CN109115843B - Cu-doped ZnFe2O4Nanoparticles, and preparation method and application thereof - Google Patents
Cu-doped ZnFe2O4Nanoparticles, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of gas sensors made of zero-dimensional metal oxide semiconductor materials, and particularly relates to Cu-doped ZnFe2O4Nanoparticles, a preparation method and application thereof. FeCl is added3、ZnCl2、CuCl2And CON2H4Dissolving the mixture into deionized water according to a molar ratio of 10:10: 8-15: 330, wherein FeCl is contained3The proportion of the deionized water and the deionized water is 1:50mol/L, and the mixture is magnetically stirred to obtain a mixed solution; washing, drying and heat treating to obtain Cu doped ZnFe2O4And (3) nanoparticles. Doping Cu with ZnFe2O4The nano particles are prepared into a gas-sensitive coating of a low-temperature gas sensor, and the gas sensor can obtain H pairs at 25-50 DEG C2The relatively high sensitivity of S gas solves the problem that the gas sensitive property of the traditional metal oxide semiconductor gas sensor is relatively poor in a low-temperature area, and the gas sensor has good development prospect.
Description
Technical Field
The present invention belongs to a zero-dimensional metal oxideThe technical field of gas sensors made of semiconductor materials, in particular to Cu-doped ZnFe2O4Nanoparticles, a preparation method and application thereof.
Background
With the rapid development of domestic economy, the progress of urbanization and industrialization is accelerating, and particularly in the fields of ore mining, coal, chemical industry, manufacturing and processing, petroleum, automobiles and the like, various toxic, harmful, flammable and explosive gases are continuously emitted in the production process and the use process of products, and if the gases leak into the air, the gases can seriously pollute the environment and are potential hazard sources for causing explosion, fire or poisoning to people. In order to effectively prevent the leakage of harmful gases and effectively protect the environment, the property of people and the personal safety, the rapid, accurate and portable detection of the harmful gases is very necessary. Therefore, the development and development of a high-performance gas sensor are imperative, the occurrence of potential safety accidents can be effectively reduced, and meanwhile, the reliable early-stage guarantee can be provided for the subsequent harmful gas treatment, so that the method has very important practical significance.
In recent years, gas sensors based on different gas sensitive materials and conduction platforms are developed rapidly, the variety of the gas sensors is various, and the gas sensors can be classified into semiconductor type gas sensors, contact combustion type gas sensors, electrochemical type gas sensors, solid electrolyte type gas sensors and the like according to the working characteristics and the sensitivity principle of the gas sensitive materials. The metal oxide semiconductor type gas sensor has the advantages of simple preparation process, low cost, controllable structure, high response speed, high sensitivity, low lower limit of gas concentration detection and the like, so that the metal oxide semiconductor type gas sensor becomes the most widely applied gas sensor at present. The conventional SnO is commonly adopted in the metal oxide semiconductor type gas sensor which is commercially available at present2、ZnO、WO3Corresponding nano films, nano particles and microspheres are used as gas sensitive materials, but all belong to single metal oxide gas sensitive materials, and due to the limitation of single metal elements in the constituent elements of the gas sensitive materials, the sensitivity of the gas sensitive element to specific gas is low and the selectivity is poor. Therefore, researchers are now focusing more attention on having a plurality of metal elementsThe multi-element metal oxide semiconductor material provides a gas sensitive material with high sensitivity, good selectivity and better performance.
ZnFe2O4As a common n-type multi-metal oxide semiconductor material, the material has very excellent photocatalysis, gas-sensitive property and magnetic property, thus having wide application in dehydrogenation catalysis, soft magnetic materials, gas sensors, waste gas treatment and the like. ZnFe2O4Common preparation methods of the nano material include a solid phase method and a liquid phase method. However, for ZnFe2O4The related research results of the gas-sensitive characteristics of the nano material are very few, and the corresponding gas-sensitive material mainly takes irregular micron-sized and submicron-sized bulk materials as main materials. Compared with irregular micron-sized and submicron-sized bulk materials, the zero-dimensional nano particles have larger specific surface area and surface activity, and thus show more excellent gas-sensitive performance. In addition, most of the existing semiconductor oxide gas sensors can obtain better gas-sensitive characteristics at the working temperature of more than 200 ℃, so that the energy consumption is high in the gas detection process and the integration of the sensors is complex. Therefore, further improvement of sensitivity and selectivity of gas sensors under low temperature operating conditions is a current research focus.
Disclosure of Invention
Aiming at the defects of the existing metal oxide semiconductor type gas sensor in the aspects of working temperature and selectivity, the invention provides a Cu-doped ZnFe2O4Nanoparticles, and preparation method and application thereof, wherein the gas-sensitive coating is Cu-doped ZnFe2O4Nanoparticle cryogenic gas sensors. Aims to prepare the Cu-doped ZnFe with the advantages of uniform appearance, good dispersity, good crystallization, large specific surface area, stable property and the like by a hydrothermal synthesis method2O4Nanoparticles and doping of ZnFe with these Cu2O4The nano particles are manufactured into the gas sensor with the advantages of low working temperature, high sensitivity, good reversibility, good selectivity and the like, so that the problems of poor selectivity, high working temperature and the like of the existing gas sensor are solved.
Cu-doped ZnFe2O4The preparation method of the nano-particles comprises the following steps: FeCl is added3、ZnCl2、 CuCl2And CON2H4Dissolving the mixture into deionized water according to a molar ratio of 10:10: 8-15: 330, wherein FeCl is contained3The ratio of the deionized water to the deionized water is 1:50mol/L, and the mixture is magnetically stirred for 10-30 min to obtain a mixed solution; placing the mixed solution in a reaction kettle, reacting for 4-13 h at 150-180 ℃ in a vacuum drying oven, washing, drying and carrying out heat treatment to obtain Cu-doped ZnFe2O4And (3) nanoparticles.
The reaction kettle is preferably a stainless steel reaction kettle with a polytetrafluoroethylene inner container.
Preferably, the washing step is washing with deionized water and absolute ethyl alcohol for 2-3 times respectively.
Preferably, the drying step is drying for 3-8 hours in a blast type drying oven at the temperature of 60-80 ℃.
Preferably, the heat treatment step is to carry out heat treatment for 2-4 hours at 500 ℃ in air.
It is a further object of the present invention to provide a Cu doped ZnFe prepared according to the method2O4Nanoparticles of said Cu doped ZnFe2O4The nano particles are spherical particles with the diameter of 30-50 nm, the crystal structure of the nano particles is a hexagonal phase spinel crystal structure, and Cu enters ZnFe in a mode of replacing Zn by crystal lattices2O4In the crystal lattice. The method is to mix Cu with ZnFe2O4The preparation method of the nano-particles comprises the following steps: FeCl is added3、ZnCl2、 CuCl2And CON2H4Dissolving the mixture into deionized water according to a molar ratio of 10:10: 8-15: 330, wherein FeCl is contained3The ratio of the deionized water to the deionized water is 1:50mol/L, and the mixture is magnetically stirred for 10-30 min to obtain a mixed solution; placing the mixed solution in a reaction kettle, reacting for 4-13 h at 150-180 ℃ in a vacuum drying oven, washing, drying and carrying out heat treatment to obtain Cu-doped ZnFe2O4And (3) nanoparticles.
The Cu of the invention is doped with ZnFe2O4The nano-particles have uniform sphere size and better dispersibility.
The invention also aims to provide a gas-sensitive coating which is Cu-doped ZnFe2O4The low-temperature gas sensor mainly comprises a platinum wire, a ceramic tube, a gas-sensitive coating, gold electrodes, heating wires and a base, wherein the heating wires penetrate through the ceramic tube, two ends of each heating wire are welded on the heating electrodes of the base, the gold electrodes cover two ends of the outer surface of the ceramic tube and are welded on four corresponding measuring electrodes of the base through the platinum wires, and the gas-sensitive coating is coated on the outer surface of the ceramic tube and completely covers the gold electrodes; the gas-sensitive coating is Cu-doped ZnFe2O4And (3) nanoparticles. The Cu is doped with ZnFe2O4The nano particles are spherical particles with the diameter of 30-50 nm, the crystal structure of the nano particles is a hexagonal phase spinel crystal structure, and Cu enters ZnFe in a mode of replacing Zn by crystal lattices2O4In the crystal lattice.
Another purpose of the invention is to provide a gas-sensitive coating which is Cu-doped ZnFe2O4The preparation method of the nanoparticle low-temperature gas sensor comprises the following steps:
preparing Cu doped ZnFe2O4Nanoparticles of said Cu doped ZnFe2O4The nano particles are spherical particles with the diameter of 30-50 nm, the crystal structure of the nano particles is a hexagonal phase spinel crystal structure, and Cu enters ZnFe in a mode of replacing Zn by crystal lattices2O4In the crystal lattice, the Cu is doped with ZnFe2O4Adding absolute ethyl alcohol into the nano particles, and grinding for 10-30 min to form pasty slurry;
secondly, a heating wire penetrates through the ceramic tube, two ends of the heating wire are welded on the heating electrodes of the base, platinum wires are welded on the four measuring electrodes of the base, and the gold electrodes are covered on two ends of the outer surface of the ceramic tube;
uniformly coating the pasty slurry on the outer surface of the ceramic tube, completely covering the gold electrode, and drying at room temperature for 10-60 min to form a gas-sensitive coating;
fourthly, placing the mixture on an aging table to carry out heat treatment for 10 to 24 hours at the temperature of between 200 and 300 ℃ to obtain a Cu-doped ZnFe gas-sensitive coating2O4Nanoparticle cryogenic gas sensors.
Preferably, the Cu is doped ZnFe2O4The preparation steps of the nano particles are as follows: FeCl is added3、 ZnCl2、CuCl2And CON2H4Dissolving the raw materials into deionized water according to a molar ratio of 10:10: 8-15: 330, and adding FeCl3The ratio of the deionized water to the deionized water is 1:50mol/L, and the mixture is magnetically stirred for 10-30 min to obtain a mixed solution; placing the mixed solution in a reaction kettle, reacting for 4-13 h at 150-180 ℃ in a vacuum drying oven, washing, drying and carrying out heat treatment to obtain Cu-doped ZnFe2O4And (3) nanoparticles.
Compared with the prior art, the invention has the characteristics and beneficial effects that:
the invention provides a Cu-doped ZnFe2O4Nanoparticles, and a preparation method and application thereof, wherein the gas-sensitive coating is Cu-doped ZnFe2O4The low-temperature gas sensor of the nano particles has the advantages of low working temperature, high sensitivity, low energy consumption, good selectivity and the like.
From the aspect of preparation method, the Cu-doped ZnFe with good crystallization, uniform appearance, good dispersity, large specific surface area, high sensitivity and good selectivity is prepared by using a hydrothermal synthesis method2O4The nano particles fill the problem of one-step synthesis of Cu-doped ZnFe by using a hydrothermal method2O4Blank of zero-dimensional nanoparticle-related research, and then doping Cu with ZnFe2O4The nano particles are uniformly coated on the surface of the ceramic tube to prepare a gas-sensitive coating, and the prepared gas-sensitive element is subjected to heat treatment on an aging table to remove absolute ethyl alcohol in the gas-sensitive coating and simultaneously keep the stability of the structure and the performance of the gas-sensitive coating. The gas sensor can obtain H pairs at a lower working temperature (25-50 ℃), and2the S gas has high sensitivity, reversibility, reproducibility and selectivity, the problem of poor gas-sensitive property of the traditional metal oxide semiconductor gas sensor in a low-temperature area is effectively solved, and the gas sensor has good development prospect.
Drawings
FIG. 1 shows that the gas-sensitive coating is Cu-doped ZnFe2O4The main structure of the nanoparticle low-temperature gas sensor is shown schematically; wherein the gas-sensitive coating 1; a platinum wire 2; a heating wire 3; a gold electrode 4; a ceramic tube 5;
FIG. 2 shows a Cu-doped ZnFe prepared by the method of the present invention2O4An X-ray diffraction pattern of the nanoparticles;
FIG. 3 shows a Cu-doped ZnFe prepared by the method of the present invention2O4Scanning electron micrographs of nanoparticles (a) low magnification and (b) high magnification;
FIG. 4 shows a Cu-doped ZnFe prepared by the method of the present invention2O4Transmission electron microscopy of nanoparticles;
FIG. 5 shows a gas sensor pair of 5ppm H prepared by the method of the present invention2The sensitivity of S gas and the working temperature;
FIG. 6 shows the sensitivity and H of the gas sensor prepared by the method of the present invention at a working temperature of 25 deg.C2S gas concentration relation graph;
FIG. 7 is a graph of the sensitivity of a gas sensor made by the method of the present invention to different gases to be detected at a working temperature of 25 ℃;
FIG. 8 shows the measured value of the gas sensor prepared by the method of the present invention for 5ppm H at an operating temperature of 25 deg.C2Graph of sensitivity of S gas over time.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
The gas sensitive coating of the embodiment is Cu doped ZnFe2O4The main structural schematic diagram of the nanoparticle low-temperature gas sensor is shown in fig. 1, and comprises a gas-sensitive coating 1; a platinum wire 2; a heating wire 3; a gold electrode 4; a ceramic tube 5; wherein the heating wire 3 passes through the ceramic tube 5 and is driven to pass throughTwo ends of the gas-sensitive coating are welded on the heating electrodes of the base, the gold electrodes 4 are covered on two ends of the outer surface of the ceramic tube 5 and are welded on the four measuring electrodes of the base through platinum wires 2, and the gas-sensitive coating 1 is coated on the outer surface of the ceramic tube 5 and completely covers the gold electrodes 4; the gas sensitive coating 1 comprises Cu-doped ZnFe2O4Nanoparticles, Cu doped ZnFe2O4The nano particles have a single hexagonal spinel crystal structure, the spheres are uniform in size, the individual dispersibility is good, and the diameter is 30-50 nm.
The gas sensitive coating of the embodiment is Cu doped ZnFe2O4The preparation method of the nanoparticle low-temperature gas sensor is carried out according to the following steps:
(1) 1mmol of ferric chloride (FeCl) was weighed3)0.162g of 1mmol of zinc chloride (ZnCl)2)0.136g, 1mmol of copper chloride (CuCl)2)0.134g and 33mmol Urea (CON)2H4) Placing 1.98g of the mixed solution in a beaker filled with 50mL of deionized water, and magnetically stirring for 15min to obtain a uniform mixed solution;
(2) transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene liner, placing the reaction kettle in a vacuum type drying oven, reacting for 12 hours at 160 ℃, respectively washing hydrothermal reaction products for 2 times by using deionized water and absolute ethyl alcohol after the reaction is finished, placing the washed products in a blast type drying oven at 60 ℃ for drying for 8 hours to obtain dried products, and finally carrying out heat treatment on the dried products in air at 500 ℃ for 2 hours to finally obtain Cu-doped ZnFe2O4A nanoparticle; the obtained Cu-doped ZnFe2O4The X-ray diffraction pattern of the nano-particles is shown in FIG. 2, and from FIG. 2, it can be seen that the generated product is single ZnFe2O4The crystal structure of hexagonal spinel has no diffraction peak of other impurities and has excellent crystallization condition; the scanning electron micrograph is shown in FIG. 3, and it can be seen from FIG. 3 that Cu is doped with ZnFe2O4The spheres of the nano particles are uniform in size and good in individual dispersibility, the diameter of the spheres is 30-50 nm, and the spheres have a large specific surface area; the TEM micrograph is shown in FIG. 4, and it can be seen from FIG. 4 that Cu is doped with ZnFe2O4Diameter of the nanoparticlesThe particle size is 30-50 nm, which is consistent with the result of scanning electron microscope photograph.
(3) Doping the obtained Cu with ZnFe2O4The nanoparticles are put into an agate mortar, added with absolute ethyl alcohol and ground in the agate mortar for 20min to prepare pasty slurry. Enabling a heating wire 3 to penetrate through a ceramic tube 5, welding two ends of the heating wire 3 on heating electrodes of a base, welding platinum wires 2 on four measuring electrodes of the base, and uniformly coating pasty slurry on the outer surface of the ceramic tube 5 to form a gas-sensitive coating 1;
(4) drying the ceramic tube 5 coated with the gas-sensitive coating 1 for 30min at room temperature to finally obtain ZnFe doped based on Cu2O4Nanoparticle gas sensors. And carrying out heat treatment on the welded gas sensitive element on an aging table at 275 ℃ for 12h to improve the stability and reliability of the gas sensitive element.
In the working temperature range of 25 ℃ to 175 ℃ at room temperature, the gas-sensitive coating is Cu-doped ZnFe2O4Nanoparticle low temperature gas sensor pair 5ppm H2The graph of the sensitivity of S gas with respect to the operating temperature is shown in fig. 5, and it can be seen from fig. 5 that the sensitivity of the gas gradually decreases as the operating temperature increases, that the sensitivity of the sensor rapidly decreases when the operating temperature increases from 25 c to 100 c, and that the sensitivity of the sensor attains a maximum value when the operating temperature is 25 c. The maximum sensitivity can be obtained at a lower working temperature of 25 ℃, which is the greatest advantage of the gas sensor of the invention and can effectively reduce the energy consumption of the gas sensor.
The gas-sensitive coating is Cu-doped ZnFe2O4Nanoparticle low-temperature gas sensor for different concentrations of H at working temperature of 25 DEG C2The sensitivity profile of S gas is shown in FIG. 6. it can be seen from FIG. 6 that the gas sensor is sensitive to H at 25 deg.C2S gas has excellent gas-sensitive characteristic, high sensitivity and gas sensitivity following H2The S gas concentration increases. Further, the gas sensor is used for H with a concentration of 500ppb2S gas still has a significant response indicating that the lower measurement limit of the gas sensor is ppb level concentration.
Gas-sensitive paintThe layer is Cu doped ZnFe2O4Nanoparticle low temperature gas sensor for 5ppm H at 25 deg.C2S, 100ppm of C2H5OH、H2、CH4、C2H6The gas sensitivity of CO and HCHO is shown in FIG. 7. from FIG. 7, it can be seen that the gas-sensitive coating is Cu-doped ZnFe2O4The sensitivity of the nanoparticle low-temperature gas sensor to 6 detected gases is in the order of H2S>C2H5OH>C2H6CO>HCHO>H2>CH4Description of the Cu-doped ZnFe based on the same detection conditions2O4Nanoparticle low temperature gas sensor pair H2The S gas has good selectivity. This indicates that the sensor can be used for H in a complex gas environment2And S is effectively identified, so that the method shows a good practical application prospect.
FIG. 8 is the sensor for 5ppm H2Sensitivity of S versus time. As can be seen from the figure, the sensitivity of the sensor fluctuates around 35 within 30 days, the variation range is small, good stability is shown, and the defect of poor long-term stability of the existing sensor can be overcome well.
Example 2
The gas sensitive coating of the embodiment is Cu doped ZnFe2O4A nanoparticle cryogenic gas sensor, as shown in fig. 1, comprises a gas sensitive coating 1; a platinum wire 2; a heating wire 3; a gold electrode 4; a ceramic tube 5; the heater strip 3 penetrates through the ceramic tube 5 and two ends of the heater strip are welded on a heating electrode of the base, the gold electrodes 4 are covered on two ends of the outer surface of the ceramic tube 5 and are welded on a measuring electrode of the base through platinum wires 2, and the gas-sensitive coating 1 is coated on the outer surface of the ceramic tube 5 and completely covers the gold electrodes 4; the gas sensitive coating 1 comprises Cu-doped ZnFe2O4Nanoparticles, Cu doped ZnFe2O4The nano particles have a single hexagonal spinel crystal structure, spheres are uniform in size, individual dispersibility is good, the diameter is 30-50 nm, and the nano particles have a large specific surface area.
ZnFe doped based on Cu in the embodiment2O4The preparation method of the nanoparticle low-temperature gas sensor is carried out according to the following steps:
(1) 1mmol of ferric chloride (FeCl) was weighed3)0.162g of 1mmol of zinc chloride (ZnCl)2)0.136g, 1.5mmol of copper chloride (CuCl)2)0.201g and 33mmol of urea (CON)2H4) Placing 1.98g of the mixed solution in a beaker filled with 50mL of deionized water, and magnetically stirring for 20min to obtain a uniform mixed solution;
(2) transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene liner, placing the reaction kettle in a vacuum type drying box, reacting for 4h at 180 ℃, respectively washing hydrothermal reaction products for 3 times by using deionized water and absolute ethyl alcohol after the reaction is finished, placing the washed products in a blast type drying box at 80 ℃ for drying for 5h, and finally performing heat treatment on the dried products in the air at 500 ℃ for 4h to finally obtain Cu-doped ZnFe2O4And (3) nanoparticles.
Through detection, the obtained Cu-doped ZnFe2O4The X-ray diffraction pattern of the nano-particles shows that the generated product is single ZnFe2O4The crystal structure of hexagonal spinel has no diffraction peak of other impurities and excellent crystallization condition.
(3) Doping the obtained Cu with ZnFe2O4The nanoparticles are put into an agate mortar, added with absolute ethyl alcohol and ground in the agate mortar for 30min to prepare pasty slurry. Then, a heating wire 3 penetrates through the ceramic tube 5, two ends of the heating wire are welded on a heating electrode of the base, a platinum wire 2 is welded on a measuring electrode of the base, and the pasty slurry is uniformly coated on the outer surface of the ceramic tube 5 to form a gas-sensitive coating 1;
(4) drying the ceramic tube 5 coated with the gas-sensitive coating 1 for 10min at room temperature to finally obtain the gas-sensitive coating which is Cu-doped ZnFe2O4Nanoparticle gas sensors. And (3) carrying out heat treatment on the welded gas sensitive element on an aging table at 300 ℃ for 10h to improve the stability and reliability of the gas sensitive element.
Through detection, the Cu-doped ZnFe prepared by the embodiment2O4Cryogenic gas of nanoparticlesThe sensor is used for detecting H under the working temperature of 25-175 DEG C2The S gas has a good response effect.
Example 3
The gas sensitive coating of the embodiment is Cu doped ZnFe2O4Nanoparticle cryogenic gas sensor, as shown in fig. 1, gas sensitive coating 1; a platinum wire 2; a heating wire 3; a gold electrode 4; a ceramic tube 5; the heater strip 3 penetrates through the ceramic tube 5 and two ends of the heater strip are welded on a heating electrode of the base, the gold electrodes 4 are covered on two ends of the outer surface of the ceramic tube 5 and are welded on a measuring electrode of the base through platinum wires 2, and the gas-sensitive coating 1 is coated on the outer surface of the ceramic tube 5 and completely covers the gold electrodes 4; the gas sensitive coating 1 comprises Cu-doped ZnFe2O4Nanoparticles, Cu doped ZnFe2O4The nano particles have a single hexagonal spinel crystal structure, spheres are uniform in size, individual dispersibility is good, the diameter is 30-50 nm, and the nano particles have a large specific surface area.
ZnFe doped based on Cu in the embodiment2O4The preparation method of the nanoparticle low-temperature gas sensor is carried out according to the following steps:
(1) 1mmol of ferric chloride (FeCl) was weighed3)0.162g of 1mmol of zinc chloride (ZnCl)2)0.136g, 0.8mmol of copper chloride (CuCl)2)0.107g and 33mmol of urea (CON)2H4) Placing 1.98g of the mixed solution in a beaker filled with 50mL of deionized water, and magnetically stirring for 10min to obtain a uniform mixed solution;
(2) transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene liner, placing the reaction kettle in a vacuum drying oven, reacting for 13h at 150 ℃, repeatedly washing the precipitated product with deionized water and absolute ethyl alcohol after the reaction is finished, placing the washed product in a blast drying oven at 60 ℃ for drying for 3h, and finally performing heat treatment on the dried product in air at 500 ℃ for 3h to finally obtain Cu-doped ZnFe2O4And (3) nanoparticles.
Through detection, the obtained Cu-doped ZnFe2O4The X-ray diffraction pattern of the nano particles shows that the generated product is single Cu-doped ZnFe2O4The crystal structure of hexagonal spinel has no diffraction peak of other impurities and excellent crystallization condition.
(3) Doping the obtained Cu with ZnFe2O4Putting the nano particles into an agate mortar, adding absolute ethyl alcohol, grinding for 10min in the agate mortar to prepare pasty slurry, then enabling a heating wire 3 to penetrate through a ceramic tube 5, welding two ends of the heating wire on a heating electrode of a base, welding a platinum wire 2 on a measuring electrode of the base, and uniformly coating the pasty slurry on the outer surface of the ceramic tube to form a gas-sensitive coating 1;
(4) drying the ceramic tube 5 coated with the gas-sensitive coating 1 for 50min at room temperature to finally obtain ZnFe doped based on Cu2O4Nanoparticle gas sensors. And (3) carrying out heat treatment on the welded gas sensitive element for 20h at 200 ℃ on an aging table to improve the stability and reliability of the gas sensitive element.
Through detection, the gas-sensitive coating prepared by the embodiment is Cu-doped ZnFe2O4The low-temperature gas sensor of the nano particles is used for H under the working temperature condition of 25-175 DEG C2The S gas has a good response effect.
Claims (8)
1. Cu-doped ZnFe2O4The preparation method of the nano-particles is characterized by comprising the following steps: FeCl is added3、ZnCl2、CuCl2And CON2H4Dissolving the mixture into deionized water according to a molar ratio of 10:10: 8-15: 330, wherein FeCl is contained3The ratio of the deionized water to the deionized water is 1:50mol/L, and the mixture is magnetically stirred for 10-30 min to obtain a mixed solution; placing the mixed solution in a reaction kettle, reacting for 4-13 h at 150-180 ℃ in a vacuum drying oven, washing, drying and carrying out heat treatment to obtain Cu-doped ZnFe2O4And (3) nanoparticles.
2. The method according to claim 1, wherein the washing step is carried out 2 to 3 times with deionized water and absolute ethanol, respectively.
3. The method according to claim 1, wherein the drying step is drying in a forced-air drying oven at 60-80 ℃ for 3-8 h.
4. The method according to claim 1, wherein the heat treatment step is a heat treatment in air at 500 ℃ for 2-4 h.
5. Cu doped ZnFe prepared by the method of claim 12O4Nanoparticles, characterized in that the Cu is doped with ZnFe2O4The nano particles are spherical particles with the diameter of 30-50 nm, the crystal structure of the nano particles is a hexagonal phase spinel crystal structure, and Cu enters ZnFe in a mode of replacing Zn by crystal lattices2O4In the crystal lattice.
6. The gas-sensitive coating is Cu-doped ZnFe2O4The low-temperature gas sensor of the nanometer granule is characterized in that the sensor mainly comprises a platinum wire, a ceramic tube, a gas-sensitive coating, a gold electrode, a heating wire and a base, wherein the heating wire penetrates through the ceramic tube, two ends of the heating wire are welded on the heating electrode of the base, the gold electrode covers two ends of the outer surface of the ceramic tube and is welded on four corresponding measuring electrodes of the base through the platinum wire, and the gas-sensitive coating is coated on the outer surface of the ceramic tube and completely covers the gold electrode; the gas sensitive coating is Cu-doped ZnFe as claimed in claim 52O4And (3) nanoparticles.
7. The gas sensitive coating of claim 6 being Cu doped ZnFe2O4The preparation method of the nanoparticle low-temperature gas sensor is characterized by comprising the following steps of:
preparing Cu doped ZnFe2O4Nanoparticles of said Cu doped ZnFe2O4The nano particles are spherical particles with the diameter of 30-50 nm, the crystal structure of the nano particles is a hexagonal phase spinel crystal structure, and Cu enters ZnFe in a mode of replacing Zn by crystal lattices2O4In the crystal lattice, the Cu is doped with ZnFe2O4Adding absolute ethyl alcohol into the nano particles, and grinding the nano particles to 10-30 min forming pasty slurry;
secondly, a heating wire penetrates through the ceramic tube, two ends of the heating wire are welded on the heating electrodes of the base, platinum wires are welded on the four measuring electrodes of the base, and the gold electrodes are covered on two ends of the outer surface of the ceramic tube;
uniformly coating the pasty slurry on the outer surface of the ceramic tube, completely covering the gold electrode, and drying at room temperature for 10-60 min to form a gas-sensitive coating;
fourthly, placing the mixture on an aging table to carry out heat treatment for 10 to 24 hours at the temperature of between 200 and 300 ℃ to obtain a Cu-doped ZnFe gas-sensitive coating2O4Nanoparticle cryogenic gas sensors.
8. The method of claim 7, wherein the Cu is doped ZnFe2O4The preparation steps of the nano particles are as follows: FeCl is added3、ZnCl2、CuCl2And CON2H4Dissolving the raw materials into deionized water according to a molar ratio of 10:10: 8-15: 330, and adding FeCl3The ratio of the deionized water to the deionized water is 1:50mol/L, and the mixture is magnetically stirred for 10-30 min to obtain a mixed solution; placing the mixed solution in a reaction kettle, reacting for 4-13 h at 150-180 ℃ in a vacuum drying oven, washing, drying and carrying out heat treatment to obtain Cu-doped ZnFe2O4And (3) nanoparticles.
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