CN108918632B - Preparation method and application of palladium nanoparticle modified indium oxide nanosheet composite material - Google Patents

Preparation method and application of palladium nanoparticle modified indium oxide nanosheet composite material Download PDF

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CN108918632B
CN108918632B CN201810699348.2A CN201810699348A CN108918632B CN 108918632 B CN108918632 B CN 108918632B CN 201810699348 A CN201810699348 A CN 201810699348A CN 108918632 B CN108918632 B CN 108918632B
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palladium
indium oxide
composite material
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indium
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CN108918632A (en
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段国韬
刘波
高磊
李科
王弘
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Hefei Institutes of Physical Science of CAS
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Abstract

The invention discloses an indium oxide nanosheet composite material modified by palladium nanoparticles, and a preparation method and application thereof. The invention not only has higher specific surface area and good gas-sensitive characteristic, but also can be used as a sensing layer of a resistance type metal oxide gas sensor to realize ultra-sensitive and high-selectivity detection of carbon disulfide gas, and has the advantages of no need of expensive detection equipment, low detection cost, simple operation, short detection time, rapidness and high efficiency.

Description

Preparation method and application of palladium nanoparticle modified indium oxide nanosheet composite material
Technical Field
The invention relates to the field of indium oxide nano materials, in particular to an ultra-thin (the ultra-thin refers to the thickness of a nano sheet being 3-10 nm) indium oxide nano sheet composite material with a three-dimensional network structure modified by ultra-fine (the ultra-fine refers to the granularity of the nano particles being 1-3 nm) palladium nano particles, and a preparation method and application thereof.
Background
Malodorous gases are commonly present at sewage treatment, sludge treatment and waste disposal facilities, and these malodorous gases mainly include methyl sulfide, methyl mercaptan, carbon disulfide, dimethyl disulfide, trimethylamine, ammonia, hydrogen sulfide, styrene and the like. Among them, carbon disulfide is a kind of chronic harmful gas, after long-term contact, it is apt to cause coronary arteriosclerosis or accelerate atherosclerosis, this has great threat to human and animal health. According to the provisions of the emission Standard of malodorous pollutants (GB 14554-93): in the atmosphere, the limit value of carbon disulfide must be less than 2.95ppm, otherwise, the carbon disulfide gas can cause serious harm to human beings and animals, and therefore, the carbon disulfide gas needs to be detected in real time.
At present, the commonly used carbon disulfide detection technology mainly comprises a gas chromatography-mass spectrometry, a catalytic luminescence detection method, a spectrum detection method and the like; however, the detection technologies inevitably have the problems of expensive detection equipment, complex operation process, long consumed time, incapability of real-time on-site monitoring and the like, so that the development of the carbon disulfide gas real-time detection technology with low cost, simple operation and short consumed time is urgently needed.
In the prior art, the resistance type metal oxide gas sensor has the advantages of small volume, low cost, high sensitivity, high response and recovery speed, simple operation and the like, but has poor detection sensitivity and selectivity on carbon disulfide gas.
Disclosure of Invention
The invention provides a palladium nanoparticle modified indium oxide nanosheet composite material, a preparation method and application thereof, aiming at solving the technical problems that detection equipment in the existing carbon disulfide detection technology is expensive, the operation process is complex, the detection time consumption is long, the real-time field monitoring cannot be carried out, the detection sensitivity and selectivity of the existing resistance type metal oxide gas sensor to carbon disulfide gas are poor, and the like.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an indium oxide nanosheet composite material modified by palladium nanoparticles comprises the following steps:
step A, mixing indium nitrate, resorcinol, N-dimethylformamide and acetone together according to the weight ratio of indium nitrate to resorcinol to N, N-dimethylformamide to acetone of 1: 0.1-0.8: 50-150: 50-100, stirring for 0.1-2 h, adding deionized water, then placing in a closed environment at 80-200 ℃ for reaction for 0.5-24 h, and then carrying out solid-liquid separation and washing to obtain an indium organic framework nanosheet with a three-dimensional network structure;
b, dispersing the indium organic framework nanosheets of the three-dimensional network structure into acetone, controlling the concentration of the indium organic framework nanosheets to be 0.05-2.5 mg/mL, stirring for 10-60 min, then adding palladium nitrate, stirring for 1-24 h, and then performing solid-liquid separation and washing to obtain palladium ion modified indium organic framework nanosheets of the three-dimensional network structure;
step C, calcining the palladium ion modified indium organic frame nanosheets with the three-dimensional network structures in the air, wherein the calcining temperature is 400-800 ℃, the heating rate is 1-10 ℃/min, and the calcining time is 0.1-10 h, so that the palladium oxide particle modified indium oxide nanosheet composite materials with the three-dimensional network structures are prepared;
and D, carrying out gas reduction treatment on the palladium oxide particle modified indium oxide nanosheet composite material with the three-dimensional network structure by adopting reducing gas, wherein the reducing temperature is 150-500 ℃, the heating rate is 1-10 ℃/min, and the reducing time is 0.1-10 h, so that the palladium nanoparticle modified indium oxide nanosheet composite material is prepared.
Preferably, in the step A, the amount of the deionized water is 0.001-0.1 times of the mass of the indium nitrate.
Preferably, in the step B, the amount of the palladium nitrate is 0.001 to 0.5 times of the mass of the indium organic framework nanosheet of the three-dimensional network structure.
Preferably, in step D, the reducing gas is H2/Ar、H2/N2、H2At least one of the components of the group/He.
The palladium nanoparticle modified indium oxide nanosheet composite material is prepared by the preparation method of the palladium nanoparticle modified indium oxide nanosheet composite material.
Preferably, in the palladium nanoparticle modified indium oxide nanosheet composite material, the particle size of the palladium nanoparticle is 1-3 nm, and the thickness of the indium oxide nanosheet is 3-10 nm.
The palladium nanoparticle modified indium oxide nanosheet composite material is used as a sensing layer of a resistance type metal oxide gas sensor and is used for carrying out ultra-sensitive and high-selectivity detection on carbon disulfide gas.
According to the technical scheme provided by the invention, the palladium nanoparticle modified indium oxide nanosheet composite material is prepared by taking indium nitrate, resorcinol, N-dimethylformamide and acetone in a specific ratio as raw materials, preparing indium organic framework nanosheets in a three-dimensional network structure by using a high-temperature and high-pressure method, preparing palladium ion modified indium organic framework nanosheets in a three-dimensional network structure through an electrostatic adsorption process, and then performing air calcination and reductive gas reduction. The invention not only has higher specific surface area and good gas-sensitive characteristic, can be used as a sensing layer of a resistance type metal oxide gas sensor to realize ultra-sensitive and high-selectivity detection of carbon disulfide gas, but also does not need expensive detection equipment, has low detection cost, simple operation, short detection time consumption, rapidness and high efficiency, and can carry out real-time detection and on-site detection on the carbon disulfide gas.
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In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
Fig. 1 is a scanning electron microscope photograph, a transmission electron microscope photograph and a high-resolution transmission electron microscope image of the palladium nanoparticle-modified indium oxide nanosheet composite material prepared in example 1 of the present invention.
Fig. 2 is a schematic diagram of a gas-sensitive performance test result obtained by detecting carbon disulfide gas with the palladium nanoparticle-modified indium oxide nanosheet composite material prepared in embodiment 1 of the invention.
Fig. 3 is a schematic diagram of a selectivity test result obtained by detecting carbon disulfide gas with the palladium nanoparticle-modified indium oxide nanosheet composite material prepared in embodiment 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The palladium nanoparticle modified indium oxide nanosheet composite material provided by the embodiment of the present invention, and the preparation method and the application thereof are described in detail below. Details which are not described in detail in the embodiments of the invention belong to the prior art which is known to the person skilled in the art.
The preparation method of the palladium nanoparticle modified indium oxide nanosheet composite material can comprise the following steps:
step A, mixing indium nitrate, resorcinol, N-dimethylformamide and acetone together according to the weight ratio of indium nitrate to resorcinol to N, N-dimethylformamide to acetone of 1: 0.1-0.8: 50-150: 50-100, stirring for 0.1-2 h, adding deionized water, then placing in a closed environment at 80-200 ℃ for reaction for 0.5-24 h, and then carrying out solid-liquid separation and washing to obtain the indium organic framework nanosheet with the three-dimensional network structure. Wherein the amount of the deionized water is 0.001-0.1 times of the mass of the indium nitrate.
And B, dispersing the indium organic framework nanosheets of the three-dimensional network structure into acetone, controlling the concentration of the indium organic framework nanosheets to be 0.05-2.5 mg/mL, stirring for 10-60 min, then adding palladium nitrate, stirring for 1-24 h, and then performing solid-liquid separation and washing to obtain the palladium ion modified indium organic framework nanosheets of the three-dimensional network structure. Wherein the dosage of the palladium nitrate is 0.001-0.5 times of the mass of the indium organic framework nanosheet with the three-dimensional network structure.
And C, calcining the palladium ion modified indium organic frame nanosheet with the three-dimensional network structure in the air at the calcining temperature of 400-800 ℃, at the heating rate of 1-10 ℃/min and for 0.1-10 h, so as to prepare the palladium oxide particle modified indium oxide nanosheet composite material with the three-dimensional network structure.
And D, carrying out gas reduction treatment on the palladium oxide particle modified indium oxide nanosheet composite material with the three-dimensional network structure by adopting reducing gas, wherein the reducing temperature is 150-500 ℃, the heating rate is 1-10 ℃/min, and the reducing time is 0.1-10 h, so that the palladium nanoparticle modified indium oxide nanosheet composite material is prepared. Wherein the reducing gas is H2/Ar、H2/N2、H2At least one of the components of the group/He.
Specifically, in the palladium nanoparticle modified indium oxide nanosheet composite material prepared by the invention, the granularity of palladium nanoparticles is 1-3 nm, and the thickness of indium oxide nanosheets is 3-10 nm, so that the palladium nanoparticle modified indium oxide nanosheet composite material prepared by the invention is an ultrathin palladium nanoparticle modified ultrathin indium oxide nanosheet composite material with a three-dimensional network structure. The ultrafine palladium particles with the particle size of 1-3 nm can enable the composite material to have better catalytic performance, and the ultrathin indium oxide material with the thickness of 3-10 nm can greatly improve the specific surface area of the composite material and is beneficial to increasing active sites, so that the palladium nanoparticle modified indium oxide nanosheet composite material prepared by the method has higher specific surface area and good gas-sensitive property. The palladium nanoparticle modified indium oxide nanosheet composite material can be used as a sensing layer of a resistance type metal oxide gas sensor and is used for carrying out ultra-sensitive and high-selectivity detection on carbon disulfide gas.
Compared with the prior art, the palladium nanoparticle modified indium oxide nanosheet composite material and the preparation method thereof provided by the invention have at least the following beneficial effects:
(1) in the palladium nanoparticle modified indium oxide nanosheet composite material provided by the invention, the thickness of the indium oxide nanosheet is 3-10 nm, the indium oxide nanosheet is of a hierarchical structure and consists of a plurality of ultra-small nanocrystals, and a plurality of gaps are formed among the nanocrystals, so that the diffusion of gas is facilitated; the palladium particles with the particle size of 1-3 nm are distributed on the whole indium oxide nanosheet with the three-dimensional net structure, so that the palladium particles can be better contacted with gas. The palladium nanoparticle modified indium oxide nanosheet composite material provided by the invention not only can provide excellent palladium catalysis, but also has a greatly improved specific surface area, and the contact area between gas and the material is increased, so that the gas-sensitive performance of the material is greatly improved.
(2) The palladium nanoparticle modified indium oxide nanosheet composite material provided by the invention can be used as a sensing material or a gas-sensitive element of a resistance type metal oxide gas sensor, and has ultra-sensitive and high-selectivity sensing performance on carbon disulfide gas. When the concentration of the carbon disulfide gas to be detected is as low as 0.5ppm, the palladium nanoparticle modified indium oxide nanosheet composite material provided by the invention can still effectively detect the carbon disulfide gas, and the detection repeatability is good. Through concentration detection of 9 different gases, the palladium nanoparticle modified indium oxide nanosheet composite material provided by the invention has high response to carbon disulfide gas only, and has almost no response to other gases.
(3) The palladium nanoparticle modified indium oxide nanosheet composite material provided by the invention can be brushed on a gas-sensitive test electrode for high-sensitivity and super-selective detection of carbon disulfide gas, so that the carbon disulfide gas detection by utilizing the palladium nanoparticle modified indium oxide nanosheet composite material provided by the invention has the advantages of low use cost, no need of expensive detection equipment, simplicity in operation, rapidness, high efficiency and the like, and the palladium nanoparticle modified indium oxide nanosheet composite material provided by the invention can be easily and widely prepared into a resistance type metal oxide gas sensor for on-site and real-time detection of carbon disulfide.
(4) The preparation method of the palladium nanoparticle modified indium oxide nanosheet composite material provided by the invention is simple, quick and efficient.
In conclusion, the embodiment of the invention has the advantages of high specific surface area and good gas-sensitive property, can be used as a sensing layer of a resistance type metal oxide gas sensor to realize ultra-sensitive and high-selectivity detection on carbon disulfide gas, does not need expensive detection equipment, has low detection cost, simple operation, short detection time, rapidness and high efficiency, and can carry out real-time detection and on-site detection on the carbon disulfide gas.
In order to more clearly show the technical scheme and the technical effects provided by the present invention, the palladium nanoparticle modified indium oxide nanosheet composite material provided by the embodiment of the present invention, and the preparation method and the application thereof are described in detail in the following with specific embodiments.
Example 1
A palladium nanoparticle modified indium oxide nanosheet composite material is prepared by the following steps:
step a1, mixing indium nitrate, resorcinol, N-dimethylformamide and acetone together according to the weight ratio of indium nitrate to resorcinol to N, N-dimethylformamide to acetone of 1: 0.1-0.8: 50-150: 50-100, stirring for 1h, adding a proper amount of deionized water, then placing in a sealed environment at 150 ℃ for reaction for 4h, and then carrying out solid-liquid separation and washing to obtain the indium organic framework nanosheet with the three-dimensional network structure.
Step b1, dispersing 50mg of the indium organic framework nanosheet with the three-dimensional network structure into 30mL of acetone, stirring for 30min, then adding 15mL of palladium nitrate with the concentration of 0.2mg/mL, stirring for 10h, and then performing solid-liquid separation and washing to obtain the palladium ion modified indium organic framework nanosheet with the three-dimensional network structure.
And c1, calcining 50mg of the palladium ion modified indium organic frame nanosheet with the three-dimensional network structure in the air, wherein the calcining temperature is 500 ℃, the heating rate is 2 ℃/min, and the calcining time is 4h, so that the palladium oxide particle modified indium oxide nanosheet composite material with the three-dimensional network structure is prepared.
And d1, carrying out gas reduction treatment on 50mg of the palladium oxide particle-modified indium oxide nanosheet composite material with a three-dimensional network structure by using a reducing gas, wherein the reduction temperature is 300 ℃, the heating rate is 2 ℃/min, and the reduction time is 4h, so that the palladium nanoparticle-modified indium oxide nanosheet composite material is prepared.
Specifically, the following morphology and performance tests are performed on the palladium nanoparticle modified indium oxide nanosheet composite material provided in embodiment 1 of the present invention:
(1) the palladium nanoparticle-modified indium oxide nanosheet composite material prepared in example 1 of the present invention is observed with a Scanning Electron Microscope (SEM), a Transmission Electron Microscope (TEM), and a high-resolution transmission electron microscope, respectively, so as to obtain a scanning electron micrograph (SEM image), a transmission electron micrograph (TEM image), and a high-resolution transmission electron micrograph as shown in fig. 1. Wherein, fig. 1a is a first SEM image of the palladium nanoparticle-modified indium oxide nanosheet composite material prepared in example 1 of the present invention, fig. 1b is a second SEM image of the palladium nanoparticle-modified indium oxide nanosheet composite material prepared in example 1 of the present invention, fig. 1c is a third SEM image of the palladium nanoparticle-modified indium oxide nanosheet composite material prepared in example 1 of the present invention, fig. 1d is a low-magnification TEM image of the material shown in fig. 1a, fig. 1e is a high-magnification TEM image of the material shown in fig. 1a, and fig. 1f is a high-resolution TEM image of the material shown in fig. 1 a. As can be seen from fig. 1: the palladium nanoparticle modified indium oxide nanosheet composite material prepared in embodiment 1 of the present invention shows a three-dimensional network structure, and the ultra-small palladium particles are uniformly distributed on the whole indium oxide nanosheet.
(2) A static gas-sensitive test system is adopted to perform gas-sensitive performance test on carbon disulfide gas on the palladium nanoparticle modified indium oxide nanosheet composite material prepared in embodiment 1 of the invention, so as to obtain a gas-sensitive performance test result schematic diagram shown in fig. 2. Fig. 2a is an optimal operating temperature test chart of the palladium nanoparticle-modified indium oxide nanosheet composite material obtained in embodiment 1 of the present invention for detecting carbon disulfide gas, fig. 2b is a response and recovery time chart of the palladium nanoparticle-modified indium oxide nanosheet composite material obtained in embodiment 1 of the present invention for detecting carbon disulfide gas, and fig. 2c is a repeatability test chart of the palladium nanoparticle-modified indium oxide nanosheet composite material obtained in embodiment 1 of the present invention for detecting carbon disulfide gas. Fig. 2d is a concentration gradient test chart of the palladium nanoparticle modified indium oxide nanosheet composite material prepared in embodiment 1 of the present invention for detecting carbon disulfide gas. As can be seen from fig. 2: the palladium nanoparticle modified indium oxide nanosheet composite material prepared in the embodiment 1 of the invention has the advantages of gas-sensitive test of carbon disulfide gas, the optimal operation temperature of 100 ℃, the response time of 52 seconds, the recovery time of 67 seconds, excellent repeatability and detection limit of 0.5 ppm.
(3) The indium oxide nanosheet composite modified by the palladium nanoparticles prepared in the embodiment 1 of the invention is used for carrying out selective gas-sensitive test on 9 different gases in a static gas-sensitive test system, so that a schematic diagram of a selectivity test result shown in fig. 3 is obtained. As can be seen from fig. 3: the palladium nanoparticle modified indium oxide nanosheet composite material prepared in the embodiment 1 of the invention has high response to carbon disulfide gas only, and has almost no response to other gases, namely, ultrahigh selectivity to carbon disulfide gas.
Example 2
A palladium nanoparticle modified indium oxide nanosheet composite material is prepared by the following steps:
step a2, mixing indium nitrate, resorcinol, N-dimethylformamide and acetone together according to the weight ratio of indium nitrate to resorcinol to N, N-dimethylformamide to acetone of 1: 0.1-0.8: 50-150: 50-100, stirring for 2 hours, adding a proper amount of deionized water, then placing in a sealed environment at 150 ℃ for reaction for 6 hours, and then carrying out solid-liquid separation and washing to obtain the indium organic framework nanosheet with the three-dimensional network structure.
Step b2, dispersing 50mg of the indium organic framework nanosheet with the three-dimensional network structure into 40mL of acetone, stirring for 30min, then adding 15mL of palladium nitrate with the concentration of 0.15mg/mL, stirring for 10h, and then performing solid-liquid separation and washing to obtain the palladium ion modified indium organic framework nanosheet with the three-dimensional network structure.
And c2, calcining 50mg of the palladium ion modified indium organic frame nanosheet with the three-dimensional network structure in the air, wherein the calcining temperature is 600 ℃, the heating rate is 2 ℃/min, and the calcining time is 2h, so that the palladium oxide particle modified indium oxide nanosheet composite material with the three-dimensional network structure is prepared.
And d2, carrying out gas reduction treatment on 50mg of the palladium oxide particle-modified indium oxide nanosheet composite material with a three-dimensional network structure by using a reducing gas, wherein the reduction temperature is 250 ℃, the heating rate is 2 ℃/min, and the reduction time is 3h, so that the palladium nanoparticle-modified indium oxide nanosheet composite material is prepared.
Example 3
A palladium nanoparticle modified indium oxide nanosheet composite material is prepared by the following steps:
step a3, mixing indium nitrate, resorcinol, N-dimethylformamide and acetone together according to the weight ratio of indium nitrate to resorcinol to N, N-dimethylformamide to acetone of 1: 0.1-0.8: 50-150: 50-100, stirring for 2 hours, adding a proper amount of deionized water, then placing in a 180 ℃ closed environment for reaction for 6 hours, and then carrying out solid-liquid separation and washing to obtain the indium organic framework nanosheet with the three-dimensional network structure.
Step b3, dispersing 40mg of the indium organic framework nanosheet with the three-dimensional network structure into 30mL of acetone, stirring for 30min, then adding 10mL of palladium nitrate with the concentration of 0.25mg/mL, stirring for 12h, and then performing solid-liquid separation and washing to obtain the palladium ion modified indium organic framework nanosheet with the three-dimensional network structure.
And c3, calcining 30mg of the palladium ion modified indium organic frame nanosheet with the three-dimensional network structure in the air, wherein the calcining temperature is 400 ℃, the heating rate is 2 ℃/min, and the calcining time is 5h, so that the palladium oxide particle modified indium oxide nanosheet composite material with the three-dimensional network structure is prepared.
And d3, performing gas reduction treatment on the indium oxide nanosheet composite material of the three-dimensional network structure modified by the palladium oxide particles by using reducing gas, wherein the reducing temperature is 200 ℃, the heating rate is 5 ℃/min, and the reducing time is 5h, so that the palladium nanoparticle modified indium oxide nanosheet composite material is prepared.
Example 4
A palladium nanoparticle modified indium oxide nanosheet composite material is prepared by the following steps:
step a4, mixing indium nitrate, resorcinol, N-dimethylformamide and acetone together according to the weight ratio of indium nitrate to resorcinol to N, N-dimethylformamide to acetone of 1: 0.1-0.8: 50-150: 50-100, stirring for 2 hours, adding a proper amount of deionized water, then placing in a sealed environment at 130 ℃ for reaction for 5 hours, and then carrying out solid-liquid separation and washing to obtain the indium organic framework nanosheet with the three-dimensional network structure.
Step b4, dispersing 50mg of the indium organic framework nanosheet with the three-dimensional network structure into 50mL of acetone, stirring for 60min, then adding 15mL of palladium nitrate with the concentration of 0.25mg/mL, stirring for 10h, and then performing solid-liquid separation and washing to obtain the palladium ion modified indium organic framework nanosheet with the three-dimensional network structure.
And c4, calcining 40mg of the palladium ion modified indium organic frame nanosheet with the three-dimensional network structure in the air, wherein the calcining temperature is 500 ℃, the heating rate is 5 ℃/min, and the calcining time is 5h, so that the palladium oxide particle modified indium oxide nanosheet composite material with the three-dimensional network structure is prepared.
And d4, carrying out gas reduction treatment on the indium oxide nanosheet composite material of the three-dimensional network structure modified by the palladium oxide particles by adopting a reducing gas, wherein the reduction temperature is 300 ℃, the heating rate is 2 ℃/min, and the reduction time is 3h, so that the palladium nanoparticle modified indium oxide nanosheet composite material is prepared.
In conclusion, the embodiment of the invention has the advantages of high specific surface area and good gas-sensitive property, can be used as a sensing layer of a resistance type metal oxide gas sensor to realize ultra-sensitive and high-selectivity detection on carbon disulfide gas, does not need expensive detection equipment, has low detection cost, simple operation, short detection time, rapidness and high efficiency, and can carry out real-time detection and on-site detection on the carbon disulfide gas.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (6)

1. A preparation method of an indium oxide nanosheet composite material modified by palladium nanoparticles is characterized by comprising the following steps:
step A, mixing indium nitrate, resorcinol, N-dimethylformamide and acetone together according to the weight ratio of indium nitrate to resorcinol to N, N-dimethylformamide to acetone of 1: 0.1-0.8: 50-150: 50-100, stirring for 0.1-2 h, adding deionized water, then placing in a closed environment at 80-200 ℃ for reaction for 0.5-24 h, and then carrying out solid-liquid separation and washing to obtain an indium organic framework nanosheet with a three-dimensional network structure;
b, dispersing the indium organic framework nanosheets of the three-dimensional network structure into acetone, controlling the concentration of the indium organic framework nanosheets to be 0.05-2.5 mg/mL, stirring for 10-60 min, then adding palladium nitrate, stirring for 1-24 h, and then performing solid-liquid separation and washing to obtain palladium ion modified indium organic framework nanosheets of the three-dimensional network structure; wherein the dosage of the palladium nitrate is 0.001-0.5 times of the mass of the indium organic framework nanosheet with the three-dimensional network structure;
step C, calcining the palladium ion modified indium organic frame nanosheets with the three-dimensional network structures in the air, wherein the calcining temperature is 400-800 ℃, the heating rate is 1-10 ℃/min, and the calcining time is 0.1-10 h, so that the palladium oxide particle modified indium oxide nanosheet composite materials with the three-dimensional network structures are prepared;
and D, carrying out gas reduction treatment on the palladium oxide particle modified indium oxide nanosheet composite material with the three-dimensional network structure by adopting reducing gas, wherein the reducing temperature is 150-500 ℃, the heating rate is 1-10 ℃/min, and the reducing time is 0.1-10 h, so that the palladium nanoparticle modified indium oxide nanosheet composite material is prepared.
2. The preparation method of the palladium nanoparticle-modified indium oxide nanosheet composite material according to claim 1, wherein in step a, the amount of deionized water is 0.001 to 0.1 times the mass of the indium nitrate.
3. The method for preparing palladium nanoparticle-modified indium oxide nanosheet composite of claim 1 or 2, wherein in step D the reducing gas is H2/Ar、H2/N2、H2At least one of the components of the group/He.
4. An indium oxide nanosheet composite modified by palladium nanoparticles, characterized by being prepared by the method for preparing an indium oxide nanosheet composite modified by palladium nanoparticles according to any one of claims 1 to 3.
5. The palladium nanoparticle-modified indium oxide nanosheet composite material of claim 4, wherein the palladium nanoparticle-modified indium oxide nanosheet composite material has a palladium nanoparticle particle size of 1-3 nm and an indium oxide nanosheet thickness of 3-10 nm.
6. Use of palladium nanoparticle modified indium oxide nanoplate composite material as described in any of claims 4 to 5 as sensing layer of resistive metal oxide gas sensor for ultra sensitive and highly selective detection of carbon disulfide gas.
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