CN112758975A - CuO doped SnO2Nanoparticles and H2S gas sensor preparation method and product - Google Patents

CuO doped SnO2Nanoparticles and H2S gas sensor preparation method and product Download PDF

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CN112758975A
CN112758975A CN202011525485.8A CN202011525485A CN112758975A CN 112758975 A CN112758975 A CN 112758975A CN 202011525485 A CN202011525485 A CN 202011525485A CN 112758975 A CN112758975 A CN 112758975A
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cuo
sno
doped
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赵海波
徐祖伟
高富昌
陈志成
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Huazhong University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/02—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • G—PHYSICS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Abstract

The invention belongs to the related technical field of gas sensors, and discloses CuO-doped SnO2Nanoparticles and H2S gas sensor preparation method and product. The preparation method of the nano-particles comprises the following steps: selecting liquid fuel, cosolvent, copper metal organic matter and tin metal organic matter, mixing to form a uniformly mixed mixture, and then burning the mixture by adopting a flame spray pyrolysis method to obtain the required SnO doped with CuO2And (3) nanoparticles. The invention also discloses the application of the nanometerParticle preparation H2An in-situ preparation method and an ex-situ preparation method of the S gas sensor. The nano particles obtained by the method have strong gas sensitivity, have extremely high responsivity and extremely high response speed when being used as a gas sensor, and have good H at lower working temperature2S concentration detection performance.

Description

CuO doped SnO2Nanoparticles and H2S gas sensor preparation method and product
Technical Field
The invention belongs to the related technical field of gas sensors, and particularly relates to CuO-doped SnO2Nanoparticles and H2S gas sensor preparation method and product.
Background
With the development of the society towards the information age, the technologies such as artificial intelligence, internet of things and the like are also rapidly developed, and a sensor as a key for sensing information and collecting data becomes an important dependence on the development of the society. The gas sensor is a device for detecting the type and concentration of gas, and plays a vital role in various fields of industrial production, household life, medical health and other production and life.
As one of the industrial and domestic sensors with the largest output and the widest application range in the world at present, the semiconductor type gas sensor has been widely recognized particularly in the household and industrial fields due to the advantages of low manufacturing cost, higher responsiveness, faster response speed, long service life, simple and convenient detection circuit and the like. However, in general, pure semiconductor oxides have difficulty meeting the requirements for making high performance sensors due to intrinsic defects of intrinsic materials. Compared with the limited reserves and the expensive price of noble metals, the heterogeneous oxide composite is formed to improve the performance of the sensor, so that the method has a development prospect. The heterogeneous oxide is compounded, two different oxide semiconductors are compounded to construct a sensitive composite material in heterogeneous contact on a micro-nano scale, and a heterostructure formed by the composite material can regulate and control the concentration of a carrier, has the function of regulating a conductive channel, and can improve the gas-sensitive property of the gas-sensitive material by influencing the conversion capability of the sensitive material.
The flame synthesis method is a novel synthesis method for preparing the nano particles in one step, the preparation process is simple and convenient, and the synthesized nano particles have good physical and chemical properties. How to exert the advantages of the flame synthesis method in the gas-sensitive field, the high-performance gas-sensitive material is synthesized by utilizing the flame synthesis method in an effective and controllable manner, and the gas sensor is manufactured on the basis of the high-performance gas-sensitive material, so that the flame synthesis method has great research significance in being applied to various gas detection.
Disclosure of Invention
In response to the above-identified deficiencies in or needs for improvement over the prior art, the present invention provides a CuO doped SnO2Nanoparticles and H2The preparation method of S gas sensor and its product are characterized by adopting flame spray pyrolysis method to prepare CuO doped SnO by one-step process2The obtained nanoparticles have strong gas sensitivity, extremely high responsivity and extremely high response speed when used as a gas sensor, and good H at a lower working temperature (125℃)2S concentration detection performance.
To achieve the above objects, according to one aspect of the present invention, there is provided a CuO-doped SnO2A method for preparing nanoparticles, the method comprising the steps of:
selecting liquid fuel and a cosolvent to mix according to the volume ratio of (3-9):1, adding a copper metal organic matter and a tin metal organic matter into the formed mixture to form a uniformly mixed precursor solution, and then combusting the precursor solution by adopting a flame spray pyrolysis method to obtain the required SnO doped with CuO2Nanoparticles of, among others, CuO doped SnO2The mass fraction of CuO in the nano particles is as follows: 0.2 to 1 percent.
Further preferably, the fuel is a liquid organic matter composed of C, H, O elements, and the cosolvent is acetic acid.
Further preferably, the metallorganic of copper is copper acetate, copper acetylacetonate or copper 2-ethylhexanoate; the metal organic matter of the tin is 2-ethyl stannous caproate.
Further preferably, the CuO doped SnO2The specific surface area of the nano-particles is more than 110m2/g。
According to another aspect of the present invention, there is providedThe CuO doped SnO prepared by the preparation method2And (3) nanoparticles.
According to yet another aspect of the present invention, there is provided a CuO doped SnO as described above2Nanoparticle in situ preparation of H2A method of S gas sensor, the method comprising the steps of:
selecting a substrate with mutually crossed metal electrodes on the front surface and heating metal electrodes on the back surface, arranging the substrate above flame for in-situ deposition, and depositing a layer of CuO doped SnO with the thickness of 50-500 nm on the crossed metal electrodes2Nanoparticles deposited with CuO doped SnO2The substrate of the nano-particles is the required H2And (S) a gas sensor.
Further preferably, the substrate is disposed 40cm to 80cm above the flame.
According to yet another aspect of the present invention, there is provided a SnO doped with CuO as described above2Ex situ nanoparticle preparation of H2S gas sensor method, characterized in that it comprises the following steps:
selecting SnO doped with CuO2Mixing the nano particles with an adhesive, coating the mixed coating on the front surface of a substrate, wherein the front surface of the substrate is provided with metal electrodes which are mutually crossed, and the back surface of the substrate is provided with a heating electrode; heating the substrate after coating to remove the adhesive, cooling to obtain the desired H2S gas sensor, wherein the CuO doped SnO2CuO doped SnO when nanoparticles are mixed with binder2The mass ratio of the nanoparticles to the adhesive is (1-5): 10.
further preferably, the adhesive is terpineol, the heating is divided into two stages of low-temperature heating and high-temperature heating, the low-temperature heating temperature is 120-200 ℃, the high-temperature heating time is 1-5 h, the high-temperature heating temperature is more than 400 ℃, and the high-temperature heating time is 10-20 h.
According to a final aspect of the invention, there is provided H obtained by the process described above2S gas sensor, said H2S gas sensingThe CuO loading in the reactor is 0.5 wt%, and the optimal working temperature is 120-150 ℃.
Generally, compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. in the invention, the CuO doped SnO is prepared by adopting a flame spray pyrolysis method2The nano particles can be used for rapidly preparing the nano material with controllable functional appearance in one step, and the nano particles with high thermal stability and high dispersion state are formed in the synthesis process;
2. according to the invention, through compounding and doping the semiconductor oxide material, the optimal loading capacity of CuO is researched, the gas-sensitive characteristic of the gas-sensitive material is improved, the defects of poor selectivity and insufficient stability of the traditional semiconductor type sensor are overcome, and the practicability of the sensor in the field of H2S gas detection is promoted;
3. in the invention, CuO-SnO is adopted2Preparation of gas-sensitive Material H2The obtained sensor has good gas-sensitive performance, such as extremely high responsivity and extremely high response speed, and has good H at lower working temperature (125℃)2S concentration detection performance.
Drawings
FIG. 1 is a CuO doped SnO constructed in accordance with a preferred embodiment of the present invention2A flow diagram of a method of making a nanoparticle gas sensor;
FIG. 2 is a CuO doped SnO constructed in accordance with a preferred embodiment of the present invention2The structure schematic diagram of the nanoparticle preparation device;
FIG. 3 is a 0.5 wt% CuO-SnO constructed in accordance with preferred embodiment 1 of the present invention2TEM images of the gas sensitive material;
FIG. 4 is a 0.5 wt% CuO-SnO constructed in accordance with preferred embodiment 1 of the present invention2H of (A) to (B)2S sensor for 10ppm H at 125 deg.C2The response-recovery curve of S;
FIG. 5 is a 0.5 wt% CuO doping level of SnO constructed in accordance with preferred embodiment 1 of the present invention2The sensor is used for 10pp under different working temperaturesThe response of H2S for m;
FIG. 6 is a 0.5 wt% CuO doping level of SnO constructed in accordance with preferred embodiment 1 of the present invention2Selectivity of the sensor to different gases.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
SnO doped with CuO2The preparation method of the nano-particles comprises the following steps:
s1, mixing liquid organic matter which is composed of C, H, O elements and has the volume ratio of (3-9) to 1 with acetic acid, wherein the acetic acid is taken as a cosolvent;
then adding a copper metal organic matter and a tin metal organic matter into the mixture, wherein the copper metal organic matter is copper acetate, copper acetylacetonate or copper 2-ethylhexanoate; the metal organic matter of the tin is 2-ethyl stannous caproate; adjusting the addition amount of copper metal organic matters so as to obtain materials with different CuO contents through flame synthesis.
S2, carrying out ultrasonic treatment on the prepared precursor solution for 5-15 minutes to ensure that all components in the precursor solution are uniformly mixed;
s3, spraying the precursor solution into fine liquid drops by an atomization device;
s4, the atomized liquid drops are ignited to form a high-temperature spray flame. The organometallic components in the precursor burn violently therein to form fine CuO-doped SnO2Particles, and collecting the synthesized nanoparticles on a filter device.
In SnO doped with CuO2In the nano gas-sensitive material of the particles, a Cu component and a Sn component are mixed in an atomic scale, and CuO is in a highly dispersed state.
CuO doped SnO2The specific surface area of the nano-particles is more than 110m2And the gas sensor has larger gas adsorption and reaction area, and is beneficial to improving the gas sensitivity of the gas sensor.
In the present invention, CuO-doped SnO is utilized2H with nanoparticles as gas-sensitive material2The S gas sensor comprises an in-situ preparation method and an ex-situ preparation method, wherein the two preparation methods are as follows:
SnO doped with CuO2H with nanoparticles as gas-sensitive material2The in-situ preparation method of the S gas sensor comprises the following steps:
1) installing a substrate with good heat conductivity, strength and insulativity, wherein the substrate is provided with printed intercrossed metal electrodes on the front surface and heating metal electrodes on the back surface, preferably an alumina substrate, above the flame of a flame spray pyrolysis device at a distance of 40-80 cm, and performing in-situ deposition with the front surface facing the flame direction;
2) adjusting the height of the substrate to adjust the particle size of the deposited nanoparticles to 10 nm-150 nm;
3) controlling the placing time of the substrate, and controlling the thickness of the nano gas-sensitive material to be 50-500 nm;
4) stopping deposition, taking out the substrate, and cooling at room temperature to obtain SnO doped with CuO2H with nanoparticles as gas-sensitive material2S gas sensor;
SnO doped with CuO2H with nanoparticles as gas-sensitive material2The ex-situ preparation method of the S gas sensor comprises the following steps:
1) uniformly mixing nano particles with a viscous liquid organic matter, preferably terpineol, taking the terpineol as a coating solvent, and grinding for 30 minutes to prepare a uniform paste, wherein the mass ratio of the nano particles to the terpineol is (1-5): 10.
2) the paste is uniformly coated on a substrate with good heat conductivity, strength and insulativity, the front surface of the substrate is provided with printed intercrossed metal electrodes, the back surface of the substrate is provided with a heating electrode, the metal electrodes are used as measuring electrodes to be connected with a skin ampere meter through leads when the sensor measures, the heating electrodes are connected with a stable voltage source through leads when the sensor measures, and the working temperature of the sensor is set by adjusting the magnitude of the heating voltage.
3) And heating the coated substrate to 120-200 ℃ in a tube furnace for 1-5 hours, and then heating at a high temperature (more than 400 ℃) for a long time to remove the terpineol and finish the aging of the sensor.
4) Naturally cooling the substrate at room temperature to obtain SnO doped with CuO2H with nanoparticles as gas-sensitive material2And (S) a gas sensor.
The working process of the gas sensor is as follows: firstly, a sensor is placed in a test environment, the heating voltage is adjusted to enable the working temperature of the sensor to be in a set value, and the resistance of the sensor under different hydrogen sulfide gas concentrations is synchronously and continuously monitored by a picoammeter by adopting a direct-current bias voltage-ampere measurement technology.
H2The CuO loading amount of the S gas sensor with the optimal gas-sensitive performance is 0.5 wt%, and the optimal working temperature is 120-150 ℃.
At H2In S gas sensor, when the doping amount of CuO is less than 0.1 wt%, it is added to H2The responsiveness of S is low, but the response time is short; when the doping amount of CuO is further increased from 0.5 wt% to 1%, the responsivity is relatively reduced and the response time is increased.
The present invention will be further illustrated with reference to specific examples.
Example 1
S1, mixing absolute ethyl alcohol and acetic acid in a volume ratio of 4:1, wherein the acetic acid is used as a cosolvent;
then adding copper acetate and 2-stannous ethyl hexanoate into the mixture, wherein the addition amount of the copper acetate is 0.095g, the mass of the 2-stannous ethyl hexanoate is 20.25g, and the concentration of the 2-stannous ethyl hexanoate is kept to be 0.5mol/L, so that nanoparticles with the CuO content of 0.5 wt% can be obtained in the subsequent process;
s2, carrying out ultrasonic treatment on the prepared precursor solution for 5-15 minutes;
s3, spraying the precursor solution into fine liquid drops by an atomization device;
s4 igniting the atomized dropletsForming a high temperature spray flame. The organometallic components in the precursor burn violently therein to form fine CuO-doped SnO2Particles, and collecting the synthesized nanoparticles on a filter device.
In situ preparation of H2The S gas sensor comprises the following steps:
mounting an alumina substrate with printed intercrossed metal platinum electrodes on the front surface and a heating metal electrode on the back surface above the flame of a flame spray pyrolysis device at a distance of 80cm, and carrying out in-situ deposition on the front surface facing to the flame direction; the placing time of the substrate is controlled, and the thickness of the nano gas-sensitive material is controlled to be 50 nm; stopping deposition, taking out the substrate, and cooling at room temperature to obtain SnO doped with CuO2H with nanoparticles as gas-sensitive material2And (S) a gas sensor.
Preparation of H by ex situ method2The S gas sensor comprises the following steps:
1) the nanoparticles were uniformly mixed with terpineol in a mass ratio of 1:10, and then ground for 30 minutes to prepare a uniform paste.
2) The paste is uniformly coated on an alumina substrate with printed interdigitated platinum electrodes on the front surface and a heating electrode on the back surface of the substrate.
3) The coated substrate was heated to 120 ℃ in a tube furnace for 1 hour and then at 400 ℃ for 12 hours to remove the terpineol and complete the aging of the sensor.
4) Naturally cooling the substrate at room temperature to obtain SnO doped with CuO2H with nanoparticles as gas-sensitive material2And (S) a gas sensor.
FIG. 3 is a 0.5 wt% CuO-SnO constructed in accordance with example 12TEM image of gas-sensitive material, synthesized nanoparticles are mainly spherical nanoparticles with particle size of 5-15 nm.
FIG. 4 is a 0.5 wt% CuO-SnO constructed in accordance with example 12H of (A) to (B)2S sensor for 10ppm H at 125 deg.C2S response-recovery curve when the sensor is exposed to H2In the S atmosphere, the resistance of the sensor is obviously reduced and thenRecovery in air and CuO doping obviously increase the H resistance of the sensor2S responsiveness and reduced response time.
FIG. 5 is a 0.5 wt% CuO doping level of SnO constructed in accordance with example 12The response of the sensor to 10ppm of H2S at different operating temperatures. As the operating temperature increases, a significant decrease in sensitivity occurs with increasing temperature. 0.5 wt% CuO doping amount of SnO2The sensor has a lower operating temperature.
FIG. 6 is a 0.5 wt% CuO doping level of SnO constructed in accordance with example 12Selectivity of the sensor to different gases. Compared with for H2S response to other gases (S)<10) Is negligible, good selectivity is advantageous for the selective detection of H in these gases by the sensor2S。
Example 2
S1, mixing absolute ethyl alcohol and acetic acid in a volume ratio of 4:1, wherein the acetic acid is used as a cosolvent;
then adding copper acetate and 2-stannous ethyl hexanoate into the mixture, wherein the addition amount of the copper acetate is 0.038g, the mass of the 2-stannous ethyl hexanoate is 20.25g, and the concentration of the 2-stannous ethyl hexanoate is kept to be 0.5mol/L, so that nanoparticles with the CuO content of 0.2 wt% can be obtained in the subsequent process;
s2, carrying out ultrasonic treatment on the prepared precursor solution for 5-15 minutes;
s3, spraying the precursor solution into fine liquid drops by an atomization device;
s4, the atomized liquid drops are ignited to form a high-temperature spray flame. The organometallic components in the precursor burn violently therein to form fine CuO-doped SnO2Particles, and collecting the synthesized nanoparticles on a filter device.
In situ preparation of H2The S gas sensor comprises the following steps:
mounting an alumina substrate with printed intercrossed metal platinum electrodes on the front surface and a heating metal electrode on the back surface above the flame of a flame spray pyrolysis device at a distance of 60cm, and carrying out in-situ deposition on the front surface facing the flame direction; controlling the placing time of the substrate and controlling the nano-meterThe thickness of the gas sensitive material is 200 nm; stopping deposition, taking out the substrate, and cooling at room temperature to obtain SnO doped with CuO2H with nanoparticles as gas-sensitive material2S gas sensor;
ex situ preparation of H2The S gas sensor comprises the following steps:
1) the nanoparticles were uniformly mixed with terpineol in a mass ratio of 4:10, and then ground for 30 minutes to prepare a uniform paste.
2) The paste is uniformly coated on an alumina substrate with printed interdigitated platinum electrodes on the front surface and a heating electrode on the back surface of the substrate.
3) The coated substrate was heated to 200 ℃ in a tube furnace for 5 hours and then at 400 ℃ for 10 hours to remove the terpineol and complete the aging of the sensor.
4) Naturally cooling the substrate at room temperature to obtain SnO doped with CuO2H with nanoparticles as gas-sensitive material2And (S) a gas sensor.
Example 3
S1, mixing dimethylbenzene and acetic acid in a volume ratio of 3:1, wherein the acetic acid is used as a cosolvent;
then adding copper acetylacetonate and 2-stannous ethyl hexanoate into the mixture, wherein the addition amount of the copper acetylacetonate is 0.498g, the mass of the 2-stannous ethyl hexanoate is 20.25g, and simultaneously keeping the concentration of the 2-stannous ethyl hexanoate at 0.5mol/L so as to obtain nano particles with the CuO content of 1 wt% in the subsequent step;
s2, carrying out ultrasonic treatment on the prepared precursor solution for 5-15 minutes;
s3, spraying the precursor solution into fine liquid drops by an atomization device;
s4, the atomized liquid drops are ignited to form a high-temperature spray flame. The organometallic components in the precursor burn violently therein to form fine CuO-doped SnO2Particles, and collecting the synthesized nanoparticles on a filter device.
In situ preparation of H2The S gas sensor comprises the following steps:
the front surface is provided with printed intercrossed metal platinum electrodesThe aluminum oxide substrate with the heating metal electrode on the back is arranged above the flame of the flame spray pyrolysis device at a distance of 40cm, and the front side of the aluminum oxide substrate faces the flame direction for in-situ deposition; the placing time of the substrate is controlled, and the thickness of the nano gas-sensitive material is controlled to be 500 nm; stopping deposition, taking out the substrate, and cooling at room temperature to obtain SnO doped with CuO2H with nanoparticles as gas-sensitive material2And (S) a gas sensor.
Preparation of H by ex situ method2The S gas sensor comprises the following steps:
1) the nanoparticles were uniformly mixed with terpineol at a mass ratio of 5:10, and then ground for 30 minutes to prepare a uniform paste.
2) The paste is uniformly coated on an alumina substrate with printed interdigitated platinum electrodes on the front surface and a heating electrode on the back surface of the substrate.
3) The coated substrate was heated to 130 ℃ in a tube furnace for 2 hours and then at 400 ℃ for 10 hours to remove the terpineol and complete the aging of the sensor.
4) Naturally cooling the substrate at room temperature to obtain SnO doped with CuO2H with nanoparticles as gas-sensitive material2And (S) a gas sensor.
Example 4
S1, mixing absolute ethyl alcohol and acetic acid in a volume ratio of 5:1, wherein the acetic acid is used as a cosolvent;
then adding copper acetylacetonate and 2-stannous ethyl hexanoate into the mixture, wherein the addition amount of the copper acetylacetonate is 0.125g, the mass of the 2-stannous ethyl hexanoate is 20.25g, and simultaneously keeping the concentration of the 2-stannous ethyl hexanoate at 0.5mol/L so as to obtain nano particles with the CuO content of 0.5 wt% in the subsequent step;
s2, carrying out ultrasonic treatment on the prepared precursor solution for 5-15 minutes;
s3, spraying the precursor solution into fine liquid drops by an atomization device;
s4, the atomized liquid drops are ignited to form a high-temperature spray flame.
In situ preparation of H2The S gas sensor comprises the following steps:
mounting an alumina substrate with printed intercrossed metal platinum electrodes on the front surface and a heating metal electrode on the back surface above the flame of a flame spray pyrolysis device at a distance of 70cm, and carrying out in-situ deposition on the front surface towards the flame direction; the placing time of the substrate is controlled, and the thickness of the nano gas-sensitive material is controlled to be 150 nm; stopping deposition, taking out the substrate, and cooling at room temperature to obtain SnO doped with CuO2H with nanoparticles as gas-sensitive material2And (S) a gas sensor.
Preparation of H by ex situ method2The S gas sensor comprises the following steps:
1) the nanoparticles were uniformly mixed with terpineol in a mass ratio of 4:10, and then ground for 30 minutes to prepare a uniform paste.
2) The paste is uniformly coated on an alumina substrate with printed interdigitated platinum electrodes on the front surface and a heating electrode on the back surface of the substrate.
3) The coated substrate was heated to 150 ℃ in a tube furnace for 3 hours and then at 400 ℃ for 15 hours to remove the terpineol and complete the aging of the sensor.
4) Naturally cooling the substrate at room temperature to obtain SnO doped with CuO2H with nanoparticles as gas-sensitive material2And (S) a gas sensor.
Example 5
S1, mixing dimethylbenzene and acetic acid in a volume ratio of 8:1, wherein the acetic acid is used as a cosolvent;
then adding copper 2-ethylhexanoate and stannous 2-ethylhexanoate into the mixture, wherein the addition amount of the copper 2-ethylhexanoate is 0.099g, the mass of the stannous 2-ethylhexanoate is 20.25g, and the concentration of the stannous 2-ethylhexanoate is kept to be 0.5mol/L, so that nanoparticles with the CuO content of 0.5 wt% can be obtained subsequently;
s2, carrying out ultrasonic treatment on the prepared precursor solution for 5-15 minutes;
s3, spraying the precursor solution into fine liquid drops by an atomization device;
s4, the atomized liquid drops are ignited to form a high-temperature spray flame. The organometallic components of the precursor burn violently therein to form fine particlesCuO doped SnO2Particles, and collecting the synthesized nanoparticles on a filter device.
In situ preparation of H2The S gas sensor comprises the following steps:
mounting an alumina substrate with printed intercrossed metal platinum electrodes on the front surface and a heating metal electrode on the back surface above the flame of a flame spray pyrolysis device at a distance of 50cm, and carrying out in-situ deposition on the front surface facing to the flame direction; the placing time of the substrate is controlled, and the thickness of the nano gas-sensitive material is controlled to be 180 nm; stopping deposition, taking out the substrate, and cooling at room temperature to obtain SnO doped with CuO2H with nanoparticles as gas-sensitive material2And (S) a gas sensor.
Preparation of H by ex situ method2The S gas sensor comprises the following steps:
1) the nanoparticles were uniformly mixed with terpineol in a mass ratio of 3:10, and then ground for 30 minutes to prepare a uniform paste.
2) The paste is uniformly coated on an alumina substrate with printed interdigitated platinum electrodes on the front surface and a heating electrode on the back surface of the substrate.
3) The coated substrate was heated to 130 ℃ in a tube furnace for 2 hours and then at 400 ℃ for 10 hours to remove the terpineol and complete the aging of the sensor.
4) Naturally cooling the substrate at room temperature to obtain SnO doped with CuO2H with nanoparticles as gas-sensitive material2And (S) a gas sensor.
S5, mixing the nanoparticles and terpineol according to the mass ratio of 5:10, and then ground for 30 minutes to prepare a uniform paste.
2) The paste is uniformly coated on an alumina substrate with printed interdigitated platinum electrodes on the front surface and a heating electrode on the back surface of the substrate.
3) The coated substrate was heated in a tube furnace to 180 ℃ for 1.5 hours and then to 450 ℃ for 20 hours to remove the terpineol and complete the aging of the sensor.
4) Allowing the substrate to cool naturally at room temperatureTo obtain SnO doped with CuO2H with nanoparticles as gas-sensitive material2And (S) a gas sensor.
Example 6
S1, firstly, the volume ratio is 9: 1, mixing absolute ethyl alcohol and acetic acid, wherein the acetic acid is used as a cosolvent;
then adding copper 2-ethylhexanoate and stannous 2-ethylhexanoate into the mixture, wherein the addition amount of the copper 2-ethylhexanoate is 0.039g, the mass of the stannous 2-ethylhexanoate is 20.25g, and the concentration of the stannous 2-ethylhexanoate is kept to be 0.5mol/L, so that nanoparticles with the CuO content of 0.2 wt% can be obtained subsequently;
s2, carrying out ultrasonic treatment on the prepared precursor solution for 5-15 minutes;
s3, spraying the precursor solution into fine liquid drops by an atomization device;
s4, the atomized liquid drops are ignited to form a high-temperature spray flame.
In situ preparation of H2The S gas sensor comprises the following steps:
mounting an alumina substrate with printed intercrossed metal platinum electrodes on the front surface and a heating metal electrode on the back surface above the flame of a flame spray pyrolysis device at a distance of 60cm, and carrying out in-situ deposition on the front surface facing the flame direction; the placing time of the substrate is controlled, and the thickness of the nano gas-sensitive material is controlled to be 170 nm; stopping deposition, taking out the substrate, and cooling at room temperature to obtain SnO doped with CuO2H with nanoparticles as gas-sensitive material2And (S) a gas sensor.
Preparation of H by ex situ method2The S gas sensor comprises the following steps:
1) the nanoparticles were uniformly mixed with terpineol in a mass ratio of 2:10, and then ground for 30 minutes to prepare a uniform paste.
2) The paste is uniformly coated on an alumina substrate with printed interdigitated platinum electrodes on the front surface and a heating electrode on the back surface of the substrate.
3) The coated substrate was heated to 170 ℃ in a tube furnace for 2 hours and then 500 ℃ for 10 hours to remove the terpineol and complete the aging of the sensor.
4) Naturally cooling the substrate at room temperature to obtain SnO doped with CuO2H with nanoparticles as gas-sensitive material2And (S) a gas sensor.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. SnO doped with CuO2A method for producing nanoparticles, the method comprising the steps of:
selecting liquid fuel and a cosolvent to mix according to the volume ratio of (3-9):1, adding a copper metal organic matter and a tin metal organic matter into the formed mixture to form a uniformly mixed precursor solution, and then combusting the precursor solution by adopting a flame spray pyrolysis method to obtain the required SnO doped with CuO2Nanoparticles of, among others, CuO doped SnO2The mass fraction of CuO in the nano particles is as follows: 0.2 to 1 percent.
2. A CuO doped SnO according to claim 12The preparation method of the nano-particles is characterized in that the fuel is a liquid organic matter composed of C, H, O elements, and the cosolvent is acetic acid.
3. A CuO doped SnO according to claim 12The preparation method of the nano-particles is characterized in that the metal organic matter of the copper is copper acetate, copper acetylacetonate or copper 2-ethylhexoate; the metal organic matter of the tin is 2-ethyl stannous caproate.
4. A CuO doped SnO according to claim 12A process for the preparation of nanoparticles, characterized in that said CuO doped SnO2The specific surface area of the nano-particles is more than 110m2/g。
5. CuO doped SnO obtained by preparation method according to any of claims 1-42And (3) nanoparticles.
6. SnO doped with CuO according to claim 52Nanoparticle in situ preparation of H2S gas sensor method, characterized in that it comprises the following steps:
selecting a substrate with mutually crossed metal electrodes on the front surface and heating metal electrodes on the back surface, arranging the substrate above flame for in-situ deposition, and depositing a layer of CuO doped SnO with the thickness of 50-500 nm on the crossed metal electrodes2Nanoparticles deposited with CuO doped SnO2The substrate of the nano-particles is the required H2And (S) a gas sensor.
7. The method of claim 6, wherein the substrate is positioned 40cm to 80cm above the flame.
8. SnO doped with CuO according to claim 52Ex situ nanoparticle preparation of H2S gas sensor method, characterized in that it comprises the following steps:
selecting SnO doped with CuO2Mixing the nano particles with an adhesive, coating the mixed coating on the front surface of a substrate, wherein the front surface of the substrate is provided with metal electrodes which are mutually crossed, and the back surface of the substrate is provided with a heating electrode; heating the substrate after coating to remove the adhesive, cooling to obtain the desired H2S gas sensor, wherein the CuO doped SnO2CuO doped SnO when nanoparticles are mixed with binder2The mass ratio of the nanoparticles to the adhesive is (1-5): 10.
9. the method of claim 8, wherein the adhesive is terpineol, the heating is divided into two stages of low-temperature heating and high-temperature heating, the low-temperature heating is performed at a temperature of 120 ℃ to 200 ℃ for 1h to 5h, and the high-temperature heating is performed at a temperature of more than 400 ℃ for 10h to 20 h.
10. H obtained by the method of any one of claims 5 to 92S gas sensor, characterized in that said H gas sensor2The CuO loading in the S gas sensor is 0.5 wt%, and the optimal working temperature is 120-150 ℃.
CN202011525485.8A 2020-12-22 2020-12-22 CuO doped SnO2Nanoparticles and H2S gas sensor preparation method and product Pending CN112758975A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120094030A1 (en) * 2004-12-09 2012-04-19 Lutz Maedler Direct formation of highly porous gas-sensing layers by in-situ deposition of flame-made nanoparticles
KR20120100025A (en) * 2011-03-02 2012-09-12 서울대학교산학협력단 Method of manufacturing oxide semiconductor gas sensing material for chemical warfare agents and method of manufacturing sensor including the same
CN107607588A (en) * 2017-07-25 2018-01-19 上海纳米技术及应用国家工程研究中心有限公司 SnO is modified for gas sensor2Nano material
CN108328649A (en) * 2018-04-12 2018-07-27 北京理工大学 A kind of sulfur doping tin dioxide nanometer material, air-sensitive component and preparation method
CN110133059A (en) * 2019-06-10 2019-08-16 山东理工大学 A kind of Pt-SnO of room temperature detection low concentration hydrogen sulphide gas2The preparation method of gas sensor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120094030A1 (en) * 2004-12-09 2012-04-19 Lutz Maedler Direct formation of highly porous gas-sensing layers by in-situ deposition of flame-made nanoparticles
KR20120100025A (en) * 2011-03-02 2012-09-12 서울대학교산학협력단 Method of manufacturing oxide semiconductor gas sensing material for chemical warfare agents and method of manufacturing sensor including the same
CN107607588A (en) * 2017-07-25 2018-01-19 上海纳米技术及应用国家工程研究中心有限公司 SnO is modified for gas sensor2Nano material
CN108328649A (en) * 2018-04-12 2018-07-27 北京理工大学 A kind of sulfur doping tin dioxide nanometer material, air-sensitive component and preparation method
CN110133059A (en) * 2019-06-10 2019-08-16 山东理工大学 A kind of Pt-SnO of room temperature detection low concentration hydrogen sulphide gas2The preparation method of gas sensor

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEN ZC ET AL.: "Flame spray pyrolysis synthesis and H2S sensing properties of CuO-doped SnO2 nanoparticles", 《PROCEEDINGS OF THE COMBUSTION INSTITUTE》 *

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Application publication date: 20210507