CN118329980B - Bimetallic oxide semiconductor gas-sensitive material, preparation method and application thereof - Google Patents
Bimetallic oxide semiconductor gas-sensitive material, preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 93
- 239000004065 semiconductor Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 111
- 230000004044 response Effects 0.000 claims abstract description 44
- 238000001514 detection method Methods 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 239000002131 composite material Substances 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
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- 238000000034 method Methods 0.000 claims description 9
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- 229910002651 NO3 Inorganic materials 0.000 claims description 5
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- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 2
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- 238000011084 recovery Methods 0.000 abstract description 10
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- 238000011065 in-situ storage Methods 0.000 abstract description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 93
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- 238000010438 heat treatment Methods 0.000 description 22
- 238000000227 grinding Methods 0.000 description 17
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 16
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract
The invention discloses a bimetallic oxide semiconductor gas-sensitive material, a preparation method and application thereof, and relates to the technical field of gas sensors, wherein the material is Ce-M-O bimetallic oxide formed by in-situ assembly of cerium oxide (CeO 2) and transition metal oxide (MO x, M is one of Fe, ni, mn, co, ti, cu, zn), the two components are uniformly and tightly compounded together in a manner of doping and forming heterojunction, and the components have strong interaction. The obtained material has an ultra-strong gas-sensitive response value (Ra/Rg) to ethyl acetate gas of hundreds of thousands and an ultra-fast recovery time of less than 5 seconds, the detection limit is as low as 10 ppb, the raw material cost is low, and the material has a wide application prospect in the field of gas sensing.
Description
Technical Field
The invention relates to the technical field of gas sensors, in particular to a bimetal oxide semiconductor gas-sensitive material, a preparation method and application thereof in ethyl acetate gas detection.
Background
Ethyl acetate (ETHYL ACETATE, EA) is a common volatile organic compound pollutant widely existing in industrial waste gases such as coating, coking, coloring, building materials and the like, and although the toxicity of the ethyl acetate is generally considered to be low, the damage to human bodies is not quite remarkable, and long-term contact of the ethyl acetate can cause irritation to eyes, nose and throat, even corneal turbidity, secondary anemia and leucocytosis. Second, in the medical field, ethyl acetate can be used as a trace biomarker for colorectal and gastric cancer, as ethyl acetate (at concentrations exceeding 1 ppm) can be detected in the exhaled gas of patients and thus can be used for non-invasive early screening of such diseases. In addition, ethyl acetate has the characteristic of inflammability and explosiveness, and explosion can be caused when the concentration exceeds a certain level in the atmosphere. China (GBZ-2002) specifies that the maximum allowable concentration of ethyl acetate vapor in air is less than 300mg/m3 (76.3 ppm). Thus, the selective detection of ethyl acetate at ppm levels and below is of great importance for environmental monitoring, food safety and disease diagnosis.
Along with the improvement of safety and environmental awareness, people also put forward higher requirements on gas sensors, and the traditional large-scale gas chromatography is not only expensive in cost but also unsuitable for field scenes, so that the light, fast and low-cost sensor becomes a new requirement. Compared to other gas sensitive materials, metal Oxide Semiconductor (MOS) sensors are distinguished by their portability, ease of integration, low cost and simple preparation methods, among many gas sensitive materials, commonly used MOS gas sensitive materials are classified as n-type and p-type materials, including ZnO, snO 2、Fe2O3、MoO3、CeO2, niO, cu 2 O, etc., whose wide bandgap makes them have a full spectrum of electronic properties (insulating + semiconductor), MOS properties are often greatly affected by material dimensions, especially on the nanoscale, materials exhibit unique properties due to nanoeffects, e.g., very significant changes in electrical properties, resulting in good gas sensitive materials, and nanoeffects make them more stable and fast-responding in high temperature or severe environments, of great importance in practical operation. The existing MOS-based resistive sensor still has some problems, because the response of the resistance change is derived from the oxidation-reduction reaction between the sensing material and the target gas to generate electrons, the response gas is not single, and many gases with similar oxidation-reduction properties and similar structures can respond to the same sensing material, so that the sensing material is difficult to distinguish the gases, and the sensing material is very plagued in identifying a single gas, which easily causes misjudgment of the sensor in practical application. With the wider application of the gas sensing material in various scenes, the performance requirements of people on the required material are improved, and the ethyl acetate sensor is taken as an example, the detection limit of the ethyl acetate sensing material reported in the prior art is at ppm level and the response value is almost less than 100, so that the ethyl acetate serving as a biomarker is not applicable in the scene of detecting the exhaled breath, and the ultra-low detection limit and the high-sensitivity response are critical for the application scene of the trace detection. Secondly, various different stress scenarios also place higher demands on the short-term reproducibility, long-term stability and resistance to environmental disturbances of the material.
Through the above analysis, the problems and defects existing in the prior art are as follows:
(1) The metal oxide semiconductor gas-sensitive material has poor selectivity to gas, generally shows a condition that a certain response exists for a plurality of gases in the same category, and is difficult to distinguish a plurality of similar gases.
(2) The metal oxide semiconductor gas-sensitive material has low sensitivity and low response value, and is not suitable for certain application scenes needing high precision and high sensitivity.
(3) Metal oxide semiconductor gas sensitive materials are generally poor in stability and difficult to recover to the most initial state of the material after multiple tests, resulting in performance degradation.
Therefore, it is of great importance to further develop gas-sensitive materials with high response and high sensitivity and with both stability and selectivity.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a bimetal oxide semiconductor gas-sensitive material, a preparation method and application thereof in ethyl acetate gas detection.
The invention adopts the following technical scheme:
A bimetal oxide semiconductor gas-sensitive material comprises two components of MOx and CeO 2, M is Fe, ni, mn, co, ti, cu or Zn, the two components are uniformly and tightly combined together in a mode of doping or forming heterojunction, and the mol ratio of MOx to CeO 2 is 1:1-10:1.
Preferably, the two components are uniformly and tightly combined by adding a binder to the precursor, and the two components of MOx and CeO 2 interact strongly, so that the sensing response value is enhanced by electron transmission during the reaction.
The invention also provides a preparation method of the bimetal oxide semiconductor gas-sensitive material, which comprises the following steps:
(1) Preparing a precursor: cerium nitrate hexahydrate, MOx corresponding nitrate and citric acid with certain molar ratio are dissolved in deionized water, the three solutions are mixed, fully stirred and mixed, evaporated to be colloid in a water bath at 50-99 ℃, then the colloid substance is transferred into an oven, foamed and dried at 60-180 ℃, and collected and ground by an agate mortar, so that a precursor of the composite material is obtained.
(2) Precursor annealing treatment: transferring the precursor powder into a muffle furnace, heating by a program of 6 ℃/min, annealing at 250-700 ℃ for 2-12 hours, and grinding and collecting again after annealing to obtain the Ce-M-O composite gas-sensitive material.
The comparative single component materials MOx and CeO 2 used can also be prepared by this method by directly calcining the corresponding nitrates in a muffle furnace.
Preferably, the molar ratio of cerium nitrate to MOx to nitrate in step (1) is 1:5-10:1; further preferably 1:1 to 10:1; most preferably 7:1.
Preferably, the citric acid solution in step (1) is a binder, and the molar ratio of the citric acid solution to the total amount of nitrate is 1:2-3:1, and more preferably 1:2-2:1; most preferably 1:1 to 2:1.
Preferably, in the stirring process in the step (1), the duration is more than 2 hours, so that the solution is uniformly mixed.
Preferably, the water bath evaporation process in the step (1) plays an important role in colloid formation, and the water bath temperature is preferably 60-90 ℃ for 3-8 hours; further preferably, the hydrothermal temperature is 65-85 ℃ and the time is 4-6 hours, and the sample is transferred and dried after being sticky.
Preferably, in the drying process in step (1), the colloidal substance is transferred to an oven, and foamed and dried at 60-180 ℃, the drying temperature is critical to the process of foaming and forming the colloid, the foaming is incomplete due to the fact that the temperature is too low, the bonding degree of the two-component oxide is affected, the sample is directly burnt due to the fact that the temperature is too high, and the drying temperature is further preferably 80-160 ℃, and most preferably 90-130 ℃.
Preferably, the temperature transferred to the oven in step (1) cannot be lower than the water bath temperature, typically 30 ℃ higher than the water bath temperature is optimal, exhibiting optimal foaming drying effect.
Preferably, in step (2), the precursor powder is transferred to a muffle furnace, heated at a temperature programmed of 6 ℃/min, annealed at 250-700 ℃ for 2-12 hours, more preferably heated at a temperature programmed of 6 ℃/min, annealed at 350-600 ℃ for 3-10 hours, most preferably heated at a temperature programmed of 6 ℃/min, and annealed at 400-550 ℃ for 4-8 hours.
Preferably, the products obtained in the step (1) and the step (2) are required to be ground into fine powder, the grinding of the products in the step (1) is beneficial to the more thorough annealing process, and the grinding of the products in the step (2) is beneficial to the collection and manufacturing of the sensor chip.
Another object of the present invention is to provide a gas-sensitive material for ethyl acetate gas detection, which is a bimetal oxide formed by compounding MOx and cerium oxide (CeO 2), wherein the two components are uniformly and tightly combined together by adding a binder into a precursor, and two combination modes including doping and heterojunction are included. The two components have strong interaction due to the in-situ synthesis process of the composite material, and in the process of dynamically detecting the target gas, the electron transmission capacity is exponentially increased due to oxidation-reduction reaction, so that the sensing performance is greatly improved.
The composite gas-sensitive material provided by the invention shows a super-strong response value (Ra/Rg) with a value up to hundred thousand and a recovery time close to three seconds in an experiment of dynamically detecting ethyl acetate gas, the response value exceeds that of almost all the existing reported chemical resistance type gas sensors, and the composite gas-sensitive material has a wide application prospect in the gas sensing field.
In combination with the technical scheme and the technical problems to be solved, the technical scheme to be protected has the following advantages and positive effects:
In order to solve the problem that the response value of the traditional sensor is not high, and the static gas distribution experiment is difficult to apply to the actual scene, the Ce-M-O bimetallic oxide gas-sensitive material is prepared by a sol-gel method, and after the material is compounded, the surface of the material has more surface oxygen vacancies, so that the formation of surface active oxygen is facilitated; and CeO 2 and MO X are tightly combined, the interaction is obvious, the electron transmission capacity is enhanced in the reaction process, the superstrong response to target gas detection is shown, the sensing accuracy degree of the sensor is greatly improved, a good foundation is laid for developing a novel metal oxide semiconductor, and a new possibility is provided for developing a high-precision integrated sensor.
As inventive supplementary evidence of the claims of the present invention, the following important aspects are also presented:
(1) The expected benefits after the technical scheme of the invention is that: the sensing material is low in cost, easy to synthesize and low in cost, is suitable for mass production, can be used for manufacturing an integrated sensing micro system by combining an MEMS (micro electro mechanical system) process with an integrated circuit, and provides a foundation and possibility for development of portable, rapid and small novel gas sensing equipment.
(2) The technical scheme of the invention fills the technical blank in the domestic and foreign industries: by date of the present invention, under dynamic gas distribution conditions, a composite metal oxide gas sensing material for detecting ethyl acetate with ultra-strong gas-sensitive response (200 ppm, ra/Rg. Apprxeq.300000) has not been reported. The technical scheme provided by the invention realizes the preparation of the super-strong gas-sensitive catalyst, has good stability, and can be used for practical detection.
(3) The technical scheme of the invention solves the technical problems that people are always desirous of solving but are not successful all the time: the metal oxide semiconductor gas-sensitive material is always limited by the problems of low response value, poor repeated utilization rate and the like, the gas-sensitive response of the ultrahigh response value is realized, the accuracy rate in detection is greatly improved, and the characteristics of quick recovery and good stability are realized.
Drawings
FIG. 1 is an XRD pattern (XRD is an abbreviation for X-ray diffraction) of a Fe-Ce-O composite gas sensitive material synthesized in example 1 of the present invention, wherein subscripts of Fe element and Ce element represent molar ratios of different components.
FIG. 2 is a microscopic morphology (TEM image, TEM is an abbreviation of Transmission Electron Microscope, i.e., transmission electron microscope) of the Fe-Ce-O composite gas sensitive material synthesized in example 1 of the present invention.
FIG. 3 is a microscopic morphology chart (SEM image, SEM is an abbreviation of Scanning Electron Microscope, scanning electron microscope) of the Fe-Ce-O composite gas sensitive material synthesized in example 1 of the present invention.
FIG. 4 is a graph showing a single response of the Fe-Ce-O composite gas sensitive material synthesized in example 1 of the present invention to 200ppm of ethyl acetate gas.
FIG. 5 is a graph showing the response of the Fe-Ce-O composite gas sensitive material synthesized in example 1 of the present invention to the concentration gradient of ethyl acetate gas at 10ppb to 200 ppm.
FIG. 6 is a graph showing the long-term stability response of the Fe-Ce-O composite gas-sensitive material synthesized in example 1 of the present invention when detecting 200ppm ethyl acetate gas (tested once every two days for 16 days).
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In order to fully understand how the invention may be embodied by those skilled in the art, this section is an illustrative embodiment in which the claims are presented for purposes of illustration.
Example 1.
Preparing a Fe-Ce-O precursor: the molar ratio of the raw materials is ferric nitrate: cerium nitrate: citric acid = 7:1:12, adding 10g in total into 30ml deionized water after mixing, stirring for 2.5 hours to fully and uniformly mix, placing a beaker filled with the uniformly mixed solution into a water bath kettle, evaporating for 5 hours at 80 ℃, removing a large amount of water to enable the solution in the beaker to be sticky and gelatinous, transferring the beaker into a 110 ℃ oven to foam and dry for 12 hours, collecting the obtained product, and grinding the product into fine powder by an agate mortar.
Preparation of Fe-Ce-O: transferring the precursor product into a muffle furnace, continuously heating to 500 ℃ at a speed of 6 ℃/min, annealing for 5 hours, naturally cooling, collecting the product, and grinding with agate to obtain the Fe-Ce-O composite gas-sensitive material. The prepared materials were subjected to simple characterization, as shown in figures 1,2 and 3, which are XRD, SEM and TEM images, respectively.
Performance test of gas sensitive material: and (3) dissolving 0.015g of the synthesized composite gas-sensitive material in 400uL of deionized water, placing a sample in an ultrasonic machine for ultrasonic treatment for 5min to uniformly disperse the sample in water, uniformly coating 5uL of dispersed sample solution on a resistance type sensing sheet by using a pipette, and coating a layer of composite gas-sensitive material on the surface of a sensing sheet after the sensing sheet is naturally dried, wherein the sensing sheet is coated on the surface of the sensing sheet by using two interdigitated gold (Au) electrodes which are lined on the surface of a silicon dioxide (SiO 2) substrate. And placing the sensing sheet on a program temperature control heating table, heating to 350 ℃ and connecting a resistance testing machine, and sequentially introducing air, 200ppm of ethyl acetate gas and air at a rate of 3L/min to obtain a response value change curve. The gas-sensitive performance is shown in fig. 4, 5 and 6, the material shows good sensing performance for ethyl acetate gas, and the response value for 200ppm ethyl acetate reaches more than 300000, and the material has response time of 63S and ultra-fast recovery time of less than 5S as seen in fig. 4; it can be found from fig. 5 that the minimum detection limit can reach 10ppb, the response value of 4.8 can be reached even at the minimum detection limit, and the response value in the concentration range of 10ppb to 200ppm has a good linear gradient; the long term stability of fig. 6 also shows that the material has good stability, providing a basis for practical use.
Example 2.
Preparing a Ni-Ce-O precursor: the molar ratio of the raw materials is nickel nitrate: cerium nitrate: citric acid = 7:1:12, adding 10g in total into 30ml deionized water after mixing, stirring for 2.5 hours to fully and uniformly mix, placing a beaker filled with the uniformly mixed solution into a water bath kettle, evaporating for 5 hours at 80 ℃, removing a large amount of water to enable the solution in the beaker to be sticky and gelatinous, transferring the beaker into a 110 ℃ oven to foam and dry for 12 hours, collecting the obtained product, and grinding the product into fine powder by an agate mortar.
Preparation of Ni-Ce-O: transferring the precursor product into a muffle furnace, continuously heating to 500 ℃ at a speed of 6 ℃/min, annealing for 5 hours, naturally cooling, collecting the product, and grinding by agate to obtain the Ni-Ce-O composite gas-sensitive material.
Performance test of gas sensitive material: and (3) dissolving 0.015g of the synthesized composite gas-sensitive material in 400ul of deionized water, placing a sample in an ultrasonic machine for ultrasonic treatment for 5min to uniformly disperse the sample in ionized water, uniformly coating 5ul of dispersed sample solution on a resistance type sensing sheet by using a pipette, and coating a layer of composite gas-sensitive material on the surface of a sensing sheet after the sensing sheet is naturally dried, wherein the surface of a silicon dioxide (SiO 2) substrate is lined with two interdigital gold (Au) electrodes. And placing the sensing sheet on a program temperature control heating table, heating to 350 ℃ and connecting a resistance testing machine, and sequentially introducing air, 200ppm of ethyl acetate gas and air at a rate of 3L/min to obtain a response value change curve. The results show that the material has a response value of 6550, a response time of 139s, a recovery time of 87s for 200ppm ethyl acetate, and a slightly lower sensing performance than the Fe-Ce-O material in example 1.
Example 3.
Preparation of Mn-Ce-O precursor: the molar ratio of the raw materials is that manganese nitrate: cerium nitrate: citric acid = 7:1:12, adding 10g in total into 30ml deionized water after mixing, stirring for 2.5 hours to fully and uniformly mix, placing a beaker filled with the uniformly mixed solution into a water bath kettle, evaporating for 5 hours at 80 ℃, removing a large amount of water to enable the solution in the beaker to be sticky and gelatinous, transferring the beaker into a 110 ℃ oven to foam and dry for 12 hours, collecting the obtained product, and grinding the product into fine powder by an agate mortar.
Preparation of Mn-Ce-O: transferring the precursor product into a muffle furnace, continuously heating to 500 ℃ at a speed of 6 ℃/min, annealing for 5 hours, naturally cooling, collecting the product, and grinding with agate to obtain the Mn-Ce-O composite gas-sensitive material.
Performance test of gas sensitive material: and (3) dissolving 0.015g of the synthesized composite gas-sensitive material in 400ul of deionized water, placing a sample in an ultrasonic machine for ultrasonic treatment for 5min to uniformly disperse the sample in water, uniformly coating 5ul of dispersed sample solution on a resistance type sensing sheet by using a pipette, and coating a layer of composite gas-sensitive material on the surface of a sensing sheet after the sensing sheet is naturally dried, wherein the sensing sheet is coated on the surface of the sensing sheet by using two interdigitated gold (Au) electrodes which are lined on the surface of a silicon dioxide (SiO 2) substrate. And placing the sensing sheet on a program temperature control heating table, heating to 350 ℃ and connecting a resistance testing machine, and sequentially introducing air, 200ppm of ethyl acetate gas and air at a rate of 3L/min to obtain a response value change curve. The results show that the material has a response value of 1870 for 200ppm ethyl acetate, a response time of 215s, a recovery time of 110s, and a slightly lower sensing performance than the Fe-Ce-O material of example 1.
Example 4.
Preparation of Co-Ce-O precursor: the molar ratio of the raw materials is cobalt nitrate: cerium nitrate: citric acid = 7:1:12, adding 10g in total into 30ml deionized water after mixing, stirring for 2.5 hours to fully and uniformly mix, placing a beaker filled with the uniformly mixed solution into a water bath kettle, evaporating for 5 hours at 80 ℃, removing a large amount of water to enable the solution in the beaker to be sticky and gelatinous, transferring the beaker into a 110 ℃ oven to foam and dry for 12 hours, collecting the obtained product, and grinding the product into fine powder by an agate mortar.
Preparation of Co-Ce-O: transferring the precursor product into a muffle furnace, continuously heating to 500 ℃ at a speed of 6 ℃/min, annealing for 5 hours, naturally cooling, collecting the product, and grinding by agate to obtain the Co-Ce-O composite gas-sensitive material.
Performance test of gas sensitive material: and (3) dissolving 0.015g of the synthesized composite gas-sensitive material in 400ul of deionized water, placing a sample in an ultrasonic machine for ultrasonic treatment for 5min to uniformly disperse the sample in water, uniformly coating 5ul of dispersed sample solution on a resistance type sensing sheet by using a pipette, and coating a layer of composite gas-sensitive material on the surface of a sensing sheet after the sensing sheet is naturally dried, wherein the sensing sheet is coated on the surface of the sensing sheet by using two interdigitated gold (Au) electrodes which are lined on the surface of a silicon dioxide (SiO 2) substrate. And placing the sensing sheet on a program temperature control heating table, heating to 350 ℃ and connecting a resistance testing machine, and sequentially introducing air, 200ppm of ethyl acetate gas and air at a rate of 3L/min to obtain a response value change curve. The results show that the material has a response value of 3340, a response time of 177s, a recovery time of 81s for 200ppm ethyl acetate, and a slightly lower sensing performance than the Fe-Ce-O material of example 1.
Example 5.
Preparing a Ti-Ce-O precursor: the molar ratio of the raw materials is that: cerium nitrate: citric acid = 7:1:12, adding 10g in total into 30ml deionized water after mixing, stirring for 2.5 hours to fully and uniformly mix, placing a beaker filled with the uniformly mixed solution into a water bath kettle, evaporating for 5 hours at 80 ℃, removing a large amount of water to enable the solution in the beaker to be sticky and gelatinous, transferring the beaker into a 110 ℃ oven to foam and dry for 12 hours, collecting the obtained product, and grinding the product into fine powder by an agate mortar.
Preparation of Ti-Ce-O: transferring the precursor product into a muffle furnace, continuously heating to 500 ℃ at a speed of 6 ℃/min, annealing for 5 hours, naturally cooling, collecting the product, and grinding with agate to obtain the Ti-Ce-O composite gas-sensitive material.
Performance test of gas sensitive material: and (3) dissolving 0.015g of the synthesized composite gas-sensitive material in 400ul of deionized water, placing a sample in an ultrasonic machine for ultrasonic treatment for 5min to uniformly disperse the sample in water, uniformly coating 5ul of dispersed sample solution on a resistance type sensing sheet by using a pipette, and coating a layer of composite gas-sensitive material on the surface of a sensing sheet after the sensing sheet is naturally dried, wherein the sensing sheet is coated on the surface of the sensing sheet by using two interdigitated gold (Au) electrodes which are lined on the surface of a silicon dioxide (SiO 2) substrate. And placing the sensing sheet on a program temperature control heating table, heating to 350 ℃ and connecting a resistance testing machine, and sequentially introducing air, 200ppm of ethyl acetate gas and air at a rate of 3L/min to obtain a response value change curve. The results show that the material has a response value of 3730 for 200ppm ethyl acetate, a response time of 149, a recovery time of 96s and a slightly lower sensing performance than the Fe-Ce-O material of example 1.
Example 6.
Preparing a Cu-Ce-O precursor: the raw material molar ratio is copper nitrate: cerium nitrate: citric acid = 7:1:12, adding 10g in total into 30ml deionized water after mixing, stirring for 2.5 hours to fully and uniformly mix, placing a beaker filled with the uniformly mixed solution into a water bath kettle, evaporating for 5 hours at 80 ℃, removing a large amount of water to enable the solution in the beaker to be sticky and gelatinous, transferring the beaker into a 110 ℃ oven to foam and dry for 12 hours, collecting the obtained product, and grinding the product into fine powder by an agate mortar.
Preparation of Cu-Ce-O: transferring the precursor product into a muffle furnace, continuously heating to 500 ℃ at a speed of 6 ℃/min, annealing for 5 hours, naturally cooling, collecting the product, and grinding by agate to obtain the Cu-Ce-O composite gas-sensitive material.
Performance test of gas sensitive material: and (3) dissolving 0.015g of the synthesized composite gas-sensitive material in 400ul of deionized water, placing a sample in an ultrasonic machine for ultrasonic treatment for 5min to uniformly disperse the sample in water, uniformly coating 5ul of dispersed sample solution on a resistance type sensing sheet by using a pipette, and coating a layer of composite gas-sensitive material on the surface of a sensing sheet after the sensing sheet is naturally dried, wherein the sensing sheet is coated on the surface of the sensing sheet by using two interdigitated gold (Au) electrodes which are lined on the surface of a silicon dioxide (SiO 2) substrate. And placing the sensing sheet on a program temperature control heating table, heating to 350 ℃ and connecting a resistance testing machine, and sequentially introducing air, 200ppm of ethyl acetate gas and air at a rate of 3L/min to obtain a response value change curve. The results show that the material has a response value of 12540 for 200ppm ethyl acetate, a response time of 99s, a recovery time of about 36s, and a slightly lower sensing performance than the Fe-Ce-O material of example 1.
Example 7.
Preparing a Zn-Ce-O precursor: the molar ratio of the raw materials is as follows: cerium nitrate: citric acid = 7:1:12, adding 10g in total into 30ml deionized water after mixing, stirring for 2.5 hours to fully and uniformly mix, placing a beaker filled with the uniformly mixed solution into a water bath kettle, evaporating for 5 hours at 80 ℃, removing a large amount of water to enable the solution in the beaker to be sticky and gelatinous, transferring the beaker into a 110 ℃ oven to foam and dry for 12 hours, collecting the obtained product, and grinding the product into fine powder by an agate mortar.
Preparation of Zn-Ce-O: transferring the precursor product into a muffle furnace, continuously heating to 500 ℃ at a speed of 6 ℃ per minute, annealing for 5 hours, naturally cooling, collecting the product, and grinding with agate to obtain the Zn-Ce-O composite gas-sensitive material.
Performance test of gas sensitive material: and (3) dissolving 0.015g of the synthesized composite gas-sensitive material in 400ul of deionized water, placing a sample in an ultrasonic machine for ultrasonic treatment for 5min to uniformly disperse the sample in water, uniformly coating 5ul of dispersed sample solution on a resistance type sensing sheet by using a pipette, and coating a layer of composite gas-sensitive material on the surface of a sensing sheet after the sensing sheet is naturally dried, wherein the sensing sheet is coated on the surface of the sensing sheet by using two interdigitated gold (Au) electrodes which are lined on the surface of a silicon dioxide (SiO 2) substrate. And placing the sensing sheet on a program temperature control heating table, heating to 350 ℃ and connecting a resistance testing machine, and sequentially introducing air, 200ppm of ethyl acetate gas and air at a rate of 3L/min to obtain a response value change curve. The results show that the material has a response value of 8120, a response time of 112s, a recovery time of 73s for 200ppm ethyl acetate, and a slightly lower sensing performance than the Fe-Ce-O material in example 1.
Claims (7)
1. The application of the bimetal oxide semiconductor gas-sensitive material is characterized in that the bimetal oxide semiconductor gas-sensitive material is applied to detection of ethyl acetate gas and comprises two components MOx and CeO 2, M is Fe, ni, mn, co, ti or Zn, the two components are uniformly and tightly combined together in a doping or heterojunction forming mode, and the mol ratio of MOx to CeO 2 is 1:1-10:1;
the preparation method of the bimetal oxide semiconductor gas-sensitive material comprises the following steps:
(1) Precursor preparation: dissolving cerium nitrate hexahydrate, MOx corresponding nitrate and citric acid in a certain molar ratio in deionized water, fully stirring and mixing, evaporating to be colloid in a water bath at 50-100 ℃, transferring colloid substances into an oven, foaming at 60-180 ℃, and drying to obtain a precursor of the composite material;
(2) Annealing: transferring the precursor powder into a muffle furnace, and annealing at 250-700 ℃ for 2-12 hours to obtain the bimetal oxide semiconductor gas-sensitive material.
2. The use of a bi-metal oxide semiconductor gas-sensitive material according to claim 1, wherein the two components are uniformly and tightly combined by adding a binder to the precursor, the two components of MOx and CeO 2 interact strongly, and the sensing response is enhanced by electron transport during the reaction.
3. The use of a bimetallic oxide semiconductor gas sensitive material as claimed in claim 1, wherein the amount of citric acid used in step (1) is 1-2 times the total amount of nitrate.
4. The use of a bi-metal oxide semiconductor gas sensitive material according to claim 1, wherein the stirring and mixing process in step (1) is continued for more than 2 hours, so that the two components are sufficiently and homogeneously mixed.
5. The use of a bimetallic oxide semiconductor gas sensitive material as claimed in claim 1, wherein the water bath temperature in step (1) is maintained above 60 ℃.
6. Use of a bi-metal oxide semiconductor gas sensitive material according to claim 1, wherein the temperature transferred to the oven in step (1) is not lower than the water bath temperature.
7. The use of a bi-metal oxide semiconductor gas sensitive material according to claim 1, wherein in step (2) the precursor powder is transferred to a muffle furnace, heated at a 6 ℃/min program and annealed at 250-700 ℃ for 2-12 hours.
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