CN110865099B - Preparation method and application of ZnO-SnO2-Zn2SnO4 porous nanofiber gas-sensitive material - Google Patents
Preparation method and application of ZnO-SnO2-Zn2SnO4 porous nanofiber gas-sensitive material Download PDFInfo
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Abstract
The invention belongs to the technical field of gas sensors, and particularly relates to ZnO-SnO2‑Zn2SnO4The invention adopts the electrostatic spinning method combined with high heat treatment temperature rise rate to prepare ZnO-SnO2‑Zn2SnO4The porous nanofiber gas-sensitive material has the advantages of simple preparation method, less flow, easy operation and good room-temperature gas-sensitive performance; meanwhile, the invention also provides ZnO-SnO2‑Zn2SnO4Application of porous nanofiber gas-sensitive material in detection or induction of alcohol gas at room temperature to prepare ZnO-SnO2‑Zn2SnO4The gas sensor has obvious response and high selectivity to alcohol at room temperature.
Description
Technical Field
The invention belongs to the technical field of gas sensors, and particularly relates to ZnO-SnO2-Zn2SnO4A preparation method and application of a porous nanofiber gas-sensitive material.
Background
The alcohol sensor is widely applied to the aspects of drunk driving detection, disease diagnosis, food industry, environmental monitoring and the like. Zn2SnO4The material has the characteristics of high conductivity, high electron mobility, potential optical performance, thermal stability and the like, and is a good gas sensitive material. At present, there is already Zn in question2SnO4The application of the nano material in alcohol detection is reported. For example, Ethanol gas sensing performance of Zn, W.C. Wang et al2SnO4nanopowder prepared via a hydrothermal route with differential solution pH values report on Zn prepared by hydrothermal method2SnO4The nano-powder has a response value to 200ppm of alcohol at 300 ℃; hydrothermal syntheses and gas sensing properties of cubic and quasic-cubic Zn by Y.Q.Jiang et al2SnO4Reports on hydrothermal methodsPrepared Zn2SnO4The nanostructures showed high response values to 600ppm of alcohol at 325 ℃. These reports all show that zinc stannate has the potential to detect alcohol, but the results are mostly carried out at high temperature (. gtoreq.300 ℃). The high operation temperature not only brings high energy consumption and potential safety hazard, but also causes the diffusion and growth of the gas sensitive material nanocrystal to reduce the stability of the sensor, which are not favorable for the miniaturization and commercialization of the sensor.
Construction based on Zn2SnO4The composite material is an effective way for improving the gas-sensitive performance and other performances. Chinese invention patent CN108940326A provides a preparation method of a visible light response zinc stannate/carbon/silver bromide nano composite photocatalyst, and Zn prepared by a hydrothermal method2SnO4Preparing Zn from nano powder by carbon modification2SnO4Preparing Zn from/C nanocrystal by in-situ precipitation2SnO4a/C/AgBr nano composite photocatalyst and Zn obtained2SnO4Visible light absorption capacity and Zn of/C/AgBr nano composite photocatalyst2SnO4Compared with the prior art, the method is greatly enhanced. Chinese patent CN108394928A discloses a ZnO/Zn2SnO4According to the preparation method, a method combining atomic layer deposition, liquid phase laser ablation and a solvothermal method is adopted, a flexible fibrous fine metal wire is used as a substrate, a zinc oxide nanorod array vertically grows on the surface of the flexible fibrous fine metal wire, a high-purity metal tin target immersed in a solution is ablated by laser, a high-activity solvothermal precursor is obtained, and a zinc oxide/zinc stannate core-shell structure heterojunction further grows on the zinc oxide array by the solvothermal method. High hly sensitive and selective triethylamine gas sensor based on a porous SnO produced by Yang et al, X.L2/Zn2SnO4compositions report hydrothermally prepared SnO2-Zn2SnO4Spherical composite material having good Triethylamine (TEA) gas-sensitive properties at high temperatures of 250 ℃. Although based on Zn2SnO4The composite material can enhance the gas-sensitive response value, but the working temperature is still higher, which is not beneficial to commercializing large scaleAnd (4) applying the model.
In order to solve the problem, the invention adopts an electrostatic spinning method combined with high heat treatment temperature rise rate to prepare ZnO-SnO2-Zn2SnO4Porous nanofiber gas-sensitive material, ZnO-SnO2-Zn2SnO4The porous nanofiber gas-sensitive material has not been reported, and has obvious response and high selectivity to alcohol at room temperature.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides ZnO-SnO2-Zn2SnO4The preparation method of the porous nanofiber gas-sensitive material is simple, few in flow, easy to operate and good in room-temperature gas-sensitive performance.
Meanwhile, the invention also provides ZnO-SnO2-Zn2SnO4Application of porous nanofiber gas-sensitive material in detection or induction of alcohol gas at room temperature to prepare ZnO-SnO2-Zn2SnO4The gas sensor has obvious response and high selectivity to alcohol.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
ZnO-SnO2-Zn2SnO4A preparation method of a porous nanofiber gas-sensitive material comprises the following steps:
(1) adding zinc acetate dihydrate and tin acetate into N, N-dimethylformamide to completely dissolve the zinc acetate dihydrate and the tin acetate;
(2) adding polyvinylpyrrolidone into the mixed solution obtained in the step (1) until the solution is viscous, and stirring at room temperature to completely dissolve the polyvinylpyrrolidone to obtain an electrostatic spinning precursor solution;
(3) performing electrostatic spinning on the electrostatic spinning precursor solution obtained in the step (2), and calcining spun yarns to obtain ZnO-SnO2-Zn2SnO4Porous nanofiber gas sensitive materials.
Further, the specific process of electrostatic spinning in the step (3) is as follows: and (3) sucking the solution obtained in the step (2) into an injector, and putting the injector into an electrostatic spinning instrument for electrostatic spinning.
Further, in the electrostatic spinning process, the voltage is 14-17 kV, the negative high voltage is-1-3 kV, the extrusion speed of a spinning nozzle is 1-1.5 mL/h, and the spinning receiving distance is 13-17 cm.
Further, the specific process of the calcination in the step (3) is as follows: and (3) placing the spun silk in a tube furnace for calcination.
Further, the heating rate of the calcining process is 8-13 ℃/min, and the temperature is kept for 1-3 hours when the calcining temperature is increased to 650-700 ℃.
Further, the mass ratio of the polyvinylpyrrolidone to the zinc acetate dihydrate, the tin acetate and the N, N-dimethylformamide is 1: 1.1-1.4: 1.0-1.2: 5 to 8.
ZnO-SnO2-Zn2SnO4Porous nanofiber gas sensitive material, the ZnO-SnO2-Zn2SnO4The porous nanofiber gas-sensitive material comprises various types of n-n heterojunctions; the ZnO-SnO2-Zn2SnO4The fiber diameter of the porous nanofiber gas-sensitive material is 180-220 nm.
ZnO-SnO2-Zn2SnO4The porous nanofiber gas-sensitive material is applied to the aspect of detecting or sensing alcohol gas at room temperature.
Further, the ZnO-SnO2-Zn2SnO4The application process of the porous nanofiber gas-sensitive material is as follows: ZnO-SnO2-Zn2SnO4Mixing the porous nanofiber gas-sensitive material with deionized water, grinding the mixture into uniform slurry, and coating the slurry on an Ag-Pd electrode to obtain ZnO-SnO with high response value and high selectivity to alcohol gas at room temperature2-Zn2SnO4A gas sensor.
ZnO-SnO2-Zn2SnO4The gas sensor is prepared from ZnO-SnO2-Zn2SnO4The porous nanofiber gas-sensitive material is mixed with deionized water, ground into uniform slurry and coated on an Ag-Pd electrode to prepare the Ag-Pd electrode material, and the Ag-Pd electrode material has high response value and high selectivity to alcohol gas at room temperature.
The invention has the beneficial effects that:
1. ZnO-SnO of the present invention2-Zn2SnO4The porous nanofiber gas-sensitive material is synthesized by utilizing electrostatic spinning combined with a high heat treatment heating rate, and the preparation method is simple, less in flow and easy to operate.
2. ZnO-SnO of the present invention2-Zn2SnO4The porous nanofiber gas sensitive material comprises Zn2SnO4-ZnO and Zn2SnO4-SnO2And the n-n heterojunction in multiple types can effectively reduce the electron hole recombination rate and enhance the resistance modulation capability. In both heterojunctions, Zn2SnO4The Fermi level of the metal oxide is higher than that of ZnO and SnO2，Zn2SnO4Electron transfer from surface to ZnO and SnO2Transition, ZnO and SnO2Hole orientation Zn of surface2SnO4And (5) transferring. These processes reduce the recombination of electron holes, Zn2SnO4The surface forms a thicker electron depletion layer, the resistance is increased, and ZnO and SnO2A charge accumulation layer is formed on the surface, active electrons on the charge accumulation layer are combined with adsorbed oxygen molecules on the surface of the material to generate adsorbed oxygen ions, and more adsorbed oxygen ions participate in the gas-sensitive reaction, so that the room-temperature alcohol gas-sensitive performance is enhanced.
3. The product obtained by the method is uniform and controllable in appearance, is porous and fibrous, is formed by assembling a plurality of small nano particles, the diameter of the fiber is 180-220 nm, the nano particles enable gas molecules to be rapidly diffused along the boundary and the pore diameter of the particles, the induction rate is high, and the gas adsorption and gas sensitivity performance are improved.
4. ZnO-SnO prepared by the invention2-Zn2SnO4The porous nanofiber gas-sensitive material has obvious response and high selectivity to alcohol gas at room temperature, and the room-temperature working condition avoids potential safety hazard, extra energy consumption and gas-sensitive material agglomeration phenomenon caused by high-temperature work, thereby being beneficial to the miniaturization and commercial application of the sensor.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a crystalline product prepared in example 2 of the present invention;
FIG. 2 is a Transmission Electron Microscope (TEM) and high magnification transmission electron microscope (HRTEM) photograph of a crystal product prepared in example 2 of the present invention;
FIG. 3 is an X-ray diffraction (XRD) pattern of the crystalline product prepared in example 2 of the present invention and the comparative example;
FIG. 4 is a graph showing the gas sensitive response of the crystalline products prepared in example 2 and comparative example of the present invention to 200ppm of alcohol at room temperature under UV irradiation;
fig. 5 is a graph comparing response values of the crystalline products prepared in example 2 and the comparative example to alcohol and an interfering gas at room temperature under uv irradiation.
Detailed Description
The present invention will now be described in detail with reference to the embodiments and the accompanying drawings.
Example 1
0.768g of zinc acetate dihydrate and 0.8392g of tin acetate are added into 5.5mL of 2mol/L N, N-dimethylformamide; and adding 0.700g of polyvinylpyrrolidone into the mixed solution to make the solution have certain viscosity, and stirring the solution at room temperature for 11.5 hours to obtain the precursor solution for electrostatic spinning. The technological parameters in the spinning process are as follows: high voltage of 17kV, negative high voltage of-1 kV, flow rate of precursor liquid of 1.0mL/h, and distance between a spinning head and a receiver of 13 cm. Calcining the precursor nanofiber obtained by spinning in the air, setting the calcining heating rate to be 8 ℃/min, heating the calcining temperature to 680 ℃, and preserving the temperature for 1 hour to finally obtain ZnO-SnO2-Zn2SnO4The porous nanofiber gas-sensitive material has the fiber diameter of 180 nm.
Example 2
Adding 0.878g of zinc acetate dihydrate and 0.7438g of tin acetate into 4.8mL of 2mol/L N, N-dimethylformamide; and adding 0.7g of polyvinylpyrrolidone into the mixed solution to make the solution have certain viscosity, and stirring the solution at room temperature for 12 hours to obtain the precursor solution for electrostatic spinning. The technological parameters in the spinning process are as follows: high voltage 15.3kV, negative high voltage 2kV, precursor liquid flow rate 1.2mL/h, spinning head and receiver distance 15 cm. The precursor obtained by spinning is sodiumCalcining the rice fiber in the air, setting the temperature rise rate of the calcination to be 10 ℃/min, raising the calcination temperature to 650 ℃, and preserving the heat for 3 hours to finally obtain ZnO-SnO2-Zn2SnO4Porous nanofiber gas sensitive materials.
In this example, a Scanning Electron Microscope (SEM) photograph, a TEM image, and an HRTEM scanning test of the prepared crystalline product are shown in fig. 1, fig. 2(a), and fig. 2(b), respectively.
From FIG. 1 it can be seen that the sample is a fibrous structure assembled from particles;
from FIG. 2(a) Single ZnO-SnO2-Zn2SnO4TEM image of the fiber, it can be seen that the fiber is porous with a diameter of 200 nm;
from FIG. 2(b) Single ZnO-SnO2-Zn2SnO4HRTEM image of nano-fiber, the measured lattice fringe spacing respectively corresponds to Zn2SnO4Crystal face (311) of (II) and SnO2(110) crystal plane of (iii).
Shows that the prepared ZnO-SnO of the invention is three-phase2-Zn2SnO4And (3) compounding the nano fibers.
Example 3
0.9801g of zinc acetate dihydrate and 0.7951g of tin acetate are added into 6.7mL of 2mol/L N, N-dimethylformamide; and adding 0.7g of polyvinylpyrrolidone into the mixed solution to make the solution have certain viscosity, and stirring the solution at room temperature for 12.5 hours to obtain the precursor solution for electrostatic spinning. The technological parameters in the spinning process are as follows: high voltage of 16kV, negative high voltage of 1kV, flow rate of the precursor liquid of 1.5mL/h, and distance between a spinning head and a receiver of 16 cm. Calcining the precursor nanofiber obtained by spinning in the air, wherein the calcining temperature rise rate is set to be 13 ℃/min, the calcining temperature is raised to 670 ℃, and the temperature is kept for 2 hours, so that ZnO-SnO is finally obtained2-Zn2SnO4The porous nanofiber gas-sensitive material has the fiber diameter of 220 nm.
Example 4
0.8254g of zinc acetate dihydrate and 0.7098g of tin acetate were added to 7.6mL of 2mol/L N, N dimethylformamide; adding 0.7g polyvinylpyrrolidone into the above mixed solution to make the solution haveThe solution is stirred for 11 hours at room temperature to obtain the precursor solution of electrostatic spinning with certain viscosity. The technological parameters in the spinning process are as follows: high voltage 14kV, negative high voltage 3kV, precursor liquid flow rate 1.3mL/h, and spinning head and receiver distance 17 cm. Calcining the precursor nanofiber obtained by spinning in the air, setting the calcining heating rate to be 11 ℃/min, heating the calcining temperature to 700 ℃, and preserving the temperature for 1 hour to finally obtain ZnO-SnO2-Zn2SnO4The porous nanofiber gas-sensitive material has the fiber diameter of 200 nm.
Comparative example 1
Adding 0.878g of zinc acetate dihydrate and 0.7098g of tin acetate into 6.2mL of 2mol/L N, N-dimethylformamide; and adding 0.7g of polyvinylpyrrolidone into the mixed solution to ensure that the solution has certain viscosity, and stirring the solution at room temperature for 11 hours to obtain the precursor solution for electrostatic spinning. The technological parameters in the spinning process are as follows: high voltage of 17kV, negative high voltage of 2kV, flow rate of precursor liquid of 1.1mL/h, and distance between a spinning head and a receiver of 17 cm. Calcining the precursor nanofiber obtained by spinning in the air, setting the temperature rise rate of the calcination to be 2 ℃/min, and keeping the temperature for 2 hours when the temperature of the calcination is raised to 670 ℃, thereby finally obtaining pure Zn2SnO4And (3) compounding the nano fibers.
Further, to illustrate the ZnO-SnO prepared by the present invention2-Zn2SnO4The ZnO-SnO prepared in the embodiment 2 of the invention has excellent performance2-Zn2SnO4Porous nanofiber gas sensitive Material and pure Zn prepared in comparative example 12SnO4The composite nanofibers were subjected to validation testing.
Verification test 1
The purpose of this proof test is to verify the microstructure and mechanism of the two materials prepared in example 2 and comparative example.
The specific test process is as follows: the X-ray diffraction (XRD) patterns of the crystalline products prepared in example 2 and comparative example were found to be in fig. 3.
Referring to FIG. 3, XRD pattern and cubic phase Zn of the crystalline product prepared by comparative ratio2SnO4Is markedThe quasi-spectra (JCPDS cards 74-2184) are compared and found to be well matched, which indicates that the crystal product prepared by the comparative example is cubic phase Zn2SnO4。
Referring to FIG. 3, by comparing XRD patterns of the crystalline products prepared in example 2 and comparative example, it was found that the main diffraction peaks of the crystalline product prepared in example 2 were identical to those of the crystalline product prepared in comparative example, and both belonged to cubic phase Zn2SnO4But the XRD pattern of the crystalline product prepared in example 1 has three more diffraction peaks, wherein the peak at 26.6 degrees is SnO2The (110) crystal plane diffraction peak of (JCPDS card: 71-0652), the peaks at 31.8 DEG and 47.6 DEG correspond to the (100) and (102) crystal plane diffraction peaks of ZnO, respectively (JCPDS card: 75-0576).
Thus, the XRD results in fig. 3 show that: example 2 the main component of the prepared crystalline product was Zn2SnO4And also contains a small amount of SnO2And ZnO; this indicates that heat treatment of the precursor nanofibers at a low temperature ramp rate (2 ℃/min) during calcination results in pure phase Zn2SnO4The nano-fiber successfully realizes the phase separation during the heat treatment at a high temperature rise rate (8-13 ℃/min) to obtain three-phase ZnO-SnO2-Zn2SnO4And (3) compounding the nano fibers.
Further, ZnO-SnO prepared in example 2 of the present invention was analyzed2-Zn2SnO4The structure of the porous nanofiber gas-sensitive material is found as follows: in ZnO-SnO2-Zn2SnO4A plurality of heterojunctions are formed among different components in the composite nanofiber, so that the modulation of resistance is enhanced, and the recombination rate of electron holes is reduced; zn2SnO4The Fermi energy level of the nano-fiber is higher than that of ZnO and SnO2，Zn2SnO4Electron transfer from surface to ZnO and SnO2Transition, ZnO and SnO2Hole orientation Zn of surface2SnO4And (5) transferring. The process reduces the recombination of electron holes, so that more photogenerated electrons can react with the adsorbed oxygen on the surface of the material to generate active adsorbed oxygen ions; at the same time, Zn2SnO4The surface will be thickerElectron depletion layer, resistance increase, and ZnO and SnO2A charge accumulation layer is formed on the surface, active electrons on the charge accumulation layer are combined with adsorbed oxygen molecules on the surface of the material to generate more adsorbed oxygen ions, and thus more adsorbed oxygen ions participate in the gas-sensitive reaction, so that the resistance (R) of the sensor before the reaction is increaseda) The resistance (R) after the reaction is reducedg) Thereby remarkably improving the gas sensitive response value.
To show that the ZnO-SnO prepared by the invention2-Zn2SnO4The products obtained in example 2 and comparative example were subjected to a gas-sensitive response experiment with 200ppm of alcohol gas, which is the superior gas-sensitive property of the porous nanofiber.
The specific test process is
1. Fabrication of gas sensors
ZnO-SnO obtained in example 22-Zn2SnO4Taking 150 mg of porous nanofiber material, mixing with 0.5mL of deionized water, grinding into uniform slurry, taking part of the slurry by using a brush, and coating the part of the slurry on an Ag-Pd electrode to obtain ZnO-SnO2-Zn2SnO4A gas sensor. The gas-sensitive layer has a thickness of about 100 μm and an area of about 7X 7mm2。
Zn obtained in comparative example2SnO4Taking 150 mg of porous nanofiber material, mixing with 0.5mL of deionized water, grinding into uniform slurry, taking part of the slurry by using a brush, and coating the part of the slurry on an Ag-Pd electrode to obtain Zn2SnO4A gas sensor. The gas-sensitive layer has a thickness of about 100 μm and an area of about 7X 7mm2。
2. Gas sensitive response experiment
The specific process is as follows: the gas sensors respectively prepared in example 2 and comparative example were placed in a test chamber (volume 1.8L) of a gas sensitive test system, and an LED ultraviolet light source was used to irradiate the sensors (wavelength 365nm, intensity 185 mW/cm)2). The gas response process is to inject test gas (200ppm alcohol gas) with a certain concentration into the test chamber through a gas-liquid dynamic gas distribution system (Beijing Airit: DGL-III model), and the recovery process is to pass gasThe hydraulic dynamic air distribution system injects air into the test chamber. The gas sensor is connected with an external power supply through two probes, and the change curve of the resistance of the gas sensor along with time is obtained through measurement.
Taking the stable resistance of the gas sensor before alcohol is introduced into the gas sensor as RaThe resistance after alcohol introduction is RgThe response value of the sensor is defined as
The alcohol gas-sensitive response curve is the change curve of the sensor response value S with time before and after alcohol is introduced. The specific variation is shown in fig. 4.
As can be seen from FIG. 4, the crystalline product (Zn) prepared in comparative example2SnO4) There was little response to 200ppm alcohol at room temperature, failing to meet the sensitivity requirements of commercial sensors. While the crystalline product (ZnO-SnO) prepared in example 22-Zn2SnO4) The response value to 200ppm alcohol at room temperature is as high as 68.3%. The results show that the Zn is pure2SnO4Comparative nanofiber, ZnO-SnO2-Zn2SnO4The nanofiber material can form various n-n heterojunctions, gas molecules can be rapidly diffused along the boundary and the aperture of particles, the nano-scale material has high induction rate, and the nano-scale material is favorable for the absorption of gas and the improvement of gas sensitivity, so that ZnO-SnO2-Zn2SnO4The composite nano-fiber has obviously enhanced gas-sensitive performance to alcohol gas at room temperature.
With pure Zn2SnO4In contrast to sensors, ZnO-SnO2-Zn2SnO4The room temperature gas sensitive response value of the composite nanofiber sensor to alcohol is obviously increased.
The products obtained in example 2 and comparative example were subjected to gas-sensitive selectivity test with alcohol gas.
1. Fabrication of gas sensors
ZnO-SnO obtained in example 22-Zn2SnO4Porous nanofiber material 150 mg of the mixed solution is mixed with 0.5mL of deionized water and ground into uniform slurry, and part of the slurry is taken out by a brush and coated on an Ag-Pd electrode to obtain ZnO-SnO2-Zn2SnO4A gas sensor. The gas-sensitive layer has a thickness of about 100 μm and an area of about 7X 7mm2。
Zn obtained in comparative example2SnO4Taking 150 mg of porous nanofiber material, mixing with 0.5mL of deionized water, grinding into uniform slurry, taking part of the slurry by using a brush, and coating the part of the slurry on an Ag-Pd electrode to obtain Zn2SnO4A gas sensor. The gas-sensitive layer has a thickness of about 100 μm and an area of about 7X 7mm2。
2. Selectivity test
Alcohol and interfering gas (CH)3OH: methanol, CH3COCH3: acetone, C3H8O: propanol, HCOOH: formic acid, C8H10: p-xylene) were all 200 ppm. Using the sensors prepared in example 2 and comparative example, respectively, the gas sensitive response curves of both sensors at room temperature for 200ppm of alcohol and the gas sensitive response curves of both sensors at room temperature for the same concentration (200ppm) of interfering gas were measured, and the results are shown in fig. 5.
The response values of the sensor to 200ppm of alcohol and various interference gases are compared, and the response value of the sensor to the alcohol is obviously higher than that of the sensor to other gases, so that the device has good alcohol selectivity.
As can be seen from FIG. 5, pure Zn prepared in example 22SnO4The response of the sensor to alcohol and interfering gases at room temperature is very low, with poor selectivity to alcohol. And ZnO-SnO prepared in example 12-Zn2SnO4The response value of the sensor to alcohol at room temperature is as high as 68.3%, the response value to other interference gases is very low, and almost no response exists, which shows that ZnO-SnO2-Zn2SnO4The sensor has excellent selective detection of alcohol at room temperature.
The ZnO-SnO of the invention can be verified by the experiment2-Zn2SnO4CrystalThe product has higher response value and selectivity to alcohol gas at room temperature as a gas sensitive material.
In conclusion, the method adopts the electrostatic spinning method and combines high heat treatment temperature rise rate to prepare the ZnO-SnO2-Zn2SnO4The porous nanofiber gas-sensitive material is simple in method, less in flow, easy to operate, good in gas-sensitive performance, obvious in response and high in selectivity to 200ppm alcohol, and capable of being operated at room temperature, so that high energy consumption and potential safety hazards caused by high operation temperature are avoided, and the stability of a sensor is reduced due to the fact that nanocrystals of the gas-sensitive material are diffused and grown up due to high temperature.
Claims (8)
1. ZnO-SnO2-Zn2SnO4The preparation method of the porous nanofiber gas-sensitive material is characterized by comprising the following steps of: the preparation method comprises the following steps:
(1) adding zinc acetate dihydrate and tin acetate into N, N-dimethylformamide to completely dissolve;
(2) adding polyvinylpyrrolidone into the mixed solution obtained in the step (1) until the solution is viscous, and stirring at room temperature to completely dissolve the polyvinylpyrrolidone to obtain an electrostatic spinning precursor solution;
(3) performing electrostatic spinning on the electrostatic spinning precursor solution obtained in the step (2), and calcining spun yarns to obtain ZnO-SnO2-Zn2SnO4A porous nanofiber gas sensitive material;
the specific process of calcining in the step (3) is as follows: placing the spun silk in a tubular furnace for calcining; the temperature rise rate in the calcination process is 8-13 ℃/min, and the calcination temperature is raised to 650-700 ℃ and then is kept for 1-3 hours.
2. The ZnO-SnO of claim 12-Zn2SnO4The preparation method of the porous nanofiber gas-sensitive material is characterized by comprising the following steps of: the specific process of electrostatic spinning in the step (3) is as follows: and (3) sucking the solution obtained in the step (2) into an injector, and putting the injector into an electrostatic spinning instrument for electrostatic spinning.
3. The ZnO-SnO of claim 22-Zn2SnO4The preparation method of the porous nanofiber gas-sensitive material is characterized by comprising the following steps of: in the electrostatic spinning process, the voltage is 14 kV-17 kV, the negative high voltage is 1 kV-3 kV, the extrusion speed of a spinning nozzle is 1 mL/h-1.5 mL/h, and the spinning receiving distance is 13 cm-17 cm.
4. The ZnO-SnO of claim 12-Zn2SnO4The preparation method of the porous nanofiber gas-sensitive material is characterized by comprising the following steps of: the mass ratio of the polyvinylpyrrolidone to the zinc acetate dihydrate, the tin acetate and the N, N-dimethylformamide is 1: 1.1-1.4: 1.0-1.2: 5 to 8.
5. A ZnO-SnO as claimed in any of claims 1 to 42-Zn2SnO4ZnO-SnO prepared by preparation method of porous nanofiber gas-sensitive material2-Zn2SnO4The porous nanofiber gas-sensitive material is characterized in that: the ZnO-SnO2-Zn2SnO4The porous nanofiber gas-sensitive material comprises various types of n-n heterojunctions; the ZnO-SnO2-Zn2SnO4The fiber diameter of the porous nanofiber gas-sensitive material is 180 nm-220 nm.
6. The ZnO-SnO as claimed in claim 52-Zn2SnO4The porous nanofiber gas-sensitive material is applied to the aspect of detecting or sensing alcohol gas at room temperature.
7. The ZnO-SnO of claim 62-Zn2SnO4The application of the porous nanofiber gas-sensitive material is characterized in that: the ZnO-SnO2-Zn2SnO4The application process of the porous nanofiber gas-sensitive material is as follows: ZnO-SnO2-Zn2SnO4Mixing the porous nanofiber gas-sensitive material with deionized water, grinding the mixture into uniform slurry, and coating the slurry on an Ag-Pd electrodeThereby obtaining ZnO-SnO with high response value and high selectivity to alcohol gas at room temperature2-Zn2SnO4A gas sensor.
8. ZnO-SnO2-Zn2SnO4A gas sensor, characterized in that: the ZnO-SnO2-Zn2SnO4The gas sensor is ZnO-SnO prepared by the method of claim 52-Zn2SnO4The porous nanofiber gas-sensitive material is mixed with deionized water, ground into uniform slurry and coated on an Ag-Pd electrode to prepare the Ag-Pd electrode material, and the Ag-Pd electrode material has high response value and high selectivity to alcohol gas at room temperature.
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