Preparation method of composite nano tin dioxide material as well as product and application of composite nano tin dioxide material
By preparing composite nanotin dioxide materials, the problem of poor conductivity of SnO2 is solved, which significantly improves its sensitivity and response time to methanol, and expands its application potential in the field of gas-sensitive sensors.
Patent Information
- Application Number
- CN202411974532.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-31
- Publication Date
- 2025-04-01
AI Technical Summary
Semiconductor metal oxides such as SnO2 have poor electrical conductivity, which affects their gas-sensitive performance and is difficult to show high sensitivity and rapid response in the field of gas-sensitive sensors.
The specific surface area and active sites of the material are enhanced by reacting the long-chain alkylamine with anhydrous tin tetrachloride and sodium hydroxide under specific conditions.
It significantly improves the stability of SnO2 materials, sensitivity to methanol and response time, making it have broader application prospects in the field of gas-sensitive sensors.
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of gas sensors, and relates to a preparation method of a composite nano-tin dioxide material, a product and an application thereof, and specifically refers to a preparation method of a composite nano-SnO2 material for a gas sensor. Background Art
[0002] Metal oxides such as Fe2O3, ZnO, SnO2, WO3, etc. are widely studied gas-sensitive materials due to their excellent performance, environmental friendliness, abundant resources, and low price. The gas-sensitive properties of materials can be improved through processes such as metal oxide surface modification and metal / precious metal doping, and they are widely used in the field of gas sensors.
[0003] The key factors that determine the sensitivity of semiconductor gas-sensitive materials include the reaction between the material surface and the gas to be measured and the conductivity of the material. The former determines the response sensitivity of the sensitive material, and the latter determines the energy consumption of the material. SnO2 has always attracted the attention of the scientific research and industry as a gas-sensitive material, but the conductivity of semiconductor metal oxides is poor. By combining with carbon materials, its conductivity can be improved, thereby improving the gas sensitivity of the material. Summary of the invention
[0004] The purpose of the invention is to provide a method for preparing a composite nano-tin dioxide material.
[0005] Another object of the present invention is to provide a composite nano-tin dioxide material product prepared by the above method.
[0006] Another object of the present invention is to provide an application of the above product.
[0007] The object of the present invention is achieved by the following scheme: a method for preparing a composite nano-tin dioxide material, the specific steps of the method are: (1) Dissolve a long-chain alkylamine in an alcohol solution to a concentration of 5-100 g / L, labeled solution A.
[0008] (2) Dissolve anhydrous tin tetrachloride and sodium hydroxide in deionized water to a molar ratio of 1:4-1:5 and mark it as solution B.
[0009] (3) Solution B is slowly added dropwise to solution A, and the reaction is carried out at normal pressure and low temperature of 0-40 °C for 2-30 h. The product is centrifuged, washed with an alcohol solution for 3-5 times, and dried in an oven at 60-80 °C to obtain product C.
[0010] (4) Dissolve 0.005-0.01 mol copper oxide in deionized water, stir for 10-20 min, then add 5-10 mL ammonia water to obtain solution D; dissolve 5-10 g sodium dodecylbenzene sulfonate in 50 mL deionized water, stir until transparent, to obtain solution E; add solution E dropwise into solution D, stir for 5-10 h, to obtain solution F; add product C into solution F, to obtain solution G; add 2-5 mmol reducing agent dropwise into solution G, and continue stirring for 3-6 h. Wash the obtained precipitate with deionized water and ethanol several times, filter and dry to obtain the final product.
[0011] The long-chain alkylamine described in the above preparation method is one of decaamine and dodecylamine or a combination thereof.
[0012] The alcohol described in the above preparation method is one or a combination of methanol, ethanol or propanol.
[0013] The reducing agent described in the above preparation method is ascorbic acid or sodium borohydride or a combination thereof.
[0014] The present invention provides a composite nano-tin dioxide material, which is characterized in that it is prepared according to any of the above methods.
[0015] The invention provides an application of a composite nano-tin dioxide material in preparing a gas sensor for detecting methanol.
[0016] The prepared powder was dispersed and coated on a six-pin ceramic tube gas-sensitive test element, placed on an aging table for one week, and tested for its response to methanol gas using a WS-30A gas-sensitive element test system at a test temperature of 200 °C. The aging table was placed in a sealed container, and methanol was injected to a concentration of 20 ppm to test its response to methanol gas.
[0017] The method provided by the present invention can greatly improve the stability, sensitivity to methanol and response time of SnO2, so that metal oxide system materials have a broader application prospect in the field of gas sensors. It can increase the specific surface area and active sites of the material surface, greatly improve the gas sensing performance of nanomaterials, and the preparation process is simple and the preparation cost is low, which has practical application value for further promoting the development of semiconductor gas sensors. Specific embodiments
[0018] The embodiments are implemented on the premise of the technical solution of the present invention, and detailed implementation methods and specific operation processes are given, but the protection scope of the present invention is not limited to the following embodiments.
[0019] Example 1 A composite nano-tin dioxide material is prepared according to the following steps: Dissolve decaamine in methanol solution to a concentration of 5 g / L, labeled as solution A; Dissolve 4.91 g of anhydrous tin tetrachloride and 5.73 g of sodium hydroxide in deionized water, labeled as solution B; Solution B was slowly added dropwise to solution A, and the reaction was carried out at normal pressure and low temperature of 0°C for 30 h. The product was centrifuged, washed with methanol solution for 3 times, and dried in an oven at 60°C to obtain product C, a composite nano-SnO2 material. Dissolve 0.01 mol of copper oxide in deionized water, stir for 10 min, and then add 10 mL of ammonia water to obtain solution D. Dissolve 10 g of sodium dodecylbenzene sulfonate in 50 mL of deionized water and stir until transparent to obtain solution E; Solution E was added dropwise to solution D, and stirred for 5 h to obtain solution F. Add the product C composite nano-SnO2 material into solution F to obtain solution G; 5 mmol of reducing agent sodium borohydride was added dropwise to solution G and stirring was continued for 6 h. The obtained precipitate was washed several times with deionized water and ethanol, and then filtered and dried to obtain the final product, composite nano-tin dioxide material.
[0020] The powder prepared in this embodiment was dispersed and coated on a six-pin ceramic tube gas sensor test element. The response to methanol gas at different concentrations was tested using a WS-30A gas sensor test system. The working temperature was 200° C., and the sensitivity to 20 ppm methanol gas reached 28.8.
[0021] Example 2 A composite nano-tin dioxide material is prepared according to the following steps: Dissolve dodecylamine in ethanol solution to a concentration of 10 g / L, labeled as solution A; Dissolve 3.85 g of anhydrous tin tetrachloride and 5.98 g of sodium hydroxide in deionized water, respectively, and mark it as solution B; Solution B was slowly added dropwise to solution A, and the reaction was carried out at normal pressure and low temperature of 10°C for 20 h. The product was centrifuged, washed with ethanol solution for 5 times, and dried in an oven at 80°C to obtain product C composite nano-SnO2 material.
[0022] Dissolve 0.02 mol of copper oxide in deionized water, stir for 10 min, then add 5 mL of ammonia water to obtain solution D; Dissolve 5 g of sodium dodecylbenzene sulfonate in 50 mL of deionized water and stir until transparent to obtain solution E; Solution E was added dropwise to solution D, and stirred for 5 h to obtain solution F. Add the prepared product C composite nano-SnO2 material into solution F to obtain solution G; 2 mmol of reducing agent ascorbic acid was added dropwise into solution G and stirring was continued for 3 h. The obtained precipitate was washed several times with deionized water and ethanol, and then filtered and dried to obtain the final product, a composite nano-tin dioxide material.
[0023] The powder prepared in this embodiment was dispersed and coated on a six-pin ceramic tube gas sensor test element. The response to methanol gas at different concentrations was tested using a WS-30A gas sensor test system. The working temperature was 200° C., and the sensitivity to 20 ppm methanol gas reached 25.8.
[0024] Example 3 A composite nano-tin dioxide material is prepared according to the following steps: Dissolve decaamine in ethanol solution to a concentration of 5 g / L, labeled as solution A; Dissolve 4.463 g of anhydrous tin tetrachloride and 7.93 g of sodium hydroxide in deionized water, respectively, and mark it as solution B; Solution B was slowly added dropwise to solution A, and the reaction was carried out at normal pressure and low temperature of 20°C for 15 h. The product was centrifuged, washed with ethanol solution for 5 times, and dried in an oven at 80°C to obtain product C, a composite nano-SnO2 material.
[0025] Dissolve 0.005 mol of copper oxide in deionized water, stir for 10 min, and then add 5 mL of ammonia water to obtain solution D. Dissolve 5 g of sodium dodecylbenzene sulfonate in 50 mL of deionized water and stir until transparent to obtain solution E; add solution E dropwise into solution D and stir for 5 h to obtain solution F; Add the prepared product C composite nano-SnO2 material into solution F to obtain solution G; 2 mmol of reducing agent sodium borohydride was added dropwise to solution G and stirring was continued for 3 h. The obtained precipitate was washed several times with deionized water and ethanol, and then filtered and dried to obtain the final product, a composite nano-tin dioxide material.
[0026] The powder prepared in this embodiment was dispersed and coated on a six-pin ceramic tube gas sensor test element. The response to methanol gas at different concentrations was tested using a WS-30A gas sensor test system. The working temperature was 200° C., and the sensitivity to 20 ppm methanol gas reached 26.7.
Claims
1. A method for preparing a composite nano-tin dioxide material, characterized in that: The steps include: Dissolve the long-chain alkylamine in an alcohol solution to a concentration of 5-100 g / L, labeled as solution A; Dissolve anhydrous tin tetrachloride and sodium hydroxide in deionized water respectively to a molar ratio of 1:4-1:5, marked as solution B; Solution B is slowly added dropwise to solution A, and the reaction is carried out at normal pressure and low temperature of 0-40 °C for 2-30 h. The product is centrifuged, washed with an alcohol solution for 3-5 times, and dried in an oven at 60-80 °C to obtain product C. Dissolve 0.005-0.01 mol of copper oxide in deionized water, stir for 10-20 min, then add 5-10 mL of ammonia water to obtain solution D. Dissolve 5-10 g of sodium dodecylbenzene sulfonate in 50 mL of deionized water and stir until transparent to obtain solution E. Add solution E dropwise into solution D and stir for 5-10 h to obtain solution F. Add product C to solution F to obtain solution G; 2-5 mmol reducing agent was added dropwise into solution G and stirring was continued for 3-6 h. The obtained precipitate was washed several times with deionized water and ethanol, and then filtered and dried to obtain the final product, composite nano-tin dioxide material.
2. The method for preparing the composite nano-tin dioxide material according to claim 1, characterized in that The long-chain alkylamine is one of decaamine and dodecylamine or a combination thereof.
3. The method for preparing the composite nano-tin dioxide material according to claim 1, characterized in that The alcohol is one of methanol, ethanol or propanol or a combination thereof.
4. The method for preparing the composite nano-tin dioxide material according to claim 1, characterized in that The reducing agent is ascorbic acid or sodium borohydride or a combination thereof.
5. The method for preparing the composite nano-tin dioxide material according to any one of claims 1 to 4, characterized in that: Prepare as follows: Dissolve decaamine in methanol solution to a concentration of 5 g / L, labeled as solution A; Dissolve 4.91 g of anhydrous tin tetrachloride and 5.73 g of sodium hydroxide in deionized water, labeled as solution B; Solution B was slowly added dropwise to solution A, and the reaction was carried out at normal pressure and low temperature of 0°C for 30 h. The product was centrifuged, washed with methanol solution for 3 times, and dried in an oven at 60°C to obtain product C, a composite nano-SnO2 material. Dissolve 0.01 mol of copper oxide in deionized water, stir for 10 min, and then add 10 mL of ammonia water to obtain solution D. Dissolve 10 g of sodium dodecylbenzene sulfonate in 50 mL of deionized water and stir until transparent to obtain solution E; Solution E was added dropwise to solution D, and stirred for 5 h to obtain solution F. Add the product C composite nano-SnO2 material into solution F to obtain solution G; 5 mmol of reducing agent sodium borohydride was added dropwise to solution G and stirring was continued for 6 h. The obtained precipitate was washed several times with deionized water and ethanol, and then filtered and dried to obtain the final product, composite nano-tin dioxide material.
6. The method for preparing the composite nano-tin dioxide material according to any one of claims 1 to 4, characterized in that: Prepare as follows: Dissolve dodecylamine in ethanol solution to a concentration of 10 g / L, labeled as solution A; Dissolve 3.85 g of anhydrous tin tetrachloride and 5.98 g of sodium hydroxide in deionized water, respectively, and mark it as solution B; Solution B was slowly added dropwise to solution A, and the reaction was carried out at normal pressure and low temperature of 10°C for 20 h. The product was centrifuged, washed with ethanol solution for 5 times, and dried in an oven at 80°C to obtain product C composite nano-SnO2 material. Dissolve 0.02 mol of copper oxide in deionized water, stir for 10 min, then add 5 mL of ammonia water to obtain solution D; Dissolve 5 g of sodium dodecylbenzene sulfonate in 50 mL of deionized water and stir until transparent to obtain solution E; Solution E was added dropwise to solution D, and stirred for 5 h to obtain solution F. Add the prepared product C composite nano-SnO2 material into solution F to obtain solution G; 2 mmol of reducing agent ascorbic acid was added dropwise into solution G and stirring was continued for 3 h. The obtained precipitate was washed several times with deionized water and ethanol, and then filtered and dried to obtain the final product, a composite nano-tin dioxide material.
7. The method for preparing the composite nano-tin dioxide material according to any one of claims 1 to 4, characterized in that: Prepare as follows: Dissolve decaamine in ethanol solution to a concentration of 5 g / L, labeled as solution A; Dissolve 4.463 g of anhydrous tin tetrachloride and 7.93 g of sodium hydroxide in deionized water, respectively, and mark it as solution B; Solution B was slowly added dropwise to solution A, and the reaction was carried out at normal pressure and low temperature of 20°C for 15 h. The product was centrifuged, washed with ethanol solution for 5 times, and dried in an oven at 80°C to obtain product C, a composite nano-SnO2 material. Dissolve 0.005 mol of copper oxide in deionized water, stir for 10 min, and then add 5 mL of ammonia water to obtain solution D. Dissolve 5 g of sodium dodecylbenzene sulfonate in 50 mL of deionized water and stir until transparent to obtain solution E; add solution E dropwise into solution D and stir for 5 h to obtain solution F; Add the prepared product C composite nano-SnO2 material into solution F to obtain solution G; 2 mmol of reducing agent sodium borohydride was added dropwise to solution G and stirring was continued for 3 h. The obtained precipitate was washed several times with deionized water and ethanol, and then filtered and dried to obtain the final product, a composite nano-tin dioxide material.
8. A composite nano-tin dioxide material, characterized in that Prepared according to any one of claims 1-7.
9. Use of the composite nano-tin dioxide material according to claim 8 in preparing a gas sensor for detecting methanol.