CN117169292A - Gas-sensitive material, gas sensor, preparation method and application thereof - Google Patents
Gas-sensitive material, gas sensor, preparation method and application thereof Download PDFInfo
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The application relates to the technical field of gas-sensitive materials, in particular to a gas-sensitive material, a gas sensor, a preparation method and application thereof. The gas-sensitive material is semiconductor material SnO modified by bimetal (metal Sm and metal Pd) 2 Sm is prepared by adopting a gel sol method 2 O 3 Doped SnO 2 The method comprises the steps of carrying out a first treatment on the surface of the Then adding Pd-containing material for mixing and calcining. The gas sensor includes a MEMS chip and a gas sensitive material distributed over interdigital electrodes of the MEMS chip. The gas-sensitive material, the gas sensor and the preparation method thereof have higher sensitivity, short response recovery time and good selectivity, and can be used for the selective detection of acetylene gas.
Description
Technical Field
The application relates to the technical field of gas-sensitive materials, in particular to a gas-sensitive material, a gas sensor, a preparation method and application thereof; the application refers to the application of the gas-sensitive material or the gas sensor in the selective detection of acetylene gas.
Background
The gas sensor is classified into a semiconductor type gas sensor, an electrochemical type gas sensor, a contact combustion type gas sensor, a photochemical type gas sensor, a polymer gas sensor, and the like according to a gas sensing mechanism. The semiconductor gas sensor can be applied to various gas detection, has the advantages of low cost, high sensitivity, low detection lower limit and the like, and research and development staff have developed various gas-sensitive materials made of different semiconductor materials, such as TiO 2 、SnO 2 ZnO, niO, and the like.
Since the mechanism of reaction of metal oxides with gases is based on electron exchange between the two, it tends to have a general sensitivity characteristic for a class of gases such as a reducing gas or an oxidizing gas. How to improve the selectivity is a key problem to be solved in the development process of the semiconductor type gas sensor at present. Has been reported to indicate that for SnO 2 The material is modified by metal doping, so that the selectivity can be effectively improved, and SnO 2 The crystal structure of the material is rutile type, the forbidden bandwidth is 3.54eV, and a large number of oxygen vacancies generated in the preparation process lead SnO to be formed 2 Becomes a typical N typeThe semiconductor sensitive material has obvious gas sensitive effect, but has poorer long-term stability, higher working temperature and other problems which limit SnO 2 Practical application of the base gas-sensitive material.
The oil-immersed power transformer is a key device in the operation of a power grid, and the reliable operation of the transformer is one of key factors for the reliable operation of the power grid. According to the detection requirements in the existing industry standard analysis and judgment rules of dissolved gas in transformer oil, seven gases such as acetylene, methane, ethane, carbon monoxide, carbon dioxide, ethylene and hydrogen are the most important fault characteristic gases of the power transformer oil. Therefore, the detection of acetylene gas and the distinction from other gases are realized, and the method has important significance for judging whether the power transformer has faults and the fault type.
Disclosure of Invention
Based on this, the object of the present application includes providing a gas sensitive material, a gas sensor, a method for its preparation and its use. Compared with the prior art, the gas-sensitive material and the gas sensor have higher sensitivity, short response recovery time and good selectivity, and can be used for the selective detection of acetylene gas.
In a first aspect of the present application, there is provided a gas-sensitive material comprising a bimetallic-modified semiconductor material, wherein the bimetallic material is metal Sm and metal Pd, and the semiconductor material comprises SnO 2 ；
The modification refers to the preparation of Sm by a gel sol method 2 O 3 Doped SnO 2 Is denoted as Sm 2 O 3 @SnO 2 The method comprises the steps of carrying out a first treatment on the surface of the Then adding Pd-containing material, mixing and calcining to prepare Pd doped Sm 2 O 3 @SnO 2 Is marked as Pd@Sm 2 O 3 @SnO 2 。
In some embodiments, the method for preparing Sm by gel sol method 2 O 3 Modified SnO 2 The method comprises the following steps:
mixing Sm salt and Sn salt, dissolving in solvent to obtain Sm/Sn salt solution,
adding a precipitant into the Sm/Sn salt solution to carry out precipitation reaction, and separating the precipitateDrying the precipitate, and taking the dried precipitate to perform first calcination at 500-700 ℃ to obtain the Sm 2 O 3 @SnO 2 。
In some embodiments, the method for preparing Sm by gel sol method 2 O 3 Modified SnO 2 The preparation conditions of (2) include at least one of the following:
1) The Sm/Sn salt solution contains Sn and Sm in a molar ratio of (30-35): 1;
2) The solution condition of the precipitation reaction is that the pH=8.5-9.5;
3) The precipitant is ammonia water solution, wherein the volume of ammonium hydroxide and water is (0.8-1.2): 1, a step of;
4) The step of separating the precipitate comprises: filtering to obtain a solid, and washing the solid with deionized water and ethanol;
5) The drying temperature is 50-70 ℃;
6) The drying time is 10-14 h;
7) The time of the first calcination is 0.5-2 h.
In some embodiments, the step of adding the Pd-containing material to the mixed calcination comprises:
pd salt is taken, sm is taken 2 O 3 @SnO 2 Mixing with water, and ultrasonic dispersing to obtain Pd salt/Sm 2 O 3 @SnO 2 A dispersion;
separating the Pd salt/Sm 2 O 3 @SnO 2 And drying the solid in the dispersion liquid, and taking the dried solid to carry out second calcination at 600-800 ℃.
In some embodiments, the preparation conditions for the mixed calcination of the added Pd-containing material include at least one of:
1) The Pd salt contains the element Pd and the Sm 2 O 3 @SnO 2 The molar weight ratio of (2) is 1mmol: (15-16) g;
2) The ultrasonic dispersion time is 20-50 min;
3) Separating the Pd salt/Sm 2 O 3 @SnO 2 Solids in dispersion and proceedingIn the step of drying: the drying temperature is 80-100 ℃ and/or the drying time is 10-14 h;
4) The second calcination time is 0.5-2 h.
In a second aspect of the present application, there is provided a gas sensor comprising:
1) A MEMS chip comprising interdigital electrodes;
2) The gas-sensitive material provided by the first aspect of the application is distributed on the interdigital electrode of the MEMS chip and completely covers the surface of the interdigital electrode;
optionally further comprising: a support film for providing a supporting force, a heater for providing an operating temperature, and a separation film for blocking an electrical connection between the heater and the interdigital electrode.
In some embodiments, the material of the support film comprises Si 3 N 4 And SiO 2 A kind of electronic device
The heater includes a heating electrode; and/or
The isolation film comprises Si 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the And/or
The interdigital electrodes include polyimide interdigital electrodes and Pt electrodes located over a substrate.
In some embodiments, the thickness of the support film is 500nm to 700nm; and/or
Si in the support film 3 N 4 And SiO 2 The grain diameter of the polymer is selected from 200nm to 400nm; and/or
The heating electrode is composed of Pt wires with line width of 4-6 mu m and line spacing of 8-12 mu m; and/or
The thickness of the isolation film is 200 nm-400 nm; and/or
The thickness of the substrate in the interdigital electrode is 100 nm-300 nm; and/or
The line width of the Pt electrode in the interdigital electrode is 4-6 mu m.
In a third aspect of the present application, there is provided a method for manufacturing a gas sensor according to the second aspect of the present application, comprising the steps of:
providing a MEMS chip as defined in the gas sensor according to the second aspect of the application;
providing the gas-sensitive material according to the first aspect of the application for grinding, adding deionized water for mixing, and grinding the obtained mixture to prepare gas-sensitive slurry;
and coating the gas-sensitive slurry on the interdigital electrode of the MEMS chip, so that the gas-sensitive slurry completely covers the surface of the interdigital electrode, and drying.
In some embodiments, after drying is completed, connecting two ends of the interdigital electrode of the MEMS chip to a side heating type hexagonal tube seat, and connecting the hexagonal tube seat to a gas-sensitive analyzer;
respectively connecting two ends of a heater of the MEMS chip to appointed pins of the singlechip;
and regulating the singlechip to ensure that the singlechip stably provides voltage for ageing the device.
In a fourth aspect of the application there is provided the use of a gas sensitive material provided in the first aspect of the application or a gas sensor provided in the second aspect of the application in the selective detection of acetylene gas.
In some embodiments, the acetylene gas concentration is in the range of 2ppm to 100ppm for the application.
In some embodiments, the selective detection of acetylene gas comprises detection of dissolved gas in transformer oil.
The gas-sensitive material of the application is prepared by using specific metals Sm and Pd and a proper modification method to semiconductor material SnO 2 The semiconductor material modified by bimetal is prepared, the sensitivity, the selectivity and the response recovery characteristic of the gas sensor using the material as a gas sensitive material are obviously improved, the defects of poor selectivity, insufficient sensitivity and long response recovery time of the traditional semiconductor sensor are overcome, the power consumption is low, the detection can be carried out at room temperature, the acetylene gas has good response and selectivity, no response to other common gases such as ethylene, carbon monoxide, methane, ethane, carbon dioxide and the like is realized, and the gas sensor can be used for detecting dissolved gases in transformer oil.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present application, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph of Pd@Sm of example 1 of the application 2 O 3 @SnO 2 XRD pattern of the material;
FIG. 2 is a graph showing the optimum operating voltage of the gas sensor according to example 3 of the present application;
FIG. 3 is a sensitivity test result of the gas sensor of example 3 of the present application;
FIG. 4 is a response-recovery time test result of the gas sensor of example 3 of the present application;
FIG. 5 is a graph showing the results of a selective test of a gas sensor according to example 3 of the present application;
FIG. 6 is a graph showing the optimum operating voltage of the gas sensor of comparative example 1 of the present application;
FIG. 7 is a sensitivity test result of the gas sensor of comparative example 1 of the present application;
FIG. 8 is a response-recovery time test result of the gas sensor of comparative example 1 of the present application;
FIG. 9 is a selective test result of the gas sensor of comparative example 1 of the present application;
FIG. 10 is a graph showing the optimum operating voltage of the gas sensor of comparative example 2 of the present application;
FIG. 11 is a sensitivity test result of the gas sensor of comparative example 2 of the present application;
FIG. 12 is a response-recovery time test result of the gas sensor of comparative example 2 of the present application;
FIG. 13 is a result of a selectivity test of the gas sensor of comparative example 2 of the present application.
Detailed Description
The application is further illustrated below in conjunction with the embodiments, examples and figures. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it is to be understood that various changes and modifications may be made by one skilled in the art after reading the teachings of the application, and such equivalents are intended to fall within the scope of the appended claims.
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 application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
Terminology
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
the term "and/or," "and/or," as used herein, includes any one of two or more of the listed items in relation to each other, as well as any and all combinations of the listed items in relation to each other, including any two of the listed items in relation to each other, any more of the listed items in relation to each other, or all combinations of the listed items in relation to each other. It should be noted that, when at least three items are connected by at least two conjunctions selected from the group consisting of "and/or", "and/or", it is to be understood that, in the present application, the technical solutions certainly include technical solutions that all use "logical and" connection, and also certainly include technical solutions that all use "logical or" connection. For example, "a and/or B" includes three parallel schemes A, B and a+b. For another example, the technical schemes of "a, and/or B, and/or C, and/or D" include any one of A, B, C, D (i.e., the technical scheme of "logical or" connection), and also include any and all combinations of A, B, C, D, i.e., any two or three of A, B, C, D, and also include four combinations of A, B, C, D (i.e., the technical scheme of "logical and" connection).
In the present application, the terms "first", "second", "third", "fourth", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying an importance or quantity of a technical feature being indicated. Moreover, the terms "first," "second," "third," "fourth," and the like are used for non-exhaustive list description purposes only, and are not to be construed as limiting the number of closed forms.
Herein, "preferred", "better", etc. are merely embodiments or examples that describe better results, and it should be understood that they do not limit the scope of the application.
In the present application, "further", "still further", "particularly" and the like are used for descriptive purposes to indicate differences in content but should not be construed as limiting the scope of the application.
In the application, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present application, a numerical range (i.e., a numerical range) is referred to, and optional numerical distributions are considered to be continuous within the numerical range and include two numerical endpoints (i.e., a minimum value and a maximum value) of the numerical range and each numerical value between the two numerical endpoints unless otherwise specified. When a numerical range merely points to integers within the numerical range, both end integers of the numerical range are included, as well as each integer between the two ends, unless expressly stated otherwise. Further, when a plurality of range description features or characteristics are provided, these ranges may be combined. In other words, unless otherwise indicated, the ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The temperature parameter in the present application is not particularly limited, and may be a constant temperature treatment or may vary within a predetermined temperature range. It should be appreciated that the constant temperature process described allows the temperature to fluctuate within the accuracy of the instrument control. Allows for fluctuations within a range such as + -5 ℃, + -4 ℃, + -3 ℃, + -2 ℃, + -1 ℃.
In the present application, the weight may be a mass unit known in the chemical industry field such as mu g, mg, g, kg.
In the present application, the dimensions, particle diameter and diameter are generally average values, unless otherwise specified.
In a first aspect, the present application relates to a gas-sensitive material, the gas-sensitive material being a bimetallic-modified semiconductor material, wherein the bimetallic material comprises a metal Sm and a metal Pd, and the semiconductor material comprises SnO 2 ；SnO 2 After the material is modified by specific metal modification, the sensitivity, selectivity and response recovery characteristics are obviously improved, and the defects of poor selectivity, insufficient sensitivity, long response recovery time and the like of the traditional semiconductor material are overcome.
In some embodiments, the gas sensitive material is a semiconductor material modified by bimetal, wherein the bimetal refers to metal Sm and metal Pd, and the semiconductor material comprises SnO 2 ；
Modification means that Sm is prepared by a gel sol method 2 O 3 Doped SnO 2 Is denoted as Sm 2 O 3 @SnO 2 The method comprises the steps of carrying out a first treatment on the surface of the Then adding Pd-containing material, mixing and calcining to prepare Pd doped Sm 2 O 3 @SnO 2 Is marked as Pd@Sm 2 O 3 @SnO 2 。
In some embodiments, sm is prepared by a gel sol process 2 O 3 Modified SnO 2 The method comprises the following steps:
mixing Sm salt and Sn salt, dissolving in solvent to obtain Sm/Sn salt solution,
adding a precipitant into the Sm/Sn salt solution for precipitation reaction, separating and drying the precipitate, and taking the dried precipitate for first calcination at 500-700 ℃ to obtain Sm 2 O 3 @SnO 2 . The purpose of drying and removing the solvent before calcination is to enable the calcination process to be a reaction of a solid phase and a gas phase, and if not drying, the calcination process is a solid-liquid-gas three-phase reaction, and the micro-nano structure of the product can be influenced.
In some embodiments, use is made ofPreparation of Sm by gel sol method 2 O 3 Modified SnO 2 The preparation conditions of (2) include at least one of the following:
1) The Sm/Sn salt solution contains Sn and Sm in the molar ratio of (30-35): 1;
2) The condition of the precipitation reaction is that the pH=8.5-9.5;
3) The precipitant is ammonia water solution containing NH 3 ·H 2 The volumes of O and water are (0.8-1.2): 1, a step of;
4) The step of separating the precipitate comprises: filtering to obtain a solid, and washing the solid with deionized water and ethanol;
5) The drying temperature is 50-70 ℃;
6) Drying time is 10-14 h;
7) The time of the first calcination is 0.5 h-2 h.
In some embodiments, the Sm/Sn salt solution contains Sn and Sm in a molar ratio of (30-35): 1, exemplified by moles such as 30:1, 31:1, 32:1, 33:1, 34:1, 100:3, 35:1, etc.
In some embodiments, the conditions of the precipitation reaction are ph=8.5 to 9.5, e.g., pH of 8.5, 9, 9.5, etc.
In some embodiments, the precipitant is an aqueous ammonia solution containing ammonium hydroxide and water in a volume of (0.8-1.2): 1, exemplary volumes such as 0.8: 1. 1: 1. 1.2:1, etc.
In some embodiments, the step of separating the precipitate comprises: the solid was filtered and washed with deionized water and ethanol.
In some embodiments, sm is prepared by a gel sol process 2 O 3 Modified SnO 2 In the step (a), the drying temperature is 50 to 70 ℃, further 55 to 65 ℃, for example, 50 ℃, 60 ℃, 70 ℃ and the like.
In some embodiments, sm is prepared by a gel sol process 2 O 3 Modified SnO 2 In the step (2), the drying time is 10 to 14 hours, and further may be 11 to 13 hours, for example, 10 hours, 12 hours, 14 hours, etc.
In some embodiments, the temperature of the first calcination is 500 ℃ to 700 ℃, further can be 550 ℃ to 650 ℃, for example, the temperature of the second calcination such as 500 ℃, 550 ℃, 600 ℃, 620 ℃, 650 ℃, 680 ℃, 700 ℃, and the like.
In some embodiments, the first calcination time is from 0.5h to 2h, further may be from 1h to 1.5h, for example, for a time of 0.5h, 1h, 1.5h, 2h, etc.
In some embodiments, the step of adding the Pd-containing material to the mixed calcination comprises:
taking Pd salt and Sm 2 O 3 @SnO 2 Mixing with water, and ultrasonic dispersing to obtain Pd salt/Sm 2 O 3 @SnO 2 A dispersion;
separation of Pd salt/Sm 2 O 3 @SnO 2 And drying the solid in the dispersion liquid, and taking the dried solid to carry out second calcination at 600-800 ℃. The purpose of drying and removing the solvent before calcination is to enable the calcination process to be a reaction of a solid phase and a gas phase, and if not drying, the calcination process is a solid-liquid-gas three-phase reaction, and the micro-nano structure of the product can be influenced.
In some embodiments, the temperature of the second calcination is 600 ℃ to 800 ℃, further may be 600 ℃ to 700 ℃, for example, the temperature of the second calcination is 600 ℃, 620 ℃, 650 ℃, 680 ℃, 700 ℃, 750 ℃, 800 ℃, and the like.
In some embodiments, the second calcination time is from 0.5h to 2h, further may be from 1h to 1.5h, for example, for a time of 0.5h, 1h, 1.5h, 2h, etc. In some embodiments, the preparation conditions for mixed calcination with addition of the Pd-containing material include at least one of the following:
1) The Pd salt contains the elements Pd and Sm 2 O 3 @SnO 2 The molar weight ratio of (2) is 1mmol: (15-16) g;
2) The ultrasonic dispersion time is 20 min-50 min;
3) Separation of Pd salt/Sm 2 O 3 @SnO 2 In the step of dispersing the solid in the liquid and drying: the drying temperature is 80-100 ℃ and/or the drying time is 10-14 h;
4) The second calcination time is 0.5 h-2 h.
In some embodiments, the Pd salt contains the elements Pd and Sm 2 O 3 @SnO 2 The molar weight ratio of (2) is 1mmol: (15-16) g; exemplary molar weights are 1mmol:15g, 1mmol:15.5g, 1mmol:16g, etc.
In some embodiments, the time of ultrasonic dispersion is 20min to 50min, further may be 20min to 40min, for example, dispersing time such as 20min, 30min, 40min, 50min, etc.
In some embodiments, pd salt/Sm is isolated 2 O 3 @SnO 2 In the step of dispersing the solid in the liquid and drying: the drying temperature is 80 to 100℃and further 80 to 90℃and, for example, 80℃82℃85℃90℃100℃and the like. In some embodiments, the drying time is 10h to 14h, further may be 11h to 13h, for example, 10h, 12h, 14h, etc.
In a second aspect the application relates to a gas sensor provided with a gas sensitive material as described above, which has a good response and selectivity to acetylene gas, low power consumption, low requirements for detection environment and convenient use.
In some embodiments, the gas sensor comprises:
1) A MEMS chip comprising interdigital electrodes;
2) The gas-sensitive material provided by the first aspect of the application is distributed on the interdigital electrode of the MEMS chip and completely covers the surface of the interdigital electrode;
optionally further comprising: a support film for providing a supporting force, a heater for providing an operating temperature, and a separation film for blocking an electrical connection between the heater and the interdigital electrode.
In some embodiments, the material of the support film comprises Si 3 N 4 And SiO 2 A kind of electronic device
The heater comprises a heating electrode; and/or
The isolation film comprises Si 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the And/or
The interdigital electrodes include polyimide interdigital electrodes and Pt electrodes located over the substrate.
In some embodiments, the thickness of the support film is 500nm to 700nm; and/or
Si in the support film 3 N 4 And SiO 2 The grain diameter of the polymer is selected from 200nm to 400nm; and/or
The heating electrode is composed of Pt wires with line width of 4-6 μm and line spacing of 8-12 μm; and/or
The thickness of the isolation film is 200 nm-400 nm; and/or
The thickness of the substrate in the interdigital electrode is 100 nm-300 nm; and/or
The line width of Pt electrode in the interdigital electrode is 4-6 μm.
In a third aspect of the present application, there is provided a method for manufacturing a gas sensor according to the second aspect of the present application, comprising the steps of:
providing a MEMS chip as defined in the gas sensor according to the second aspect of the application;
providing the gas-sensitive material of the second aspect of the application for grinding, adding deionized water for mixing, and grinding the obtained mixture to prepare gas-sensitive slurry;
coating the gas-sensitive slurry on the interdigital electrode of the MEMS chip, so that the gas-sensitive slurry completely covers the surface of the interdigital electrode, and drying;
further, the drying mode comprises the following steps:
baking under infrared lamp and oven drying.
In some embodiments, after drying is completed, connecting two ends of the interdigital electrode of the MEMS chip to a side heating type hexagonal tube seat, and connecting the hexagonal tube seat to a gas-sensitive analyzer;
respectively connecting two ends of a heater of the MEMS chip to appointed pins of the singlechip;
and regulating the singlechip to ensure that the singlechip stably provides voltage for ageing the device.
In a fourth aspect of the application there is provided the use of a gas sensitive material provided in the first aspect of the application or a gas sensor provided in the second aspect of the application in the selective detection of acetylene gas.
In some embodiments, the concentration of acetylene gas is from 2ppm to 100ppm.
In some embodiments, the selective detection of acetylene gas comprises detection of dissolved gas in transformer oil. In some embodiments, from 3% Sm 2 O 3 1% PdO doped SnO 2 The power consumption of the gas sensor prepared by the material is only 22mW at 1.35v, the detection range of the gas sensor for acetylene gas is 2 ppm-100 ppm, and the gas sensor has no response to other common gases (ethylene, carbon monoxide, methane, ethane, carbon dioxide and the like) generated by the decomposition of transformer oil, and has good selectivity.
The following are some specific examples.
The experimental parameters not specified in the following specific examples are preferentially referred to the guidelines given in the present document, and may also be referred to the experimental manuals in the art or other experimental methods known in the art, or to the experimental conditions recommended by the manufacturer.
The starting materials and reagents referred to in the following specific examples may be obtained commercially or may be prepared by known means by those skilled in the art.
Example 1
The embodiment provides a specific preparation method of a gas-sensitive material, which comprises the following steps:
(1) Preparation of Sm/Sn salt solution
40ml deionized water, 17.5g SnCl was added to a beaker 4 ·5H 2 O and 0.55g SmCl 3 ·6H 2 O. The beaker was placed on a constant temperature magnetic stirrer and stirred for 30min to prepare a Sm/Sn salt solution as a precursor solution.
(2) Preparation of Sm 2 O 3 @SnO 2
Into another beaker was added 20ml NH 3 ·H 2 O and 20ml deionized water to prepare NH 3 ·H 2 Aqueous ammonia solution with the volume ratio of O to deionized water being 1:1;
slowly dropping ammonia water solution into the prepared precursor solution by using a rubber head dropper until the pH value is=9, and then alternately using deionizationThe resulting precipitate was washed with water and ethanol, and then dried in an air atmosphere at 60℃for 12 hours. Calcining in a tube furnace at 600 ℃ for 1h after drying to obtain Sm 2 O 3 Nanoparticle doped SnO 2 Material (Sm) 2 O 3 @SnO 2 )。
(3) Preparation of Pd@Sm 2 O 3 @SnO 2
15.65g of the above-mentioned material Sm was added to 40ml of deionized water 2 O 3 @SnO 2 0.22g pd (OAc) 2 . The prepared solution was placed in an ultrasonic apparatus for 30min and then dried in an air atmosphere at 80℃for 12h. Calcining the material in a tube furnace at 600 ℃ for 1h after the material is dried, thereby obtaining the SnO doped with the bimetallic SmPd nano particles 2 Material (Pd@Sm) 2 O 3 @SnO 2 ) The XRD detection result of the material is shown in figure 1.
Example 2
This example uses Pd@Sm obtained in example 1 2 O 3 @SnO 2 The material is used as a gas-sensitive material to prepare a gas sensor, and the preparation method comprises the following steps:
(1) Providing a MEMS chip with the size of 1.0x1.0x0.5 mm, comprising the following structure: 1) A supporting film with a thickness of 600nm and 300nm Si 3 N 4 Material and 300nm SiO 2 The material is formed, the supporting film provides structural support for the sensitive area, and the structural strength of the device is ensured; 2) The heater comprises a heating electrode, wherein the square structure of the heating electrode with the size of 160 mu m multiplied by 160 mu m is formed by Pt wires with the line width of 5 mu m and the line interval of 10 mu m, and the heating electrode is used as a heating element to provide the working temperature for the sensor; 3) Isolation film of 300nm thick Si 3 N 4 A material used to block electrical connection between the heater and the interdigital electrode; 4) The interdigital electrode comprises a measuring electrode and a substrate, wherein the substrate is Polyimide (PI) with the thickness of 200nm, the electrode material, the Pt material and the line width of 5 mu m are used for measuring the resistance change of the gas-sensitive material of the sensor, and the measuring electrode is positioned at the left upper corner and the right lower corner of the chip and has the dimensions of 200 mu m multiplied by 200 mu m.
The prepared gas-sensitive material was ground for about 15 minutes, and then the powder was mixed with deionized water in an agate mortar to form a paste, and after grinding again for 15 minutes, the paste was dipped with a brush and uniformly coated on the interdigital electrode at the center of the MEMS chip so as to completely cover the surface of the interdigital electrode.
(2) The MEMS chip coated with the gas sensitive material was baked under an infrared lamp for 15 minutes.
(3) After baking, the two ends of the interdigital electrode of the MEMS chip are connected to the side heating type hexagonal tube seat, the two ends of the heater of the device are respectively connected to the appointed pin of the singlechip, and the singlechip is controlled by a program to provide appointed voltage for the device.
(4) And regulating the voltage provided by the singlechip to 1.8v and connecting the hexagonal pipe seat to the CGS-8 intelligent gas-sensitive analysis system instrument.
(5) Aging the device obtained in the step (4) in an air environment at a voltage of 1.8v for 7 days.
Example 3
This example uses the gas sensor prepared in example 2 to detect acetylene and perform sensor effect evaluation, including:
(1) Optimum operating voltage
The gas sensor was tested in acetylene atmosphere at room temperature and the resulting optimum operating voltage curve is shown in fig. 2, the sensor having an optimum operating voltage of 1.35v for 50ppm acetylene, corresponding to an optimum operating temperature of 220 c and a corresponding power consumption of 20mW.
(2) Sensitivity of
As shown in FIG. 3, the detection range of acetylene gas is 2ppm to 100ppm, which shows that the sensor has good response to acetylene gas and the sensitivity to 50ppm acetylene gas under the heating of 1.35v voltage reaches 74.99. This value is a graph of the portion of FIG. 3 into which 50ppm acetylene gas was fed, and is obtained by using the base resistance/50 ppm acetylene medium resistance, and is shown in FIG. 2.
(3) Response-recovery time
The response time is a certain percentage of the time required for the sensor signal to rise from the zero point to the ventilation balance point, and the recovery time is a parameter for expressing the speed of signal recovery when the sensor recovers from the standard gas to the zero point gas. The single cycle response recovery curve is shown in figure 4. The results showed that the response recovery time of the sensor to 50ppm acetylene gas was 2s and 32s, respectively, under heating at a voltage of 1.35 v.
(4) Selectivity of
For 50ppm of C 2 H 4 ,C 2 H 2 ,CO,CO 2 ,CH 4 ,C 2 H 6 The sensitivity of the gas was tested and the test results are shown in fig. 5. For 50ppm C 2 H 2 The sensitivity of the gas reaches 74.99, but the gas does not respond to other 5 gases, so that the sensor has good selectivity.
From the above embodiments, it can be seen that the gas sensor provided by the present application has good sensitivity, good response recovery characteristic and selectivity to acetylene gas, and has the characteristics of low power consumption. Effectively improve undoped SnO 2 The gas sensor has low sensitivity, poor selectivity and the like.
Comparative example 1
Sm of example 1 was used in this comparative example 2 O 3 @SnO 2 A gas sensor was prepared directly for a gas sensitive material, the preparation method being referred to in example 2.
The gas sensor is used for detecting acetylene and evaluating the effect of the sensor, and comprises the following steps:
(1) Optimum operating voltage
The gas sensor was tested in acetylene atmosphere at room temperature and the resulting optimum operating voltage curve is shown in fig. 6, the sensor operating at an optimum voltage of 1.2v for 50ppm acetylene corresponding to an optimum operating temperature of 190 c and a corresponding power consumption of 18mW.
(2) Sensitivity of
As shown in FIG. 7, the resistance-time curve obtained by measuring acetylene at different concentrations shows that the measurement range of acetylene gas is 1 to 100ppm, but the response is low at 5ppm or less, and the sensitivity to 50ppm acetylene gas under heating at a voltage of 1.2v is only 2.45, as is clear from FIG. 7.
(3) Response-recovery time
The single cycle response recovery curve is shown in figure 8. The results showed that the response recovery time of the sensor to 50ppm acetylene gas was 2s and 4s, respectively, under 1.2v voltage heating.
(4) Selectivity of
For 50ppm of C 2 H 4 ,C 2 H 2 ,CO,CO 2 ,CH 4 ,C 2 H 6 The sensitivity of the gas was tested and the test results are shown in fig. 9. For 50ppm C 2 H 2 The sensitivity for gas reached 2.45 and for ethylene reached 1.39, with poorer selectivity than in example 3.
From the above comparative examples, it can be seen that the sensitivity and selectivity of the gas sensor to acetylene gas are greatly reduced after the doping of PdO material is omitted.
Comparative example 2
This comparative example a gas sensitive material was prepared in substantially the same manner as in example 1. The difference is that SmCl is not added in the step (1) 3 ·6H 2 O produces a precursor solution containing only metal Sm. The gas sensor was prepared by the method of reference example 2.
The gas sensor is used for detecting acetylene and evaluating the effect of the sensor, and comprises the following steps:
(1) Optimum operating voltage
The gas sensor was tested in acetylene atmosphere at room temperature and the resulting optimum operating voltage curve is shown in fig. 10, with the sensor operating at an optimum voltage of 1.1v for 50ppm acetylene, corresponding to an optimum operating temperature of 170 c and a corresponding power consumption of 16mW.
(2) Sensitivity of
As shown in FIG. 11, the detection range of acetylene gas is 5 to 100ppm, and the device has a low response to 50ppm acetylene gas when the concentration of acetylene gas is 5ppm or less, and the sensitivity to 50ppm acetylene gas when heated at a voltage of 1.1v is only 5.37.
(3) Response-recovery time
The single cycle response recovery curve is shown in figure 12. The results show that the response recovery time of the sensor to 50ppm acetylene gas under the heating of 1.2v is 24s and 124s respectively, and the response recovery time is far greater than that of the embodiment 3.
(4) Selectivity of
For 50ppm of C 2 H 4 ,C 2 H 2 ,CO,CO 2 ,CH 4 ,C 2 H 6 The sensitivity of the gas was tested and the test results are shown in fig. 13. For 50ppm C 2 H 2 The sensitivity of the gas was 5.37, the sensitivity to ethylene was 1.37, and the selectivity was better, but the selectivity was not good enough compared to example 3.
As can be seen from the above comparative examples, sm was omitted 2 O 3 After doping the material, the sensitivity, response recovery time and selectivity of the gas sensor to acetylene gas are greatly reduced.
All documents mentioned in this disclosure are incorporated by reference in this disclosure as if each were individually incorporated by reference. Unless otherwise indicated to the contrary by the intent and/or technical scheme of the present application, all references to which this application pertains are incorporated by reference in their entirety for all purposes. When reference is made to a cited document in the present application, the definitions of the relevant technical features, terms, nouns, phrases, etc. in the cited document are also incorporated. In the case of the cited documents, examples and preferred modes of the cited relevant technical features are also incorporated into the present application by reference, but are not limited to being able to implement the present application. It should be understood that when a reference is made to the description of the application in conflict with the description, the application is modified in light of or adaptive to the description of the application.
The technical features of the above-described embodiments and examples may be combined in any suitable manner, and for brevity of description, all of the possible combinations of the technical features of the above-described embodiments and examples are not described, however, as long as there is no contradiction between the combinations of the technical features, they should be considered to be within the scope described in the present specification.
The above examples merely represent a few embodiments of the present application and are not to be construed as limiting the scope of the claims. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Further, it is understood that various changes and modifications of the present application may be made by those skilled in the art after reading the above teachings, and equivalents thereof are intended to fall within the scope of the present application. It should also be understood that, based on the technical solutions provided by the present application, those skilled in the art obtain technical solutions through logical analysis, reasoning or limited experiments, all of which are within the scope of protection of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.
Claims (13)
1. A gas-sensitive material is characterized in that the material is a semiconductor material modified by bimetal, wherein the bimetal refers to metal Sm and metal Pd, and the semiconductor material comprises SnO 2 ；
The modification refers to the preparation of Sm by a gel sol method 2 O 3 Doped SnO 2 Is denoted as Sm 2 O 3 @SnO 2 The method comprises the steps of carrying out a first treatment on the surface of the Then adding Pd-containing material, mixing and calcining to prepare Pd doped Sm 2 O 3 @SnO 2 Is marked as Pd@Sm 2 O 3 @SnO 2 。
2. The gas-sensitive material as claimed in claim 1, wherein said Sm is prepared by a gel sol process 2 O 3 Modified SnO 2 The method comprises the following steps:
mixing Sm salt and Sn salt, dissolving in solvent to obtain Sm/Sn salt solution,
adding a precipitant into the Sm/Sn salt solution for precipitation reaction, separating and drying the precipitate, and taking the dried precipitate for first calcination at 500-700 ℃ to obtain the Sm 2 O 3 @SnO 2 。
3. The gas-sensitive material as claimed in claim 2, wherein said Sm is prepared by a gel sol process 2 O 3 Modified SnO 2 The preparation conditions of (2) include at least one of the following:
1) The Sm/Sn salt solution contains Sn and Sm in a molar ratio of (30-35): 1;
2) The solution condition of the precipitation reaction is that the pH=8.5-9.5;
3) The precipitant is ammonia water solution containing NH 3 ·H 2 The volumes of O and water are (0.8-1.2): 1, a step of;
4) The step of separating the precipitate comprises: filtering to obtain a solid, and washing the solid with deionized water and ethanol;
5) The drying temperature is 50-70 ℃;
6) The drying time is 10-14 h;
7) The time of the first calcination is 0.5-2 h.
4. The gas sensitive material of claim 1, wherein the step of adding the Pd-containing material to mix calcine comprises:
pd salt is taken, sm is taken 2 O 3 @SnO 2 Mixing with water, and ultrasonic dispersing to obtain Pd salt/Sm 2 O 3 @SnO 2 A dispersion;
separating the Pd salt/Sm 2 O 3 @SnO 2 And drying the solid in the dispersion liquid, and taking the dried solid to carry out second calcination at 600-800 ℃.
5. The gas sensitive material of claim 4, wherein the preparation conditions for the mixed calcination of the added Pd-containing material include at least one of:
1) The Pd salt contains the element Pd and the Sm 2 O 3 @SnO 2 The molar weight ratio of (2) is 1mmol: (15-16) g;
2) The ultrasonic dispersion time is 20-50 min;
3) Separating the Pd salt/Sm 2 O 3 @SnO 2 In the step of dispersing the solid in the liquid and drying: the drying temperature is 80-100 ℃ and/or the drying time is 10-14 h;
4) The second calcination time is 0.5-2 h.
6. A gas sensor, comprising:
1) A MEMS chip comprising interdigital electrodes;
2) The gas-sensitive material of any one of claims 1 to 5, which is distributed over the interdigital electrodes and completely covers the surfaces of the interdigital electrodes;
optionally further comprising: a support film for providing a supporting force, a heater for providing an operating temperature, and a separation film for blocking an electrical connection between the heater and the interdigital electrode.
7. A gas sensor according to claim 6, wherein,
the material of the supporting film comprises Si 3 N 4 And SiO 2 A kind of electronic device
The heater includes a heating electrode; and/or
The isolation film comprises Si 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the And/or
The interdigital electrodes include polyimide interdigital electrodes and Pt electrodes located over a substrate.
8. The gas sensor of claim 7, wherein the support film has a thickness of 500nm to 700nm; and/or
Si in the support film 3 N 4 And SiO 2 The grain diameter of the polymer is selected from 200nm to 400nm; and/or
The heating electrode is composed of Pt wires with line width of 4-6 mu m and line spacing of 8-12 mu m; and/or
The thickness of the isolation film is 200 nm-400 nm; and/or
The thickness of the substrate in the interdigital electrode is 100 nm-300 nm; and/or
The line width of the Pt electrode in the interdigital electrode is 4-6 mu m.
9. A method of manufacturing a gas sensor according to any one of claims 6 to 8, comprising the steps of:
providing a MEMS chip as defined in any one of claims 6 to 8;
grinding the gas-sensitive material according to any one of claims 1 to 5, adding deionized water, mixing, and grinding the obtained mixture to obtain gas-sensitive slurry;
and coating the gas-sensitive slurry on the interdigital electrode of the MEMS chip, so that the gas-sensitive slurry completely covers the surface of the interdigital electrode, and drying.
10. The method of claim 9, wherein after drying, connecting two ends of the interdigital electrode of the MEMS chip to a side-heating type hexagonal tube holder, and connecting the hexagonal tube holder to a gas-sensitive analyzer;
respectively connecting two ends of a heater of the MEMS chip to appointed pins of the singlechip;
and regulating the singlechip to ensure that the singlechip stably provides voltage for ageing the device.
11. Use of a gas sensitive material according to any one of claims 1 to 5 or a gas sensor according to any one of claims 6 to 8 for the selective detection of acetylene gas.
12. The use according to claim 11, wherein the concentration of acetylene gas is 2ppm to 100ppm.
13. The use according to claim 11 or 12, characterized in that the selective detection of acetylene gas comprises detection of dissolved gas in transformer oil.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6165336A (en) * | 1995-09-29 | 2000-12-26 | Matsushita Electric Industrial Co. Ltd. | Gas sensor |
| CN104556193A (en) * | 2015-01-19 | 2015-04-29 | 陕西科技大学 | Method for preparing Sm2O3/SnO2 nano composite by heat-assisted sol-gel process |
| CN110697763A (en) * | 2019-10-21 | 2020-01-17 | 云南大学 | Self-supporting SnO2Preparation method and application of nanorod ordered array material |
| CN110988050A (en) * | 2019-12-10 | 2020-04-10 | 武汉微纳传感技术有限公司 | MEMS gas sensor with temperature sensing function and preparation method thereof |
| KR20200121762A (en) * | 2020-07-09 | 2020-10-26 | 연세대학교 산학협력단 | Acetylene detecting sensor and acetylene detecting apparatus comprising the same |
-
2023
- 2023-09-21 CN CN202311232283.8A patent/CN117169292A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6165336A (en) * | 1995-09-29 | 2000-12-26 | Matsushita Electric Industrial Co. Ltd. | Gas sensor |
| CN104556193A (en) * | 2015-01-19 | 2015-04-29 | 陕西科技大学 | Method for preparing Sm2O3/SnO2 nano composite by heat-assisted sol-gel process |
| CN110697763A (en) * | 2019-10-21 | 2020-01-17 | 云南大学 | Self-supporting SnO2Preparation method and application of nanorod ordered array material |
| CN110988050A (en) * | 2019-12-10 | 2020-04-10 | 武汉微纳传感技术有限公司 | MEMS gas sensor with temperature sensing function and preparation method thereof |
| KR20200121762A (en) * | 2020-07-09 | 2020-10-26 | 연세대학교 산학협력단 | Acetylene detecting sensor and acetylene detecting apparatus comprising the same |
Non-Patent Citations (3)
| Title |
|---|
| 夏刚强;韩毓旺;张红漫;: "钯掺杂对SnO_2纳米纤维气体传感器的线性化改性", 广东化工, no. 14, 30 July 2016 (2016-07-30), pages 1 - 3 * |
| 张彤, 孙良彦, 邹恩新: "用于检测变压器油中的乙炔气体敏感元件", 传感器技术, no. 05, 30 October 1998 (1998-10-30), pages 24 - 26 * |
| 范会涛;张彤;漆奇;刘丽;: "掺Sm_2O_3的SnO_2纳米粉体对C_2H_2气敏特性的研究", 半导体学报, no. 02, 15 February 2008 (2008-02-15), pages 319 - 323 * |
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