CSHS reaction device and application thereof in preparation of semiconductor hydrogen sulfide sensing material

Abstract

The CSHS reaction device comprises a liquid phase conveying system, a reaction system, a temperature control system and a sample collection system, the liquid phase conveying system consists of three same high-pressure conveying pumps for liquid chromatography, corresponding liquid phase pipelines and adapters; the reaction system consists of two sets of electric heating devices, corresponding liquid phase pipelines and adapters; the temperature control system controls the two sets of electric heating devices to enable the electric heating devices to be subjected to programmed temperature rise and stabilize the temperature to be 400 DEG C or above; and the sample collection system consists of a water cooling device, a filter and a back pressure valve. The CSHS reaction device is applied to preparation of a semiconductor H2S sensing material, is good in structural consistency and excellent in sensing performance, and can meet application requirements.

Description

Technical Field

[0001] The present invention relates to the technical field of metal oxide semiconductor gas sensing materials, and in particular to a continuous supercritical hydrothermal synthesis (CSHS) reaction device and an application thereof in preparing semiconductor hydrogen sulfide (H2S) sensing materials. Technical Background

[0002] H2S is a colorless gas with a strong odor and is neurotoxic. H2S usually accumulates in closed places with insufficient ventilation, such as basements and sewer pipes. The odor threshold of H2S is 0.012-0.03 mg / m 3 , below the minimum concentration that causes harm. When the H2S concentration reaches 5ppm, it has a strong, pungent smell of rotten eggs; at high concentrations, people may lose their sense of smell to H2S, which increases the risk of exposure to harmful levels. When the H2S concentration exceeds 100ppm, the H2S gas will quickly paralyze the human body's olfactory nerves and cause the sense of smell to disappear; when the H2S concentration exceeds 1000ppm, it will cause instant paralysis and "electric shock-like" death.

[0003] Gas sensors based on metal oxide semiconductor materials are widely favored in the fields of environmental protection, pollution prevention, safety monitoring, etc. due to their excellent sensing ability, easy integration, and low cost. They are an important tool for effectively detecting toxic and harmful gases. However, for the detection of H2S gas, there are still problems such as high detection limit, poor selectivity, and inability to fully recover. Therefore, the study of H2S gas sensing materials with low detection limit, high selectivity, and good response-recovery ability is the development frontier and research hotspot of the sensor industry. At present, the preparation methods of H2S sensing materials include the general hydrothermal method and calcination method disclosed in CN 113049646 A and CN116973409 A. Compared with them, CSHS technology has obvious advantages, such as no need to use organic additives in the reaction, no need for calcination, continuous and efficient preparation, short preparation cycle, and high output. Summary of the invention

[0004] In view of the problems existing in the background technology, the object of the present invention is to provide a CSHS reaction device and its application in preparing semiconductor H2S sensing materials.

[0005] The technical solution for implementing the present invention is as follows:

[0006] A CSHS reaction device comprises a liquid phase delivery system, a reaction system, a temperature control system and a sample collection system.

[0007] Furthermore, the liquid phase delivery system is composed of three identical high-pressure delivery pumps for liquid chromatography and corresponding liquid phase pipelines and adapters, which are used to deliver deionized water, precursor solution and auxiliary solution respectively.

[0008] Furthermore, the reaction system consists of two sets of electric heating devices and corresponding liquid phase pipelines and adapters. The first set of electric heating devices is used to heat room temperature high-pressure deionized water to 400°C-550°C to achieve a supercritical state; the second set of electric heating devices is used to insulate the straight pipe section at the mixer outlet so that the contact time between the mixed solution of the precursor and the additive and the supercritical water reaches more than 2s.

[0009] Furthermore, the temperature control system controls the two sets of electric heating devices to program the temperature rise and stabilize the temperature at above 400°C.

[0010] Furthermore, the sample collection system is composed of a water cooling device, a filter, and a back pressure valve. The prepared nanomaterial flows out of the sample collection system in the form of a suspension after cooling and pressure relief.

[0011] The present invention also provides an application of a CSHS reaction device in preparing a semiconductor H2S sensing material, comprising the following steps:

[0012] Step 1: Prepare the precursor solution of Sn element;

[0013] Step 2: preparing a precursor solution of Sb element;

[0014] Step 3: using a CSHS reaction device to synthesize and prepare SnO2 semiconductor H2S sensing materials doped with different contents of Sb, and obtaining suspensions of nano SnO2 semiconductor H2S sensing materials doped with different contents of Sb;

[0015] Step 4: After the reaction is completed, the nano suspension is collected and precipitated, and then centrifuged and washed repeatedly, and then frozen using a freeze dryer, the powder is taken out, ground and placed in a glass container, the air in the bottle is exhausted using argon gas, and the edge is sealed with a sealing tape to obtain nano SnO2 semiconductor H2S sensing material powders doped with different contents of Sb;

[0016] Step 5: Weigh nano-SnO2 semiconductor H2S sensing material powders doped with different contents of Sb, put ultrapure water in a sample tube, mix evenly, then absorb the mixed liquid, drop it on the interdigitated electrode sheet, dry it on a heating table and let it stand to obtain the electrode sheet for testing the H2S sensing performance.

[0017] Furthermore, the method for preparing a precursor solution of the Sn element in step one comprises the following steps: measuring a target volume of ultrapure water with a measuring cylinder, placing it in a reagent bottle, measuring the density of SnCl4, measuring a target volume of liquid SnCl4 with a pipette, placing it in a reagent bottle, placing the reagent bottle on a magnetic stirrer after the solute is dissolved, and stirring for a certain period of time to obtain a precursor solution of the Sn element.

[0018] Furthermore, the method for preparing a precursor solution of the Sb element in step 2 comprises the following steps: measuring a target volume of ultrapure water into a reagent bottle using a measuring cylinder, weighing a certain amount of SbCl3 crystals, placing them in the reagent bottle, and adding a certain amount of NaOH to the SbCl3 solution; after the solute is dissolved, placing the reagent bottle on a magnetic stirrer, stirring for a certain period of time, to obtain a precursor solution of the Sb element.

[0019] Furthermore, the total concentration of metal ions in the precursor solution of the Sn element and the precursor solution of the Sb element is controlled to be 0.02 mol / L.

[0020] Furthermore, the molar percentage of the Sb element in the total concentration of metal ions in the two bottles of precursor solutions is 1-10%, and the molar percentage of the Sn element in the total concentration of metal ions in the two bottles of solutions is 99%-90%.

[0021] Compared with the prior art, the present invention has the following advantages:

[0022] (1) CSHS technology has the characteristics of environmentally friendly process, suitable for preparing multi-component composite metal oxide materials, continuous and rapid preparation, controllable reaction conditions, low production cost and conducive to industrialization. Therefore, the present invention uses CSHS technology to prepare nano SnO2 semiconductor H2S sensing materials, and introduces Sb elements to dope and modify nano SnO2 semiconductor H2S sensing materials during the synthesis process by adjusting the type and concentration of the precursor solution and adjusting the reaction conditions, which is of great value in improving the H2S sensing performance of SnO2 semiconductor materials.

[0023] (2) The present invention uses a CSHS reaction device to prepare a semiconductor H2S sensing material, which has good structural consistency and excellent sensing performance. The preparation method is green, energy-saving, and efficient, and can achieve 24h continuous preparation with a large material output. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 : Schematic diagram of the CSHS device.

[0025] Figure 2 : The sensing response value of the 1% Sb-doped nano-SnO2 semiconductor H2S sensing material in Example 1 to 100ppmH2S at different temperatures; test conditions: H2S concentration: 100ppm, O2 concentration: 20%, N2 as supplementary gas, total flow rate: 3L / min, reaction temperature 50-240℃.

[0026] Figure 3: Sensing response recovery curves of nano-SnO2 semiconductor H2S sensing materials doped with different contents of Sb in Example 1, Example 2 and Example 3 to 100ppm H2S at 240°C; Test conditions: H2S concentration: 100ppm, O2 concentration: 20%, N2 as supplementary gas, total gas volume: 3L / min, reaction temperature 240°C.

[0027] Figure 4 : The selectivity of the 1% Sb-doped nano-SnO2 semiconductor H2S sensing material in Example 1 to five gases at 240°C.

[0028] Figure 5 : Sensing response recovery curves of the 1% Sb-doped nano-SnO2 semiconductor H2S sensing material prepared using supercritical hydrothermal technology in Example 1 and the 1% Sb-doped SnO2 semiconductor H2S sensing material prepared using traditional co-precipitation method to 100ppmH2S at 240°C; Test conditions: H2S concentration: 100ppm, O2 concentration: 20%, N2 as supplementary gas, total gas volume: 3L / min, reaction temperature 240°C.

[0029] Figure 6 : XRD patterns of nano-SnO2 semiconductor H2S sensing materials doped with different contents of Sb in Example 1, Example 2 and Example 3.

[0030] Note: The Sb-doped nano SnO2 semiconductor H2S sensing material prepared in the present invention is an N-type semiconductor. For an N-type semiconductor, the sensitivity S is defined as the ratio of the resistance value (Ra) of the gas sensor element in clean air to the resistance value (Rg) in the target gas, that is, S = Ra / Rg. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and examples. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. On the contrary, the present invention encompasses any substitutions, modifications, equivalent methods and schemes made on the essence and scope of the present invention as defined by the claims. Further, in order to enable the public to have a better understanding of the present invention, some specific details are described in detail in the detailed description of the present invention below. For those skilled in the art, the present invention can be fully understood without the description of these details.

[0032] Example 1

[0033] An application of a CSHS reaction device in preparing a semiconductor H2S sensing material comprises the following steps:

[0034] Step 1: Prepare 1L of Sn element precursor solution. Use a measuring cylinder to accurately measure 1L of ultrapure water and place it in a reagent bottle. Take 1000μL of liquid SnCl4 and weigh it. Measure the density three times and take the average value as 2.17g / ml. Use a pipette to measure 2395μL of liquid SnCl4 and place it in a reagent bottle. After the solute is dissolved, place the reagent bottle on a magnetic stirrer and stir at 600r / min for 30min to obtain 1L of Sn element precursor solution.

[0035] Step 2: Prepare 1L of precursor solution of Sb element. Use a measuring cylinder to accurately measure 1L of ultrapure water into a reagent bottle, use a balance to accurately weigh 46mg of SbCl3 crystals, place them in a reagent bottle, and add a certain amount of NaOH to the SbCl3 solution to inhibit the hydrolysis of SbCl3. After the solute is dissolved, place the reagent bottle on a magnetic stirrer and stir at a speed of 600r / min for 30min to obtain 1L of precursor solution of Sb element. The total concentration of metal ions in the two bottles of precursor solutions is controlled to be 0.02mol / L. At this time, the molar percentage of Sb element in the total concentration of metal ions in the two bottles of precursor solutions is 1%, and the molar percentage of Sn element in the total concentration of metal ions in the two bottles of solutions is 99%.

[0036] Step 3: Use the self-built CSHS reaction device (see Figure 1 ) was used to synthesize and prepare 1% Sb-doped SnO2 semiconductor H2S sensing material.

[0037] The process of preparing 1% Sb-doped SnO2 semiconductor H2S sensing material using the CSHS device: three high-pressure delivery pumps for liquid chromatography pump ultrapure water, Sn element precursor solution, and Sb element precursor solution at room temperature at 20mL / min, 10mL / min, and 10mL / min respectively, and give the three pipelines an initial pressure of 22.5Mpa. The back pressure valve at the end outlet of the system is used to maintain the internal pressure of the entire system stable. The precursor solutions of Sn and Sb elements at room temperature and high pressure are introduced into a three-way mixer for primary mixing. At the same time, ultrapure water at room temperature and high pressure flows through an electric heating device (large) and is heated to 450°C to reach a supercritical state. Then, the precursor mixed solution of Sn and Sb elements and supercritical water are introduced into a four-way mixer for secondary mixing. After being fully mixed, they flow into the electric heating device (small). The temperature is still maintained at 450°C, and the precursor mixed solution of Sn and Sb elements is fully contacted with supercritical water for more than 2s to react. After contacting with supercritical water, the precursor mixed solution of Sn and Sb elements reacts rapidly and crystallizes to generate nano-oxides. After the reaction liquid flows out of the electric heating device (small), it enters the sample collection system for cooling, pressure relief, and filtration, and finally a suspension of 1% Sb-doped nano-SnO2 semiconductor H2S sensing material is obtained.

[0038] Step 4: After the reaction is completed, the nano suspension is collected and settled for 12 hours, and then centrifuged and washed repeatedly for 6 times, and then frozen for 4 hours in a freeze dryer and freeze-dried for 24 hours. The powder is taken out, ground and placed in a glass container, and the air in the bottle is exhausted with argon gas. The edge is sealed with sealing tape to obtain 1% Sb-doped nano SnO2 semiconductor H2S sensing material powder.

[0039] Step 5: Use a balance to weigh 100 mg of the 1% Sb-doped nano-SnO2 semiconductor H2S sensing material powder obtained in step 4, use a pipette to measure 500 μL of ultrapure water, put it in a sample tube, mix it evenly, use a pipette to absorb 2.5 μL of the mixture, and drop it on the interdigitated electrode sheet on the gold substrate. Use a 70°C heating table to dry it and let it stand for 30 minutes to obtain an electrode that can be used to test the H2S sensing performance.

[0040] Example 2

[0041] An application of a CSHS reaction device in preparing a semiconductor H2S sensing material comprises the following steps:

[0042] Step 1: Prepare 1L of Sn element precursor solution. Use a measuring cylinder to accurately measure 1L of ultrapure water and place it in a reagent bottle. Take 1000μL of liquid SnCl4 and weigh it. Measure the density three times and take the average value as 2.17g / ml. Use a pipette to measure 2347μL of liquid SnCl4 and place it in a reagent bottle. After the solute is dissolved, place the reagent bottle on a magnetic stirrer and stir at 600r / min for 30min to obtain 1L of Sn element precursor solution.

[0043] Step 2: Prepare 1L of precursor solution of Sb element. Use a measuring cylinder to accurately measure 1L of ultrapure water into a reagent bottle, use a balance to accurately weigh 138mg of SbCl3 crystals, place them in a reagent bottle, and add a certain amount of NaOH to the SbCl3 solution to inhibit the hydrolysis of SbCl3. After the solute is dissolved, place the reagent bottle on a magnetic stirrer and stir at a speed of 600r / min for 30min to obtain 1L of precursor solution of Sb element. The total concentration of metal ions in the two bottles of precursor solutions is controlled to be 0.02mol / L. At this time, the molar percentage of Sb element in the total concentration of metal ions in the two bottles of precursor solutions is 3%, and the molar percentage of Sn element in the total concentration of metal ions in the two bottles of solutions is 97%.

[0044] Step 3: Use the self-built CSHS reaction device (see Figure 1 ) was used to synthesize and prepare 3% Sb-doped SnO2 semiconductor H2S sensing material.

[0045] The process of preparing 3% Sb-doped SnO2 semiconductor H2S sensing material using the CSHS device: three high-pressure delivery pumps for liquid chromatography pump ultrapure water, Sn element precursor solution, and Sb element precursor solution at room temperature at 20mL / min, 10mL / min, and 10mL / min respectively, and give the three pipelines an initial pressure of 22.5Mpa. The back pressure valve at the end outlet of the system is used to maintain the internal pressure of the entire system stable. The precursor solutions of Sn and Sb elements at room temperature and high pressure are introduced into a three-way mixer for primary mixing. At the same time, ultrapure water at room temperature and high pressure flows through an electric heating device (large) and is heated to 450°C to reach a supercritical state. Then, the precursor mixed solution of Sn and Sb elements and supercritical water are introduced into a four-way mixer for secondary mixing. After being fully mixed, they flow into the electric heating device (small). The temperature is still maintained at 450°C, and the precursor mixed solution of Sn and Sb elements is fully contacted with supercritical water for more than 2s to react. After contacting with supercritical water, the precursor mixed solution of Sn and Sb elements reacts rapidly and crystallizes to generate nano-oxides. After the reaction liquid flows out of the electric heating device (small), it enters the sample collection system for cooling, pressure relief, and filtration, and finally a suspension of 3% Sb-doped nano-SnO2 semiconductor H2S sensing material is obtained.

[0046] Step 4: After the reaction is completed, the nano suspension is collected and settled for 12 hours, and then centrifuged and washed repeatedly for 6 times, and then frozen for 4 hours in a freeze dryer and freeze-dried for 24 hours. The powder is taken out, ground and placed in a glass container, and the air in the bottle is exhausted with argon gas. The edge is sealed with sealing tape to obtain 3% Sb-doped nano SnO2 semiconductor H2S sensing material powder.

[0047] Step 5: Use a balance to weigh 100 mg of the 3% Sb-doped nano-SnO2 semiconductor H2S sensing material powder obtained in step 4, use a pipette to measure 500 μL of ultrapure water, put it in a sample tube, mix it evenly, use a pipette to absorb 2.5 μL of the mixture, and drop it on the interdigitated electrode sheet on the gold substrate. Use a 70°C heating table to dry it and let it stand for 30 minutes to obtain an electrode that can be used to test the H2S sensing performance.

[0048] Example 3

[0049] An application of a CSHS reaction device in preparing a semiconductor H2S sensing material comprises the following steps:

[0050] Step 1: Prepare 1L of Sn element precursor solution. Use a measuring cylinder to accurately measure 1L of ultrapure water and place it in a reagent bottle. Take 1000μL of liquid SnCl4 and weigh it. Measure the density three times and take the average value as 2.17g / ml. Use a pipette to measure 2299μL of liquid SnCl4 and place it in a reagent bottle. After the solute is dissolved, place the reagent bottle on a magnetic stirrer and stir at 600r / min for 30min to obtain 1L of Sn element precursor solution.

[0051] Step 2: Prepare 1L of precursor solution of Sb element. Use a measuring cylinder to accurately measure 1L of ultrapure water into a reagent bottle, use a balance to accurately weigh 230mg of SbCl3 crystals, place them in the reagent bottle, and add a certain amount of NaOH to the SbCl3 solution to inhibit the hydrolysis of SbCl3. After the solute is dissolved, place the reagent bottle on a magnetic stirrer and stir at a speed of 600r / min for 30min to obtain 1L of precursor solution of Sb element. The total concentration of metal ions in the two bottles of precursor solutions is controlled to be 0.02mol / L. At this time, the molar percentage of Sb element in the total concentration of metal ions in the two bottles of precursor solutions is 5%, and the molar percentage of Sn element in the total concentration of metal ions in the two bottles of solutions is 95%.

[0052] Step 3: Use the self-built CSHS reaction device (see Figure 1 ) was used to synthesize and prepare 5% Sb-doped SnO2 semiconductor H2S sensing material.

[0053] The process of preparing 5% Sb-doped SnO2 semiconductor H2S sensing material using the CSHS device: three high-pressure delivery pumps for liquid chromatography pump ultrapure water, Sn element precursor solution, and Sb element precursor solution at room temperature at 20mL / min, 10mL / min, and 10mL / min respectively, and give the three pipelines an initial pressure of 22.5Mpa. The back pressure valve at the end outlet of the system is used to maintain the internal pressure of the entire system stable. The precursor solutions of Sn and Sb elements at room temperature and high pressure are introduced into a three-way mixer for primary mixing. At the same time, ultrapure water at room temperature and high pressure flows through an electric heating device (large) and is heated to 450°C to reach a supercritical state. Then, the precursor mixed solution of Sn and Sb elements and supercritical water are introduced into a four-way mixer for secondary mixing. After being fully mixed, they flow into the electric heating device (small). The temperature is still maintained at 450°C, and the precursor mixed solution of Sn and Sb elements is fully contacted with supercritical water for more than 2s to react. After contacting with supercritical water, the precursor mixed solution of Sn and Sb elements reacts rapidly and crystallizes to generate nano-oxides. After the reaction liquid flows out of the electric heating device (small), it enters the sample collection system for cooling, pressure relief, and filtration, and finally a suspension of 5% Sb-doped nano-SnO2 semiconductor H2S sensing material is obtained.

[0054] Step 4: After the reaction is completed, the nano suspension is collected and settled for 12 hours, and then centrifuged and washed repeatedly for 6 times, and then frozen for 4 hours in a freeze dryer, freeze-dried for 24 hours, the powder is taken out, ground and placed in a glass container, argon is used to exhaust the air in the bottle, and the edge is sealed with sealing tape to obtain 5% Sb-doped nano SnO2 semiconductor H2S sensing material powder.

[0055] Step 5: Use a balance to weigh 100 mg of the 5% Sb-doped nano-SnO2 semiconductor H2S sensing material powder obtained in step 4, use a pipette to measure 500 μL of ultrapure water, put it in a sample tube, mix it evenly, use a pipette to absorb 2.5 μL of the mixture, and drop it on the interdigitated electrode sheet on the gold substrate. Use a 70°C heating table to dry it and let it stand for 30 minutes to obtain an electrode that can be used to test the H2S sensing performance.

[0056] like Figure 2 As shown, 1% Sb-doped nano-SnO2 semiconductor H2S sensing material has the best sensing response at 240℃.

[0057] like Figure 3 As shown, the nano-SnO2 semiconductor H2S sensing materials doped with different contents of Sb in Example 1, Example 2 and Example 3 all exhibited good sensing responses to 100ppm H2S at 240°C. The response values ​​and specific surface areas of different materials are shown in the following table:

[0058]

[0059] like Figure 4 As shown, the 1% Sb-doped nano-SnO2 semiconductor H2S sensing material in Example 1 exhibits excellent selectivity. As the H2S gas concentration increases, the sensitivity of the sensing material in Example 1 is significantly improved, and a good linear growth relationship is shown between the sensitivity and the concentration.

[0060] like Figure 5 As shown, the performance of the 1% Sb-doped nano-SnO2 semiconductor H2S sensing material prepared by supercritical hydrothermal technology in Example 1 is significantly better than that of the 1% Sb-doped SnO2 semiconductor H2S sensing material prepared by traditional co-precipitation method.

[0061] like Figure 6 As shown, there are no impurity peaks of other phases in the XRD spectra of the nano SnO2 semiconductor H2S sensing materials doped with different contents of Sb in Examples 1, 2 and 3, which are consistent with the standard card. According to the Scherrer formula, the average particle size of the prepared material is between 10-13nm.

Claims

1. A CSHS reaction device, characterized in that: It includes liquid phase delivery system, reaction system, temperature control system and sample collection system.

2. The CSHS reaction device according to claim 1, characterized in that: The liquid phase delivery system is composed of three identical high-pressure delivery pumps for liquid chromatography and corresponding liquid phase pipelines and adapters, which are used to deliver deionized water, precursor solution and auxiliary agent solution respectively.

3. The CSHS reaction device according to claim 1, characterized in that: The reaction system consists of two sets of electric heating devices and corresponding liquid phase pipelines and adapters. The first set of electric heating devices is used to heat room temperature high-pressure deionized water to 400°C-550°C to make it reach a supercritical state; the second set of electric heating devices is used to keep the straight pipe section at the mixer outlet warm so that the contact time between the mixed solution of the precursor and the additive and the supercritical water reaches more than 2s.

4. The CSHS reaction device according to claim 1, characterized in that: The temperature control system controls two sets of electric heating devices to program the temperature rise and stabilize the temperature at above 400°C.

5. The CSHS reaction device according to claim 1, characterized in that: The sample collection system is composed of a water cooling device, a filter and a back pressure valve. The prepared nanometer material flows out of the sample collection system in the form of a suspension after being cooled and depressurized.

6. An application of the CSHS reaction device according to any one of claims 1 to 5 in preparing semiconductor H2S sensing materials, characterized in that: The following steps are involved: Step 1: Prepare the precursor solution of Sn element; Step 2: preparing a precursor solution of Sb element; Step 3: using a CSHS reaction device to synthesize and prepare SnO2 semiconductor H2S sensing materials doped with different contents of Sb, and obtaining suspensions of nano SnO2 semiconductor H2S sensing materials doped with different contents of Sb; Step 4: After the reaction is completed, the nano suspension is collected and precipitated, and then centrifuged and washed repeatedly, and then frozen using a freeze dryer, the powder is taken out, ground and placed in a glass container, the air in the bottle is exhausted using argon gas, and the edge is sealed with a sealing tape to obtain nano SnO2 semiconductor H2S sensing material powders doped with different contents of Sb; Step 5: Weigh nano-SnO2 semiconductor H2S sensing material powders doped with different contents of Sb, put ultrapure water in a sample tube, mix evenly, then absorb the mixed liquid, drop it on the interdigitated electrode sheet, dry it on a heating table and let it stand to obtain the electrode sheet for testing the H2S sensing performance.

7. The use of the CSHS reaction device according to claim 6 in preparing semiconductor H2S sensing materials, characterized in that: The method for preparing a precursor solution of the Sn element in step one comprises the following steps: measuring a target volume of ultrapure water with a measuring cylinder, placing it in a reagent bottle, measuring the density of SnCl4, measuring a target volume of liquid SnCl4 with a pipette, placing it in a reagent bottle, placing the reagent bottle on a magnetic stirrer after the solute is dissolved, stirring for a certain period of time, and obtaining a precursor solution of the Sn element.

8. The use of the CSHS reaction device according to claim 6 in preparing semiconductor H2S sensing materials, characterized in that: The method for preparing a precursor solution of the Sb element in step 2 comprises the following steps: using a measuring cylinder to measure a target volume of ultrapure water into a reagent bottle, weighing a certain amount of SbCl3 crystals, placing them in the reagent bottle, and adding a certain amount of NaOH to the SbCl3 solution; after the solute is dissolved, placing the reagent bottle on a magnetic stirrer, stirring for a certain period of time, and obtaining a precursor solution of the Sb element.

9. The use of the CSHS reaction device according to claim 6 in preparing semiconductor H2S sensing materials, characterized in that: The total concentration of metal ions in the precursor solution of the Sn element and the precursor solution of the Sb element is controlled to be 0.02 mol / L.

10. The use of the CSHS reaction device according to claim 9 in preparing semiconductor H2S sensing materials, characterized in that: The molar percentage of the Sb element in the total concentration of metal ions in the two bottles of precursor solutions is 1-10%, and the molar percentage of the Sn element in the total concentration of metal ions in the two bottles of solutions is 99%-90%.

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