirring for 5 h, and drying the centrifugally precipitated sample at 60 ℃ for 8 h;
(4) premixing the dried sample and urea according to the mass ratio of 1:3, and then carrying out heat treatment to obtain g-C3N4Modified SnO2The nano material powder, wherein the heat treatment condition is air atmosphere, and the temperature is as follows: 200 ℃, 3 hours, 350 ℃, 1.5 hours, 600 ℃, 1.5 hours, and the heating rate is 2 ℃/min.
Electronic scanning display FIG. 1 shows SnO of the present invention2Nanomaterial and g-C3N4As shown in a composite electronic scanning and developing (SEM) diagram, the powder prepared in this example was dispersedly coated on a six-legged ceramic tube gas-sensitive test element, and a WS-30A type gas-sensitive element test system was used to test the response to acetone gas at different concentrations, with a working temperature of 130 ℃ and a sensitivity of 19.8 to 10ppm acetone gas.
Example 2
g-C for gas sensor3N4Modified SnO2The nano material is obtained by the following preparation method, and comprises the following steps:
(1) taking anhydrous stannic chloride as a raw material, mixing 1.5 mL of N, N-dimethylformamide and 28.5 mL of deionized water, and then adding 6 mmol of anhydrous stannic chloride to prepare a solution A;
(2) premixing 20 mmol of 1, 2-methylimidazole and 30 mLN, N-dimethylformamide, and stirring for 20min to obtain a solution B;
(3) mixing the solution A and the solution B, stirring at room temperature for 30 min, transferring the solution into a water bath kettle heated to 95 ℃, stirring for 5 h, and drying the centrifugally precipitated sample at 70 ℃ for 12 h;
(4) premixing the dried sample and urea according to the mass ratio of 1:5, and then carrying out heat treatment to obtain g-C3N4Modified SnO2The nanometer material powder has the heat treatment condition of air atmosphere at 250 deg.c, 1.5 hr, 350 deg.c, 2 hr, 550 deg.c and 5 hr, and the temperature raising speed of 1 ~ 4 deg.c/min.
The powder prepared in the embodiment is dispersedly coated on a six-pin ceramic tube gas-sensitive test element, a WS-30A type gas-sensitive element test system is adopted to test the response to acetone gas under different concentrations, the working temperature is 130 ℃, and the sensitivity to 10ppm of acetone gas reaches 21.3.
Example 3
g-C for gas sensor3N4Modified SnO2The nano material is obtained by the following preparation method, and comprises the following steps:
(1) taking anhydrous stannic chloride as a raw material, mixing 3 mL of N, N-dimethylformamide and 27 mL of deionized water, and then adding 3 mmol of anhydrous stannic chloride to prepare a solution A;
(2) premixing 12 mmol of 1, 2-methylimidazole auxiliary and 30 mLN, N-dimethylformamide, and stirring for 20min to obtain a solution B;
(3) mixing the solution A and the solution B, stirring at room temperature for 30 min, transferring the solution into a water bath kettle heated to 85 ℃, stirring for 4 h, and drying the centrifugally precipitated sample at 70 ℃ for 12 h;
(4) premixing the dried sample and urea according to the mass ratio of 1:8, and then carrying out heat treatment to obtain g-C3N4Modified SnO2The nanometer material powder has the heat treatment condition of air atmosphere at 250 deg.c, 1.5 hr, 350 deg.c, 2 hr, 550 deg.c and 5 hr, and the temperature raising speed of 1 ~ 4 deg.c/min.
The powder prepared in the embodiment is dispersedly coated on a six-pin ceramic tube gas-sensitive test element, a WS-30A type gas-sensitive element test system is adopted to test the response to acetone gas under different concentrations, the working temperature is 130 ℃, and the sensitivity to 10ppm of acetone gas reaches 18.4.
As shown in FIG. 2, the present invention g-C3N4Modified SnO2The sensitivity of the nano material with the same concentration is higher than that of SnO2。
Claims (3)
1. Modified SnO for gas sensor2A nanomaterial prepared by the following methodObtaining, comprising the steps of:
(1) dissolving anhydrous stannic chloride into 30 mL of premixed solvent by using the anhydrous stannic chloride as a raw material, wherein the concentration of the anhydrous stannic chloride solution is between 0.05mol/l ~ 0.2.2 mol/l;
(2) premixing the adjuvant with 30 mLN, N-dimethylformamide, and stirring for 10 ~ 20min to obtain adjuvant solution;
(3) mixing anhydrous tin tetrachloride solution and adjuvant solution, stirring at room temperature for 20 ~ 30 min, transferring the solution into water bath heated to 60 ~ 95 deg.C, stirring for 2 ~ 5 h, and drying centrifugally precipitated sample at 60 ~ 70 deg.C for 4 ~ 12 hr;
(4) premixing the dried sample and urea according to the mass ratio of 1:3 ~ 10, and then carrying out heat treatment to obtain g-C3N4Modified SnO2The nanometer material has the heat treatment condition of air atmosphere, the temperature is 200 ~ 250 deg.C, 1 ~ 3 hr, 300 ~ 350 deg.C, 1.5 ~ 2.5.5 hr, 500 ~ 600 deg.C, 1.5 ~ 5 hr, and the heating rate is 1 ~ 4 deg.C/min;
the premixed solvent is prepared by mixing N, N-dimethylformamide and deionized water, wherein the volume ratio of the N, N-dimethylformamide to the deionized water is 5 ~ 20: 100;
the molar ratio of anhydrous tin tetrachloride to adjuvant was 1:3 ~ 5.
2. Modified SnO for gas sensor according to claim 12Nanomaterial characterized by: the auxiliary agent is one or the combination of 1-methylimidazole, 2-methylimidazole and 1, 2-methylimidazole.
3. Modified SnO for gas sensor according to claim 1 or 22The application of the nano material is used for an acetone gas detection gas sensor.
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| CN110396006B (en) * | 2019-07-16 | 2021-11-09 | 济南大学 | ZIF-8 film coated SnO2Composite gas-sensitive material and preparation method and application thereof |
| CN110841682B (en) * | 2019-11-09 | 2022-09-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of tin oxide modified graphite-like phase carbon nitride nanosheet, product and application thereof |
| CN110927219A (en) * | 2019-12-10 | 2020-03-27 | 苏州慧闻纳米科技有限公司 | Gas sensitive material, preparation method thereof and manufacturing method of gas sensor |
| CN112758975A (en) * | 2020-12-22 | 2021-05-07 | 华中科技大学 | CuO doped SnO2Nanoparticles and H2S gas sensor preparation method and product |
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