A sensor for high-sensitivity detection of hydrogen sulfide gas in livestock and poultry breeding and application thereof

Abstract

The application relates to the technical field of material design, and particularly discloses a sensor for high-sensitivity detection of hydrogen sulfide gas in livestock and poultry breeding and application, which comprises the following steps: weighing tin oxide nanoparticle precursors, uniformly mixing the tin oxide nanoparticle precursors with deionized water, stirring the mixture for the first time by using a magnetic stirrer, mixing the above mixture with ammonium carbonate, adding a ruthenium acetylacetone solution, stirring the mixture for the second time by using the magnetic stirrer, centrifuging by using a centrifuge, obtaining supernatant and precipitate, placing the precipitate in an oven for drying, and then annealing under an air atmosphere, so that a sensing layer material of the high-sensitivity gas detection sensor is prepared. The application realizes high-sensitivity and selective detection of hydrogen sulfide gas, does not need expensive detection equipment, has low detection cost, is simple to operate, has short detection time, is rapid and efficient, and can realize real-time monitoring and on-site detection of hydrogen sulfide gas.

Description

Technical Field

[0001] This invention relates to the field of materials design technology, specifically to a sensor and its application for highly sensitive detection of hydrogen sulfide gas in livestock and poultry farming. Background Technology

[0002] Hydrogen sulfide is a colorless gas with a rotten egg smell. It is soluble in water, ethanol, gasoline, kerosene, and crude oil. When dissolved in water, it forms mild sulfuric acid. It is chemically unstable, and its combustion decomposition product is sulfur oxide. It tends to accumulate in low-lying areas and can form explosive mixtures when mixed with air. It can ignite and explode when exposed to open flames or high temperatures. If exposed to high heat, the pressure inside the container increases, posing a risk of cracking and explosion. Hydrogen sulfide is a potent neurotoxin with a strong irritant effect on mucous membranes. At low concentrations, it has a significant local irritant effect on the respiratory tract and eyes. The higher the concentration, the more pronounced the systemic effects, manifesting as central nervous system symptoms and asphyxiation symptoms. At high concentrations, it can directly inhibit the respiratory center, causing rapid asphyxiation and death. Long-term exposure to low concentrations of hydrogen sulfide can cause neurasthenia syndrome and autonomic nervous system disorders. Chronic effects on the eyes include conjunctivitis and corneal damage.

[0003] Chinese invention patent CN115924959A discloses a hydrogen sulfide gas-sensitive material and a method for preparing a hydrogen sulfide gas sensor. The method involves subjecting a solution doped with indium nitrate and urea to a first hydrothermal reaction to obtain a first product containing an In source; then subjecting a green mixture doped with the first product and copper acetate to a second hydrothermal reaction to obtain a target hydrogen sulfide gas-sensitive material containing both an In source and a Cu source, namely CuO-In2O3 hydrogen sulfide nanomaterial.

[0004] However, existing hydrogen sulfide gas detection technologies suffer from several technical problems, including expensive detection equipment, complex operation, excessively long detection time, inability to perform real-time on-site monitoring, and low sensitivity and poor selectivity of existing resistive metal oxide gas sensors for hydrogen sulfide gas. Summary of the Invention

[0005] To address the technical problems of existing hydrogen sulfide gas detection technologies, such as expensive detection equipment, complex operation, excessive detection time, inability to perform real-time on-site monitoring, and low sensitivity and poor selectivity of existing resistive metal oxide gas sensors for hydrogen sulfide gas, this invention provides a method for preparing a ruthenium oxide nanoparticle-catalyzed tin oxide nanosphere composite gas-sensitive material and its gas-sensitive application. This material not only possesses a large specific surface area and excellent sensitivity characteristics, making it suitable as the sensing layer of a metal oxide gas sensor to achieve extremely high sensitivity and selectivity for hydrogen sulfide gas detection, but also eliminates the need for expensive detection equipment, resulting in low detection costs, simple operation, short detection time, and rapid and efficient detection. It enables real-time monitoring and on-site detection of hydrogen sulfide gas.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] A highly sensitive sensor for detecting hydrogen sulfide gas in livestock and poultry farming, comprising:

[0008] Weigh out the tin oxide nanoparticle precursor and mix it evenly with deionized water to obtain a tin oxide nanoparticle precursor mixed solution.

[0009] A tin oxide nanoparticle precursor mixture was mixed with an ammonium carbonate solution, and then a ruthenium acetylacetone solution was added. The mixture was stirred and centrifuged to obtain a supernatant and a precipitate. The precipitate was dried in an oven and then annealed in air to obtain the sensing layer material for a gas high-sensitivity detection sensor.

[0010] As a further aspect of the present invention, the ratio of the amount of the tin oxide nanoparticle precursor, deionized water, ammonium carbonate solution, and ruthenium acetylacetone solution is: 0.100g-0.120g: 5mL: 2.5mL: 10mL.

[0011] As a further aspect of the present invention, the molar concentration of the ammonium carbonate solution is 1 mol / L.

[0012] As a further aspect of the present invention, the mass concentration of the ruthenium acetylacetone solution is 0.1 mg / mL.

[0013] As a further aspect of the present invention: the preparation method of the tin oxide nanoparticle precursor is as follows:

[0014] Hydrochloric acid was added dropwise to a mixed solution of tin tetrachloride pentahydrate to carry out the reaction. The supernatant of the mixed solution was removed after the reaction to obtain a mixture. The mixture was then treated to remove impurities and dried to obtain a tin oxide nanoparticle precursor.

[0015] As a further aspect of the present invention, the amount of hydrochloric acid used is 0.8 mL.

[0016] As a further aspect of the present invention, the molar concentration of the hydrochloric acid is 12 mol / L.

[0017] As a further aspect of the present invention, the method for preparing the tin tetrachloride pentahydrate mixed solution is as follows: tin tetrachloride pentahydrate is placed in an organic solvent and stirred to make the substances in the solution uniformly mixed, thereby obtaining the tin tetrachloride pentahydrate mixed solution.

[0018] As a further aspect of the present invention, the ratio of the amount of tin tetrachloride pentahydrate to the organic solvent is 0.800-0.840g:60mL.

[0019] As a further aspect of the present invention: the organic solvent comprises the following components in parts by weight: 50 parts anhydrous ethanol and 10 parts deionized water;

[0020] Application of a sensing layer material for a highly sensitive gas detection sensor: The sensing layer material prepared by the above method is applied to the field of hydrogen sulfide odor gas detection in livestock and poultry farming.

[0021] The beneficial effects of this invention are:

[0022] (1) The sensing layer material design method of the gas high-sensitivity detection sensor provided by this invention can be used as the sensing material or gas-sensitive element of a resistive metal oxide gas sensor, and has ultra-sensitive and highly selective sensing performance for hydrogen sulfide gas. When the concentration of the measured hydrogen sulfide gas is as low as 10 ppm, the ruthenium oxide nanoparticle-catalyzed tin oxide nanosphere composite material provided by this invention still exhibits high sensitivity characteristics. After detecting the concentration of 9 different gases, the ruthenium oxide nanoparticle-catalyzed tin oxide nanosphere composite material provided by this invention has an ultra-high response only to hydrogen sulfide gas, and almost no response to other gases.

[0023] (2) The sensing layer material design method of the gas high-sensitivity detection sensor provided by this invention can be used as the sensing material of a resistive metal oxide gas sensor. It can be drop-coated onto a gas-sensitive test electrode, and the prepared sensor has extremely high sensitivity and selectivity for hydrogen sulfide gas. Therefore, using ruthenium oxide nanoparticle-catalyzed tin oxide nanosphere composite material for hydrogen sulfide gas detection has advantages such as low cost, no need for expensive detection equipment, simple and easy operation, and rapid and efficient operation. This makes the ruthenium oxide nanoparticle-catalyzed tin oxide nanosphere composite material provided by this invention widely applicable to the fabrication of resistive metal oxide gas sensors for real-time monitoring and on-site detection of hydrogen sulfide gas.

[0024] (3) The preparation method of the sensing layer material design method of the gas high-sensitivity detection sensor provided by the present invention is simple, fast and efficient.

[0025] In summary, the embodiments of the present invention not only have a large specific surface area and excellent gas-sensing characteristics, which can be used as the sensing layer of a resistive metal oxide gas sensor to achieve ultrasensitive and highly selective detection of hydrogen sulfide gas, but also do not require expensive detection equipment, have low detection costs, are easy to operate, have short detection time, and are fast and efficient, enabling real-time and on-site detection of hydrogen sulfide gas. Attached Figure Description

[0026] The invention will now be further described with reference to the accompanying drawings.

[0027] Figure 1The image shows a scanning electron microscope (SEM) image of tin oxide nanospheres catalyzed by ruthenium oxide nanoparticles, provided in an embodiment of the present invention.

[0028] Figure 2 This is a transmission electron microscope image of ruthenium oxide nanoparticles catalyzing tin oxide nanospheres provided in an embodiment of the present invention;

[0029] Figure 3 The response (Rg / Ra ir)-T i me(s) curves of tin oxide nanospheres catalyzed by ruthenium oxide nanoparticles prepared in this embodiment of the invention were tested at a working temperature of 160°C for a high concentration gradient of hydrogen sulfide gas.

[0030] Figure 4 The response and recovery time of ruthenium oxide nanoparticles loaded with tin oxide nanospheres provided in the embodiments of the present invention to 10 ppm hydrogen sulfide gas at 160 °C;

[0031] Figure 5 The ruthenium oxide nanoparticles catalyzing tin oxide nanospheres provided in this embodiment of the invention were used to perform gas-sensitivity testing (Response(Rg / Ra ir)-T ime(s)) on nine gases—ammonia, methane, sulfur dioxide, nitrogen dioxide, acetone, hydrogen, ethanol, trimethylamine, and hydrogen sulfide—at an operating temperature of 160°C.

[0032] Figure 6 The image shows a repeatability test result of 10 ppm hydrogen sulfide gas on tin oxide nanospheres catalyzed by ruthenium oxide nanoparticles provided in this embodiment of the invention at an operating temperature of 160°C and a test humidity of 50%. Detailed Implementation

[0033] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0034] Example 1

[0035] Please see Figure 1-6 As shown, this invention is a highly sensitive sensor for detecting hydrogen sulfide gas in livestock and poultry farming. The specific steps are as follows:

[0036] Step 1: First, weigh 0.800 g of tin tetrachloride pentahydrate (SnCl4·5H2O), mix it with 50 mL of anhydrous ethanol and 10 mL of deionized water, and mix the mixture evenly with a magnetic stirrer. Then, add 0.8 mL of hydrochloric acid dropwise to the mixture and stir the solution at 800 r / min for 30 min. Then, transfer the mixture to a high-pressure reactor lined with polytetrafluoroethylene and place it in an oven at 125°C for 7.5 h.

[0037] Step 2: Remove the supernatant from the above mixed solution, wash the remaining mixture with 15 mL of anhydrous ethanol and 15 mL of deionized water, and sonicate for 5 min until evenly dispersed. Then centrifuge at 8000 r / min for 5 min. Repeat the washing and centrifugation process 3 times. Then place the mixture after removing the supernatant in an oven at 60℃ and dry for 6 h to obtain the tin oxide nanoparticle precursor.

[0038] Step 3: Weigh 0.100g of the prepared tin oxide nanoparticle precursor and mix it evenly with 5mL of deionized water. Stir the mixture at 800r / min for 15min using a magnetic stirrer. Then, mix the above mixture with 2.5mL of 1mol / L ammonium carbonate and add 10mL of 0.1mg / mL ruthenium acetylacetone solution. Stir the mixture at 1000r / min for 2h using a magnetic stirrer. Finally, centrifuge the mixture at 8000r / min for 5min. Place the precipitate after removing the supernatant in an oven at 80℃ and dry it for 4h. Then, anneal it at 500℃ in air to obtain the sensing layer material of the gas high-sensitivity detection sensor (the sensing layer material of the gas high-sensitivity detection sensor is the tin oxide nanosphere composite material catalyzed by ruthenium oxide nanoparticles).

[0039] Example 2

[0040] Please see Figure 1-6 As shown, this invention is a highly sensitive sensor for detecting hydrogen sulfide gas in livestock and poultry farming. The specific steps are as follows:

[0041] Step 1: First, weigh 0.820 g of tin tetrachloride pentahydrate (SnCl4·5H2O), mix it with 50 mL of anhydrous ethanol and 10 mL of deionized water, and mix the mixture evenly with a magnetic stirrer. Then, add 0.8 mL of hydrochloric acid dropwise to the mixture and stir the solution at 800 r / min for 30 min. Then, transfer the mixture to a high-pressure reactor lined with polytetrafluoroethylene and place it in an oven at 160 °C for 11 h.

[0042] Step 2: Remove the supernatant of the above mixed solution, wash the remaining mixture with 15 mL of anhydrous ethanol and 15 mL of deionized water, and sonicate for 7.5 min until uniformly dispersed. Then centrifuge at 8000 r / min for 5 min. Repeat the washing and centrifugation process 3 times. Then place the mixture after removing the supernatant in an oven at 60℃ and dry for 9 h to obtain the tin oxide nanoparticle precursor.

[0043] Step 3: Weigh 0.110 g of the prepared tin oxide nanoparticle precursor and mix it evenly with 5 mL of deionized water. Stir the mixture at 800 r / min for 15 min using a magnetic stirrer. Then, mix the above mixture with 2.5 mL of 1 mol / L ammonium carbonate and add 10 mL of 0.1 mg / mL ruthenium acetylacetone solution. Stir the mixture at 1000 r / min for 2 h using a magnetic stirrer. Finally, centrifuge the mixture at 8000 r / min for 5 min. Place the precipitate after removing the supernatant in an oven at 80 °C and dry it for 4 h. Then, anneal it at 500 °C in air to obtain the sensing layer material of the gas high-sensitivity detection sensor (the sensing layer material of the gas high-sensitivity detection sensor is the tin oxide nanosphere composite material catalyzed by ruthenium oxide nanoparticles).

[0044] Example 3

[0045] Please see Figure 1-6 As shown, this invention is a highly sensitive sensor for detecting hydrogen sulfide gas in livestock and poultry farming. The specific steps are as follows:

[0046] Step 1: First, weigh 0.840 g of tin tetrachloride pentahydrate (SnCl4·5H2O), mix it with 50 mL of anhydrous ethanol and 10 mL of deionized water, and mix the mixture evenly with a magnetic stirrer. Then, add 0.8 mL of hydrochloric acid dropwise to the mixture and stir the solution at 800 r / min for 30 min. Then, transfer the mixture to a high-pressure reactor lined with polytetrafluoroethylene and place it in an oven at 200 °C for 15 h.

[0047] Step 2: Remove the supernatant of the above mixed solution, wash the remaining mixture with 15 mL of anhydrous ethanol and 15 mL of deionized water, and sonicate for 10 min until evenly dispersed. Then centrifuge at 8000 r / min for 5 min. Repeat the washing and centrifugation process 3 times. Then place the mixture after removing the supernatant in an oven at 60℃ and dry for 12 h to obtain the tin oxide nanoparticle precursor.

[0048] Step 3: Weigh 0.120g of the prepared tin oxide nanoparticle precursor and mix it evenly with 5mL of deionized water. Stir the mixture at 800r / min for 15min using a magnetic stirrer. Then, mix the above mixture with 2.5mL of 1mol / L ammonium carbonate and add 10mL of 0.1mg / mL ruthenium acetylacetone solution. Stir the mixture at 1000r / min for 2h using a magnetic stirrer. Finally, centrifuge the mixture at 8000r / min for 5min. Place the precipitate after removing the supernatant in an oven at 80℃ and dry it for 4h. Then, anneal it at 500℃ in air to obtain the sensing layer material of the gas high-sensitivity detection sensor (the sensing layer material of the gas high-sensitivity detection sensor is the tin oxide nanosphere composite material catalyzed by ruthenium oxide nanoparticles).

[0049] Example 4

[0050] Based on the above embodiments one, two and three, the present invention provides a gas-sensing application of ruthenium oxide nanoparticles catalyzed by ruthenium oxide nanoparticles. The ruthenium oxide nanoparticles catalyzed by ruthenium oxide nanoparticles are dispersed in anhydrous ethanol, then drop-coated onto a flat electrode using a minimum-gradient pipette, and dried in an oven at 60-80℃. This serves as the sensing layer of a resistive metal oxide gas sensor for ultra-sensitive and highly selective detection of hydrogen sulfide gas.

[0051] The working principle of this invention: This invention provides a method for preparing a ruthenium oxide nanoparticle-catalyzed tin oxide nanosphere composite material and its gas-sensing application. Using the prepared tin oxide nanospheres as a precursor, ruthenium is loaded onto the surface of the tin oxide nanospheres to prepare ruthenium oxide nanoparticle-catalyzed tin oxide nanospheres. Therefore, the ruthenium oxide nanoparticle-catalyzed tin oxide nanosphere composite material prepared by this invention has a large specific surface area. Using ruthenium oxide nanoparticles to catalyze tin oxide nanospheres can significantly enhance the sensitivity and selectivity of the sensor for hydrogen sulfide gas. This ruthenium oxide nanoparticle-catalyzed tin oxide nanosphere composite material can be used as the sensing layer of a resistive metal oxide gas sensor for ultra-sensitive and highly selective detection of hydrogen sulfide gas.

[0052] The foregoing has provided a detailed description of one embodiment of the present invention, but this description is merely a preferred embodiment and should not be construed as limiting the scope of the invention. All equivalent variations and modifications made within the scope of the claims of this invention should still fall within the patent coverage of this invention.

Claims

1. A sensor for highly sensitive detection of hydrogen sulfide gas in livestock and poultry farming, characterized in that, The design methods for sensor sensing layer materials include: Weigh out the tin oxide nanoparticle precursor and mix it evenly with deionized water to obtain a tin oxide nanoparticle precursor mixed solution. A tin oxide nanoparticle precursor mixed solution was mixed with an ammonium carbonate solution, and then an acetylacetone ruthenium solution was added. The mixture was stirred and centrifuged to obtain a supernatant and a precipitate. The precipitate was placed in an oven to dry and then annealed in an air atmosphere to obtain the sensing layer material of a gas high-sensitivity detection sensor. The method for preparing the tin oxide nanoparticle precursor is as follows: Hydrochloric acid was added dropwise to a mixed solution of tin tetrachloride pentahydrate to carry out the reaction. The supernatant of the mixed solution was removed after the reaction to obtain a mixture. The mixture was then treated to remove impurities and dried to obtain a tin oxide nanoparticle precursor.

2. The sensor for highly sensitive detection of hydrogen sulfide gas in livestock and poultry farming according to claim 1, characterized in that, The ratio of the amount of the tin oxide nanoparticle precursor, deionized water, ammonium carbonate solution, and ruthenium acetylacetone solution is (0.100-0.120) g: 5 mL: 2.5 mL: 10 mL.

3. The sensor for highly sensitive detection of hydrogen sulfide gas in livestock and poultry farming according to claim 1, characterized in that, The ammonium carbonate solution has a molar concentration of 1 mol / L; the ruthenium acetylacetone solution has a mass concentration of 0.1 mg / mL.

4. The sensor for highly sensitive detection of hydrogen sulfide gas in livestock and poultry farming according to claim 1, characterized in that, The amount of hydrochloric acid used is 0.8 mL.

5. A sensor for highly sensitive detection of hydrogen sulfide gas in livestock and poultry farming according to claim 4, characterized in that, The molar concentration of the hydrochloric acid is 12 mol / L.

6. The sensor for highly sensitive detection of hydrogen sulfide gas in livestock and poultry farming according to claim 4, characterized in that, The method for preparing the tin tetrachloride pentahydrate mixed solution is as follows: tin tetrachloride pentahydrate is placed in an organic solvent and stirred to mix the substances in the solution evenly, thereby obtaining the tin tetrachloride pentahydrate mixed solution.

7. A sensor for highly sensitive detection of hydrogen sulfide gas in livestock and poultry farming according to claim 4, characterized in that, The ratio of tin tetrachloride pentahydrate to organic solvent is (0.800-0.840) g: 60 mL.

8. A sensor for highly sensitive detection of hydrogen sulfide gas in livestock and poultry farming according to claim 7, characterized in that, The organic solvent comprises the following components in parts by weight: 50 parts anhydrous ethanol and 10 parts deionized water.

9. An application of a sensor for highly sensitive detection of hydrogen sulfide gas in livestock and poultry farming, characterized in that, The sensing layer material prepared by the method according to any one of claims 1-8 is applied to the field of detecting hydrogen sulfide odor gas in livestock and poultry farming.

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