CN111484084A - Acetone gas-sensitive material and preparation method thereof - Google Patents
Acetone gas-sensitive material and preparation method thereof Download PDFInfo
- Publication number
- CN111484084A CN111484084A CN202010254753.0A CN202010254753A CN111484084A CN 111484084 A CN111484084 A CN 111484084A CN 202010254753 A CN202010254753 A CN 202010254753A CN 111484084 A CN111484084 A CN 111484084A
- Authority
- CN
- China
- Prior art keywords
- gas
- sensitive material
- acetone
- sensitive
- gas sensitive
- 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.)
- Pending
Links
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 abstract description 40
- 229910001308 Zinc ferrite Inorganic materials 0.000 abstract description 12
- 229910000859 α-Fe Inorganic materials 0.000 abstract description 9
- 229910052596 spinel Inorganic materials 0.000 abstract description 7
- 239000011029 spinel Substances 0.000 abstract description 7
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 229910016516 CuFe2O4 Inorganic materials 0.000 abstract description 4
- 150000001768 cations Chemical class 0.000 abstract description 4
- 238000001514 detection method Methods 0.000 abstract description 4
- 206010012601 diabetes mellitus Diseases 0.000 abstract description 4
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 abstract description 4
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 2
- 238000011896 sensitive detection Methods 0.000 abstract 2
- 230000000241 respiratory effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 66
- 239000010949 copper Substances 0.000 description 36
- 239000003960 organic solvent Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 6
- -1 zinc-substituted copper Chemical class 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 239000003570 air Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003745 diagnosis Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 206010010071 Coma Diseases 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910002535 CuZn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 208000003443 Unconsciousness Diseases 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- DXKGMXNZSJMWAF-UHFFFAOYSA-N copper;oxido(oxo)iron Chemical compound [Cu+2].[O-][Fe]=O.[O-][Fe]=O DXKGMXNZSJMWAF-UHFFFAOYSA-N 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 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
- 239000000696 magnetic material Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0063—Mixed oxides or hydroxides containing zinc
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- 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
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 discloses an acetone gas-sensitive material and a preparation method thereof. The material has the following structure: cuxZn1‑xFe2O4Wherein x =0.25-1, the copper-zinc mixed ferrite hollow sphere acetone gas-sensitive material is prepared by adopting a one-step solvothermal method and high-temperature heat treatment, and the Cu ions are successfully used for gradually replacing Zn ions to obtain the novel spinel structure gas-sensitive material. The preparation method is simple, efficient and safe, the cost is low, the practical application value is high, the gas-sensitive material realizes cation redistribution, has a hollow structure, and compared with a zinc ferrite hollow sphere, the mixed spinel structure gas-sensitive material and CuFe2O4Hollow spheres at lower temperatures (125)oC) The gas-sensitive performance of the gas-sensitive detection reagent for low-concentration acetone is more excellent, the gas-sensitive performance comprises high sensitivity, quick response and excellent selectivity, and the gas-sensitive detection reagent shows wide application prospect in the field of quick nondestructive detection of the respiratory gas (acetone) of the diabetic patient.
Description
Technical Field
The invention relates to the technical field of gas-sensitive materials, in particular to a mixed ferrite acetone gas-sensitive material, a preparation method and gas-sensitive application thereof.
Background
Over the past few decades, Metal Oxide Semiconductors (MOS) have received much attention due to their excellent gas sensing properties, e.g., α -Fe2O3，SnO2，In2O3，WO3ZnO, NiO, etc., have been widely studied and applied to gas sensors due to their small size, low cost, and low power consumption. In recent years, spinel oxide (AB)2O4) It has attracted considerable attention due to its excellent gas sensitivity, and the response to certain gases is generally higher than that of a single metal oxide. As a typical spinel ferrite (AFe)2O4(ii) a A = Mn, Zn, Co, Ni, Cd), zinc ferrite (ZnFe)2O4) The semiconductor has a narrow forbidden band width (1.9 eV), has various excellent characteristics, and is of great interest in the field of gas sensing. In recent years, ZnFe2O4The preparation method of the gas-sensitive material mainly comprises a coprecipitation method, a sol-gel method, a template method and the like, and ZnFe with different morphologies can be prepared2O4Nanomaterials, such as nanorods and hollow spheres, are mostly used to detect reducing gases.
Many efforts have been made to increase ZnFe2O4Gas-sensitive property of the nano material. By regulating ZnFe2O4Nanomaterials achieve different morphologies, such as nanoparticles, nanorods, nanotubes, etc. However, most are based on ZnFe2O4The gas sensor is still at 175-300-oC, which severely limits their practical applications. Therefore, it would be of great significance to reduce the operating temperature of the gas sensor. Of course, several methods exist to reduce the operating temperature and improve the gas sensing properties of MOS nanomaterials, including surface functionalization, noble metal doping and functional material compositing. Meanwhile, the gas-sensitive performance of the nano material can be effectively improved and enhanced by doping the metal ions.
Acetone, as a volatile organic compound, has certain dangerousness, the boiling point of the acetone is only 56.5 ℃, the acetone is volatile, has active chemical properties and is extremely flammable, and even can form explosive substances to generate explosion when being mixed with air. In addition, it has certain irritation and toxicity, and can pose a threat to human health if the article is contacted for a long time. When the concentration of the acetone is 500-1000 ppm, the nose, the throat and the eyes can be stimulated, 1000 ppm can cause headache and dizziness, 2000-10000 ppm can cause drunk feeling, nausea and vomiting, and high concentration can cause unconsciousness, coma and death, so that the detection and monitoring of the concentration of the acetone in the ambient air have important significance. In addition, acetone is also a fat metabolite in human bodies, and the concentration of acetone in the exhaled air of healthy people is lower than 0.9 ppm. According to the report of clinical medicine and related literature, the content of acetone in the gas exhaled by a diabetic patient is higher than that of normal people and is higher than 1.8 ppm, so that the quantitative analysis of low-concentration acetone is helpful for the nondestructive diagnosis of diabetes.
At present, few research reports about Cu-Zn mixed ferrite acetone gas-sensitive materials are reported. Patent CN 109115843A discloses a method for synthesizing Cu-doped ZnFe with spinel structure by hydrothermal method and heat treatment process without using any surfactant2O4Method for nano particles (Cu-ZFNPS) and research on H of Cu-ZFNPS gas sensor2S gas-sensitive property. The document "Materials Chemistry and Physics" 212 (2018) pp. 292-2O4Nanoparticles (Zn)1-xCuxFe2O4) And the structural characteristics and the optical characteristics of the nano material are researched. In the document "Journal of Magnetic and Magnetic Materials" 419 (2016) pp. 407-411 ", zinc-substituted copper ferrite nanopowder Cu was synthesized by sol-gel auto-combustion1-xZnxFe2O4(x is more than or equal to 0 and less than or equal to 1.0), and the structural characteristics and the electromagnetic properties of the material are researched. Therefore, the preparation method of the copper-zinc ferrite gas-sensitive material is still under study and development.
Disclosure of Invention
In order to overcome the above ZnFe2O4The sensitivity of nano particles and the like to low-concentration acetone gas is low, and the working temperature and the detection limit are highThe invention aims to provide an acetone gas-sensitive material and a preparation method thereof. The material has the advantages of low working temperature, high sensitivity, excellent selectivity, low detection limit and the like for acetone gas.
The purpose of the invention can be realized by the following technical scheme: an acetone gas sensitive material having the structure: cuxZn1-xFe2O4(x = 0.25-1) 。
Preferably, the material is a hollow sphere structure having an average diameter of about 1 μm.
Preferably, x is preferably 0.25, 0.5, 0.75 and 1, more preferably 1.
Preferably, the material has low acetone gas sensitivity, wherein the low concentration is not more than 0.8 ppm.
The preparation method of the acetone gas-sensitive material comprises the following steps:
(1) mixing Cu (CH)3COO)2·H2O，Zn(CH3COO)2·2H2O and Fe (NO)3)3·9H2O is represented by the molar mass ratio of x: 1-x: 1 adding the mixture into a mixed solvent while stirring;
(2) transferring the solution obtained in the step (1) into a high-pressure reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 12 h, naturally cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain a precursor material;
(3) and (3) placing the precursor material obtained in the step (2) in air, carrying out heat treatment for 2 h at 400 ℃, and then naturally cooling to room temperature to obtain the gas sensitive material.
Preferably, the mixed solvent is prepared by mixing isopropanol and glycerol in a volume ratio of 30: 8.
Preferably, in the step (2), drying refers to drying at 60 ℃ for 12 h.
Preferably, in the step (3), the heating rate is 4 ℃/min.
The invention also provides a gas sensor, which is prepared from the gas sensitive material.
Specifically, the gas sensitive material is added into deionized water and ground to form paste, then the paste is uniformly coated on the outer surface of a gas sensor substrate and a gold electrode is completely covered, the paste is dried for 30min at room temperature to form a gas sensitive coating, and then the gas sensitive coating is moved to an aging table and is kept stand for 24 h at 120 ℃, and finally the gas sensitive element is obtained.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention prepares Cu by combining simple one-step synthesis method and high-temperature heat treatment methodxZn1-xFe2O4Hollow sphere gas-sensitive material, CuxZn1-xFe2O4The average diameter of the hollow spheres is about 1 mu m, and Cu successfully replaces Zn and induces the redistribution of cations to obtain the mixed spinel ferrite hollow sphere material. The application is to use CuxZn1-xFe2O4Low-temp gas sensor with gas-sensitive layer and preparing pure ZnFe2O4Hollow spheres as a comparison, show CuxZn1-xFe2O4The acetone gas sensor has the advantages of lower working temperature, higher sensitivity, lower energy consumption, better selectivity and the like.
(2) The invention provides a hollow structure CuxZn1-xFe2O4Has good appearance and structure, improves the electronic characteristics of the material by introducing equivalent copper ions with different contents, effectively enhances the gas-sensitive performance, has simple, convenient and safe preparation method, low cost and high practicability, and fills the problem of one-step Cu synthesis by using a solvothermal methodxZn1-xFe2O4Blank of three-dimensional hollow sphere related studies. The series of sensors have good gas-sensitive performance to acetone gas at 125 ℃, have high selectivity and stability to acetone, have a response value of up to 2.42 to 0.8ppm acetone, can be applied to the safety monitoring of industrial production environment, and are a preferred new material for the nondestructive diagnosis of diabetes.
Drawings
FIG. 1 is CuxZn1-xFe2O4(x =0.25, 0.5, 0.75) SEM image of composite material: (a) cu0.25Zn0.75Fe2O4, (b) Cu0.5Zn0.5Fe2O4And (c) Cu0.75Zn0.25Fe2O4。
FIG. 2 shows Cu prepared in example 30.75Zn0.25Fe2O4TEM image of (a).
FIG. 3 is ZnFe2O4And CuxZn1-xFe2O4Response of gas sensor to 1 ppm acetone-operating temperature curve.
FIG. 4 is CuxZn1-xFe2O4(x =0, 0.75, 1) dynamic response curve of gas sensor to 0.8ppm acetone.
Detailed Description
The present invention will be further described with reference to the following detailed description and accompanying drawings, and it is to be understood that the present invention includes, but is not limited to, the embodiments described herein.
The invention provides a process for preparing Cu2+By substitution of equivalent ions for Zn2+Preparation of CuxZn1-xFerrite hollow sphere, i.e. CuxZn1- xFe2O4(x = 0.25-1) method for producing gas-sensitive material, Cu2+Successfully realizes the equivalent replacement of Zn positioned in tetrahedral gaps2 +And then enters into crystal lattice to induce the redistribution of cations to form a mixed ferrite gas-sensitive material, and the inverse spinel type CuFe is successfully prepared2O4Hollow sphere gas sensitive material.
The preparation method of the gas-sensitive material provided by the invention comprises the following steps:
(1) and (4) preparing an organic solvent. At normal temperature, isopropanol (30 ml) and glycerol (8 ml) were poured into a 250 ml beaker in sequence and magnetically stirred for a period of time to obtain a homogeneous organic solvent system.
(2) And (4) preparing a mixed solution. At normal temperature, adding Cu (CH)3COO)2·H2O，Zn(CH3COO)2·2H2O and Fe (NO)3)3·9H2O represents that the molar mass ratio is x mmol: 1-x mmol: 1 mmol (x =0.25,0.5, 0.75 and 1) adding into the organic solvent system in the step (1) while stirring, and magnetically stirring for a certain time to obtain a uniform solution.
(3) And (4) carrying out autoclave reaction. And (3) transferring the uniform solution obtained in the step (2) into a 100 ml stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, standing at 180 ℃ for 12 h, naturally cooling to room temperature after the reaction is finished, centrifuging, washing, and drying the product at 60 ℃ for 12 h to obtain a precursor material.
(4) And (5) calcining the precursor. Carrying out high-temperature air atmosphere heat treatment on the precursor material obtained in the step (3), wherein the heating rate is 4 ℃/min, the temperature is kept for 2 h at 400 ℃, and then, naturally cooling to room temperature to obtain CuxZn1-xFe2O4(x =0.25, 0.5, 0.75, 1) hollow sphere gas sensitive material.
(5) The final product obtained was in turn: cu0.25Zn0.75Fe2O4，Cu0.5Zn0. 5Fe2O4，Cu0.75Zn0.25Fe2O4，CuFe2O4。
(6) Subjecting the hollow structure Cu obtained in the step (5)xZn1-xFe2O4Adding deionized water into the powder, grinding to form paste, uniformly coating the paste on the outer surface of a sensor substrate and completely covering a gold electrode, drying at room temperature for 30min to form a gas-sensitive coating, then moving to an aging table, standing at 120 ℃ for 24 h to finally obtain CuxZn1-xFe2O4A gas sensor.
The chemical raw materials required by the invention can be purchased from the market.
Example 1
At normal temperature, 8 ml of glycerol and 30 ml of isopropanol are mixed and stirred magnetically to obtain a uniform organic solvent. 0.125mmol of Cu (CH)3COO)2·H2O，0.375 mmol Zn(CH3COO)2·2H2O and 1 mmol Fe (NO)3)3·9H2And adding the O into the mixed solvent while stirring, and stirring for a certain time to obtain a uniform solution. Subsequently transferring itSealing the reaction product in a 100 ml stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, keeping the reaction product at 180 ℃ for 12 h, naturally cooling the reaction product to room temperature after the reaction is finished, centrifuging the reaction product, washing the reaction product, and drying the product at 60 ℃ for 12 h to obtain a precursor material. Finally, carrying out high-temperature heat treatment on the obtained precursor material at the temperature of 400 ℃, preserving the heat for 2 h at the heating rate of 4 ℃/min, and then naturally cooling to the room temperature to obtain the hollow structure Cu0.25Zn0.75Fe2O4A gas sensitive material. Adding deionized water into the powder, grinding to form paste, uniformly coating the paste on the outer surface of a sensor substrate, completely covering a gold electrode, drying at room temperature for 30min to form a gas-sensitive coating, then moving to an aging table, standing at 120 ℃ for 24 h to finally obtain Cu0.25Zn0.75Fe2O4The low-temperature gas-sensitive element, as shown in FIG. 3, not only reduces the optimal working temperature, but also has better gas-sensitive performance than pure ZnFe2O4。
Example 2
At normal temperature, 8 ml of glycerol and 30 ml of isopropanol are mixed and stirred magnetically to obtain a uniform organic solvent. Adding 0.25 mmol Cu (CH)3COO)2·H2O，0.25 mmol Zn(CH3COO)2·2H2O and 1 mmol Fe (NO)3)3·9H2And adding the O into the mixed solvent while stirring, and stirring for a certain time to obtain a uniform solution. And then transferring the precursor material into a 100 ml stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, keeping at 180 ℃ for 12 h, naturally cooling to room temperature after the reaction is finished, centrifuging, washing, and drying the product at 60 ℃ for 12 h to obtain a precursor material. Finally, carrying out high-temperature heat treatment on the obtained precursor material at the temperature of 400 ℃, preserving the heat for 2 h at the heating rate of 4 ℃/min, and then naturally cooling to the room temperature to obtain the hollow structure Cu0.5Zn0.5Fe2O4A gas sensitive material. Adding the powder into deionized water, grinding to form paste, uniformly coating the paste on the outer surface of the sensor substrate and completely covering the gold electrode, drying at room temperature for 30min to form a gas-sensitive coating, then moving to an aging table, and standing at 120 DEG C24 h, finally obtaining Cu0.5Zn0.5Fe2O4The low-temperature gas-sensitive element, as shown in FIG. 3, not only reduces the optimal working temperature, but also has better gas-sensitive performance than pure ZnFe2O4。
Example 3
At normal temperature, 8 ml of glycerol and 30 ml of isopropanol are mixed and stirred magnetically to obtain a uniform organic solvent. 0.375mmol of Cu (CH)3COO)2·H2O、0.125 mmol Zn(CH3COO)2·2H2O and 1 mmol Fe (NO)3)3·9H2And adding the O into the mixed solvent while stirring, and stirring for a certain time to obtain a uniform solution. And then transferring the precursor material into a 100 ml stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, keeping at 180 ℃ for 12 h, naturally cooling to room temperature after the reaction is finished, centrifuging, washing, and drying the product at 60 ℃ for 8 h to obtain a precursor material. Finally, carrying out high-temperature heat treatment on the obtained precursor material at the temperature of 400 ℃, preserving the heat for 2 h at the heating rate of 4 ℃/min, and then naturally cooling to room temperature to obtain Cu0.75Zn0.25Fe2O4Hollow sphere gas sensitive material. Adding the powder into deionized water, grinding to form paste, uniformly coating the paste on the outer surface of a sensor substrate, completely covering a gold electrode, drying at room temperature for 30min to form a gas-sensitive coating, transferring to an aging table, and carrying out heat treatment at 120 ℃ for 24 h to finally obtain Cu0.75Zn0.25Fe2O4Low temperature gas sensor, tested at 125oThe excellent gas-sensitive performance of the low-concentration acetone is shown under the condition C, and is shown in a figure 4. Cu2+Successfully substitute part of Zn2+Entering the crystal lattice and initiating cation redistribution in the CuZn ferrite crystal structure, when x =0.75, the corresponding structural formula can be represented as: [ Zn ]0.25Cu0.75-αFe1-β]A[CuαFeβ]BO4α =0-0.75 and β =0-1 in the structural formula, a and B refer to tetrahedral and octahedral gaps, respectively.
Example 4
At normal temperature, 8 ml of glycerol and 30 ml of isopropanol are mixed and stirred magnetically to obtain a uniform organic solvent. Adding 0.5 mmol Cu (CH)3COO)2·H2O and 1 mmol Fe (NO)3)3·9H2And adding the O into the mixed solvent while stirring, and stirring for a certain time to obtain a uniform solution. And then transferring the precursor material into a 100 ml stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, keeping at 180 ℃ for 12 h, naturally cooling to room temperature after the reaction is finished, centrifuging, washing, and drying the product at 60 ℃ for 8 h to obtain a precursor material. Finally, carrying out high-temperature heat treatment on the obtained precursor material at the temperature of 400 ℃, preserving the heat for 2 h at the heating rate of 4 ℃/min, and then naturally cooling to room temperature to obtain CuFe2O4Hollow sphere gas sensitive material. Adding the powder into deionized water, grinding to form paste, uniformly coating the paste on the outer surface of a sensor substrate, completely covering a gold electrode, drying at room temperature for 30min to form a gas-sensitive coating, transferring to an aging table, and carrying out heat treatment at 120 ℃ for 24 h to finally obtain CuFe2O4The low-temperature gas sensor, as shown in fig. 4, shows the optimal low-concentration acetone gas-sensing performance at the optimized temperature after being tested.
Claims (10)
1. An acetone gas sensitive material, characterized in that the material has the following structure: cuxZn1-xFe2O4Wherein x = 0.25-1.
2. The acetone gas sensitive material of claim 1, wherein the material is a hollow sphere structure having an average diameter of about 1 μm.
3. The acetone gas-sensitive material of claim 1, wherein x is 0.25, 0.5, 0.75 or 1, more preferably x is 1.
4. The acetone gas sensitive material of claim 1, wherein the acetone gas sensitive material has a low concentration acetone gas sensitive property, wherein the low concentration acetone gas sensitive property is not more than 0.8 ppm.
5. The method for preparing an acetone gas-sensitive material as claimed in any of claims 1 to 4, comprising the steps of:
(1) mixing Cu (CH)3COO)2·H2O，Zn(CH3COO)2·2H2O and Fe (NO)3)3·9H2O is represented by the molar mass ratio of x: 1-x: 1 adding the mixture into a mixed solvent while stirring;
(2) transferring the solution obtained in the step (1) into a high-pressure reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 12 h, naturally cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain a precursor material;
(3) and (3) placing the precursor material obtained in the step (2) in air, carrying out heat treatment for 2 h at 400 ℃, and then naturally cooling to room temperature to obtain the gas sensitive material.
6. The method of claim 5, wherein the mixed solvent is a mixture of isopropanol and glycerol in a volume ratio of 30: 8.
7. The method of claim 5, wherein in step (2), drying is performed at 60 ℃ for 12 hours.
8. The method according to claim 5, wherein in the step (3), the temperature increase rate is 4 ℃/min.
9. A gas sensor prepared from the gas sensitive material according to any one of claims 1 to 4.
10. The element of claim 9, wherein the gas sensitive material is added into deionized water and ground to form a paste, then the paste is uniformly coated on the outer surface of the gas sensor substrate and the gold electrode is completely covered, the gas sensitive coating is formed after drying for 30min at room temperature, and then the gas sensitive coating is moved to an aging table and is kept stand at 120 ℃ for 24 h to obtain the gas sensitive element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010254753.0A CN111484084A (en) | 2020-04-02 | 2020-04-02 | Acetone gas-sensitive material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010254753.0A CN111484084A (en) | 2020-04-02 | 2020-04-02 | Acetone gas-sensitive material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111484084A true CN111484084A (en) | 2020-08-04 |
Family
ID=71798114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010254753.0A Pending CN111484084A (en) | 2020-04-02 | 2020-04-02 | Acetone gas-sensitive material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111484084A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113353987A (en) * | 2021-07-16 | 2021-09-07 | 中国科学院兰州化学物理研究所 | Spinel type ferrite material based on rare earth element lanthanum or cerium doping |
| CN114797874A (en) * | 2022-05-31 | 2022-07-29 | 西安交通大学 | Spinel ferrite catalyst doped with metallic copper, preparation method and application |
| CN115321583A (en) * | 2022-05-05 | 2022-11-11 | 云南大学 | Acetone gas-sensitive Pt-In with low Pt loading 2 O 3 Preparation method and application of nanotube |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106684376A (en) * | 2016-12-28 | 2017-05-17 | 西北大学 | Method for preparing zinc ferrite nanosheet assembled hollow microsphere by utilizing hydrothermal and calcination methods, and application |
| CN108802116A (en) * | 2018-06-19 | 2018-11-13 | 扬州睿德石油机械有限公司 | A kind of preparation method of acetone gas sensitive material |
| CN109001264A (en) * | 2018-06-22 | 2018-12-14 | 吉林大学 | One kind being based on porous C uFe2O4The acetone gas sensor and preparation method thereof of microballoon sensitive material |
-
2020
- 2020-04-02 CN CN202010254753.0A patent/CN111484084A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106684376A (en) * | 2016-12-28 | 2017-05-17 | 西北大学 | Method for preparing zinc ferrite nanosheet assembled hollow microsphere by utilizing hydrothermal and calcination methods, and application |
| CN108802116A (en) * | 2018-06-19 | 2018-11-13 | 扬州睿德石油机械有限公司 | A kind of preparation method of acetone gas sensitive material |
| CN109001264A (en) * | 2018-06-22 | 2018-12-14 | 吉林大学 | One kind being based on porous C uFe2O4The acetone gas sensor and preparation method thereof of microballoon sensitive material |
Non-Patent Citations (1)
| Title |
|---|
| TAREQ MANZOOR等: "Facile synthesis of CuxZn1−xFe2O4 nanoparticles and their thermo‑physical properties evaluation", 《APPLIED PHYSICS A》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113353987A (en) * | 2021-07-16 | 2021-09-07 | 中国科学院兰州化学物理研究所 | Spinel type ferrite material based on rare earth element lanthanum or cerium doping |
| CN113353987B (en) * | 2021-07-16 | 2023-10-31 | 中国科学院兰州化学物理研究所 | Spinel type ferrite material doped with rare earth element lanthanum or cerium |
| CN115321583A (en) * | 2022-05-05 | 2022-11-11 | 云南大学 | Acetone gas-sensitive Pt-In with low Pt loading 2 O 3 Preparation method and application of nanotube |
| CN114797874A (en) * | 2022-05-31 | 2022-07-29 | 西安交通大学 | Spinel ferrite catalyst doped with metallic copper, preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wu et al. | Room temperature gas sensors based on Ce doped TiO2 nanocrystals for highly sensitive NH3 detection | |
| Lv et al. | Sb-doped three-dimensional ZnFe2O4 macroporous spheres for N-butanol chemiresistive gas sensors | |
| CN111484084A (en) | Acetone gas-sensitive material and preparation method thereof | |
| Yang et al. | Ultrafast response and recovery trimethylamine sensor based on α-Fe2O3 snowflake-like hierarchical architectures | |
| Wu et al. | VOCs gas sensor based on MOFs derived porous Au@ Cr2O3-In2O3 nanorods for breath analysis | |
| Zhang et al. | Facile synthesis of highly ethanol-sensitive SnO2 nanoparticles | |
| Sakthivel et al. | Self-templating hydrothermal synthesis of carbon-confined double-shelled Ni/NiO hollow microspheres for diphenylamine detection in fruit samples | |
| Zhang et al. | Preparation of Ce-doped SnO2 cuboids with enhanced 2-butanone sensing performance | |
| Guo et al. | Synthesis of the ZnFe2O4/ZnSnO3 nanocomposite and enhanced gas sensing performance to acetone | |
| Zhou et al. | High sensitivity and low detection limit of acetone sensor based on NiO/Zn2SnO4 pn heterojunction octahedrons | |
| Guo et al. | MOF-derived Co3O4 hierarchical porous structure for enhanced acetone sensing performance with high sensitivity and low detection limit | |
| Mishra et al. | A highly stable, selective, and high-performance VOC sensor using a SnS 2 nano-lotus structure | |
| Geng et al. | The self-assembly of octahedral CuxO and its triethylamine-sensing properties | |
| Zhang et al. | Improvement of gas sensing performance for tin dioxide sensor through construction of nanostructures | |
| Xing et al. | In-situ construction of carbon-doped ZnO hollow spheres for highly efficient dimethylamine detection | |
| Yuan et al. | Zeolitic imidazolate framework-derived n-ZnO/p-Co3O4 heterojunction by ion-etching method for superior CO toxic gas sensor | |
| Bi et al. | Synthesis of Ag-functionalized α-Fe2O3 nanocomposites for ppb-level triethylamine detection | |
| CN102012386A (en) | Preparation method of nitric oxide gas sensor element based on pseudodirected tungsten trioxide nano tape | |
| Zeng et al. | Hydrothermal synthesis of monodisperse α-Fe2O3 hollow microspheroids and their high gas-sensing properties | |
| Zhu et al. | ZnO/ZnSe heterojunction nanocomposites with oxygen vacancies for acetone sensing | |
| Liang et al. | Rapid synthesis of rhombohedral In2O3 nanoparticles via a microwave-assisted hydrothermal pathway and their application for conductometric ethanol sensing | |
| Zhang et al. | Ionic liquid-assisted synthesis of tungsten oxide nanoparticles with enhanced NO2 sensing properties at near room temperature | |
| Zhang et al. | Microwave-assisted synthesis of La/ZnO hollow spheres for trace-level H2S detection | |
| Zhang et al. | High sensitivity and surface mechanism of MOFs-derived metal oxide Co3O4-SnO2 hollow spheres to ethanol | |
| Xu et al. | Synthesis of ZnO/ZnCo2O4 hollow tube clusters by a template method for high-sensitive H2S sensor |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200804 |