Composite material based on In2O3 and Ti3C2Tx as well as preparation method and application of composite material

Abstract

The invention relates to the field of composite materials and sensors, and discloses a composite material based on In2O3 and Ti3C2Tx as well as a preparation method and application of the composite material. The composite material based on the In2O3 and the Ti < 3 > C < 2 > T < x > comprises the Ti < 3 > C < 2 > T < x > and the In2O3 nanoparticles loaded on the Ti < 3 > C < 2 > T < x >. The composite material based on In2O3 and Ti3C2Tx has a relatively large specific surface area and excellent catalytic activity, can work under a room temperature condition when being applied to a sensor, is high in response speed to H2S, wide in detectable H2S volume concentration range and low in detection lower limit, and is simple in preparation process operation and easy to industrialize.

Description

Technical Field

[0001] The present invention relates to the field of composite materials and sensors, and in particular to a composite material based on In2O3 and Ti3C2T x Composite materials, preparation methods and applications thereof. Background Art

[0002] Hydrogen sulfide (H2S) is a highly toxic and flammable gas widely used in the petroleum, chemical, metallurgical, and pharmaceutical industries. However, H2S leaks pose a serious threat to the production and working environment, potentially causing fires, explosions, and other accidents. It can also cause serious harm to human health. Low concentrations of H2S can cause symptoms such as headaches, dizziness, and nausea, while high concentrations can lead to suffocation and death. Achieving high-performance H2S detection allows for early detection of leaks and the implementation of appropriate measures, ensuring safe industrial production and protecting people in their workplaces and living environments from the threat of H2S poisoning.

[0003] Therefore, it is crucial to achieve quantitative detection of hydrogen sulfide through reliable gas sensors. Traditional chemiresistive gas sensors are usually made of low-cost, small-volume metal oxide semiconductors (MOSs), and play an important role in the field of hydrogen sulfide detection. Among them, In2O3 is a typical N-type MOS material with a wide band gap (3.7eV) and strong oxidation ability. It can effectively promote the oxidation of volatile organic gases. In2O3 has been widely used in the field of gas sensing, but its chemical reaction conditions are relatively harsh, making it not outstanding in practical applications. In addition, single-component In2O3 has problems such as long response recovery time, poor selectivity for target gas and low gas sensitivity in hydrogen sulfide detection, which limits its commercial use in the field of gas sensing. Currently, Ti3C2T x As a high-performance room-temperature conductive two-dimensional material, it has attracted more attention. Summary of the Invention

[0004] The purpose of the present invention is to overcome the problems of low sensitivity, poor selectivity and long response recovery time of H2S sensors in the prior art, and to provide a H2S sensor based on In2O3 and Ti3C2T x Composite materials based on In2O3 and Ti3C2T x The composite material has (In2O3@Ti3C2T x ) has a large specific surface area and excellent catalytic activity. When used in sensors, it can work at room temperature and has a fast response speed to H2S. It can detect a wide range of H2S volume concentrations and has a low detection limit. The preparation process is simple to operate and easy to industrialize.

[0005] In order to achieve the above object, the present invention provides a method based on In2O3 and Ti3C2T xComposite materials based on In2O3 and Ti3C2T x Composite materials include Ti3C2T x and loaded on Ti3C2T x In2O3 nanoparticles on.

[0006] Preferably, the substrate is based on In2O3 and Ti3C2T x Based on the total weight of the composite material, the content of the In2O3 nanoparticles is 5 to 30 wt%, preferably 10 to 20 wt%.

[0007] Preferably, the Ti3C2T x The thickness is 5 to 150 nm, preferably 10 to 100 nm.

[0008] Preferably, the particle size of the In2O3 nanoparticles is 5 to 80 nm, preferably 5 to 40 nm.

[0009] The second aspect of the present invention provides a method for preparing a method based on In2O3 and Ti3C2T x A method for producing a composite material, the method comprising the steps of:

[0010] (1) In2O3 nanoparticles, Ti3C2T x mixing with a first solvent;

[0011] (2) The material obtained in step (1) is subjected to solid-liquid separation, and then the obtained solid phase material is freeze-dried.

[0012] Preferably, in step (1), Ti3C2T x The weight ratio of the amount of the nanoparticles to the amount of In2O3 is 1:0.05-0.5, preferably 1:0.1-0.3.

[0013] Preferably, in step (1), Ti3C2T x The weight ratio of the amount of the first solvent is 1:80-150.

[0014] Preferably, the first solvent is selected from one or more of water, ethanol, acetone and n-hexane.

[0015] Preferably, in step (1), the mixing conditions include: temperature of 60 to 80° C. and time of 8 to 24 hours.

[0016] Preferably, in step (1), the Ti3C2T x The preparation method includes: mixing Ti3AlC2 with a solution containing fluoride ions and hydrogen ions and then performing a first reaction.

[0017] Preferably, the first reaction is carried out at a temperature of 10-50℃ for 24-48h.

[0018] Preferably, in step (1), the In2O3 nanoparticles are prepared by mixing an indate, urea and water, and then carrying out a hydrothermal reaction and a heat treatment.

[0019] Preferably, the concentration of the indate is 0.2-0.5mol / L in terms of indium element.

[0020] Preferably, the concentration of the urea is 0.2-0.8mol / L.

[0021] Preferably, the molar ratio of the indate to the urea is 1:1.5-2.5, wherein the indate is in terms of indium element.

[0022] Preferably, the hydrothermal reaction is carried out at a temperature of 110-180℃ for 8-36h.

[0023] Preferably, the heat treatment is carried out at a temperature of 450-550℃ for 3-10h.

[0024] Preferably, in step (2), the freeze-drying is carried out at a temperature of -70--40℃ for 5-24h.

[0025] The third aspect of the present application provides an In2O3 and Ti3C2T x based composite material prepared by the above method.

[0026] The fourth aspect of the present application provides an application of the above In2O3 and Ti3C2T x based composite material in hydrogen sulfide detection.

[0027] The fifth aspect of the present application provides a hydrogen sulfide sensor, which comprises the above In2O3 and Ti3C2T x based composite material.

[0028] The sixth aspect of the present application provides a method for preparing the above hydrogen sulfide sensor, which comprises the following steps: mixing the above In2O3 and Ti3C2T x based composite material and an organic solvent, and grinding, then coating on the surface of a ceramic tube with an electrode to form a sensing film, and finally vacuum drying.

[0029] Preferably, the weight ratio of the In2O3 and Ti3C2T x based composite material to the organic solvent is 1:1-10, preferably 1:1-5.

[0030] Preferably, the thickness of the sensing film is 100-2000 μm; preferably 200-1000 μm.

[0031] The seventh aspect of the present application provides a method for detecting hydrogen sulfide, which comprises contacting the hydrogen sulfide sensor described above with a mixed gas containing hydrogen sulfide.

[0032] Compared with the prior art, the technical scheme of the present application has the following advantages:

[0033] (1) The composite material based on In2O3 and Ti3C2T x applied in the sensor can work at room temperature, has a fast response speed to H2S, a wide detection range of H2S concentration and a low lower limit of detection, can respond to 0.05 ppm H2S within 10 s, and the detection range is 0.05 ppm-100 ppm. This is mainly because the In2O3 nanoparticles act as active sites to quickly adsorb and dissociate H2S. In addition, the composite material based on In2O3 and Ti3C2T x has a clear hierarchical structure, provides an ideal diffusion channel for the rapid diffusion of H2S, and the In2O3 nanoparticles are embedded in the Ti3C2T x internal hierarchy, which avoids the aggregation of In2O3 nanoparticles and inhibits the collapse of Ti3C2T x , and is conducive to the improvement of charge migration, transmission and sensing performance.

[0034] (2) The method for preparing the composite material based on In2O3 and Ti3C2T x has a simple process operation, is easy to industrialize, and is conducive to the large-scale production and application of the sensor. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 is a scanning electron microscope image of Ti3C2T x prepared in Example 1;

[0036] Figure 2 is a scanning electron microscope image of In2O3 nanoparticles prepared in Example 1;

[0037] Figure 3 is a scanning electron microscope image of In2O3@Ti3C2T x prepared in Example 1;

[0038] Figure 4 is a curve graph of the change of resistance of the hydrogen sulfide sensor prepared in Example 1, Comparative Example 1 and Comparative Example 2 in different concentrations of hydrogen sulfide. DETAILED DESCRIPTION

[0039] The specific embodiments of the present application will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative and explanatory and are not intended to limit the present application.

[0040] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and values are provided as approximate descriptions of the ranges and values. The endpoints of the ranges of values stated are not to be understood as being limited to the precise values recited as endpoints, but rather are meant to be understood flexibly to also include values near the recited range endpoints. For numeric values, the endpoints of the ranges of values are not to be understood as the only values that are included in the range. Rather, the range of values is meant to be flexible and to include values near the recited range endpoints, as well as the recited endpoints.

[0041] In one aspect, the present application provides a composite material based on In2O3 and Ti3C2T x The composite material based on In2O3 and Ti3C2T x includes Ti3C2T x and In2O3 nanoparticles loaded on the Ti3C2T x .

[0042] In a preferred embodiment, in order to improve the stability and sensitivity to hydrogen sulfide gas of the composite material based on In2O3 and Ti3C2T x , the content of the In2O3 nanoparticles is 5-30 wt%, preferably 10-20 wt%, based on the total weight of the composite material based on In2O3 and Ti3C2T x . Specifically, the content of the In2O3 nanoparticles can be 10 wt%, 15 wt% or 20 wt%.

[0043] In a preferred embodiment, the thickness of the Ti3C2T x is 5-150 nm, preferably 10-100 nm. Specifically, the thickness of the Ti3C2T x may be 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm or 100 nm.

[0044] In a preferred embodiment, the particle size of the In2O3 nanoparticles is 5-80 nm, preferably 5-40 nm. Specifically, the particle size of the In2O3 nanoparticles is 5 nm, 8 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm or 40 nm.

[0045] The composite material based on In2O3 and Ti3C2T xThe composite material based on In2O3 and Ti3C2T x xerogel has good conductivity and stability, and good sensitivity and response performance to hydrogen sulfide, which is mainly due to the In2O3 nanoparticles as active sites can quickly adsorb and dissociate H2S, and the Ti3C2T x xerogel can further improve the sensitivity to H2S. In addition, the In2O3 nanoparticles embedded in the Ti3C2T x xerogel inside the hierarchical level avoids the aggregation of In2O3 nanoparticles on the surface and inhibits the collapse of Ti3C2T x xerogel, which is beneficial to the improvement of charge migration, transmission and sensing performance, and improves the utilization rate of In2O3 nanoparticles.

[0046] The second aspect of the application provides a method for preparing a composite material based on In2O3 and Ti3C2T x xerogel, the method comprising the following steps:

[0047] (1) mixing In2O3 nanoparticles, Ti3C2T x xerogel and a first solvent;

[0048] (2) performing solid-liquid separation on the material obtained in step (1), and then freeze-drying the obtained solid material.

[0049] In a preferred embodiment, in order to improve the stability of the composite material based on In2O3 and Ti3C2T x xerogel and the sensitivity to hydrogen sulfide gas, in step (1), the weight ratio of the amount of Ti3C2T x xerogel to the amount of In2O3 nanoparticles is 1:0.05-0.5, preferably 1:0.1-0.3; specifically, the weight ratio of the amount of Ti3C2T x xerogel to the amount of In2O3 nanoparticles can be 1:0.1, 1:0.2 or 1:0.3.

[0050] In a preferred embodiment, in order to better disperse Ti3C2T x xerogel, in step (1), the weight ratio of the amount of Ti3C2T x xerogel to the amount of the first solvent is 1:80-150, preferably 1:100-150; specifically, the weight ratio of the amount of Ti3C2T x xerogel to the amount of the first solvent can be 1:100, 1:110, 1:120, 1:130, 1:140 or 1:150.

[0051] In the present application, there is no special requirement for the first solvent, and any conventional one in the art can be used. In a preferred embodiment, the first solvent is selected from one or more than two of water, ethanol, acetone and n-hexane; in a specific embodiment, the first solvent is water and ethanol, wherein the weight ratio of the amounts of water and ethanol is 1:1-5, preferably 1:1-3.

[0052] In a specific embodiment, in order to further disperse Ti3C2T x In step (1), Ti3C2T x is mixed with the first solvent, followed by ultrasonic treatment, and then mixed with In2O3nanoparticles.

[0053] In a preferred embodiment, in step (1), the ultrasonic treatment is performed under the following conditions: power 300-800 W, temperature 0-30°C, and time 10-300 min; more preferably, the ultrasonic treatment is performed under the following conditions: power 300-600 W, temperature 0-20°C, and time 60-200 min.

[0054] In a preferred embodiment, in order to further improve the stability and sensitivity to hydrogen sulfide gas of the composite material based on In2O3and Ti3C2T x In step (1), the mixing is performed under the following conditions: temperature 60-80°C and time 8-24 h; specifically, the temperature can be 60°C, 65°C, 70°C, 75°C or 80°C, and the time can be 8 h, 12 h, 16 h, 20 h or 24 h.

[0055] In a preferred embodiment, in step (1), the Ti3C2T x is prepared by mixing Ti3AlC2with a solution containing fluoride ions and hydrogen ions, followed by a first reaction.

[0056] In a preferred embodiment, the first reaction is performed under the following conditions: temperature 10-50°C and time 24-48 h; specifically, the temperature can be 10°C, 20°C, 30°C, 35°C, 40°C or 50°C, and the time can be 24 h, 36 h or 48 h.

[0057] In a preferred embodiment, the preparation method of Ti3C2T x further comprises solid-liquid separation, washing, vacuum filtration, drying, ultrasonic treatment and solid-liquid separation of the material after the first reaction, wherein the solid-liquid separation, washing, drying and ultrasonic treatment are conventional in the art.

[0058] In a specific embodiment, the vacuum filtration of the washed material is performed using a polytetrafluoroethylene membrane with a pore size of 0.22 μm.

[0059] In specific embodiments, the Ti3C2T x The preparation method specifically comprises the following steps: mixing Ti3AlC2 and hydrofluoric acid and then performing a reaction, then performing solid-liquid separation and washing until the pH value of the supernatant is 6, then performing vacuum filtration on the washed material by using a polytetrafluoroethylene membrane with a pore size of 0.22 μm, then performing drying in a vacuum drying box, then dispersing the dried material in water and performing low-temperature ultrasonic treatment, and finally performing solid-liquid separation.

[0060] In the present application, the solution containing fluorine ions and hydrogen ions has no special requirements, as long as the fluorine ions and hydrogen ions contained in the solution can remove Al atoms in Ti3AlC2, for example, it can be a mixed solution of hydrofluoric acid or inorganic acid and fluorinated salt.

[0061] The Ti3C2T x prepared by the above method has an accordion-like sheet layer with a thickness of 5-150 nm, which is beneficial to embedding In2O3 nanoparticles inside the Ti3C2T x layer, avoiding the aggregation of In2O3 nano-materials and inhibiting the collapse of Ti3C2T x , and is beneficial to improving the charge migration, transmission and sensing performance, and can also provide an ideal diffusion channel for H2S.

[0062] In preferred embodiments, in step (1), the preparation method of the In2O3 nanoparticles comprises the following steps: mixing indate, urea and water, then performing hydrothermal reaction and heat treatment.

[0063] In preferred embodiments, the concentration of the indate is 0.2-0.5 mol / L in terms of indium element; specifically, the concentration of the indate can be 0.2 mol / L, 0.3 mol / L, 0.4 mol / L or 0.5 mol / L.

[0064] In preferred embodiments, the concentration of the urea is 0.2-0.8 mol / L; specifically, the concentration of the urea can be 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L or 0.8 mol / L.

[0065] In preferred embodiments, the molar ratio of the amount of use of the indate to the amount of use of the urea is 1:1.5-2.5, wherein the indate is in terms of indium element; specifically, the molar ratio of the amount of use of the indate to the amount of use of the urea is 1:1.5, 1:2 or 1:2.5.

[0066] In a preferred embodiment, the conditions of the hydrothermal reaction include a temperature of 110-180℃ and a time of 8-36h; specifically, the temperature can be 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃ or 180℃; and the time can be 8h, 12h, 16h, 20h, 24h, 28h, 32h or 36h.

[0067] In a preferred embodiment, the conditions of the heat treatment include a temperature of 450-550℃ and a time of 3-10h; specifically, the temperature can be 450℃, 500℃ or 550℃; and the time can be 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h.

[0068] In a preferred embodiment, the method for preparing the In2O3 nanoparticles further comprises solid-liquid separation, washing and drying of the intermediate material before the heat treatment after the hydrothermal reaction, which are all conventional methods in the art.

[0069] In a specific embodiment, the method for preparing the In2O3 nanoparticles specifically comprises mixing the indate, urea and water, then placing them in a hydrothermal kettle for hydrothermal reaction, performing solid-liquid separation on the intermediate material after the hydrothermal reaction, then washing with ethanol and water and placing them in a vacuum drying oven for drying, and finally placing them in a muffle furnace for heat treatment.

[0070] In the method for preparing the In2O3 nanoparticles, there is no special requirement for the indate, and any indate commonly used in the art can be used, for example, the indate can be indium chloride.

[0071] In a preferred embodiment, in step (2), the solid-liquid separation is performed by centrifugation at a speed of 3000-15000r / min; more preferably, the centrifugation is performed at a speed of 6000-10000r / min.

[0072] In a preferred embodiment, in step (2), the conditions of the freeze-drying include a temperature of -70--40℃ and a time of 5-24h; specifically, the temperature can be -70℃, -65℃, -60℃, -55℃, -50℃, -45℃ or -40℃; and the time can be 5h, 10h, 12h, 16h, 20h or 24h.

[0073] The In2O3 nanoparticles prepared by the above method have a large specific surface area and excellent catalytic activity, and can quickly adsorb and catalyze hydrogen sulfide.

[0074] The third aspect of the present application provides a composite material based on In2O3 and Ti3C2T x prepared by the above method.

[0075] The fourth aspect of the present application provides application of the above-mentioned composite material based on In2O3 and Ti3C2T x in hydrogen sulfide detection.

[0076] The fifth aspect of the present application provides a hydrogen sulfide sensor, which comprises the above-mentioned composite material based on In2O3 and Ti3C2T x .

[0077] The composite material based on In2O3 and Ti3C2T x in the present application has high sensitivity to hydrogen sulfide, can directly face the leakage monitoring and detection problem of hydrogen sulfide in the atmospheric environment, can rapidly and selectively detect the leaked hydrogen sulfide in the environment at room temperature, reduces the harm caused by hydrogen sulfide leakage, and thus ensures the safety of personnel, environment and equipment.

[0078] The sixth aspect of the present application provides a method for preparing the above-mentioned hydrogen sulfide sensor, which comprises the following steps: mixing and grinding the above-mentioned composite material based on In2O3 and Ti3C2T x , an organic solvent, and then coating the mixture on the surface of a ceramic tube with an electrode to form a sensing film, and finally vacuum drying.

[0079] In a preferred embodiment, the weight ratio of the use amount of the composite material based on In2O3 and Ti3C2T x and the organic solvent is 1:1-10, preferably 1:1-5; specifically, the weight ratio of the use amount of the composite material based on In2O3 and Ti3C2T x and the organic solvent can be 1:1, 1:2, 1:3, 1:4 or 1:5; based on this, the dispersion liquid is not too dilute to be unable to be coated due to too much use amount of the organic solvent, and the dispersion liquid is not too thick to cause uneven coating and affect the gas sensitivity of the hydrogen sulfide sensor due to too little use amount of the organic solvent.

[0080] In the present application, there is no special requirement for the organic solvent, and the commonly used ones in the art can be used, for example, ethanol, acetone, glycerol or terpineol.

[0081] In the present application, there is no special requirement for the conditions of vacuum drying, and the commonly used conditions in the art can be used.

[0082] In a preferred embodiment, in order to further improve the sensitivity of the hydrogen sulfide sensor, the thickness of the sensing film is 100-2000 μm, preferably 200-1000 μm; specifically, the thickness of the sensing film can be 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm or 1000 μm.

[0083] The seventh aspect of the present application provides a method for detecting hydrogen sulfide, which comprises contacting the hydrogen sulfide sensor described above with a mixed gas containing hydrogen sulfide.

[0084] The application further discloses a preparation method and application of the composite material based on In2O3 and Ti3C2T x The application is not limited to the following examples.

[0085] In the following examples, the experimental methods are all conventional methods in the field unless otherwise specified. The experimental materials and experimental instruments used in the following examples are commercially available unless otherwise specified, wherein the scanning electron microscope is a Hitachi SU3800, and the energy spectrometer is a Hitachi SU3800.

[0086] Example 1

[0087] Preparation of Ti3C2T x (S1):

[0088] A1: 1 g of Ti3AlC2 is added to 30 ml of hydrofluoric acid with a mass concentration of 30%, and stirred at 30 DEG C for 26 h, and then centrifuged by a centrifuge, and washed with deionized water until the pH value of the supernatant is 6, and the precipitate is collected;

[0089] A2: The precipitate collected in step A1 is washed with deionized water again, and then vacuum filtered by using a polytetrafluoroethylene membrane with a pore size of 0.22 microns, and then dried in a vacuum drying oven at 60 DEG C for 24 h;

[0090] A3: The intermediate material obtained in step A2 is dispersed in deionized water, and ultrasonically treated at 20 DEG C for 30 min, and then separated by a centrifuge to obtain Ti3C2T x (S1);

[0091] Preparation of In2O3 nanoparticles (M1)

[0092] B1: Indium chloride and urea are dissolved in deionized water, wherein the concentration of the indium chloride is 0.2 mol / L, the concentration of the urea is 0.3 mol / L, and the molar ratio of the indium chloride to the urea is 1:1.5, the above mixed solution is placed in a polytetrafluoroethylene-lined hydrothermal kettle, and reacted at a temperature of 150 DEG C for 12 h, after the reaction, solid-liquid separation is carried out, then the solid-phase intermediate product is washed by centrifugation with ultrapure water and ethanol for three times, and placed in a vacuum drying oven at 70 DEG C for 12 h, and finally placed in a 500 DEG C muffle furnace for heat treatment for 5 h to obtain In2O3 nanoparticles (M1);

[0093] Preparation of In2O3@Ti3C2T x (K1)

[0094] (1) 0.2 g Ti3C2T x (S1) was added into 20 g of the first solvent (V(ethanol):V(water) = 5:1) and then ultrasonically treated at a power of 400 W and a temperature of 30°C for 60 min. Then, 0.04 g of In2O3 nanoparticles (M1) was added and stirred for 2 h in the dark, followed by refluxing at 60°C for 6 h;

[0095] (2) The intermediate product was subjected to solid-liquid separation by centrifugation at a speed of 10000 r / min, washed with deionized water, and freeze-dried at a temperature of -50°C for 8 h to obtain In2O3@Ti3C2T x (K1) (the microstructure of which is shown in Figure 3 ).

[0096] Example 2

[0097] Preparation of Ti3C2T x (S2):

[0098] A1: 2 g of Ti3AlC2 was added into 40 mL of 9 mol / L HCl aqueous solution containing 3 g of LiF, stirred at 35°C for 24 h, then centrifuged by a centrifuge, washed with deionized water until the pH value of the supernatant was 6, and the precipitate was collected;

[0099] A2: The precipitate collected in step A1 was washed with deionized water, then vacuum filtered by a polytetrafluoroethylene membrane with a pore size of 0.22 μm, and then dried in a vacuum drying oven at 60°C for 8 h;

[0100] A3: The intermediate material obtained in step A2 was dispersed in deionized water, ultrasonically treated at 0°C for 30 min, and then separated by a centrifuge to obtain Ti3C2T x (S2);

[0101] Preparation of In2O3 nanoparticles (M2)

[0102] B1: indium chloride and urea were dissolved in deionized water, wherein the concentration of indium chloride was 0.3 mol / L, the concentration of urea was 0.6 mol / L, and the molar ratio of indium chloride to urea was 1:2, the above mixed solution was placed in a polytetrafluoroethylene lined autoclave, and reacted at a temperature of 170°C for 10h, after the reaction was completed, solid-liquid separation was carried out, then the intermediate product in solid phase was washed by centrifugation with ultrapure water and ethanol for three times, and then placed in a vacuum drying oven at 60°C for 12h, and finally placed in a muffle furnace at 450°C for heat treatment for 6h, to obtain In2O3 nanoparticles (M2);

[0103] Preparation of In2O3@Ti3C2T x (K2)

[0104] (1) 0.5g Ti3C2T x (S2) was added to 50g of the first solvent (V(ethanol):V(water) was 5:1) and ultrasonic treatment was performed, the power of the ultrasonic treatment was 800W, the temperature was 30°C, and the time was 20min, then 0.15g of In2O3 nanoparticles (M2) was added, stirring was performed under light shielding conditions for 2h, and then reflux was performed at 50°C for 6h;

[0105] (2) The above intermediate product was separated by centrifugation, the speed of the centrifugation was 7000r / min, then washed with deionized water, and freeze-dried at a temperature of -60°C for 10h, to obtain In2O3@Ti3C2T x (K2).

[0106] Example 3

[0107] Preparation of Ti3C2T x (S3):

[0108] A1: 2g Ti3AlC2 was added to 40mL of 9mol / L HCl aqueous solution containing 3g LiF, stirring was performed at 45°C for 48h, then centrifugation was performed by a centrifuge, and the precipitate was collected after washing with deionized water until the pH value of the supernatant was 6;

[0109] A2: The precipitate collected in step A1 was washed with deionized water, then vacuum filtration was performed by using a polytetrafluoroethylene membrane with a pore size of 0.22μm, and then dried in a vacuum drying oven at 60°C for 18h;

[0110] A3: The intermediate material obtained in step A2 was dispersed in deionized water, ultrasonic treatment was performed at 20°C for 30min, and then separated by a centrifuge, to obtain Ti3C2T x (S3);

[0111] Preparation of In2O3 nanoparticles (M3)

[0112] B1: Dissolve indium chloride and urea in deionized water, wherein the concentration of indium chloride is 0.3 mol / L, the concentration of urea is 0.75 mol / L, and the molar ratio of indium chloride to urea is 1:2.5, place the above mixed solution in a polytetrafluoroethylene-lined autoclave, react at a temperature of 170°C for 12h, after the reaction is completed, perform solid-liquid separation, then centrifugally wash the solid-phase intermediate product with ultrapure water and ethanol three times, place it in a vacuum drying oven at 60°C for 24h, and finally place it in a 500°C muffle furnace for heat treatment for 8h to obtain In2O3nanoparticles (M3);

[0113] Preparation of In2O3@Ti3C2T x (K3)

[0114] (1) Mix 0.3g of Ti3C2T x (S3) and 30g of the first solvent (V(ethanol):V(water) is 4:1) and perform ultrasonic treatment, the power of the ultrasonic treatment is 800W, the temperature is 25°C, and the time is 300min, then add 0.12g of In2O3nanoparticles (M3), stir in the dark for 2h, and then reflux at 50°C for 6h;

[0115] (2) Perform solid-liquid separation on the above intermediate product by centrifugation at a speed of 7000r / min, then wash with deionized water, and freeze-dry at a temperature of -60°C for 12h to obtain In2O3@Ti3C2T x (K3).

[0116] Example 4

[0117] Preparation of Ti3C2T x (S4):

[0118] A1: Add 2g of Ti3AlC2to 50ml of hydrofluoric acid with a mass concentration of 35%, stir at 30°C for 36h, then perform centrifugation by a centrifuge, wash with deionized water until the pH value of the upper clear liquid is 6, and collect the precipitate;

[0119] A2: Re-wash the precipitate collected in step A1 with deionized water, then perform vacuum filtration using a polytetrafluoroethylene membrane with a pore size of 0.22μm, and then dry in a vacuum drying oven at 80°C for 8h;

[0120] A3: Disperse the intermediate material obtained in step A2 in deionized water, ultrasonic treat at 15°C for 30min, then separate by a centrifuge to obtain Ti3C2T x (S4);

[0121] Preparation of In2O3nanoparticles (M4)

[0122] B1: indium chloride and urea were dissolved in deionized water, wherein the concentration of indium chloride was 0.3 mol / L, the concentration of urea was 0.54 mol / L, the molar ratio of indium chloride to urea was 1:1.8, the above mixed solution was placed in a polytetrafluoroethylene lined autoclave, and reacted at a temperature of 150°C for 24h, after the reaction was completed, solid-liquid separation was carried out, then the intermediate product in solid phase was washed by centrifugation with ultrapure water and ethanol for three times, and was placed in a vacuum drying oven at 60°C for 36h, and finally was placed in a 500°C muffle furnace for heat treatment for 5h, to obtain In2O3 nanoparticles (M4);

[0123] Preparation of In2O3@Ti3C2T x (K4)

[0124] (1) 0.5g Ti3C2T x (S4) and 50g of the first solvent (V(ethanol):V(water) was 2.5:1) were mixed and ultrasonic treated, the power of ultrasonic treatment was 700W, the temperature was 30°C, and the time was 240min, then 0.13g of In2O3 nanoparticles (M4) was added, stirred for 2h in the dark, and then refluxed at 60°C for 6h;

[0125] (2) The above intermediate product was separated by centrifugation, the speed of centrifugation was 8000r / min, then washed with deionized water, and freeze-dried at a temperature of -60°C for 10h, to obtain In2O3@Ti3C2T x (K4).

[0126] Example 5

[0127] Preparation of Ti3C2T x (S1):

[0128] A1: 1g Ti3AlC2 was added to 30ml of hydrofluoric acid with a mass concentration of 30%, stirred at 30°C for 26h, then centrifuged by a centrifuge, washed with deionized water until the pH value of the upper clear liquid was 6, and the precipitate was collected;

[0129] A2: The precipitate collected in step A1 was washed with deionized water, then vacuum filtered by a polytetrafluoroethylene membrane with a pore size of 0.22μm, and then dried in a vacuum drying oven at 60°C for 24h;

[0130] A3: The intermediate material obtained in step A2 was dispersed in deionized water, ultrasonic treated at 20°C for 30min, and then separated by a centrifuge, to obtain Ti3C2T x (S1);

[0131] Preparation of In2O3 nanoparticles (M1)

[0132] B1: indium chloride and urea were dissolved in deionized water, wherein the concentration of indium chloride was 0.2 mol / L, the concentration of urea was 0.3 mol / L, and the molar ratio of indium chloride to urea was 1:1.5, the above mixed solution was placed in a polytetrafluoroethylene lined autoclave, and reacted at a temperature of 150°C for 12h, after the reaction was completed, solid-liquid separation was carried out, then the intermediate product in solid phase was washed by centrifugation with ultrapure water and ethanol for three times, and then placed in a vacuum drying oven at 70°C for 12h, and finally placed in a muffle furnace at 500°C for heat treatment for 5h, to obtain In2O3 nanoparticles (M1);

[0133] Preparation of In2O3@Ti3C2T x (K5)

[0134] (1) 0.2g Ti3C2T x (S1) and 20g of the first solvent (V(ethanol):V(water) was 5:1) were mixed and ultrasonically treated, the ultrasonic treatment power was 400W, the temperature was 30°C, and the time was 60min, then 0.2g of In2O3 nanoparticles (M1) was added, stirred in the dark for 2h, and then refluxed at 60°C for 6h;

[0135] (2) The above intermediate product was separated by centrifugation at a speed of 10000r / min, then washed with deionized water, and freeze-dried at a temperature of-50°C for 8h, to obtain In2O3@Ti3C2T x (K5).

[0136] Example 6

[0137] Preparation of Ti3C2T x (S1):

[0138] A1: 1g of Ti3AlC2 was added to 30ml of hydrofluoric acid with a mass concentration of 30%, stirred at 30°C for 26h, then centrifuged by a centrifuge, washed with deionized water until the pH value of the upper clear liquid was 6, and the precipitate was collected;

[0139] A2: The precipitate collected in step A1 was washed with deionized water, then vacuum filtered by a polytetrafluoroethylene membrane with a pore size of 0.22μm, and then dried in a vacuum drying oven at 60°C for 24h;

[0140] A3: The intermediate material obtained in step A2 was dispersed in deionized water, ultrasonically treated at 20°C for 30min, and then separated by a centrifuge, to obtain Ti3C2T x (S1);

[0141] Preparation of In2O3 nanoparticles (M1)

[0142] B1: indium chloride and urea were dissolved in deionized water, wherein the concentration of indium chloride was 0.2 mol / L, the concentration of urea was 0.3 mol / L, and the molar ratio of indium chloride to urea was 1:1.5, the above mixed solution was placed in a polytetrafluoroethylene lined autoclave, and reacted at a temperature of 150°C for 12h, after the reaction was completed, solid-liquid separation was carried out, then the intermediate product in solid phase was washed by centrifugation with ultrapure water and ethanol for three times, and then placed in a vacuum drying oven at 70°C for 12h, and finally placed in a muffle furnace at 500°C for heat treatment for 5h, to obtain In2O3 nanoparticles (M1);

[0143] Preparation of In2O3@Ti3C2T x (K6)

[0144] (1) 0.2g Ti3C2T x (S1) and 20g of the first solvent (V(ethanol):V(water) was 5:1) were mixed and ultrasonically treated, the power of ultrasonic treatment was 400W, the temperature was 30°C, and the time was 60min, then 0.01g of In2O3 nanoparticles (M1) was added, stirred in the dark for 2h, and then refluxed at 60°C for 6h;

[0145] (2) The above intermediate product was separated by centrifugation at a speed of 10000r / min, then washed with deionized water, and freeze-dried at a temperature of-50°C for 8h, to obtain In2O3@Ti3C2T x (K6).

[0146] Example 7

[0147] Preparation of Ti3C2T x (S1):

[0148] A1: 1g of Ti3AlC2 was added to 30ml of hydrofluoric acid with a mass concentration of 30%, stirred at 30°C for 26h, then centrifuged by a centrifuge, washed with deionized water until the pH value of the upper clear liquid was 6, and the precipitate was collected;

[0149] A2: The precipitate collected in step A1 was washed with deionized water, then vacuum filtered by a polytetrafluoroethylene membrane with a pore size of 0.22μm, and then dried in a vacuum drying oven at 60°C for 24h;

[0150] A3: The intermediate material obtained in step A2 was dispersed in deionized water, ultrasonically treated at 20°C for 30min, and then separated by a centrifuge, to obtain Ti3C2T x (S1);

[0151] Preparation of In2O3 nanoparticles (M7)

[0152] B1: indium chloride and urea were dissolved in deionized water, wherein the concentration of indium chloride was 0.1 mol / L, the concentration of urea was 0.15 mol / L, and the molar ratio of indium chloride to urea was 1:1.5. The mixed solution was placed in a polytetrafluoroethylene-lined autoclave and reacted at a temperature of 150°C for 12h. After the reaction, solid-liquid separation was performed, and then the intermediate product in the solid phase was washed by centrifugation with ultrapure water and ethanol for three times. The intermediate product was placed in a vacuum drying oven at 70°C for 12h, and finally placed in a muffle furnace at 500°C for heat treatment for 5h to obtain In2O3 nanoparticles (M7);

[0153] Preparation of In2O3@Ti3C2T x (K7)

[0154] (1) 0.2g Ti3C2T x (S1) and 20g of the first solvent (V(ethanol):V(water) was 5:1) were mixed and ultrasonically treated, the power of ultrasonic treatment was 400W, the temperature was 30°C, and the time was 60min. Then 0.04g of In2O3 nanoparticles (M7) was added, and stirred in the dark for 2h, and then refluxed at 60°C for 6h;

[0155] (2) The intermediate product was separated by centrifugation at a speed of 10000r / min, and then washed with deionized water and freeze-dried at a temperature of-50°C for 8h to obtain In2O3@Ti3C2T x (K7).

[0156] Example 8

[0157] Preparation of Ti3C2T x (S1):

[0158] A1: 1g of Ti3AlC2 was added to 30ml of hydrofluoric acid with a mass concentration of 30%, stirred at 30°C for 26h, and then centrifuged by a centrifuge, washed with deionized water until the pH value of the upper clear liquid was 6, and the precipitate was collected;

[0159] A2: The precipitate collected in step A1 was washed with deionized water, and then vacuum filtered by a polytetrafluoroethylene membrane with a pore size of 0.22μm, and then dried in a vacuum drying oven at 60°C for 24h;

[0160] A3: The intermediate material obtained in step A2 was dispersed in deionized water, and ultrasonically treated at 20°C for 30min, and then separated by a centrifuge to obtain Ti3C2T x (S1);

[0161] Preparation of In2O3 nanoparticles (M8)

[0162] B1: indium chloride and urea were dissolved in deionized water, wherein the concentration of indium chloride was 0.2 mol / L, the concentration of urea was 0.2 mol / L, and the molar ratio of indium chloride to urea was 1:1. The mixed solution was placed in a polytetrafluoroethylene-lined hydrothermal kettle and reacted at a temperature of 150°C for 12h. After the reaction was completed, solid-liquid separation was performed, and then the intermediate product in the solid phase was washed by centrifugation with ultrapure water and ethanol for three times. The intermediate product was placed in a vacuum drying box at 70°C for 12h, and finally was placed in a muffle furnace at 500°C for heat treatment for 5h to obtain In2O3 nanoparticles (M8);

[0163] Preparation of In2O3@Ti3C2T x (K8)

[0164] (1) 0.2g Ti3C2T x (S1) and 20g of the first solvent (V(ethanol):V(water) was 5:1) were mixed and ultrasonically treated, the power of ultrasonic treatment was 400W, the temperature was 30°C, and the time was 60min. Then 0.04g of In2O3 nanoparticles (M8) was added, and stirred in the dark for 2h, and then refluxed at 60°C for 6h;

[0165] (2) The intermediate product was separated by centrifugation at a speed of 10000r / min, and then washed with deionized water and freeze-dried at a temperature of-50°C for 8h to obtain In2O3@Ti3C2T x (K8).

[0166] Example 9

[0167] Preparation of Ti3C2T x (S1):

[0168] A1: 1g of Ti3AlC2 was added to 30ml of hydrofluoric acid with a mass concentration of 30%, stirred at 30°C for 26h, and then centrifuged by a centrifuge, washed with deionized water until the pH value of the upper clear liquid was 6, and the precipitate was collected;

[0169] A2: The precipitate collected in step A1 was washed with deionized water, and then vacuum filtered by a polytetrafluoroethylene membrane with a pore size of 0.22μm, and then dried in a vacuum drying box at 60°C for 24h;

[0170] A3: The intermediate material obtained in step A2 was dispersed in deionized water, and ultrasonically treated at 20°C for 30min, and then separated by a centrifuge to obtain Ti3C2T x (S1);

[0171] Preparation of In2O3 nanoparticles (M1)

[0172] B1: indium chloride and urea were dissolved in deionized water, wherein the concentration of indium chloride was 0.2 mol / L, the concentration of urea was 0.3 mol / L, and the molar ratio of indium chloride to urea was 1:1.5, the above mixed solution was placed in a polytetrafluoroethylene lined autoclave, and reacted at a temperature of 150°C for 12h, after the reaction was completed, solid-liquid separation was carried out, then the intermediate product in solid phase was washed by centrifugation with ultrapure water and ethanol for three times, and then placed in a vacuum drying oven at 70°C for 12h, and finally placed in a muffle furnace at 500°C for heat treatment for 5h, to obtain In2O3 nanoparticles (M1);

[0173] Preparation of In2O3@Ti3C2T x (K9)

[0174] (1) 0.2g Ti3C2T x (S1) and 70g of the first solvent (V(ethanol):V(water) was 5:1) were mixed and ultrasonically treated, the power of ultrasonic treatment was 400W, the temperature was 30°C, and the time was 60min, then 0.04g of In2O3 nanoparticles (M1) was added, stirred in the dark for 2h, and then refluxed at 60°C for 6h;

[0175] (2) The above intermediate product was separated by centrifugation at a speed of 10000r / min, then washed with deionized water, and freeze-dried at a temperature of-50°C for 8h, to obtain In2O3@Ti3C2T x (K9).

[0176] Example 10

[0177] Preparation of Ti3C2T x (S1):

[0178] A1: 1g of Ti3AlC2 was added to 30ml of hydrofluoric acid with a mass concentration of 30%, stirred at 30°C for 26h, then centrifuged by a centrifuge, washed with deionized water until the pH value of the upper clear liquid was 6, and the precipitate was collected;

[0179] A2: The precipitate collected in step A1 was washed with deionized water, then vacuum filtered by a polytetrafluoroethylene membrane with a pore size of 0.22μm, and then dried in a vacuum drying oven at 60°C for 24h;

[0180] A3: The intermediate material obtained in step A2 was dispersed in deionized water, ultrasonically treated at 20°C for 30min, and then separated by a centrifuge, to obtain Ti3C2T x (S1);

[0181] Preparation of In2O3 nanoparticles (M1)

[0182] B1: Dissolve indium chloride and urea in deionized water, wherein the concentration of indium chloride is 0.2 mol / L, the concentration of urea is 0.3 mol / L, and the molar ratio of indium chloride to urea is 1:1.5. Place the mixed solution in a polytetrafluoroethylene-lined autoclave and react at a temperature of 150°C for 12 h. After the reaction is completed, perform solid-liquid separation, then centrifugally wash the solid-phase intermediate product with ultrapure water and ethanol three times, place it in a vacuum drying oven at 70°C for 12 h, and finally place it in a 500°C muffle furnace for heat treatment for 5 h to obtain In2O3 nanoparticles (M1);

[0183] Preparation of In2O3@Ti3C2T x (K10)

[0184] (1) Disperse 0.2 g of Ti3C2T x (S1) in 10 g of a first solvent (V(ethanol):V(water) is 5:1) and perform ultrasonic treatment, with a power of 400 W and a temperature of 30°C for 60 min. Then add 0.04 g of In2O3 nanoparticles (M1), stir in the dark for 2 h, and then reflux at 60°C for 6 h;

[0185] (2) Perform solid-liquid separation on the intermediate product by centrifugation at a speed of 10,000 r / min, then wash with deionized water, and freeze-dry at a temperature of -50°C for 8 h to obtain In2O3@Ti3C2T x (K10).

[0186] Comparative Example 1

[0187] Preparation of Ti3C2T x (S1):

[0188] A1: Add 1 g of Ti3AlC2 to 30 ml of hydrofluoric acid with a mass concentration of 30%, stir at 30°C for 24 h, then perform centrifugation by centrifuge, wash with deionized water until the pH value of the upper clear liquid is 6, and collect the precipitate;

[0189] A2: Re-wash the precipitate collected in step A1 with deionized water, then perform vacuum filtration using a polytetrafluoroethylene membrane with a pore size of 0.22 μm, and then dry in a vacuum drying oven at 60°C for 24 h;

[0190] A3: Disperse the intermediate material obtained in step A2 in deionized water, ultrasonic at 20°C for 30 min, then separate by centrifuge to obtain Ti3C2T x (S1) (the micro-morphology of which is shown in Figure 1 ).

[0191] Comparative Example 2

[0192] Preparation of In2O3 nanoparticles (M1)

[0193] B1: Indium chloride and urea were dissolved in deionized water, wherein the concentration of indium chloride was 0.2 mol / L, the concentration of urea was 0.3 mol / L, and the molar ratio of indium chloride to urea was 1:1.5. The mixed solution was placed in a polytetrafluoroethylene-lined hydrothermal reactor and reacted at a temperature of 150°C for 12 hours. After the reaction, solid-liquid separation was performed. The solid intermediate product was then centrifuged and washed three times with ultrapure water and ethanol, placed in a vacuum drying oven at 70°C for 12 hours, and finally placed in a muffle furnace at 500°C for heat treatment for 5 hours to obtain In2O3 nanoparticles (M1) (its micromorphology is as shown in FIG. Figure 2 shown).

[0194] Test Case

[0195] (1) The Ti3C2T prepared in Examples 1-4 was observed using a scanning electron microscope. x , In2O3 nanoparticles and In2O3@Ti3C2T x Composite material and Ti3C2T prepared in Comparative Example 1 x The morphology of In2O3 nanoparticles prepared in Comparative Example 2 was characterized. Figure 1 The Ti3C2T prepared in Comparative Example 1 x Scanning electron microscope images of Figure 2 This is a scanning electron microscope image of the In2O3 nanoparticles prepared in Comparative Example 2. Figure 3 In2O3@Ti3C2T prepared in Example 1 x SEM images of Ti3C2T x The test results of the thickness and size of In2O3 nanoparticles are shown in Table 1;

[0196] Depend on Figure 1 It can be seen that Ti3C2T x It is a layered nanosheet with a thickness of about 100nm; Figure 2 It can be seen that the In2O3 nanoparticles are spherical and about 5nm in size; Figure 3 It can be seen that In2O3 nanoparticles are loaded onto Ti3C2T x In2O3@Ti3C2T x ;

[0197] (2) The products prepared in Examples 1-10 and Comparative Examples 1-2 were subjected to semi-quantitative EDS spectrum analysis using an energy dispersive spectrometer to calculate the loading amount of In2O3 nanoparticles. The results are shown in Table 1.

[0198] (3) The sensing performance of the products prepared in the test examples and the comparative examples was tested by the following method: 2 mg of terpineol was taken in a mortar, then 1 mg of the product was added and ground for 5 min, then the above-mentioned materials were coated on a ceramic tube of interdigital gold electrodes to form a sensing film by using a brush, and a hydrogen sulfide sensor was obtained after vacuum drying, the thickness of the sensing film and the original resistance of the sensor were measured, then the sensor was placed in hydrogen sulfide with a concentration of 0.05 ppm, and the resistance change thereof was measured, and the results are shown in Table 2, wherein, Figure 4 is a graph of the resistance change of the sensors prepared in Example 1, Comparative Example 1 and Comparative Example 2 in different concentrations of hydrogen sulfide;

[0199] (4) The In2O3@Ti3C2T x sensor prepared in Example 1 was tested for response to interfering gases, wherein the interfering gases included carbon dioxide, methane, carbon monoxide, nitric oxide;

[0200] The In2O3@Ti3C2T x sensor prepared in Example 1 was placed in different volume concentrations of carbon dioxide, and the results showed that, under the same volume concentration, the response intensity of carbon dioxide was only 1% of that of hydrogen sulfide; the In2O3@Ti3C2T x sensor prepared in Example 1 was placed in different volume concentrations of methane gas, and the results showed that, under the same volume concentration, the response intensity of methane was only 0.8% of that of hydrogen sulfide; the In2O3@Ti3C2T x sensor prepared in Example 1 was placed in different volume concentrations of carbon monoxide gas, and the results showed that, under the same volume concentration, the response intensity of carbon monoxide was only 0.8% of that of hydrogen gas; the In2O3@Ti3C2T x sensor prepared in Example 1 was placed in different volume concentrations of nitric oxide gas, and the results showed that, under the same volume concentration, the response intensity of nitric oxide was only 0.8% of that of hydrogen sulfide.

[0201] The above results show that the In2O3@Ti3C2T x sensor prepared in the application has selectivity to gases, and only when the detected gas is hydrogen sulfide does it have high sensitivity and fast response.

[0202] Table 1

[0203]

[0204]

[0205] Table 2

[0206]

[0207] As can be seen from the results in Table 1, the Ti3C2T x prepared by the application has a thickness of 90-150 nm, the In2O3 nanoparticles have a size of 5-25 nm, and the loading amount of the In2O3 nanoparticles is 10-20%.

[0208] As can be seen from the results in Table 2, the sensor prepared by the In2O3@Ti3C2T x application has high sensitivity to H2S, fast response speed, and low lower limit of the detectable volume concentration of H2S, and can respond to H2S with a volume concentration of 0.05 ppm within 10 s.

[0209] The preferred embodiments of the application are described in detail above, but the application is not limited thereto. Within the technical concept of the application, various simple modifications can be made to the technical solutions of the application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the application and fall within the protection scope of the application.

Claims

1. A method based on In2O3 and Ti3C2T x The composite material is characterized in that The In2O3 and Ti3C2T x Composite materials include Ti3C2T x and loaded on Ti3C2T x In2O3 nanoparticles on.

2. The method according to claim 1 based on In2O3 and Ti3C2T x The composite material is characterized in that Based on In2O3 and Ti3C2T x Based on the total weight of the composite material, the content of the In2O3 nanoparticles is 5 to 30 wt%, preferably 10 to 20 wt%.

3. The method according to claim 1 or 2 based on In2O3 and Ti3C2T x The composite material is characterized in that The Ti3C2T x The thickness is 5 to 150 nm, preferably 10 to 100 nm.

4. The method according to any one of claims 1 to 3, wherein the method is based on In2O3 and Ti3C2T x The composite material is characterized in that The particle size of the In2O3 nanoparticles is 5 to 80 nm, preferably 5 to 40 nm.

5. A method for preparing a nanostructured carbon nanotube based on In2O3 and Ti3C2T x A method of making a composite material, characterized in that The method comprises the following steps: (1) In2O3 nanoparticles, Ti3C2T x mixing with a first solvent; (2) The material obtained in step (1) is subjected to solid-liquid separation, and then the obtained solid phase material is freeze-dried.

6. The method according to claim 5, characterized in that In step (1), Ti3C2T x The weight ratio of the amount of the nanoparticles to the amount of In2O3 is 1:0.05-0.5, preferably 1:0.1-0.

3.

7. The method according to claim 5 or 6, characterized in that In step (1), Ti3C2T x The weight ratio of the amount of the first solvent is 1:80-150.

8. The method according to claim 7, characterized in that The first solvent is selected from one or more of water, ethanol, acetone and n-hexane.

9. The method according to claim 7, characterized in that In step (1), the mixing conditions include: temperature of 60 to 80° C. and time of 8 to 24 hours.

10. The method according to claim 5, characterized in that In step (1), the Ti3C2T x The preparation method includes: mixing Ti3AlC2 with a solution containing fluoride ions and hydrogen ions and then performing a first reaction.

11. The method according to claim 10, characterized in that The conditions for the first reaction include: temperature of 10 to 50° C. and time of 24 to 48 hours.

12. The method according to claim 5, characterized in that In step (1), the preparation method of the In2O3 nanoparticles includes: mixing indium salt, urea and water, and then performing hydrothermal reaction and heat treatment.

13. The method according to claim 12, characterized in that Calculated as indium element, the concentration of indium salt is 0.2-0.5 mol / L.

14. The method according to claim 12 or 13, characterized in that The concentration of urea is 0.2~0.8mol / L.

15. The method according to claim 12, characterized in that The molar ratio of the indium salt to the urea is 1:1.5-2.5, wherein the indium salt is calculated based on the indium element.

16. The method according to any one of claims 12 to 15, characterized in that The conditions of the hydrothermal reaction include: temperature of 110 to 180° C. and time of 8 to 36 hours.

17. The method according to claim 16, characterized in that The heat treatment conditions include: temperature of 450-550° C. and time of 3-10 hours.

18. The method according to claim 5, characterized in that In step (2), the freeze-drying conditions include: a temperature of -70 to -40°C and a time of 5 to 24 hours.

19. The method according to any one of claims 5 to 18, wherein the method comprises the steps of: preparing a crystalline solid based on In2O3 and Ti3C2T x composite materials.

20. The method based on In2O3 and Ti3C2T according to any one of claims 1 to 4 or 19 x Application of composite materials in hydrogen sulfide detection.

21. A hydrogen sulfide sensor, characterized in that: The hydrogen sulfide sensor comprises the In2O3 and Ti3C2T3 based sensor according to any one of claims 1 to 4 or 19. x composite materials.

22. A method for preparing the hydrogen sulfide sensor according to claim 21, characterized in that: The method comprises the following steps: x The composite material is mixed with an organic solvent and ground, then coated on the surface of a ceramic tube with electrodes to form a sensing film, and finally vacuum dried.

23. The method according to claim 22, characterized in that Based on In2O3 and Ti3C2T x The weight ratio of the composite material to the organic solvent is 1:1 to 10, preferably 1:1 to 5.

24. The method according to claim 22 or 23, characterized in that The thickness of the sensing film is 100-2000 μm, preferably 200-1000 μm.

25. A method for detecting hydrogen sulfide, characterized in that: The method comprises contacting the hydrogen sulfide sensor according to claim 21 with a mixed gas containing hydrogen sulfide.

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