A method for constructing a hydrogen sulfide gas sensor driven by a metal monatomic atom and application thereof

Abstract

The application relates to the technical field of hydrogen sulfide gas sensors, in particular to a metal single-atom driven hydrogen sulfide gas sensor construction method and application, which comprises the following steps: dissolving indium trichloride tetrahydrate and thiourea in isopropyl alcohol and deionized water, uniformly stirring, and obtaining a precursor transparent solution; performing a hydrothermal reaction on the precursor solution; obtaining a first dry sample; calcining the first dry sample to obtain an indium oxide nanosphere precursor; uniformly mixing the indium oxide nanosphere precursor with deionized water to obtain a first mixed solution; mixing the first mixed solution with an ammonium carbonate solution, adding a ruthenium acetylacetone solution for mixing to obtain a second mixed solution, centrifuging, and drying to obtain a second dry sample. The second dry sample is calcined to obtain an indium oxide nanosphere gas-sensitive material; the indium oxide nanosphere gas-sensitive material is dispersed in anhydrous ethanol, is drop-coated onto the surface of a planar electrode, and is constructed into a hydrogen sulfide gas sensor; and the application realizes efficient detection of hydrogen sulfide gas.

Description

Technical Field

[0001] This invention relates to the field of hydrogen sulfide gas sensor technology, specifically to a method for constructing and applying a metal single-atom driven hydrogen sulfide gas sensor. Background Technology

[0002] Hydrogen sulfide gas, an acidic and harmful air pollutant, not only has a strong rotten egg smell but is also a colorless, flammable, and corrosive gas. Due to the lack of oxygen in sewers, sulfur-containing organic matter in wastewater is directly decomposed by anaerobic microorganisms, producing hydrogen sulfide gas, which is widely emitted in cities. Among all toxic gases, its toxicity is second only to hydrogen cyanide, and its high toxicity has made it a focus of environmental safety research. Studies have shown that exposure to hydrogen sulfide gas can lead to a range of health effects in humans, including respiratory, nervous, metabolic, reproductive, and even death problems. Long-term exposure to low concentrations of H2S can cause discomfort to the central nervous system; short-term exposure to high concentrations of H2S can cause loss of smell and even death. Therefore, there is a need for a highly efficient, miniaturized, highly sensitive, fast-response, and low-power H2S gas sensor.

[0003] Indium oxide (IO) is a wide-bandgap n-type metal oxide semiconductor (Eg = 3.55–3.75 eV) with abundant oxygen vacancies, excellent conductivity, and superior electrochemical stability. As a highly sensitive gas-sensitive material, it is widely used in gas sensors. However, most metal oxide semiconductors suffer from drawbacks such as slow response recovery, poor selectivity, and poor stability. A deeper understanding of the application areas of single-atom catalysts has revealed that modifying metal oxide semiconductors with noble metal single atoms exhibits higher selectivity and sensitivity compared to metal oxide semiconductors alone. However, there are few reports on using single-atom catalysis to detect hydrogen sulfide gas in resistive metal oxide gas sensors with the achievement of high sensitivity and selectivity.

[0004] Therefore, the hydrogen sulfide gas sensor based on ruthenium single-atom catalytic indium oxide nanosphere composite gas-sensitive material that we proposed has a wide range of applications. It can not only protect human health, but also monitor the environment and contribute to environmental protection. Summary of the Invention

[0005] The purpose of this invention is to provide a method for constructing a semiconductor gas sensor for detecting hydrogen sulfide gas and its application, so as to solve the problems mentioned above.

[0006] The technical problem solved by this invention is:

[0007] The objective of this invention can be achieved through the following technical solutions:

[0008] A method for constructing a metal single-atom driven hydrogen sulfide gas sensor includes the following steps:

[0009] Indium trichloride tetrahydrate and thiourea were dissolved in isopropanol and deionized water and stirred evenly to obtain a transparent precursor solution; the precursor solution was subjected to a hydrothermal reaction for 16 hours.

[0010] After the hydrothermal reaction was completed, the sample was naturally cooled to room temperature, washed, centrifuged, and dried to obtain the first dried sample.

[0011] The first dried sample was calcined in air at 500°C for 2 hours to obtain indium oxide nanosphere precursor.

[0012] The indium oxide nanosphere precursor was mixed with deionized water to obtain a first mixed solution. The first mixed solution was then mixed with ammonium carbonate solution, and then ruthenium acetylacetone solution was added and mixed to obtain a second mixed solution. Finally, the second mixed solution was centrifuged and dried to obtain a second dried sample.

[0013] The second dried sample was calcined at 500°C for 2 hours in an argon atmosphere to obtain ruthenium single-atom catalyzed indium oxide nanosphere gas-sensitive material;

[0014] Ruthenium single-atom catalyzed indium oxide nanospheres were dispersed in anhydrous ethanol and further drop-coated onto the surface of a planar electrode to construct a hydrogen sulfide gas sensor.

[0015] As a further embodiment of the present invention, the ratio of indium trichloride tetrahydrate, thiourea, isopropanol and deionized water is 586.4 mg: 456.8 mg: 22 mL: 4 mL.

[0016] As a further aspect of the present invention: the washing, centrifugation, and drying process of the first dried sample includes: centrifugation washing 4 times, centrifugation speed of 8000 rpm, and centrifugation time of 5 min.

[0017] As a further aspect of the present invention: the drying temperature of the first dried sample and the second dried sample is 60-80℃, and the drying time is 6-48h.

[0018] As a further aspect of the present invention: the heating rate during the calcination process of the first and second dried samples is 2°C·min. -1 .

[0019] As a further aspect of the present invention: the parameters for centrifuging the second mixed solution are: centrifugation washing once, centrifugation speed of 8000 rpm, and centrifugation time of 5 min.

[0020] As a further aspect of the present invention: the morphology of the ruthenium single-atom catalyzed indium oxide nanosphere composite gas-sensitive material is spherical.

[0021] As a further aspect of the present invention, the particle size of the ruthenium single-atom catalyzed indium oxide nanosphere composite gas-sensitive material is 7 μm.

[0022] An application of a metal single-atom driven hydrogen sulfide gas sensor, such as the ruthenium single-atom catalytic indium oxide nanosphere composite gas-sensitive material prepared by the above method, wherein the ruthenium single-atom catalytic indium oxide nanosphere composite gas-sensitive material is dispersed in anhydrous ethanol, and then drop-coated onto the surface of a planar electrode by a pipette, and after it is completely dried, a gas sensor is formed, which is further used for hydrogen sulfide gas sensing and testing.

[0023] The beneficial effects of this invention are:

[0024] The preparation method of the indium oxide nanosphere composite gas-sensitive material catalyzed by ruthenium single atom in this invention is simple and easy to operate. The sensor constructed based on the obtained indium oxide nanosphere composite gas-sensitive material catalyzed by ruthenium single atom exhibits excellent sensing characteristics such as high sensitivity, high stability and high selectivity for hydrogen sulfide gas.

[0025] In the process of constructing a hydrogen sulfide gas sensor using ruthenium single-atom catalyzed indium oxide nanosphere composite gas-sensitive material, the prepared ruthenium single-atom catalyzed indium oxide nanosphere composite gas-sensitive material is processed through a sensor sensitive thin film process to construct a hydrogen sulfide gas sensor, which can realize a rapid sensing response to hydrogen sulfide gas and exhibit excellent gas-sensing characteristics. Attached Figure Description

[0026] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0027] Figure 1 These are SEM images of the ruthenium single-atom catalyzed indium oxide nanosphere composite gas-sensitive material sample prepared according to the present invention;

[0028] Figure 2 These are XRD images of the ruthenium single-atom catalyzed indium oxide nanosphere composite gas-sensitive material provided by this invention;

[0029] Figure 3 The gas-sensing performance (Response(R)) of the ruthenium single-atom catalyzed indium oxide nanosphere composite gas-sensing material prepared in this invention to hydrogen sulfide gas at an operating temperature of 175°C was tested. air / R gas )-Time(s) curve;

[0030] Figure 4The bar graph shows the gas-sensing response values ​​of the ruthenium single-atom catalyzed indium oxide nanosphere composite gas-sensing material prepared in this invention to seven gases—hydrogen, methane, ammonia, sulfur dioxide, nitrogen dioxide, trimethylamine, and hydrogen sulfide—at an operating temperature of 175°C. Detailed Implementation

[0031] To enable those skilled in the art to better understand the present invention, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. 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 should fall within the scope of protection of the present invention.

[0032] Example 1

[0033] The present invention provides a method for constructing a metal single-atom driven hydrogen sulfide gas sensor, which specifically includes the following steps:

[0034] Step 1: Weigh 586.4 mg of indium trichloride tetrahydrate and 456.8 mg of thiourea, dissolve them simultaneously in 22 ml of isopropanol and 4 mL of deionized water, stir evenly for 30 min to obtain a transparent precursor solution; transfer the transparent precursor solution to a 50 mL polytetrafluoroethylene liner, seal the liner and place it in a reaction vessel, and place the reaction vessel in an oven for hydrothermal reaction for 16 h;

[0035] Step 2: After the hydrothermal reaction is completed, wait for the reactor to cool naturally to room temperature, open the reactor and take out the liner. Transfer the suspension in the liner to a 50mL centrifuge tube, wash and centrifuge the brick-red precipitate in the liner with deionized water and anhydrous ethanol, and dry the collected brick-red precipitate.

[0036] Among them, the brick-red precipitate in the lining was centrifuged and washed 4 times at a speed of 8000 rpm for 5 minutes; the drying temperature was 60-80℃ and the drying time was 6-48 hours.

[0037] Step 3: Calcine the obtained dried sample at 500℃ in air for 2 hours to obtain indium oxide gas-sensitive material;

[0038] The heating rate during the calcination process is 2℃·min. -1 ;

[0039] Step 4: Weigh 0.100g of the prepared indium oxide nanosphere precursor, mix it with 5mL of deionized water, stir with a magnetic stirrer for 5min to obtain the first mixed solution, mix the first mixed solution with 2.5ml of 1mol / L ammonium carbonate solution, add 50μL of ruthenium acetylacetone solution, stir the above mixed solution with a magnetic stirrer for 2h to obtain the second mixed solution, and finally centrifuge the second mixed solution in a centrifuge for 5min, and dry the precipitate after removing the supernatant;

[0040] The drying temperature is 60-80℃, and the drying time is 6-48 hours.

[0041] Step 5: Calcine the dried sample obtained in Step 4 at 500℃ for 2 hours in an argon atmosphere to obtain ruthenium single-atom catalyzed indium oxide nanosphere gas-sensitive material;

[0042] The heating rate during the calcination process is 2℃·min. -1 The morphology of the ruthenium single-atom catalyzed indium oxide nanosphere composite gas-sensitive material is spherical with a particle size of about 7 μm.

[0043] Step 6: Disperse 2 mg of ruthenium single-atom catalyzed indium oxide nanospheres in 30 μL of anhydrous ethanol, and further drop-coat them onto the surface of a planar electrode to construct a semiconductor sensor that can be used to detect hydrogen sulfide gas.

[0044] The preparation process of the ruthenium single-atom catalyzed indium oxide nanosphere composite gas-sensitive material is simple and easy, and the sensor constructed based on the ruthenium single-atom catalyzed indium oxide nanosphere composite gas-sensitive material exhibits high sensitivity, high stability, and high selectivity in the detection of hydrogen sulfide gas.

[0045] Example 2

[0046] This invention provides an application of a metal single-atom driven hydrogen sulfide gas sensor. The ruthenium single-atom catalyzed indium oxide nanosphere composite gas-sensitive material prepared in the above embodiments can be used for the rapid detection of hydrogen sulfide gas. Specifically:

[0047] Two mg of ruthenium single-atom catalyzed indium oxide nanospheres were dispersed in 30 μL of anhydrous ethanol and then further drop-coated onto the surface of a planar electrode to construct a semiconductor sensor that can be used to detect hydrogen sulfide gas.

[0048] In the production process of using ruthenium single-atom catalyzed indium oxide nanosphere composite gas-sensitive material for hydrogen sulfide gas sensors, the ruthenium single-atom catalyzed indium oxide nanosphere composite gas-sensitive material prepared in the above embodiments is used to construct a hydrogen sulfide gas sensor through sensor sensitive film technology. This enables rapid sensing response to hydrogen sulfide gas and quickly exhibits excellent gas-sensing characteristics.

[0049] Performance testing

[0050] During the morphology observation and performance testing of the ruthenium single-atom catalyzed indium oxide nanosphere composite gas-sensitive material samples prepared in the above embodiments, the following results were obtained:

[0051] (1) such as Figure 1 As shown, from Figure 1 The synthesized ruthenium single-atom catalyzed indium oxide nanospheres have a diameter of approximately 7 μm. SEM characterization reveals that the indium oxide nanospheres are composed of single atoms with an uneven surface. This structure gives the ruthenium single-atom catalyzed indium oxide nanospheres a large specific surface area, increasing the contact area between gas molecules and the material, and promoting adsorption and diffusion. The introduction of ruthenium single atoms generates numerous adsorption sites on the indium oxide surface, thereby improving the sensitivity and selectivity for hydrogen sulfide gas and ensuring stability in practical applications.

[0052] (2) For example Figure 2 As shown, it is evident that there are distinct diffraction peaks at 21.50°, 30.58°, 35.47°, 45.69°, 51.04°, 55.99°, and 60.68° at the 2θ angle, corresponding to the (211), (222), (400), (431), (440), (611), and (622) crystal planes of indium oxide, respectively. The XRD diffraction pattern agrees well with the standard card (JCPDS No. 06–0416), confirming the presence of indium oxide in the composite sample. Furthermore, no additional diffraction peaks were observed in the sample, indicating its high crystallinity and the absence of impurity peaks.

[0053] In the gas-sensitive application of the indium oxide nanomaterial described above in this invention, the indium oxide nanomaterial is dispersed in a small amount of ethanol, then drop-coated onto the surface of a planar electrode using a pipette, and after natural drying, it is further constructed into a gas sensor, which is then used for gas-sensitive detection. The sensor is used to perform gas-sensitive testing on hydrogen sulfide gas at an operating temperature of 175°C.

[0054] (3) such as Figure 3 The figure shows the dynamic response curves of a sensor fabricated using indium oxide nanospheres based on ruthenium single-atom catalysis to different concentrations (1 to 10 ppm) of hydrogen sulfide gas at an operating temperature of 175°C and a humidity of 40%. The figure shows that the sensor based on indium oxide nanospheres using ruthenium single-atom catalysis has a response value of 3.5 at 1 ppm and reaches 70.43 at 10 ppm, highlighting its excellent sensing performance. Furthermore, the sensitivity of this gas sensor increases with increasing hydrogen sulfide gas concentration, indicating that the fabricated sensor has good reversibility.

[0055] (4) such as Figure 4 The figure shows a bar graph illustrating the response values ​​of a sensor fabricated using indium oxide nanospheres based on ruthenium single-atom catalysis to seven gases (hydrogen, methane, ammonia, sulfur dioxide, nitrogen dioxide, trimethylamine, and hydrogen sulfide) at a concentration of 10 ppm, operating at 40% humidity and 175°C. The graph demonstrates that the sensor based on indium oxide nanospheres using ruthenium single-atom catalysis exhibits a good response to hydrogen sulfide.

[0056] In summary, the ruthenium single-atom catalyzed indium oxide nanosphere composite gas-sensitive material of the present invention exhibits excellent gas-sensing performance at 175°C.

[0057] 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 method for constructing a metal single-atom driven hydrogen sulfide gas sensor, characterized in that, Includes the following steps: Indium trichloride tetrahydrate and thiourea were dissolved in isopropanol and deionized water and stirred evenly to obtain a transparent precursor solution; the precursor solution was subjected to a hydrothermal reaction for 16 hours. After the hydrothermal reaction was completed, the sample was naturally cooled to room temperature, washed, centrifuged, and dried to obtain the first dried sample. The first dried sample was calcined in air at 500°C for 2 hours to obtain indium oxide nanosphere precursor. The indium oxide nanosphere precursor was mixed with deionized water to obtain a first mixed solution. The first mixed solution was then mixed with ammonium carbonate solution, and then ruthenium acetylacetone solution was added and mixed to obtain a second mixed solution. Finally, the second mixed solution was centrifuged and dried to obtain a second dried sample. The second dried sample was calcined at 500°C for 2 hours in an argon atmosphere to obtain ruthenium single-atom catalyzed indium oxide nanosphere gas-sensitive material; Ruthenium single-atom catalyzed indium oxide nanospheres were dispersed in anhydrous ethanol and further drop-coated onto the surface of a planar electrode to construct a hydrogen sulfide gas sensor. The ratio of indium trichloride tetrahydrate, thiourea, isopropanol, and deionized water is 586.4 mg: 456.8 mg: 22 mL: 4 mL; A ruthenium single-atom catalyzed indium oxide nanosphere composite gas-sensitive material was developed, and at 175°C, the response value reached 70.43 at a concentration of 10 ppm.

2. The method for constructing a metal single-atom driven hydrogen sulfide gas sensor according to claim 1, characterized in that, The washing, centrifugation, and drying process of the first dried sample includes: centrifugation washing 4 times, centrifugation speed of 8000 rpm, and centrifugation time of 5 min.

3. The method for constructing a metal single-atom driven hydrogen sulfide gas sensor according to claim 1, characterized in that, The drying temperature for the first and second dried samples was 60-80℃, and the drying time was 6-48h.

4. The method for constructing a metal single-atom driven hydrogen sulfide gas sensor according to claim 1, characterized in that, The heating rate during the calcination process of the first and second dried samples was 2℃·min. -1 .

5. The method for constructing a metal single-atom driven hydrogen sulfide gas sensor according to claim 1, characterized in that, The parameters for centrifuging the second mixed solution were: centrifugation wash once, centrifugation speed of 8000 rpm, and centrifugation time of 5 min.

6. The method for constructing a metal single-atom driven hydrogen sulfide gas sensor according to claim 1, characterized in that, The morphology of the ruthenium single-atom catalyzed indium oxide nanosphere composite gas-sensitive material is spherical.

7. The method for constructing a metal single-atom driven hydrogen sulfide gas sensor according to claim 1, characterized in that, The particle size of the ruthenium single-atom catalyzed indium oxide nanosphere composite gas-sensitive material is 7 μm.

8. An application of a metal single-atom driven hydrogen sulfide gas sensor, characterized in that, The ruthenium single-atom catalytic indium oxide nanosphere composite gas-sensitive material prepared by the method according to any one of claims 1-7 is dispersed in anhydrous ethanol, then drop-coated onto the surface of a planar electrode by a pipette, and after it is completely dried, it is used to form a gas sensor and further used for hydrogen sulfide gas sensing test.

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