CN114609198A - Tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification as well as preparation method and application thereof - Google Patents
Tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification, and a preparation method and application thereof. The material has good crystallinity, and the morphology is spherical particles with the diameter of 1-2 mu m. The preparation method is simple, low in cost and easy for batch production, and is energy-saving and environment-friendly. The tin oxide-based hydrogen sensor prepared from the prepared material has the advantages of high sensitivity, good selectivity, short response recovery time and low detection lower limit when used for detecting hydrogen.
Description
Technical Field
The invention belongs to the technical field of metal oxide semiconductor gas sensor materials, and particularly relates to a tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification, and a preparation method and application thereof.
Background
With the diversified pursuit of energy structures in modern society, the limitation of traditional fossil fuels and the problems of greenhouse effect and environmental protection brought by the traditional fossil fuels, new clean energy becomes a hot research. Hydrogen is a secondary energy source with the most development prospect at present as an energy source form with abundant reserves, regeneration and no pollution. However, hydrogen gas is a colorless and odorless gas with high diffusion rate, low ignition energy, wide explosion limit, and can have serious consequences in case of leakage and explosion. Therefore, the development of a hydrogen sensor with high sensitivity and fast response time is crucial for detecting hydrogen leakage in production, storage, transportation and practical applications. The metal oxide semiconductor gas sensor has the advantages of high stability, convenient operation, small volume, low cost, short response time, short recovery time and the like, and occupies an important position in the detection of hydrogen. Generally, the hydrogen sensing mechanism of tin dioxide is due to the redox reaction of hydrogen with oxygen adsorbed on the surface of tin dioxide, which results in a change in the resistance of tin dioxide. The tin dioxide gas sensor can play a role of a catalyst or a surface site for gas adsorption through operations such as doping of noble metal, loading of organic materials and the like, so that the surface adsorption effect is improved, and the sensing performance of the sensor is improved. The existing traditional hydrogen sensor has the problems of poor stability, complex preparation process, high cost, long response time and recovery time and poor selectivity to hydrogen, and cannot meet the requirements of modern industry. Therefore, the development of a hydrogen sensor which has the advantages of novel material, high sensitivity, quick reaction, high selectivity and low detection lower limit has important significance. The tin oxide-based gas sensor modified and doped by the noble metal and the rare earth element provides possibility for further improving the hydrogen detection performance and avoiding safety accidents caused by hydrogen leakage.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification aiming at the defects in the prior art, and the preparation method is simple, low in cost, environment-friendly and environment-friendly in used solvent and suitable for large-scale production.
The invention also aims to provide the application of the rare earth element doped and precious metal modified tin oxide-based hydrogen sensing material in a hydrogen sensor.
The invention also aims to provide a hydrogen sensor using the tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification and a manufacturing method thereof.
The invention solves the technical problems through the following technical means:
a preparation method of a tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification is characterized by comprising the following specific steps:
(1) dissolving sodium hydroxide and tin salt in a mixed solution of deionized water and absolute ethyl alcohol or deionized water, adding PVP template agent, stirring at room temperature, and carrying out hydrothermal reaction to obtain tin oxide microspheres, wherein the hydrothermal reaction temperature is 100-250 ℃, and the time is 10-20 h;
(2) Adding the tin oxide microspheres, scandium salt and urea in the step (1) into deionized water, stirring at room temperature, carrying out hydrothermal reaction on the obtained product and a noble metal compound solution in an inner container of a hydrothermal kettle at the temperature of 80-120 ℃ for 5-20 minutes, standing, centrifuging, washing after the reaction is finished, and drying in a drying oven to obtain a tin oxide-based product;
(3) and (3) annealing the tin oxide-based product obtained in the step (2) at the temperature of 300-800 ℃ for 1-5h, and cooling along with the furnace after the heat treatment is finished to obtain the tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification.
The tin salt is selected from one of stannic chloride pentahydrate, stannous chloride dihydrate and stannous sulfate.
The mixing volume ratio of the deionized water to the absolute ethyl alcohol in the step (1) is 1: 1; the sodium hydroxide is added according to the mass-volume ratio of 0.01-0.05g/mL, and the tin salt is added according to the molar ratio of the tin element to the sodium element of 0.1664: 1.
The relative molecular mass of the PVP template in the step (1) is 10000-1300000, and the PVP template is prepared according to the weight ratio of 0.01-1 g: 40mL of the solution was added to a mixed solution of deionized water and absolute ethanol or deionized water.
The scandium salt is selected from one of scandium nitrate, scandium nitrate hydrate, scandium chloride hexahydrate and scandium carbonate; the noble metal compound solution is one of chloroauric acid solution, platinic acid solution, chloropalladite solution and silver nitrate solution.
In the step (2), the tin oxide microspheres, the scandium salt and the urea are mixed according to a molar ratio of 1: 0.7: 2.1 into 30mL of deionized water; the concentration of the noble metal ions in the noble metal compound solution is 0.05-0.1mol/mL, and the noble metal compound solution is added into deionized water according to the volume ratio of 1-32mL to 30 mL.
The tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification is obtained by the preparation method.
The tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification is applied to a hydrogen sensor.
The hydrogen sensor which uses the tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification has the working temperature of 200-250 ℃, the lower limit value of the detection of the hydrogen concentration of 3.6ppb, the response time of 1s-5s and the recovery time of 5s-10 s.
The manufacturing method of the hydrogen sensor comprises the following steps:
(1) preparing mixed slurry: grinding 0.1g of tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification for 10-30min, dropwise adding 2mL of ethanol, and stirring and fully mixing to form mixed slurry;
(2) coating a ceramic tube: application of the Mixed slurry to Al with Au electrodes2O3And drying the outer wall of the ceramic tube at the temperature of 80-100 ℃ to obtain the hydrogen sensor.
The hydrogen sensor based on the rare earth element doped and precious metal modified tin oxide-based hydrogen sensing material is subjected to hydrogen sensitivity performance test after aging is stable. The test method is as follows: the testing gas is kept for a period of time in the air environment before being tested, and the gas to be tested is injected into the testing cabin through the injector during testing. At the test temperature of 200-250 ℃, the stable resistance value of the gas sensitive element in the air is the initial resistance, after the gas sensitive element is contacted with the gas to be tested, the resistance value of the gas sensitive element is changed, after the response is complete, the gas sensitive element is placed in the air for desorption, the resistance value is recovered to the initial state, and the response sensitivity of the gas sensitive element and the gas is calculated through the change of the resistance value. The calculation formula of the sensitivity (S) is that S is Ra/Rg, wherein Ra is the stable resistance value of the gas sensitive element in the air at a certain working temperature, and Rg is the resistance value of the gas sensitive element in test gas with a certain concentration at a certain working temperature.
The invention has the beneficial effects that: 1. the scandium element is doped in the tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification to improve the hydrogen sensing performance for the first time, and a heterostructure is formed among the scandium element, the precious metal and the tin oxide to promote electron transfer, so that the hydrogen sensing performance is improved. 2. The synthesis method of the material is simple, the cost is low, the used solvent is environment-friendly, green and environment-friendly, and the material is suitable for large-scale production, wherein the sodium hydroxide is added to form initial small crystal grains, so that the crystal growth of the material is facilitated. 3. The tin oxide-based hydrogen sensing material prepared by the invention is spherical tin oxide doped with scandium elements and modified by noble metals, has good crystallinity, has the characteristic of rapid response recovery speed, has a response value of 33.5 to 5ppm low-concentration hydrogen at the working temperature of 240 ℃, and completes response within 1s and recovery within 5 s; has a low detection limit, the minimum concentration tested is 125 ppb, and the lower detection limit calculated by mathematical fitting is 3.6 ppb; the method has good repeatability and stability, and still keeps good response after repeated times; has excellent selectivity.
Drawings
FIG. 1 is an XRD spectrum of tin oxide microspheres in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a rare earth element doped and noble metal modified tin oxide-based hydrogen sensing material in example 1 of the present invention;
FIG. 3 is a schematic diagram of a hydrogen sensor based on a rare earth doped noble metal modified tin oxide based hydrogen sensing material according to example 1 of the present invention;
FIG. 4 is a histogram of the response of a hydrogen sensor sample based on a rare earth doped, noble metal modified tin oxide based hydrogen sensing material to various gases in example 1 of the present invention;
FIG. 5 is a response recovery curve of a hydrogen sensor based on a rare earth element doped and noble metal modified tin oxide-based hydrogen sensing material at 240 ℃ for hydrogen with different concentrations in example 1 of the present invention;
FIG. 6 is a repeated response curve of a hydrogen sensor based on a rare earth element doped, noble metal modified tin oxide based hydrogen sensing material at 240 ℃ to 5ppm hydrogen in example 1 of the present invention;
fig. 7 is a fitting graph of the response of the hydrogen sensor based on the rare earth element doped and noble metal modified tin oxide-based hydrogen sensing material to hydrogen with different concentrations at 240 ℃ in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a rare earth element doping and precious metal modification based tin oxide-based hydrogen sensing material comprises the following specific steps:
(1) weighing 4g of sodium hydroxide and 3.7548g of stannous chloride dihydrate, dissolving in 40mL of deionized water and 40mL of absolute ethyl alcohol mixed solution, adding 1g of PVP template agent with the relative molecular mass of 1300000, stirring for 30 minutes at room temperature, adding into an inner container of a hydrothermal kettle, and carrying out hydrothermal reaction at 250 ℃ for 20 hours to obtain stannic oxide microspheres, wherein the diameter of the stannic oxide microspheres is 1-2 mu m;
(2) adding 1.2057g of tin oxide microspheres, 1.3941g of scandium nitrate hydrate and 1.0080g of urea into 30mL of deionized water, stirring for 10 minutes at room temperature, adding 1mL of 0.1mol/mL of chloropalladate solution, carrying out hydrothermal reaction for 20 minutes at 120 ℃, standing, centrifuging, washing, and drying in an oven at 80 ℃;
(3) And annealing the dried product at 800 ℃ for 5h, and cooling the product along with the furnace after the heat treatment is finished to obtain the tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification.
The method for manufacturing the hydrogen sensor by using the tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification obtained by the preparation method specifically comprises the following steps:
(1) weighing 0.1g of tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification, fully grinding for 10min, dropwise adding 2mL of absolute ethyl alcohol, and fully mixing to form mixed slurry;
(2) dipping the mixed slurry by a cotton swab and coating the mixed slurry on Al with an Au electrode2O3And drying the outer wall of the ceramic tube at 80 ℃ to obtain the hydrogen sensor.
The obtained hydrogen sensor in this example had a detection range of 125ppb to 5ppm at a working temperature of 240 ℃, a response time of 1s, a recovery time of 5s, and a response value to hydrogen gas having a concentration of 5ppm of 33.5. As shown in figure 1, the XRD diffraction pattern of the prepared tin oxide microsphere conforms to the crystal structure of tin oxide. As can be seen from the scanning electron microscope image shown in FIG. 2, the microscopic size of the sample is in the micron order, and the appearance of the sample is nearly spherical. As shown in fig. 4, which is a bar graph of the response of a hydrogen sensor sample based on the rare earth element doped and noble metal modified tin oxide-based hydrogen sensing material to various gases, the hydrogen concentration in the test is 5ppm, the carbon monoxide concentration is 1000ppm, and all other gases are 100ppm, it can be seen that the response of the sensor to hydrogen is much higher than that of other gases, which indicates that the hydrogen sensor based on the rare earth element doped and noble metal modified tin oxide-based hydrogen sensing material has ultrahigh sensitivity and good selectivity to hydrogen. Fig. 5 is a response recovery curve of a hydrogen sensor based on a rare earth element doped and precious metal modified tin oxide-based hydrogen sensing material to hydrogen with different concentrations at 240 ℃. It can be seen that the response of the sensor increases as the measured hydrogen concentration increases, and that a clear jump in the curve occurs at increasing gas concentration, indicating that the sensor responds well to hydrogen. Fig. 6 shows a repeated response curve of the hydrogen sensor based on the rare earth element doped and noble metal modified tin oxide-based hydrogen sensing material to 5ppm hydrogen at 240 ℃, which shows that the sensor still shows good stability in repeated tests, and the repeated response curve also shows that the response time of the sensor is 1 second and the recovery time is about 5 seconds. Fig. 7 is a fitting graph of response of the hydrogen sensor based on the rare earth element doped and noble metal modified tin oxide-based hydrogen sensing material to hydrogen with different concentrations at 240 ℃, and the theoretical detection lower limit of the sensor can be fitted from the fitting graph, and the sensor has good resolution. The lower detection limit calculated by mathematical fitting was 3.6 ppb.
Example 2
A preparation method of a tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification comprises the following specific steps:
(1) weighing 0.4g of sodium hydroxide and 0.5834g of stannic chloride pentahydrate, dissolving in 40mL of deionized water, adding 0.01g of PVP template agent with the relative molecular mass of 10000, stirring for 5 minutes at room temperature, adding into a hydrothermal kettle liner, and carrying out hydrothermal reaction at 100 ℃ for 20 hours to obtain stannic oxide microspheres, wherein the diameter of the stannic oxide microspheres is 1-2 mu m;
(2) adding 0.12050g of tin oxide microspheres, 0.14497g of scandium chloride hexahydrate and 0.10080g of urea into 30mL of deionized water, stirring for 5 minutes at room temperature, adding 32mL of 0.05mol/mL silver nitrate solution, carrying out hydrothermal reaction for 20 minutes at 80 ℃, standing, carrying out centrifugal washing, and drying in an oven at 50 ℃;
(3) and annealing the dried product at 300 ℃ for 1h, and cooling along with the furnace after the heat treatment is finished to obtain the tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification.
The method for manufacturing the hydrogen sensor by using the tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification obtained by the preparation method specifically comprises the following steps:
(1) weighing 0.1g of tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification, fully grinding for 30min, dropwise adding 2mL of absolute ethyl alcohol, and fully mixing to form mixed slurry;
(2) Dipping the mixed slurry with a cotton swab and coating the mixed slurry on Al with an Au electrode2O3And drying the outer wall of the ceramic tube at 80 ℃ to obtain the hydrogen sensor.
The hydrogen sensor obtained in this example had a detection range of 125ppb to 5ppm, a response time of 3s, a recovery time of 8s, and a response value to hydrogen gas having a concentration of 5ppm of 26 at a working temperature of 200 ℃.
Example 3
A preparation method of a rare earth element doping and precious metal modification based tin oxide-based hydrogen sensing material comprises the following specific steps:
(1) weighing 0.72g of sodium hydroxide and 1.05g of tin pentahydrate, dissolving in 40mL of deionized water, adding 0.05g of PVP template agent with the relative molecular mass of 35000, stirring for 20 minutes at room temperature, adding into an inner container of a hydrothermal kettle, and carrying out hydrothermal reaction at 150 ℃ for 15 hours to obtain tin oxide microspheres, wherein the diameter of the tin oxide microspheres is 1-2 mu m;
(2) adding 0.1205g of tin oxide microspheres, 0.1293g of scandium nitrate and 0.1008g of urea into 30mL of deionized water, stirring for 10 minutes at room temperature, adding 15mL of 0.075mol/mL chloroauric acid solution, carrying out hydrothermal reaction for 10 minutes at 90 ℃, standing, centrifuging, washing, and drying in an oven at 70 ℃;
(3) and annealing the dried product at 600 ℃ for 2h, and cooling the product along with the furnace after the heat treatment is finished to obtain the rare earth element doping and precious metal modification-based tin oxide-based hydrogen sensing material.
The method for manufacturing the hydrogen sensor by using the tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification obtained by the preparation method specifically comprises the following steps:
(1) weighing 0.1g of tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification, fully grinding for 10min, dropwise adding 2mL of absolute ethyl alcohol, and fully mixing to form mixed slurry;
(2) dipping the mixed slurry by a cotton swab and coating the mixed slurry on Al with an Au electrode2O3And drying the outer wall of the ceramic tube at 80 ℃ to obtain the hydrogen sensor.
The hydrogen sensor obtained in this example had a detection range of 125ppb to 5ppm, a response time of 5s, a recovery time of 10s, and a response value to hydrogen gas having a concentration of 5ppm of 28 at a working temperature of 250 ℃.
Example 4
A preparation method of a rare earth element doping and precious metal modification based tin oxide-based hydrogen sensing material comprises the following specific steps:
(1) weighing 4g of sodium hydroxide and 3.5741g of stannous sulfate, dissolving the sodium hydroxide and the 3.5741g of stannous sulfate in a mixed solution of 40mL of deionized water and 40mL of absolute ethyl alcohol, adding 1g of PVP template agent with the relative molecular mass of 1300000, stirring the mixture for 30 minutes at room temperature, adding the mixture into an inner container of a hydrothermal kettle, and carrying out hydrothermal reaction for 10 hours at 250 ℃ to obtain stannic oxide microspheres, wherein the diameter of the stannic oxide microspheres is 1-2 mu m;
(2) Adding 1.20570g of tin oxide microspheres, 1.61223g of scandium carbonate and 1.0080g of urea into 30mL of deionized water, stirring for 10 minutes at room temperature, adding 1mL of 0.1mol/mL platinum chloric acid solution, carrying out hydrothermal reaction for 5 minutes at 120 ℃, standing, centrifuging, washing, and drying in an oven at 80 ℃;
(3) and annealing the dried product at 800 ℃ for 5h, and cooling the product along with the furnace after the heat treatment is finished to obtain the tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification.
The method for manufacturing the hydrogen sensor by using the tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification obtained by the preparation method specifically comprises the following steps:
(1) weighing 0.1g of tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification, fully grinding for 10min, dropwise adding 2mL of absolute ethyl alcohol, and fully mixing to form mixed slurry;
(2) dipping the mixed slurry by a cotton swab and coating the mixed slurry on Al with an Au electrode2O3And drying the outer wall of the ceramic tube at 100 ℃ to obtain the hydrogen sensor.
The hydrogen sensor obtained in this example has a detection range of 125ppb to 5ppm, a response time of 4s, a recovery time of 7s, and a response value to hydrogen having a concentration of 5ppm of 21 at an operating temperature of 250 ℃.
Comparative example 1: the comparative example differs from example 1 only in that: no scandium nitrate hydrate was added. The hydrogen sensor obtained in the comparative example has a detection range of 125ppb to 5ppm, a response time of 20s, a recovery time of 25s, and a response value to hydrogen gas having a concentration of 5ppm of 12 at an operating temperature of 240 ℃, and has a significant difference from the effect of example 1.
Comparative example 2: this comparative example differs from example 2 only in that: excess sodium hydroxide was added. The amount of sodium hydroxide added was 5 g. The excessive addition of sodium hydroxide leads to larger pH value of the solution, thus leading the size of the prepared tin oxide microspheres to be reduced and the diameter to be 50 nm; the hydrogen sensor device obtained in this comparative example had a detection range of 125ppb to 5ppm, a response time of 30s, a recovery time of 48s, and a response value to hydrogen gas having a concentration of 5ppm of 9 at an operating temperature of 200 ℃. The effect is remarkably different from that in example 2.
Comparative example 3: this comparative example differs from example 3 only in that: no chloroauric acid solution was added. The hydrogen sensor device obtained in this comparative example had a detection range of 125ppb to 5ppm, a response time of 29s, a recovery time of 46s, and a response value to hydrogen gas having a concentration of 5ppm of 7 at an operating temperature of 250 ℃. The effect was remarkably different from that in example 3.
Comparative example 4: the comparative example differs from example 1 only in that: 80mL of excess absolute ethanol was added. The hydrogen sensor device obtained in this comparative example had a detection range of 125ppb to 5ppm, a response time of 50s, a recovery time of 55s, and a response value to hydrogen gas having a concentration of 5ppm of 11 at an operating temperature of 240 ℃. The detection results were far inferior to those of example 1.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a rare earth element doping and precious metal modification based tin oxide-based hydrogen sensing material is characterized by comprising the following specific steps:
(1) dissolving sodium hydroxide and tin salt in a mixed solution of deionized water and absolute ethyl alcohol or deionized water, adding PVP template agent, stirring at room temperature, and carrying out hydrothermal reaction to obtain tin oxide microspheres, wherein the hydrothermal reaction temperature is 100-250 ℃, and the time is 10-20 h;
(2) Adding the tin oxide microspheres, scandium salt and urea in the step (1) into deionized water, stirring at room temperature, carrying out hydrothermal reaction on the obtained product and a noble metal compound solution in an inner container of a hydrothermal kettle at the temperature of 80-120 ℃ for 5-20 minutes, standing, centrifuging, washing after the reaction is finished, and drying in a drying oven to obtain a tin oxide-based product;
(3) and (3) annealing the tin oxide-based product obtained in the step (2) at 300-800 ℃ for 1-5h, and cooling along with the furnace after the heat treatment is finished to obtain the rare earth element doping and precious metal modification-based tin oxide-based hydrogen sensing material.
2. The preparation method of the tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification according to claim 1, characterized in that: the tin salt is selected from one of stannic chloride pentahydrate, stannous chloride dihydrate and stannous sulfate.
3. The preparation method of the tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification according to claim 1 or 2, characterized by comprising the following steps: the mixing volume ratio of the deionized water to the absolute ethyl alcohol in the step (1) is 1: 1; the sodium hydroxide is added according to the mass-volume ratio of 0.01-0.05g/mL, and the tin salt is added according to the molar ratio of the tin element to the sodium element of 0.1664: 1.
4. The preparation method of the tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification according to claim 3, characterized in that: the relative molecular mass of the PVP template in the step (1) is 10000-: 40mL of the solution was added to a mixed solution of deionized water and absolute ethanol or deionized water.
5. The preparation method of the tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification as claimed in claim 1 or 4, wherein the preparation method comprises the following steps: the scandium salt is selected from one of scandium nitrate, scandium nitrate hydrate, scandium chloride hexahydrate and scandium carbonate; the noble metal compound solution is one of chloroauric acid solution, platinic acid solution, chloropalladite solution and silver nitrate solution.
6. The preparation method of the tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification according to claim 5, characterized in that: in the step (2), the tin oxide microspheres, the scandium salt and the urea are mixed according to a molar ratio of 1: 0.7: 2.1 adding into 30mL deionized water; the concentration of noble metal ions in the noble metal compound solution is 0.05-0.1mol/mL, and the noble metal compound solution is added into deionized water according to the volume ratio of 1-32mL:30 mL.
7. Tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification obtained by the preparation method according to any one of the preceding claims.
8. The use of the rare earth element-doped noble metal-modified tin oxide-based hydrogen sensing material according to claim 7 in a hydrogen sensor.
9. The hydrogen sensor using the rare earth element-doped noble metal-modified tin oxide-based hydrogen sensing material according to claim 7, wherein: the working temperature is 200 ℃ and 250 ℃, the lower limit value of the detection of the hydrogen concentration is 3.6ppb, the response time is 1s-5s, and the recovery time is 5s-10 s.
10. A method for producing a hydrogen sensor according to claim 9, characterized by comprising the steps of:
(1) preparing mixed slurry: grinding 0.1g of tin oxide-based hydrogen sensing material based on rare earth element doping and precious metal modification for 10-30min, dropwise adding 2mL of ethanol, and stirring and fully mixing to form mixed slurry;
(2) coating a ceramic tube: application of the Mixed slurry to Al with Au electrodes2O3And drying the outer wall of the ceramic tube at the temperature of 80-100 ℃ to obtain the hydrogen sensor.
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