CN114994145A - Preparation method of precious metal modified indium oxide gas-sensitive material - Google Patents

Preparation method of precious metal modified indium oxide gas-sensitive material Download PDF

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CN114994145A
CN114994145A CN202210586352.4A CN202210586352A CN114994145A CN 114994145 A CN114994145 A CN 114994145A CN 202210586352 A CN202210586352 A CN 202210586352A CN 114994145 A CN114994145 A CN 114994145A
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noble metal
gas
sensitive material
indium oxide
oxide gas
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杨黎
张德起
郭胜惠
高冀芸
侯明
杜倩
麻艳佳
朱烨
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Kunming University of Science and Technology
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    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D53/8625—Nitrogen oxides
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    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
    • G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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Abstract

The invention discloses a preparation method of a noble metal modified indium oxide gas-sensitive material, belonging to the technical field of gas-sensitive materials; adding In into the noble metal solution 2 O 3 Then carrying out heat treatment to obtain the noble metal modified indium oxide gas-sensitive material; noble metal modified In prepared by the invention 2 O 3 The gas-sensitive material has the advantages of low working temperature, good selectivity, low energy consumption and better gas-sensitive response performance, and can be used for treating low-concentration NO 2 The gas still has high gas-sensitive response; the preparation method has simple process, and the prepared noble metal modified In 2 O 3 Gas sensitive materials for low concentration NO 2 Completely meet the requirements of NO in the fields of indoor environment, industrial safety and the like 2 The low concentration detection precision is required, and the method has practical application value.

Description

Preparation method of noble metal modified indium oxide gas-sensitive material
Technical Field
The invention belongs to the technical field of gas-sensitive materials, and particularly relates to a preparation method of a noble metal modified indium oxide gas-sensitive material.
Background
With the rapid development of society and the increasing improvement of human living standard, various air environmental pollution problems are followed. In particular, the density of vehicles is rapidly increased, and a large amount of Nitrogen Oxides (NO) in automobile exhaust gas 2 ) Harmful and toxic gases such as carbon monoxide (CO) and hydrocarbons are released into the atmosphere. Wherein NO 2 Is one of the most dangerous air pollutants, can not only stimulate the respiratory tract after being inhaled to cause symptoms of dry cough or pharyngeal discomfort, but also destroy ozone (O) 3 ) Layer and cause of acid rain formation. NO in homes and offices according to the standards of the occupational health and safety administration system (OHSAS18001) 2 Should not exceed a permissible contact limit of 5ppm (9 mg/m) 3 ). Thus, for NO 2 The monitoring of the gas has important significance for environmental protection and human health.
The gas sensor is an effective device for detecting toxic and harmful gases, wherein the metal oxide semiconductor gas sensor has the advantages of low cost, high response, signal benefit for modulation and the like, so that the metal oxide semiconductor gas sensor is widely applied and researched In the field of gas sensing, including indium oxide (In) which is a relatively large number of semiconductor oxide gas-sensitive materials researched at present 2 O 3 ) Due to its unique characteristics of low resistivity and good catalytic activity, it is widely used in gas sensors, Wang et al [ Rapid and acid detection of high purity toxixiNO ] 2 gas based on catkins biomass-derived porous In 2 O 3 microtubes at low temperature.Sensors and Actuators:B.Chemical,2022,361.]By simple chlorinationAfter the indium solution is soaked In the waste cat skin template, the waste cat skin template is calcined In the air at the temperature of 600 ℃, and the biological In is successfully prepared 2 O 3 Sensing material (In) 2 O 3 -600). At 92 ℃ In 2 O 3 600 sensor vs. 10ppm NO 2 The response value of (a) is as high as 193. Ma et al [ Room temperature photo electric NO ] 2 gas sensor based on direct growth of walnut-like In 2 O 3 nanostructures.Journal of Alloys and Compounds,2018,782:1121-1126.]Directly growing walnut-shaped In on the interdigital electrode substrate by a simple hydrothermal method and appropriate heat treatment 2 O 3 A nanostructure. Synthesized walnut-like In 2 O 3 The nanostructure was exposed to ultraviolet light (λ 365nm) at 1.2mW/cm 2 Under irradiation, for 50ppm NO 2 Has a gas sensitive response value of 219. In conclusion, although In was produced 2 O 3 Gas sensitive material to NO 2 Has a certain gas sensitive response, but pure In 2 O 3 The gas sensitive material has higher working temperature, large energy consumption and lower sensitivity, can not meet the current increasingly higher environmental detection requirement, and is not suitable for the preparation of low-temperature wearable gas sensors.
In order to solve the above problems, various scholars adopt different ways. Raad et al [ Hydrothermal Synthesis of In 2 O 3 :Ag Nanostructures for NO 2 Gas Sensor.Silicon,2019,11(3):2475-2478.]Successfully synthesizing Ag-doped In by a simple hydrothermal process 2 O 3 The gas-sensitive response value of the nano-structure material with the doping concentration of 9% Ag is 79% at the working temperature of 100 ℃. Han et al [ Construction of In 2 O 3 /ZnO yolk-shell nanofibers for room-temperature NO 2 detection under UV illumination.Journal of Hazardous Materials,2021,403.]Preparation of In 2 O 3 ZnO yolk shell nanofiber sensor with 1ppm NO under ultraviolet irradiation 2 Gas sensitive response value of 6.0. All of the above work improved In to varying degrees 2 O 3 The gas sensor has the gas-sensitive response performance, but still has the defect of high working temperature.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a noble metal modified indium oxide gas-sensitive material.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a preparation method of a noble metal modified indium oxide gas-sensitive material, which comprises the following steps: adding In into the noble metal solution 2 O 3 And then carrying out heat treatment to obtain the noble metal modified indium oxide gas-sensitive material.
Further, the noble metal solution refers to a noble metal ion solution.
Further, the In 2 O 3 The preparation method comprises the following steps: dissolving indium salt, glycerol and glycol In water, then carrying out hydrothermal reaction, centrifuging, washing, drying and calcining the obtained product to obtain the In 2 O 3 。
Further, the indium salt includes In (NO) 3 ) 3 Or InCl 3 。
Furthermore, the using amount ratio of the indium salt, the glycerol and the glycol is (1-2) mmol to (3-8) mL to (5-15) mL.
Glycerol and ethylene glycol are chemical additives with the aim of facilitating the formation of nanoparticulate indium oxide.
Further, the temperature of the hydrothermal reaction is 150-200 ℃, and the time is 10-15 h.
Further, the washing is centrifugal washing for 3-5 times by using ethanol and deionized water, and the drying temperature is 40-80 ℃.
Furthermore, the calcination temperature is 450-500 ℃, and the calcination time is 1-3 h.
Further, the noble metal element In the noble metal solution includes one of Ir, Au, Pt, Ru, Ag, Pd and Rh, and In 2 O 3 The molar ratio of the noble metal element to the noble metal element is 1 to (0.001-0.01).
Still further, the noble metal solution includes IrCl 3 、AuCl 3 、H 2 PtCl 6 ·6H 2 O、RuCl 3 ·3H 2 O、AgNO 3 、PdCl 2 And RhCl 3 ·3H 2 One of aqueous solutions of O.
Further, the heat treatment comprises the following specific steps: under the protection of inert atmosphere, firstly preserving heat for 1-2 h at 250-350 ℃, and then preserving heat for 2-3 h at 500-600 ℃.
The invention also provides the noble metal modified indium oxide gas-sensitive material prepared by the preparation method of the noble metal modified indium oxide gas-sensitive material.
The invention also provides the noble metal modified indium oxide gas-sensitive material in NO 2 Application in detection; especially at low concentrations of NO 2 And (3) application in detection.
Compared with the prior art, the invention has the following beneficial effects:
the invention uses noble metal to react In 2 O 3 Surface modification is carried out, and the surface gas-sensitive reaction is directly influenced by changing the surface form of the metal oxide gas-sensitive material; meanwhile, In can be enriched by surface modification 2 O 3 The surface defects of the gas sensitive material enhance the surface effect and can effectively improve In modified by noble metals 2 O 3 The gas sensitive response properties of the gas sensitive material.
In the surface modification process, the noble metal can reduce the adsorption activation energy of the gas to be detected through the self-catalysis effect, so that the gas is easier to be adsorbed on the surface of the material; meanwhile, gas adsorption active sites can be provided for gas-sensitive reaction, so that the difference between the resistance of the material before and after gas adsorption is increased, and the gas-sensitive performance of the material is improved.
Noble metal modified In prepared by the invention 2 O 3 The gas-sensitive material has the advantages of low working temperature, good selectivity, low energy consumption and better gas-sensitive response performance, and can be used for treating low-concentration NO 2 The gas still has a high gas sensitive response.
The preparation method has simple process, and the prepared noble metal modified In 2 O 3 Gas sensitive materials for low concentration NO 2 Completely meet the requirements of NO in the fields of indoor environment, industrial safety and the like 2 Low concentrationThe accuracy requirement of detection is met, and the method has practical application value.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described 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 without creative efforts.
FIG. 1 is a schematic representation of a high throughput apparatus used in example 1;
FIG. 2 shows In prepared In example 1 2 O 3 Scanning electron microscopy of + 0.5% Rh composite;
FIG. 3 shows In prepared In example 1 2 O 3 A surface scan elemental profile of + 0.5% Rh composite;
FIG. 4 shows the composite materials prepared In examples 1 to 7 and In prepared In step 1 of example 1 2 O 3 For NO at different temperatures 2 A gas sensitive response performance graph of (a);
FIG. 5 shows the results of the composite materials prepared in examples 1-7 at 50 ℃ for 0.5-100ppm NO 2 A gas sensitive response performance graph of (a);
FIG. 6 shows the results of the composite materials prepared in examples 1-7 at 50 ℃ for 0.5ppm and 1ppm NO 2 A gas sensitive response performance graph of (a);
FIG. 7 shows that the composite materials prepared in examples 1 to 7 are aligned to 5ppmNO at 50 DEG C 2 The gas-sensitive response stability test result chart.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the documents are cited. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including but not limited to.
In the following embodiments, the high-throughput equipment used is a self-made equipment, the experimental platform mainly comprises two parts, one part is a premixing module under the control of a PC-end program, and the liquid in the raw material solution chamber is injected into the premixing solution chamber according to different proportions through a peristaltic pump and a liquid-transferring needle head to obtain premixing solutions with different components; the other part is a transfer module, and the premixed solution in the mixing cavity is transferred to a stage substrate through a liquid-transferring needle to form a gas-sensitive material film.
Example 1
The preparation method of the noble metal modified indium oxide gas-sensitive material comprises the following steps:
step 1: 1.5mmol of In (NO) 3 ) 3 ·5H 2 Adding 5.0mL of glycerol and 10.0mL of glycol into 5mL of deionized water, and forming a uniform solution under continuous strong stirring; then transferring the stirred solution into a 50mL reaction kettle, and uniformly heating at 180 ℃ for 12 h; after the reaction, naturally cooling the sample to room temperature, centrifugally washing the obtained white precipitate respectively by deionized water and ethanol for 3 times, and then carrying out air drying at 60 ℃ for 2 hours; finally calcining at 500 ℃ for 2h to obtain In 2 O 3 And (3) powder.
Step 2: in accordance with 2 O 3 With Rh 3+ In a molar ratio of 1: 0.005, passing In through a high throughput apparatus 2 O 3 The powder was mixed with 0.01g/mL RhCl 3 ·3H 2 After the O solution is uniformly mixed, calcining the mixture for 2 hours at 350 ℃ under the protection of argon, and then annealing the mixture for 2 hours at 550 ℃ to obtain In with the surface modified by the precious metal Rh 2 O 3 + 0.5% Rh composite.
The schematic diagram of the high-throughput device used in step 2 of this embodiment is shown in fig. 1, and the solution is quantitatively mixed by program control of a PC terminal, so that human errors in the experimental process are reduced, and the material synthesis efficiency is improved.
In obtained In step 2 of this example 2 O 3 The scanning electron microscope image of the + 0.5% Rh composite material is shown in fig. 2, and it can be seen from fig. 2 that the gas sensitive material has good film formation consistency and uniform pores.
In obtained In step 2 of this example 2 O 3 The profile of the surface-scan element distribution of the + 0.5% Rh composite is shown In FIG. 3, from which it can be seen that In 2 O 3 The + 0.5% Rh composite material has three elements of In, O and Rh, and Rh is uniformly distributed In the whole scanning range, i.e. In 2 O 3 + 0.5% Rh and In the Rh material 2 O 3 The whole distribution is uniform.
Examples 2 to 7
The same as example 1, with the difference that RhCl in step 2 is reacted 3 ·3H 2 Replacing O solution with AuCl respectively 3 Solution, PdCl 2 Solution, IrCl 3 Solution, H 2 PtCl 6 ·6H 2 O solution, RuCl 3 ·3H 2 O solution and AgNO 3 Solutions, separately prepared to obtain In 2 O 3 +0.5％Au、In 2 O 3 +0.5％Pd、In 2 O 3 +0.5％Ir、In 2 O 3 +0.5％Pt、In 2 O 3 + 0.5% Ru and In 2 O 3 + 0.5% Ag composite (corresponding to examples 2-7, respectively).
Observing the composite materials prepared in the embodiments 2-7 by using a scanning electron microscope, and finding that the composite materials have good film-forming consistency and uniform pores; as can be seen from the surface-scanning element distribution diagram of each composite material, the noble metal elements In each material are uniformly distributed In 2 O 3 In (1).
In obtained In examples 1 to 7 2 O 3 +0.5％Rh、In 2 O 3 +0.5％Au、In 2 O 3 +0.5％Pd、In 2 O 3 +0.5％Ir、In 2 O 3 +0.5％Pt、In 2 O 3 + 0.5% Ru and In 2 O 3 + 0.5% Ag composite and In prepared In step 1 of example 1 2 O 3 For NO at different temperatures 2 The gas-sensitive response performance of the composite material is tested, the obtained result is shown in fig. 4, and as can be seen from fig. 4, the composite materials prepared in examples 1 to 7 are used for NO 2 The optimum response temperatures were all 50 ℃, In prepared In step 1 of example 1 2 O 3 For NO 2 The optimum response temperature of (a) is 75 ℃.
0.5-100ppm NO of the composite material pair prepared in examples 1-7 at 50 DEG C 2 The gas-sensitive response performance of the composite material prepared in examples 1 to 7 was tested, and the results are shown in FIG. 5, where the composite material prepared in examples 1 to 7 was used for 0.5ppm and 1ppm of NO at 50 ℃ 2 The gas-sensitive response properties of (A) are shown in FIG. 6, and it can be seen from FIGS. 5 and 6 that at 50 ℃ each composite material is paired with NO 2 Response value of with NO 2 Increases with increasing concentration of (c). The composite material prepared In examples 1 to 7 and In prepared In step 1 of example 1 at 50 DEG C 2 O 3 For NO 2 The detection limit of (2) is as low as 0.5 ppm. 50Each composite and In prepared In step 1 of example 1 was processed at DEG C 2 O 3 For 5ppmNO 2 Response value to 0.5ppm NO 2 The response values of (A) are shown in Table 1 (R) gas /R air Is the ratio of the resistance value of the material when stable in the gas to be detected and the resistance value when stable in air at the same temperature).
TABLE 1
Figure BDA0003666101040000061
Meanwhile, the composite materials prepared In examples 1 to 7 and In prepared In step 1 of example 1 2 O 3 Respectively at 50 ℃ for 5ppm of NH 3 The response properties of ethanol, formaldehyde and benzene were measured, and the obtained response values are shown in table 2. As can be seen from tables 1-2, the composite material prepared by the invention can not only treat NO at low temperature and low concentration 2 Has excellent response performance, low detection limit and good selectivity.
TABLE 2
Figure BDA0003666101040000071
As can be seen from tables 1-2, the same as pure In 2 O 3 Compared with the prepared gas sensitive material, In modified by noble metal 2 O 3 The composite material has lower working temperature and lower energy consumption, and the gas-sensitive response performance is greatly improved after the composite material is modified by precious metals Rh, Au, Pd, Ru and Ag.
The composite materials prepared in examples 1-7 have a NO content of 5ppm at 50 DEG C 2 The results of the gas response stability measurements of (1) are shown in FIG. 7, at 50 ℃ for 9 consecutive weeks of operating time, with 5ppm NO 2 The response values of the composite materials have no obvious change, which shows that the composite materials have good stability.
Example 8
The preparation method of the noble metal modified indium oxide gas-sensitive material comprises the following steps:
step 1: 1mmol of InCl 3 Adding 3.0mL of glycerol and 5.0mL of glycol into 5mL of deionized water, and forming a uniform solution under continuous strong stirring; then transferring the stirred solution into a 50mL reaction kettle, and uniformly heating for 15h at 150 ℃; after the reaction, naturally cooling the sample to room temperature, respectively centrifugally washing the obtained white precipitate with deionized water and ethanol for three times, and then air-drying at 40 ℃ for 4 hours; finally calcining at 450 ℃ for 3h to obtain In 2 O 3 And (3) powder.
And 2, step: in accordance with 2 O 3 With Rh 3+ In a molar ratio of 1: 0.001, passing In through a high-throughput device 2 O 3 Powder with 0.01g/mL RhCl 3 ·3H 2 After the O solution is uniformly mixed, the mixture is calcined for 2 hours at 250 ℃ under the protection of argon, and then the mixture is annealed for 3 hours at 500 ℃ to obtain In modified by the surface of the precious metal Rh 2 O 3 + 0.1% Rh composite.
Example 9
The preparation method of the noble metal modified indium oxide gas-sensitive material comprises the following steps:
step 1: 2mmol of In (NO) 3 ) 3 ·5H 2 Adding 8.0mL of glycerol and 15.0mL of glycol into 5mL of deionized water, and forming a uniform solution under continuous strong stirring; then transferring the stirred solution into a 50mL reaction kettle, and uniformly heating at 200 ℃ for 10 h; after the reaction, naturally cooling the sample to room temperature, respectively centrifugally washing the obtained white precipitate with deionized water and ethanol for three times, and then air-drying at 80 ℃ for 2 hours; finally calcining at 480 ℃ for 2h to obtain In 2 O 3 And (3) powder.
Step 2: in accordance with 2 O 3 With Rh 3+ In a molar ratio of 1: 0.01, directly adding In 2 O 3 Powder with 0.01g/mL RhCl 3 ·3H 2 After the O solution is mixed evenly, the mixture is calcined for 1h at 300 ℃ under the protection of argon, and then the mixture is annealed for 2h at 600 ℃ to obtain In modified by the surface of the noble metal Rh 2 O 3 + 1.0% Rh composite.
For the composite materials prepared in examples 8 to 9, NO 2 Optimum response temperature of gasThe detection is carried out, and the NO is detected 2 The optimal response temperature is 50 ℃; at 50 ℃ it is NO 2 The detection limit of (a) is as low as 0.5 ppm; the composite material prepared in examples 8 to 9 is treated with 5ppm NO at 50 DEG C 2 The response values of the composite materials are 606.6 and 934.6 respectively, and the composite materials prepared in the examples 8 to 9 have a response value of 0.5ppmNO at 50 DEG C 2 The response values of (a) are 2.8 and 4.5, respectively; composite material prepared in example 8 at 50 ℃ to 5ppm NH 3 The response values of ethanol, formaldehyde and benzene are respectively as follows: 3.2, 2.1, 1.6 and 1.1, composite materials prepared in example 9 at 50 ℃ to 5ppm NH 3 The response values of ethanol, formaldehyde and benzene are respectively as follows: 3.7, 2.8, 2.3, 1.4 and 1.3.
The above description is only for the preferred embodiment of the present invention, and the protection scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical scope of the present invention, the technical solution and the inventive concept of the present invention equivalent or change within the technical scope of the present invention.

Claims (10)

1. A preparation method of a noble metal modified indium oxide gas-sensitive material is characterized by comprising the following steps: adding In into the noble metal solution 2 O 3 And then carrying out heat treatment to obtain the noble metal modified indium oxide gas-sensitive material.
2. The method for preparing the noble metal-modified indium oxide gas-sensitive material according to claim 1, wherein In is 2 O 3 The preparation method comprises the following steps: dissolving indium salt, glycerol and glycol In water, then carrying out hydrothermal reaction, centrifuging, washing, drying and calcining the obtained product to obtain the In 2 O 3 。
3. The method of claim 2, wherein the indium salt comprises In (NO) 3 ) 3 Or InCl 3 。
4. The preparation method of the noble metal modified indium oxide gas-sensitive material as claimed in claim 2, wherein the using amount ratio of the indium salt, glycerol and glycol is (1-2) mmol to (3-8) mL to (5-15) mL.
5. The preparation method of the noble metal modified indium oxide gas-sensitive material according to claim 2, wherein the hydrothermal reaction is carried out at a temperature of 150-200 ℃ for 10-15 h.
6. The preparation method of the noble metal modified indium oxide gas-sensitive material according to claim 2, wherein the calcining temperature is 450 to 500 ℃ and the calcining time is 1 to 3 hours.
7. The method for preparing the noble metal-modified indium oxide gas-sensitive material according to claim 1, wherein the noble metal element In the noble metal solution comprises one of Ir, Au, Pt, Ru, Ag, Pd and Rh, and In is 2 O 3 The molar ratio of the noble metal element to the noble metal element is 1 to (0.001-0.01).
8. The preparation method of the noble metal modified indium oxide gas-sensitive material according to claim 1, wherein the heat treatment comprises the following steps: under the protection of inert atmosphere, firstly preserving heat for 1-2 h at 250-350 ℃, and then preserving heat for 2-3 h at 500-600 ℃.
9. The precious metal modified indium oxide gas-sensitive material prepared by the preparation method of the precious metal modified indium oxide gas-sensitive material according to any one of claims 1 to 8.
10. The noble metal modified indium oxide gas-sensitive material of claim 9 in the presence of NO 2 Application in detection.
CN202210586352.4A 2022-05-27 2022-05-27 Preparation method of precious metal modified indium oxide gas-sensitive material Pending CN114994145A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115541665A (en) * 2022-11-28 2022-12-30 南方电网数字电网研究院有限公司 Oxygen gas-sensitive material and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115541665A (en) * 2022-11-28 2022-12-30 南方电网数字电网研究院有限公司 Oxygen gas-sensitive material and preparation method and application thereof

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