CN110596196A - Semiconductor heterojunction gas sensitive material and preparation method and application thereof - Google Patents
Semiconductor heterojunction gas sensitive material and preparation method and application thereof Download PDFInfo
- Publication number
- CN110596196A CN110596196A CN201910872026.8A CN201910872026A CN110596196A CN 110596196 A CN110596196 A CN 110596196A CN 201910872026 A CN201910872026 A CN 201910872026A CN 110596196 A CN110596196 A CN 110596196A
- Authority
- CN
- China
- Prior art keywords
- gas
- sensitive material
- semiconductor heterojunction
- nickel
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
- C01G9/03—Processes of production using dry methods, e.g. vapour phase processes
-
- 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
-
- 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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention relates to a semiconductor heterojunction gas sensitive material and a preparation method and application thereof. The gas sensitive material is lamellar microspheres with the diameter of 1.6-2.5 mu m and the specific surface area of 20.9m2g‑1‑23.9m2g‑1The microsphere is a composite material consisting of zinc oxide and nickel oxide, and the composite material of the zinc oxide and the nickel oxide is in a hexagonal crystal form. The mole percentage of nickel oxide is 0.1-1%. The composite material has the advantages of high response speed, high response value and good selectivity within the range of 100-160 ℃.
Description
Technical Field
The invention belongs to the technical field of preparation of semiconductor gas sensitive materials, and particularly relates to a semiconductor heterojunction gas sensitive material and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
With the rapid development of industry, the emission of toxic and combustible gases produced by the combustion of urban industry and fossil energy has increased correspondingly. The exhausted gas comprising nitrogen dioxide (NO)2) Carbon monoxide (CO), sulfur dioxide (SO)2) And hydrogen sulfide (H)2S), wherein sulfur dioxide, one of the most common atmospheric pollutants, forms acid rain, pollutes the environment and destroys the respiratory system of the human body. When people are exposed to 500ppm of sulfur dioxide, pulmonary edema symptoms, even asphyxia, may appear. The effective monitoring and management of the emission of the polluted gas becomes an indispensable treatment means at present. Therefore, there is a strong need for devices and related sensitive materials that can rapidly and efficiently detect sulfur dioxide in the atmosphere. ZnO is taken as a typical N-type semiconductor material, has higher concentration of free electrons and faster electron mobility, and the higher concentration of the free electrons increases the number of test gas molecules and chemically adsorbed oxygen interacting with the surface of the material, thereby enlarging the detection limit of the material on the test gas; the high electron mobility increases the resistance change rate of the gas-sensitive material in the test process, is favorable for improving the response and recovery speed of the material to the test gas and realizing the purpose of rapid detection, and is already used for SO2And (4) detecting the gas. However, the intrinsic zinc oxide semiconductor is insufficient in detecting the existence of low-concentration gas at low temperature, such as low sensitivity, poor selectivity, high working temperature and the like, and the physical properties of materials, such as electricity and the like, are improved by modifying pure metal oxides, SO that the intrinsic zinc oxide semiconductor can realize low-concentration SO at low temperature2The gas-sensitive metal oxide semiconductor material is used for detecting gas. For this reason, the document J Hazard Mater,381(2019)120944, modifying ZnO with Pt, improves its performance under low temperature conditions, but is affected by the size, shape and uniformity of metal particles, and is difficult to satisfy the "sound" of high performance gas sensitive materialHigh response value, low working temperature and short response time recovery time; in addition, the complex preparation process and the high manufacturing cost are difficult to meet the requirement of large-scale industrial production. In recent years, researchers find that a composite metal oxide structure can form a heterojunction, and charge transfer caused by different Fermi levels generally forms a charge depletion layer and a potential barrier at an interface, so that the electron concentration of the material is changed, and the gas-sensitive performance of the material is enhanced.
In the preparation process of the composite semiconductor material, researchers often use two-step hydrothermal synthesis and electrostatic self-assembly, in the two-step hydrothermal synthesis of the composite material, firstly a target semiconductor is synthesized, and then another semiconductor preparation means is continuously synthesized by hydrothermal synthesis, which is described in the literature, a ceramics International45(2019) 15134-15142. However, these methods have the defects of complicated operation, nonuniform semiconductor composition, long synthesis period, etc., and these defects also result in that these methods cannot be used in the preparation of a large amount of composite semiconductor heterojunction materials.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a semiconductor heterojunction gas-sensitive material, and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
in a first aspect, the gas sensitive material is a lamellar microsphere with the diameter of 1.6-2.5 μm and the specific surface area of 20.9m2g-1-23.9m2g-1The microsphere is a composite material consisting of zinc oxide and nickel oxide, and the composite material of the zinc oxide and the nickel oxide is in a hexagonal crystal form.
In some embodiments, the mole percent of nickel oxide is 0.1-1%; preferably, 0.3-0.6%; more preferably, 0.5%.
Zinc oxide, as a typical N-type semiconductor material, has problems of low sensitivity and poor selectivity at relatively low temperatures. The invention forms p-n heterojunction on the surface of the material by selecting the combination of zinc oxide and nickel oxide due to Fermi levelIn contrast, charge transfer at the interface usually forms a charge depletion layer at the interface, changes the electron concentration of the material itself, enhances the gas-sensitive performance of the composite material, and the nickel oxide zinc oxide composite material has SO in the same temperature range (100 ℃ C. and 160 ℃ C.)2The gas response value is obviously improved compared with pure zinc oxide.
In the second aspect, a preparation method of the semiconductor heterojunction gas sensitive material is that divalent inorganic zinc salt and divalent inorganic nickel salt are dissolved in water, surfactant and precipitator are added, and a product obtained by reaction is washed and dried to obtain a precursor material;
and annealing the precursor material in an air atmosphere to obtain the composite metal oxide porous microsphere gas-sensitive material.
The composite material prepared by the invention is a microsphere system consisting of lamellar, the monolithic layer structure has larger specific surface area and porous structure, the abundant pore structure and large specific surface area provide a channel for the diffusion of gas on the material, the diffusion rate is accelerated, the contact between the gas and the material is more sufficient, the electronic exchange is more frequent, and the sensitivity of the material is favorably improved.
In some embodiments, the reaction system is an aqueous solution, and the inorganic salt is generally very hydrophilic, so the inorganic salt is selected to provide metal ions to the system, and the zinc salt is zinc acetate dihydrate (Zn (CH)3COO)2 .2H2O) or zinc nitrate hexahydrate (Zn (NO)3)2.6H2O). In some embodiments, the divalent nickel salt is selected from nickel acetate tetrahydrate (Ni (CH)3COO)2.4H2O) or nickel nitrate hexahydrate (Ni (NO)3)2.6H2O). In some embodiments, the surfactant is polyvinylpyrrolidone (PVP) or sodium benzenesulfonate (LAS). In some embodiments, the precipitating agent is ammonium carbonate or sodium hydroxide. In some embodiments, the mass ratio of the mixture of divalent inorganic zinc salt and divalent inorganic nickel salt to the surfactant and precipitant is 1:1 to 1.5:0.8 to 1.2.
In some embodiments, the precursor is formed under reaction conditions of 100-400 ℃ for 2-30 hours; preferably, the reaction condition is 150-; further preferably, the reaction conditions are 180 ℃ for 2 h. In the range of the reaction temperature, the precursor with the porous microsphere structure is formed by agglomeration.
In some embodiments, the conditions under which the precursors react under an air atmosphere are: the reaction temperature is 200 ℃ and 600 ℃ for 1-3 hours; preferably, the reaction temperature is 400-500 ℃ for 1-3 hours; further preferably, the reaction is carried out at 450 ℃ for 1.5 to 2.5 hours. Within the above temperature range, the precursor is further shaped to obtain an oxide form with excellent properties.
In some embodiments, the mole percent of nickel oxide in the composite metal oxide porous microsphere gas sensitive material is 0.1-1%; preferably, 0.3-0.6%; more preferably, 0.5%. Nickel oxide is used to form a heterojunction with zinc oxide that lowers the barrier height and improves the response. Composite material formed by matching nickel oxide and zinc oxide to SO2Has good detection sensitivity and is resistant to SO2Has selectivity.
In a third aspect, the semiconductor heterojunction gas-sensitive material or the semiconductor heterojunction gas-sensitive material prepared by the preparation method is used for detecting SO2Application in gas.
Preferably, the detection temperature is 100-240 ℃; more preferably, 120 ℃ to 240 ℃, and still more preferably, 140 ℃ to 180 ℃. The invention overcomes the problem of low detection sensitivity under the condition of low temperature, namely SO2The detection of (2) provides a wider range of applications.
The semiconductor heterojunction gas-sensitive material or the semiconductor heterojunction gas-sensitive material prepared by the preparation method is applied to preparation of a gas-sensitive sensor.
In a fourth aspect, a method for preparing a gas sensor comprises the following steps:
and mixing the semiconductor heterojunction gas-sensitive material with ethyl cellulose and terpineol to prepare slurry, coating the obtained slurry on the surface of a ceramic substrate, and aging to obtain the gas-sensitive sensor. Ethyl cellulose is a non-ionic surfactant with the functions of thickening, suspending, binding and protecting colloid, and terpineol has the function of binding conductive particles together.
In some embodiments, the mass ratio of ethylcellulose to terpineol is 1: 8-10. In some embodiments, the ethyl cellulose and the terpineol form a mixed solution, and the mass ratio of the gas sensitive material to the mixed solution is 1: 3-5.
The gas sensor is used for detecting SO2Application in gas.
Preferably, the detection temperature is 100-240 ℃; more preferably, 120 ℃ to 240 ℃, and still more preferably, 140 ℃ to 180 ℃.
The invention has the beneficial effects that:
(1) the invention provides a low-concentration SO catalyst with higher specific surface area and low temperature2The gas has excellent performance. The higher specific surface area provides more active sites for the adsorption of gas on the surface of the material, and the porous structure provides rich channels for the diffusion of the gas on the surface of the material, which is beneficial to improving the sensitivity and response recovery time of the material. The heterojunction is formed at the interface of the two different semiconductors, so that the barrier height is reduced, the transport efficiency of carriers is improved, and the response is improved.
(2) The composite metal oxide semiconductor gas-sensitive material prepared by the invention effectively solves a series of problems of low sensitivity, poor selectivity and the like of the existing pure zinc oxide semiconductor gas-sensitive material, and expands the application range of the material. The gas sensor aims at low-concentration SO2The gas has high sensitivity and selectivity, can work at a lower temperature of 100-160 ℃ and has a higher response value, namely sensitivity.
(3) The invention effectively solves the problem of the modified concentration of the composite metal oxide, the modified metal salts with different concentrations are arranged to meet the requirements of the composite metal oxide gas-sensitive material on different free electron concentrations, the thickness of the depletion layer of the metal oxide gas-sensitive material can be more efficiently controlled by controlling the concentration of the modified metal salts, the requirements of the gas-sensitive material on different free electron concentrations are met, but if the modified concentration is too low, the heterojunction content of the composite metal oxide gas-sensitive material is less, and the influence on the free electron concentration is small; however, if the modification concentration is too high, the influence of the concentration on free electrons is smaller and smaller along with the increase of the concentration of the modification amount, and on the contrary, the raw material waste is more and more; if the concentration of the modified metal salt is too high or too low, the free electron concentration of the metal oxide gas-sensitive material cannot be effectively controlled, so that the control efficiency is low or the raw materials are wasted.
(4) The composite metal oxide semiconductor gas-sensitive material has good dispersibility, and avoids the problem of uneven smearing caused by agglomeration in the preparation process of a gas-sensitive element.
(5) The invention provides a safe, effective and convenient microspherical composite semiconductor gas-sensitive material which can be obtained in one step, and has one-step hydrothermal synthesis, simple process and easy operation.
(6) The preparation method is safe and effective, the required equipment is simple and easy to operate, the process parameters are convenient to control, the use cost of raw materials and instruments and equipment is low, and the like.
Drawings
The accompanying drawings, which form a part of the specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a scanning electron micrograph of a pure zinc oxide porous microsphere prepared in comparative example 2;
FIG. 2 is a scanning electron micrograph of a nickel oxide-zinc oxide composite metal oxide prepared in example 1;
fig. 3 is an X-ray diffraction energy spectrum of the pure zinc oxide prepared in comparative example 2 and the nickel oxide zinc oxide composite metal oxide prepared in examples 1 to 3;
fig. 4 is a BET specific surface area spectrum and a pore size distribution diagram of the nickel oxide-zinc oxide composite metal oxide prepared in example 1.
FIG. 5 shows the comparison of pure zinc oxide prepared in comparative example 2 and nickel oxide-zinc oxide composite metal oxide microspheres prepared in example 1 at different temperatures for 10ppm SO2The response value of the gas;
FIG. 6 shows a composite metal of nickel oxide and zinc oxide prepared in example 1Oxide microspheres for different concentrations of SO at 160 DEG C2Gas sensitivity performance test chart of gas;
FIG. 7 is a bar graph of the response values of the nickel oxide-zinc oxide composite metal oxide gas-sensitive material prepared in example 1 to different gases of 10 ppm.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" include plural forms unless the context clearly dictates otherwise, and further, it is understood that when the terms "comprises" and/or "comprising" are used in this specification, it indicates the presence of the features, steps, operations, devices, components and/or combinations thereof.
The invention will be further illustrated by the following examples
Example 1:
a zinc oxide and nickel oxide porous microsphere gas-sensitive material is a lamellar microsphere with the diameter of 2 mu m and the specific surface of 20.9m2g-1-23.9m2g-1As shown in fig. 4.
With zinc acetate dihydrate Zn (CH)3COO)2 .2H2O, Nickel acetate tetrahydrate Ni (CH)3COO)2 .4H2Taking O as a raw material, taking polyvinylpyrrolidone (PVP-K30) as a surfactant and also as a dispersing agent, taking deionized water as a solvent, adding 0.19g of ammonium carbonate after dissolving metal salt (zinc salt and nickel salt) and the surfactant according to the mass ratio of 1:1.25, reacting for 2 hours at 180 ℃, washing and drying a product to obtain the zinc oxide and nickel oxide precursor. And (3) keeping the prepared precursor at 450 ℃ for two hours, and calcining to prepare the zinc oxide and nickel oxide microsphere gas-sensitive material. Mole percent of nickel oxideThe ratio was 0.5%.
The X-ray powder diffraction pattern (XRD) of the obtained zinc oxide nickel oxide microsphere gas-sensitive material sample (as shown in figure 3) shows that the synthesized zinc oxide nickel oxide composite material is in a hexagonal crystal form, and the comparison with standard diffraction data (JCPDS-361451) shows that the purity of the synthesized zinc oxide is very high. Scanning Electron Microscopy (SEM) (fig. 1) microspheres showed lamellar microspheres with precursor particle diameter of 2 μm, and Scanning Electron Microscopy (SEM) (fig. 2) showed that the addition of nickel oxide did not change the structure of the zinc oxide.
The gas sensor was prepared from the zinc oxide nickel oxide composite material of example 1 and the test experiments were as follows:
adding the composite metal oxide gas-sensitive material prepared in the embodiment 1 into a solution prepared from ethyl cellulose and terpineol according to the mass ratio of 1:9 to prepare slurry, wherein the mass ratio of the powdery composite gas-sensitive material to the solution is 1:4, coating the gas-sensitive material slurry on one surface of a ceramic substrate according to needs for three times, welding the ceramic substrate and a four-foot base together, and carrying out gas-sensitive test after the sensor is aged for 7 days. The test result shows that the response value of the composite material is firstly increased and then reduced along with the increase of the temperature, the response value to sulfur dioxide is the highest at 160 ℃, and the response value to 10ppm can reach 107.
Example 2
A zinc oxide and nickel oxide porous microsphere gas-sensitive material is a lamellar microsphere with the diameter of 2 mu m and the specific surface of 20.9m2g-1-23.9m2g-1。
With zinc acetate dihydrate Zn (CH)3COO)2 .2H2O, Nickel acetate tetrahydrate Ni (CH)3COO)2 .4H2Taking O as a raw material, taking polyvinylpyrrolidone (PVP-K30) as a surfactant and also as a dispersing agent, taking deionized water as a solvent, adding 0.1g of ammonium carbonate after the salt is dissolved, reacting for 1.8 hours at 150 ℃, washing and drying the product to obtain the zinc oxide and nickel oxide precursor, wherein the mass ratio of the metal salt to the surfactant is 1:1. And (3) keeping the prepared precursor at 400 ℃ for two hours, and calcining to prepare the zinc oxide and nickel oxide microsphere gas-sensitive material. Oxidation by oxygenThe molar percentage of nickel is 1%.
The gas sensor was prepared from the zinc oxide nickel oxide composite material of example 1 and the test experiments were as follows:
adding the composite metal oxide gas-sensitive material prepared in the embodiment 1 into a solution prepared from ethyl cellulose and terpineol according to the mass ratio of 1:9 to prepare slurry, wherein the mass ratio of the powdery composite gas-sensitive material to the solution is 1:4, coating the gas-sensitive material slurry on one surface of a ceramic substrate according to needs for three times, welding the ceramic substrate and a four-foot base together, and carrying out gas-sensitive test after the sensor is aged for 7 days. The test result shows that the response value of the composite material is firstly increased and then reduced along with the increase of the temperature, the response value to sulfur dioxide is the highest at 160 ℃, and the response value to 10ppm can reach 107.
The gas sensor was prepared from the zinc oxide nickel oxide composite material of example 2 and the test experiments were as follows:
the composite metal oxide gas-sensitive material prepared in example 2 was added to a solution prepared from ethyl cellulose and terpineol in a mass ratio of 1:10 to prepare a slurry, and the mass ratio of the powdery composite gas-sensitive material to the solution was 1: 3.5. And (3) coating the gas-sensitive material slurry on one surface of the ceramic substrate for three times according to requirements, welding the ceramic substrate and the four-sole base together, and carrying out gas-sensitive test after the sensor is aged for 7 days. The test result shows that the response value of the composite material is firstly increased and then reduced along with the increase of the temperature, the response value to sulfur dioxide is the highest at 160 ℃, and the response value to 10ppm can reach 32.
Example 3
Compared with the embodiment 1, the zinc oxide and nickel oxide porous microsphere gas sensitive material is a lamellar microsphere with the diameter of 2 mu m and the specific surface of 20.9m2g-1-23.9m2g-1。
With zinc acetate dihydrate Zn (CH)3COO)2 .2H2O, Nickel acetate tetrahydrate Ni (CH)3COO)2 .4H2O as raw material, polyvinylpyrrolidone (PVP-K30) as surfactant and dispersant, deionized water as solvent, and metalThe mass ratio of the salt to the surfactant is 1:1.5, 0.23g of ammonium carbonate is added after the salt is dissolved, the reaction is carried out for 2.2 hours at 200 ℃, and the product is washed and dried to obtain the zinc oxide and nickel oxide precursor. And (3) performing heat preservation on the prepared precursor at 500 ℃ for two and a half hours for calcination treatment to prepare the zinc oxide and nickel oxide microsphere gas-sensitive material. The molar percentage of nickel oxide was 0.25%.
Adding the composite metal oxide gas-sensitive material prepared in the embodiment 3 into a solution prepared from ethyl cellulose and terpineol according to the mass ratio of 1:8 to prepare slurry, wherein the mass ratio of the powdery composite gas-sensitive material to the solution is 1:3, coating the gas-sensitive material slurry on one surface of a ceramic substrate according to needs for three times, welding the ceramic substrate and a four-foot base together, and carrying out gas-sensitive test after the sensor is aged for 7 days. The test result shows that the response value of the composite material is firstly increased and then reduced along with the increase of the temperature, the response value to sulfur dioxide is the highest at 160 ℃, and the response value to 10ppm can reach 44.
Comparative example 1:
zinc oxide nickel oxide microspheres were prepared as described in example 1, except that the ratio of added salt to PVP was changed to 1:2, and Scanning Electron Microscope (SEM) characterization showed that the synthesized microspheres were poorly dispersible.
Comparative example 2:
as in example 1, except that: the zinc oxide is not compounded in the step (1). The obtained ZnO porous microsphere gas-sensitive material is prepared into a corresponding gas-sensitive element according to the method of the embodiment 1, and the gas-sensitive performance detection result is shown in fig. 5, SO that the nickel oxide-zinc oxide composite metal oxide gas-sensitive material of the embodiment 1 has a response value far better than that of a pure zinc oxide gas-sensitive material, and has low-concentration SO of 10ppm2Exhibit more excellent performance.
Comparative example 3:
the procedure is as described in example 1, except that no surfactant is added to the precursor preparation. Scanning Electron Microscopy (SEM) characterization showed that no intact spheres were formed, all in the form of scattered platelets.
Examples 1-3 and comparative example 2 at different temperatures, 10ppm SO2Gas sensitive detection under gas conditionsThe measurement result is shown in FIG. 5, which shows that the gas-sensitive property of the nickel oxide-zinc oxide composite metal oxide material has a certain change with the increase of the modified concentration of nickel oxide, and 0.5 mol% of nickel oxide modified zinc oxide has a certain change at 160 ℃ to 10ppm SO2The gas has a relatively good response.
FIG. 6 shows the temperature of the nickel oxide-zinc oxide composite metal oxide microspheres prepared in example 1 at 160 ℃ for different concentrations of SO2Gas sensitivity performance test chart of gas; as can be seen from FIG. 6, at an operating temperature of 160 deg.C, the sensor showed good response and recovery curves for sulfur dioxide, indicating that the sensor can be used to detect sulfur dioxide gas in ppm levels, with SO2The response value of the nickel oxide-zinc oxide composite metal oxide microspheres is increased from 6 to 172 from the concentration of 1 to 50 ppm.
FIG. 7 is a bar graph of response values of the gas-sensitive material of nickel oxide and zinc oxide composite metal oxide prepared in example 1 to different gases; as can be seen from FIG. 7, the nickel oxide zinc oxide sensor is sensitive to 10ppm NO2、CH4、H2、NH3、SO2The response values of the nickel oxide and zinc oxide sensors are respectively 4.6, 2.7, 1, 1.5 and 107, and the SO of the nickel oxide and zinc oxide sensors can be obviously detected2Has good selectivity.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A semiconductor heterojunction gas sensitive material, characterized in that: the gas sensitive material is lamellar microspheres with the diameter of 1.6-2.5 mu m and the specific surface area of 20.9m2g-1-23.9m2g-1The microsphere is a composite material consisting of zinc oxide and nickel oxide, and the zinc oxide and nickel oxide composite material is in a hexagonal crystal form.
2. The semiconductor heterojunction gas-sensitive material of claim 1, wherein: the mole percentage of nickel oxide is 0.1-1%; preferably, the mole percentage of nickel oxide is 0.3-0.6%; more preferably, the molar percentage of nickel oxide is 0.5%.
3. The method for preparing a semiconductor heterojunction gas-sensitive material as claimed in any one of claims 1 to 2, wherein: dissolving divalent inorganic zinc salt and divalent inorganic nickel salt in water, adding a surfactant and a precipitator, washing and drying a product obtained by reaction to obtain a precursor material;
the precursor material reacts in the air atmosphere to obtain the composite metal oxide porous microsphere gas-sensitive material;
preferably, the divalent inorganic zinc salt is zinc acetate dihydrate or zinc nitrate hexahydrate;
preferably, the divalent nickel salt is selected from nickel acetate tetrahydrate or nickel nitrate hexahydrate;
preferably, the surfactant is polyvinylpyrrolidone or sodium benzenesulfonate;
preferably, the precipitant is ammonium carbonate or sodium hydroxide;
preferably, the reaction condition for generating the precursor is 100-400 ℃ for 2-30 hours; further preferably, the reaction condition is 150-; more preferably, the reaction conditions are 180 ℃ for 2 h.
4. The method for preparing the semiconductor heterojunction gas-sensitive material according to claim 3, wherein: the mass ratio of the divalent inorganic zinc salt to the divalent inorganic nickel salt to the surfactant to the precipitator is 1:1-1.5: 0.8-1.2.
5. The method for preparing the semiconductor heterojunction gas-sensitive material according to claim 3, wherein: the reaction conditions of the precursor under the air atmosphere are as follows: the reaction temperature is 200 ℃ and 600 ℃ for 1-3 hours; preferably, the reaction temperature is 400-500 ℃ for 1-3 hours; further preferably, the reaction is carried out at 450 ℃ for 1.5 to 2.5 hours.
6. The method for preparing the semiconductor heterojunction gas-sensitive material according to claim 3, wherein: the mol percentage of nickel oxide in the composite metal oxide porous microsphere gas-sensitive material is 0.1-1%; preferably, 0.3-0.6%; more preferably, 0.5%.
7. Use of the semiconductor heterojunction gas-sensitive material of any one of claims 1 to 2 or the semiconductor heterojunction gas-sensitive material obtained by the preparation method of the semiconductor heterojunction gas-sensitive material of any one of claims 3 to 6 in detecting SO2The application in gas;
preferably, the detection temperature is 100-240 ℃; more preferably, 120 ℃ to 240 ℃, and still more preferably, 140 ℃ to 180 ℃.
8. Use of the semiconductor heterojunction gas-sensitive material of any one of claims 1 to 2 or the semiconductor heterojunction gas-sensitive material obtained by the method for preparing the semiconductor heterojunction gas-sensitive material of any one of claims 3 to 6 in the preparation of a gas sensor.
9. A preparation method of a gas sensor is characterized by comprising the following steps: the method comprises the following specific steps:
the semiconductor heterojunction gas-sensitive material of any one of claims 1 to 2, ethyl cellulose and terpineol are mixed to prepare slurry, the obtained slurry is coated on the surface of a ceramic substrate, and the gas-sensitive sensor is obtained after aging;
preferably, the mass ratio of the ethyl cellulose to the terpineol is 1: 8-10;
preferably, the ethyl cellulose and the terpineol form a mixed solution, and the mass ratio of the gas-sensitive material to the mixed solution is 1: 3-5.
10. The gas sensor of claim 9 in detecting SO2The application in gas;
preferably, the detection temperature is 100-240 ℃; more preferably, 120 ℃ to 240 ℃, and still more preferably, 140 ℃ to 180 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910872026.8A CN110596196B (en) | 2019-09-16 | 2019-09-16 | Semiconductor heterojunction gas sensitive material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910872026.8A CN110596196B (en) | 2019-09-16 | 2019-09-16 | Semiconductor heterojunction gas sensitive material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110596196A true CN110596196A (en) | 2019-12-20 |
| CN110596196B CN110596196B (en) | 2020-09-18 |
Family
ID=68859846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910872026.8A Active CN110596196B (en) | 2019-09-16 | 2019-09-16 | Semiconductor heterojunction gas sensitive material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110596196B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112129823A (en) * | 2020-09-13 | 2020-12-25 | 中国海洋大学 | Ni @ NiO @ ZnO @ CS composite metal wire for copper ion detection and preparation method and application thereof |
| CN114460141A (en) * | 2022-01-18 | 2022-05-10 | 山东大学 | Composite fiber gas-sensitive material and preparation method and application thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62124454A (en) * | 1985-11-26 | 1987-06-05 | Nippon Telegr & Teleph Corp <Ntt> | Hetero junction type gas sensor |
| US20080006531A1 (en) * | 2005-12-12 | 2008-01-10 | Holt Christopher T | Ceramic H2S sensor |
| US20090148347A1 (en) * | 2007-12-10 | 2009-06-11 | Electronics And Telecommunications Research Institute | Nano-crystalline composite-oxide thin film, environmental gas sensor using the thin film, and method of manufacturing the environmental gas sensor |
| CN103412000A (en) * | 2013-07-29 | 2013-11-27 | 浙江大学 | ZnO/NiO single bending nanowire heterojunction biosensor and preparation method thereof |
| CN105274555A (en) * | 2015-11-12 | 2016-01-27 | 中国海洋大学 | NiO@PANI@ZnO three-dimensional nano composite material and preparation method thereof |
| CN105548275A (en) * | 2016-01-14 | 2016-05-04 | 吉林大学 | Acetone sensor based on NiO/ZnO heterostructure nanoflower sensitive material and preparation method of acetone sensor |
| US20160161443A1 (en) * | 2013-08-30 | 2016-06-09 | Murata Manufacturing Co., Ltd. | Gas sensor, method for manufacturing gas sensor, and method for detecting gas concentration |
| CN105776357A (en) * | 2016-03-21 | 2016-07-20 | 西北工业大学 | Method for preparing nickel oxide/zinc oxide heterojunction nanometer materials |
| US20160319461A1 (en) * | 2015-04-29 | 2016-11-03 | The Board Of Trustees Of The University Of Illinois | Composition comprising an engineered defect concentration |
| CN106093140A (en) * | 2016-07-19 | 2016-11-09 | 山东大学 | For NO2the composite construction doped air-sensitive material of gas, gas sensor and preparation method thereof and application |
| CN109592704A (en) * | 2018-11-30 | 2019-04-09 | 太原理工大学 | A kind of preparation method of three-dimensional zinc oxide/nickel oxide sensitive material |
| CN109607593A (en) * | 2019-01-10 | 2019-04-12 | 沈阳化工大学 | A kind of preparation and its application of NiO-ZnO flower-like structure composite material |
-
2019
- 2019-09-16 CN CN201910872026.8A patent/CN110596196B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62124454A (en) * | 1985-11-26 | 1987-06-05 | Nippon Telegr & Teleph Corp <Ntt> | Hetero junction type gas sensor |
| US20080006531A1 (en) * | 2005-12-12 | 2008-01-10 | Holt Christopher T | Ceramic H2S sensor |
| US20090148347A1 (en) * | 2007-12-10 | 2009-06-11 | Electronics And Telecommunications Research Institute | Nano-crystalline composite-oxide thin film, environmental gas sensor using the thin film, and method of manufacturing the environmental gas sensor |
| CN103412000A (en) * | 2013-07-29 | 2013-11-27 | 浙江大学 | ZnO/NiO single bending nanowire heterojunction biosensor and preparation method thereof |
| US20160161443A1 (en) * | 2013-08-30 | 2016-06-09 | Murata Manufacturing Co., Ltd. | Gas sensor, method for manufacturing gas sensor, and method for detecting gas concentration |
| US20160319461A1 (en) * | 2015-04-29 | 2016-11-03 | The Board Of Trustees Of The University Of Illinois | Composition comprising an engineered defect concentration |
| CN105274555A (en) * | 2015-11-12 | 2016-01-27 | 中国海洋大学 | NiO@PANI@ZnO three-dimensional nano composite material and preparation method thereof |
| CN105548275A (en) * | 2016-01-14 | 2016-05-04 | 吉林大学 | Acetone sensor based on NiO/ZnO heterostructure nanoflower sensitive material and preparation method of acetone sensor |
| CN105776357A (en) * | 2016-03-21 | 2016-07-20 | 西北工业大学 | Method for preparing nickel oxide/zinc oxide heterojunction nanometer materials |
| CN106093140A (en) * | 2016-07-19 | 2016-11-09 | 山东大学 | For NO2the composite construction doped air-sensitive material of gas, gas sensor and preparation method thereof and application |
| CN109592704A (en) * | 2018-11-30 | 2019-04-09 | 太原理工大学 | A kind of preparation method of three-dimensional zinc oxide/nickel oxide sensitive material |
| CN109607593A (en) * | 2019-01-10 | 2019-04-12 | 沈阳化工大学 | A kind of preparation and its application of NiO-ZnO flower-like structure composite material |
Non-Patent Citations (5)
| Title |
|---|
| H. TIAN ET AL.: "NiO/ZnO p-n heterostructures and their gas sensing properties for reduced operating temperature", 《RSC ADVANCES》 * |
| L. ZHANG ET AL.: "Porous ZnO/NiO microspherical structures prepared by thermolysis of heterobimetallic metal-organic framework as supercapacitor electrodes", 《JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY》 * |
| L. ZHOU ET AL.: "A facile one-step hydrothermal synthesis of a novel NiO/ZnO nanorod composite and its enhanced ethanol sensing property", 《MATERIALS LETTERS》 * |
| Q. ZHOU ET AL.: "High sensitive and low-concentration sulfur dioxide(SO2) gas sensor application of heterostructure NiO-ZnO nanodisks", 《SENSORS & ACTUATORS: B. CHEMICAL》 * |
| W. SI ET AL.: "One-pot hydrothermal synthesis of nano-sheet assembled NiO/ZnO microspheres for efficient sulfur dioxide detection", 《CERAMICS INTERNATIONAL》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112129823A (en) * | 2020-09-13 | 2020-12-25 | 中国海洋大学 | Ni @ NiO @ ZnO @ CS composite metal wire for copper ion detection and preparation method and application thereof |
| CN112129823B (en) * | 2020-09-13 | 2022-04-08 | 中国海洋大学 | Preparation method of Ni @ NiO @ ZnO @ CS composite metal wire for copper ion detection |
| CN114460141A (en) * | 2022-01-18 | 2022-05-10 | 山东大学 | Composite fiber gas-sensitive material and preparation method and application thereof |
| CN114460141B (en) * | 2022-01-18 | 2024-05-28 | 山东大学 | Composite fiber gas-sensitive material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110596196B (en) | 2020-09-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | An excellent triethylamine (TEA) sensor based on unique hierarchical MoS2/ZnO composites composed of porous microspheres and nanosheets | |
| Tan et al. | Self-template derived CuO nanowires assembled microspheres and its gas sensing properties | |
| Liang et al. | Controllable preparation of faceted Co3O4 nanocrystals@ MnO2 nanowires shish-kebab structures with enhanced triethylamine sensing performance | |
| Chen et al. | Preparation, characterization and gas-sensing properties of SnO2–In2O3 nanocomposite oxides | |
| CN110217759B (en) | For low-concentration NO at low temperature2Oxygen vacancy modified metal oxide gas-sensitive material for gas detection and preparation method thereof | |
| CN102680539B (en) | Preparation method of porous nickel oxide/tin dioxide micro/nano spheres | |
| CN110732323A (en) | α -MnO for catalyzing oxidation of volatile organic compounds2Process for preparing catalyst | |
| CN113740390B (en) | Nickel-doped indium oxide nano-particle and preparation method and application thereof | |
| CN112657487A (en) | High porosity cerium and zirconium containing oxides | |
| Teoh et al. | High sensitivity semiconductor NO 2 gas sensor based on mesoporous WO 3 thin film | |
| CN110596196B (en) | Semiconductor heterojunction gas sensitive material and preparation method and application thereof | |
| Bai et al. | An α-Fe 2 O 3/NiO p–n hierarchical heterojunction for the sensitive detection of triethylamine | |
| Tian et al. | Design and fabrication of spinel nanocomposites derived from perovskite hydroxides as gas sensing layer for volatile organic compounds detection | |
| Li et al. | Enhancement of gas-sensing abilities in p-type ZnWO4 by local modification of Pt nanoparticles | |
| Sun et al. | CuO-sensitized amorphous ZnSnO3 hollow-rounded cubes for highly sensitive and selective H2S gas sensors | |
| Liang et al. | The modification effect of Fe 2 O 3 nanoparticles on ZnO nanorods improves the adsorption and detection capabilities of TEA | |
| Zhang et al. | The synthesis and fast ethanol sensing properties of core–shell SnO 2@ ZnO composite nanospheres using carbon spheres as templates | |
| CN110836913A (en) | Iron-doped porous indium oxide gas-sensitive material and preparation method and application thereof | |
| Wang et al. | Synthesis of 1D SnO2 nanorods/2D NiO porous nanosheets pn heterostructures for enhanced ethanol gas sensing performance | |
| Wu et al. | Ce-doped LaCoO3 film as a promising gas sensor for ethanol | |
| Si et al. | One-pot hydrothermal synthesis of nano-sheet assembled NiO/ZnO microspheres for efficient sulfur dioxide detection | |
| Khan et al. | Sm 2 O 3 and Sm 2 O 3-based nanostructures for photocatalysis, sensors, CO conversion, and biological applications | |
| Wang et al. | Growth of Ag/g-C3N4 nanocomposites on nickel foam to enhance photocatalytic degradation of formaldehyde under visible light | |
| CN108760831B (en) | Preparation method of indium oxide gas-sensitive element | |
| Yin et al. | Enhanced detection of ppb-level NO2 by uniform Pt-doped ZnSnO3 nanocubes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |