CN110780037A - Micron-sized cobaltosic oxide/stannic oxide volatile organic compound sensing material and preparation method and application thereof - Google Patents
Micron-sized cobaltosic oxide/stannic oxide volatile organic compound sensing material and preparation method and application thereof Download PDFInfo
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- CN110780037A CN110780037A CN201911002879.2A CN201911002879A CN110780037A CN 110780037 A CN110780037 A CN 110780037A CN 201911002879 A CN201911002879 A CN 201911002879A CN 110780037 A CN110780037 A CN 110780037A
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- cobaltosic oxide
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 142
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 34
- 239000011540 sensing material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000002245 particle Substances 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000010457 zeolite Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000006073 displacement reaction Methods 0.000 claims abstract description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 16
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 13
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 12
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 12
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 12
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 12
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000005642 Oleic acid Substances 0.000 claims description 12
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 12
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 12
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 12
- 150000001868 cobalt Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical group [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 45
- 230000035945 sensitivity Effects 0.000 abstract description 17
- -1 zeolite imidazole ester Chemical class 0.000 abstract description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000012544 monitoring process Methods 0.000 abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 description 10
- 238000001514 detection method Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- FFYTTYVSDVWNMY-UHFFFAOYSA-N 2-Methyl-5-nitroimidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1 FFYTTYVSDVWNMY-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
- G01N33/0047—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
The invention belongs to the technical field of monitoring of volatile organic compound gases, and particularly relates to a micron-sized cobaltosic oxide/tin dioxide volatile organic compound sensing material as well as a preparation method and application thereof. The method comprises the steps of firstly preparing a micron-sized zeolite imidazole ester framework structure material-67, then carrying out heat treatment to obtain cobaltosic oxide, and then carrying out Galvanic displacement reaction to obtain the micron-sized cobaltosic oxide/stannic oxide. The method utilizes zeolite imidazole ester framework structure material-67 to obtain micron-sized cobaltosic oxide with a large specific surface area and a zeolite framework structure, improves the contact area of particles and gas, and avoids agglomeration caused by the particles being too fine. On the basis, cobalt atoms in the cobaltosic oxide are replaced by tin atoms by using Galvanic replacement reaction, and the specific surface area of the material is increased by further using the precipitation of cobalt ions, so that the sensitivity of the material to volatile organic compound gases such as toluene, formaldehyde and the like is further improved, and the sensitivity to 100ppm toluene is 5-10.
Description
Technical Field
The invention belongs to the technical field of monitoring of volatile organic compound gases, and particularly relates to a micron-sized cobaltosic oxide/tin dioxide volatile organic compound sensing material as well as a preparation method and application thereof.
Background
Along with the progress of society and the improvement of the quality of life of people, people pay more and more attention to the problem of environmental pollution. The air pollution is closely related to the work life of each person. Volatile organic compound gas is a common toxic substance in air pollution, and comprises hydrocarbons, halogenated hydrocarbons, benzene series, organic ketones and other gases. The indoor decoration material mainly comes from paint, wallpaper, ground, heat-insulating materials, adhesives and other decoration materials. When the volatile organic compounds in a room reach a certain concentration, the volatile organic compounds can cause great discomfort of a human body, such as headache, nausea, vomiting and the like, and even can affect internal organs and nerves of the human body in severe cases, so that the volatile organic compounds have great harm. Meanwhile, part of organic compounds can cause cancers, such as formaldehyde, benzene compounds and the like, and when a human body is in a room with excessive gases for a long time, the risk of suffering from the cancers is greatly increased. Therefore, the method has extremely important significance for real-time monitoring of the volatile organic compound gas.
Tricobalt tetroxide is a P-type semiconductor material with a forbidden band width of 1.5eV (at normal temperature), and has certain sensitivity to many toxic and harmful gases, such as ethanol, acetone, hydrogen sulfide, benzene, toluene and homologs thereof. Compared with semiconductor sensors widely applied, such as tin dioxide, zinc oxide and the like, the cobaltosic oxide gas sensor has the advantages of lower working temperature and low resistance. However, cobaltosic oxide has disadvantages such as low sensitivity, poor gas selectivity, long response/recovery time, etc. There are currently two main approaches to address these shortcomings. Firstly, the specific surface area of the material is increased through morphology control and microstructure design so as to improve the gas-sensitive performance; secondly, the material performance such as gas-sensitive performance is changed or improved by doping with noble metal, other metal oxides, organic matters and the like. The existing method for increasing the specific surface area of cobaltosic oxide is mainly to prepare cobaltosic oxide nanoparticles, however, the diameter of the cobaltosic oxide prepared at present is generally smaller than 100 nanometers, and although the theoretical specific surface area is larger, the actual contact surface area of the particles and gas is reduced due to agglomeration in practical use. In addition, pure cobaltosic oxide has relatively weak gas-sensitive property, and the material property needs to be further improved.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention mainly aims to provide a preparation method of a micron-sized cobaltosic oxide/tin dioxide volatile organic compound sensing material. The method combines the advantages of micron-sized zeolite framework materials and Galvanic displacement reaction, and on one hand, the prepared micron-sized cobaltosic oxide effectively reduces the agglomeration of particles, thereby improving the gas-sensitive performance of the material. On the other hand, the cobaltosic oxide/tin dioxide composite particles are obtained while the special microstructure of the cobaltosic oxide is kept through Galvanic displacement reaction, so that the gas-sensitive performance is further improved, and finally the micron-sized cobaltosic oxide/tin dioxide volatile organic compound sensing material is provided.
The invention also aims to provide a micron-sized cobaltosic oxide/tin dioxide volatile organic compound sensing material obtained by the preparation method. The material is micron particles with a high specific surface area, and tin oxide can be uniformly doped in the cobaltosic oxide particles, so that the material has high sensitivity to toluene gas.
The invention further aims to provide application of the micron-sized cobaltosic oxide/tin dioxide.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a micron-sized cobaltosic oxide/stannic oxide volatile organic compound sensing material comprises the following steps: reacting 2-methylimidazole with cobalt salt in a solvent to prepare a micron-sized zeolite imidazolate framework structure material-67, then carrying out heat treatment to obtain cobaltosic oxide, and then using the cobaltosic oxide, oleylamine, oleic acid, concentrated hydrochloric acid and tin salt as raw materials to prepare the micron-sized cobaltosic oxide/tin dioxide volatile organic compound sensing material through Galvanic displacement reaction.
Preferably, the cobalt salt is cobalt nitrate hexahydrate, cobalt acetate or cobalt chloride.
Preferably, the molar ratio of the cobalt salt to the 2-methylimidazole is 4: 1-2: 1.
Preferably, the solvent is methanol.
Preferably, the concentration of the 2-methylimidazole in the solvent is 0.15mol/L to 0.45 mol/L.
Preferably, the reaction temperature of the 2-methylimidazole and the cobalt salt is 25-50 ℃, and the reaction time is 12-36 h.
Preferably, the particle size of the zeolite imidazole ester framework material-67 is 1-4 μm.
Preferably, the temperature of the heat treatment is 300-500 ℃, the time is 2 hours, and the heating rate is 1-5 ℃/min.
Preferably, the tin salt is tin nitrate, tin acetate or tin chloride.
Preferably, the Galvanic displacement reaction is specifically performed as follows: dissolving tin salt in concentrated hydrochloric acid to obtain a hydrochloric acid solution of the tin salt, dispersing cobaltosic oxide, oleylamine and oleic acid in an organic solvent, and adding the hydrochloric acid solution of the tin salt for reaction.
More preferably, the organic solvent is toluene.
More preferably, the concentration of the hydrochloric acid solution of tin salt is 1mol/L to 3 mol/L.
More preferably, the concentration of cobaltosic oxide in the organic solvent is 0.008-0.016 g/mL.
More preferably, the concentration of cobaltosic oxide in the organic solvent is 0.012 g/mL.
More preferably, the concentration of oleylamine in the organic solvent is 0.1g/mL to 0.3 g/mL.
More preferably, the concentration of oleylamine in the organic solvent is 0.2 g/mL.
More preferably, the concentration of oleic acid in the organic solvent is 0.007-0.028 g/mL.
More preferably, the concentration of oleic acid in the organic solvent is 0.014 g/mL.
More preferably, the Galvanic substitution reaction is carried out at a temperature of 90 to 110 ℃ for 1 to 3 hours.
The invention further provides the micron-sized cobaltosic oxide/stannic oxide obtained by the preparation method, the material has the characteristics of a zeolite imidazole ester structure material, microscopic particles are octahedron or dodecahedron, the particle size is 1-4 mu m, holes are distributed on the surface of the particles, and the mass percentage of the stannic oxide is 5-30%.
The invention further provides application of the micron-sized cobaltosic oxide/tin dioxide in the aspect of gas-sensitive sensing materials, wherein the materials are used for detecting volatile organic compounds, and the sensitivity of the materials to 100ppm of toluene is 5-10.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the zeolite imidazole ester framework structure material-67 utilized by the invention is a novel organic metal framework structure material, has larger specific surface area, can obtain cobaltosic oxide with zeolite framework structure with large specific surface area after high-temperature calcination, and the cobaltosic oxide is micron-sized particles, thereby not only improving the actual contact area of the particles and gas and obviously improving the gas-sensitive performance of the material, but also avoiding particle agglomeration caused by the excessively fine particles. On the basis, the invention utilizes Galvanic displacement reaction to replace cobalt atoms in cobaltosic oxide with tin atoms through the oxidation-reduction reaction among ions, and further utilizes the precipitation of cobalt ions to increase the specific surface area of the material while keeping the zeolite structure with large specific surface area, so that the sensitivity of the material to volatile organic compound gases such as toluene, formaldehyde and the like is further improved, the sensitivity to 100ppm toluene is 5-10, and the invention has important application prospects in the fields of indoor air quality detection, industrial gas monitoring and the like.
Drawings
Fig. 1 is a scanning electron microscope image of the micron-sized cobaltosic oxide/tin dioxide prepared in example 2.
FIG. 2 is a graph showing the gas sensitivity of cobaltosic oxide obtained in example 1 to 100ppm of toluene, with a sensitivity of 1.5.
FIG. 3 is a graph of the gas sensitivity performance of cobaltosic oxide/tin dioxide obtained in example 1 to 100ppm toluene, with a sensitivity of 7.3.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto. For process parameters not specifically noted, reference may be made to conventional techniques.
Example 1
The embodiment provides a cobaltosic oxide/tin dioxide volatile organic compound sensing material with the particle size of 1 mu m and a preparation method thereof.
The method comprises the following specific steps:
dissolving cobalt nitrate and 2-methylimidazole in a methanol solution with the concentration of 0.45mol/L in 200ml of methanol according to the molar ratio of 4:1, reacting at 30 ℃ for 12 hours, centrifugally drying, separating, and then preserving the temperature at 350 ℃ for 2 hours at the heating rate of 5 ℃/min to obtain cobaltosic oxide particles. 0.16g of the above particles were dispersed in 10mL of toluene, 3g of oleylamine and 0.28g of oleic acid were added, 5mL of 3mol/L tin nitrate hydrochloric acid solution was added at 100 ℃, and after 3 hours of reaction, tricobalt tetroxide/tin dioxide particles having a size of about 1 μm were obtained, in which the mass percentage of tin dioxide was 30%.
The obtained cobaltosic oxide particles and water are ground into slurry by a mortar according to the mass ratio of 1:10, the slurry is coated on a gas-sensitive ceramic tube to prepare a gas-sensitive sensor, and a bright blowing-30A gas-sensitive element testing system is used as a detection device, so that the sensitivity of the gas-sensitive sensor to 100ppm of toluene at 200 ℃ is 1.5.
The obtained cobaltosic oxide/tin dioxide particles and water are ground into slurry according to the mass ratio of 1:10 by using a mortar, the slurry is coated on a gas-sensitive ceramic tube to prepare a gas-sensitive sensor, and the sensitivity of the gas-sensitive sensor to 100ppm of toluene at 200 ℃ is found to be 7.3 by using a Weishenws-30A gas-sensitive element testing system as a detection device.
Example 2
The embodiment provides a cobaltosic oxide/tin dioxide volatile organic compound sensing material with the particle size of 2 mu m and a preparation method thereof.
The method comprises the following specific steps:
dissolving cobalt acetate and 2-methylimidazole in methanol of 200ml according to the molar ratio of 3:1, wherein the concentration of 2-methylimidazole in the methanol solution is 0.3mol/L, reacting at 50 ℃ for 24 hours, centrifugally drying, separating, and then preserving heat at 300 ℃ for 5 hours at the heating rate of 2 ℃/min to obtain cobaltosic oxide particles. 0.12g of the above particles were dispersed in 10mL of toluene, and 2g of oleylamine and 0.14g of oleic acid were added, 5mL of a 2mol/L solution of tin acetate in hydrochloric acid was added at 90 ℃ to obtain cobaltosic oxide/tin dioxide particles having a size of about 2 μm after 2 hours of reaction, wherein the mass percentage of tin dioxide was 30%.
The obtained cobaltosic oxide/tin dioxide particles and water are ground into slurry according to the mass ratio of 1:10 by using a mortar, the slurry is coated on a gas-sensitive ceramic tube to prepare a gas-sensitive sensor, and the sensitivity of the gas-sensitive sensor to 100ppm of toluene at 200 ℃ is found to be 8 by using a Weishenws-30A gas-sensitive element testing system as a detection device.
Example 3
The embodiment provides a cobaltosic oxide/tin dioxide volatile organic compound sensing material with the particle size of 4 mu m and a preparation method thereof.
The method comprises the following specific steps:
dissolving cobalt chloride and 2-methylimidazole in methanol of 200ml according to the molar ratio of 2:1, reacting for 36 hours at 25 ℃ with the concentration of nitro 2-methylimidazole in the methanol solution at 0.15mol/L, centrifugally drying, separating, and then preserving the temperature at 400 ℃ for 3 hours at the heating rate of 1 ℃/min to obtain the cobaltosic oxide particles. 0.08g of the particles are dispersed in 10mL of toluene, 1g of oleylamine and 0.07g of oleic acid are added, 5mL of 3mol/L stannic chloride hydrochloric acid solution is added at 110 ℃, and cobaltosic oxide/stannic oxide particles with the size of about 4 mu m are obtained after reaction for 1 hour, wherein the mass percent of stannic oxide is 5%.
The obtained cobaltosic oxide/tin dioxide particles and water are ground into slurry according to the mass ratio of 1:10 by using a mortar, the slurry is coated on a gas-sensitive ceramic tube to prepare a gas-sensitive sensor, and the sensitivity of the gas-sensitive sensor to 100ppm of toluene at 200 ℃ is found to be 5 by using a Weishenws-30A gas-sensitive element testing system as a detection device.
Example 4
The embodiment provides a cobaltosic oxide/tin dioxide volatile organic compound sensing material with the particle size of 3 mu m and a preparation method thereof.
The method comprises the following specific steps:
dissolving cobalt nitrate and 2-methylimidazole in a methanol solution with the concentration of 0.15mol/L in 200ml of methanol according to the molar ratio of 2:1, reacting for 24 hours at 35 ℃, centrifugally drying, separating, and then preserving the temperature at 500 ℃ for 2 hours at the heating rate of 1 ℃/min to obtain cobaltosic oxide particles. 0.12g of the above particles were dispersed in 10mL of toluene, and 2g of oleylamine and 0.21g of oleic acid were added, 5mL of a 2mol/L tin nitrate hydrochloric acid solution was added at 95 ℃ to react for 1.5 hours to obtain cobaltosic oxide/tin dioxide particles having a size of about 3 μm, wherein the mass percentage of tin dioxide was 20%.
The obtained cobaltosic oxide/tin dioxide particles and water are ground into slurry according to the mass ratio of 1:10 by using a mortar, the slurry is coated on a gas-sensitive ceramic tube to prepare a gas-sensitive sensor, and the sensitivity of the gas-sensitive sensor to 100ppm of toluene at 200 ℃ is found to be 10 by using a Weishenws-30A gas-sensitive element testing system as a detection device.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a micron-sized cobaltosic oxide/stannic oxide volatile organic compound sensing material is characterized by comprising the following steps: reacting 2-methylimidazole with cobalt salt in a solvent to prepare a micron-sized zeolite imidazolate framework structure material-67, then carrying out heat treatment to obtain cobaltosic oxide, and then using the cobaltosic oxide, oleylamine, oleic acid, concentrated hydrochloric acid and tin salt as raw materials to prepare the micron-sized cobaltosic oxide/tin dioxide volatile organic compound sensing material through Galvanic displacement reaction.
2. The method for preparing micron-sized cobaltosic oxide/tin dioxide volatile organic compound sensing material according to claim 1, wherein the method comprises the following steps:
the cobalt salt is cobalt nitrate hexahydrate, cobalt acetate or cobalt chloride;
the solvent is methanol;
the tin salt is tin nitrate, tin acetate or tin chloride.
3. The method for preparing micron-sized cobaltosic oxide/tin dioxide volatile organic compound sensing material according to claim 1, wherein the method comprises the following steps:
the molar ratio of the cobalt salt to the 2-methylimidazole is 4: 1-2: 1;
the concentration of the 2-methylimidazole in the solvent is 0.15-0.45 mol/L.
4. The method for preparing micron-sized cobaltosic oxide/tin dioxide volatile organic compound sensing material according to claim 1, wherein the method comprises the following steps:
the reaction temperature of the 2-methylimidazole and the cobalt salt is 25-50 ℃, and the reaction time is 12-36 hours;
the temperature of the heat treatment is 300-500 ℃, the time is 2h, and the heating rate is 1-5 ℃/min.
5. The method for preparing micron-sized cobaltosic oxide/tin dioxide volatile organic compound sensing material according to claim 1, wherein the Galvanic substitution reaction is specifically performed as follows: dissolving tin salt in concentrated hydrochloric acid to obtain a hydrochloric acid solution of the tin salt, dispersing cobaltosic oxide, oleylamine and oleic acid in an organic solvent, and adding the hydrochloric acid solution of the tin salt for reaction.
6. The method for preparing micron-sized cobaltosic oxide/tin dioxide volatile organic compound sensing material according to claim 5, wherein the method comprises the following steps:
the organic solvent is toluene;
the concentration of the hydrochloric acid solution of the tin salt is 1-3 mol/L;
in the organic solvent, the concentration of cobaltosic oxide is 0.008-0.016 g/mL;
in the organic solvent, the concentration of oleylamine is 0.1 g/mL-0.3 g/mL;
in the organic solvent, the concentration of the oleic acid is 0.007 g/mL-0.028 g/mL.
7. The method for preparing micron-sized cobaltosic oxide/tin dioxide volatile organic compound sensing material according to claim 6, wherein the method comprises the following steps:
in the organic solvent, the concentration of cobaltosic oxide is 0.012 g/mL;
in the organic solvent, the concentration of oleylamine is 0.2 g/mL;
in the organic solvent, the concentration of oleic acid is 0.014 g/mL.
8. The method for preparing micron-sized cobaltosic oxide/tin dioxide volatile organic compound sensing material according to claim 5, wherein the method comprises the following steps: the Galvanic displacement reaction is carried out at the temperature of 90-110 ℃ for 1-3 h.
9. A micron-sized cobaltosic oxide/stannic oxide volatile organic compound sensing material is characterized in that: the material is obtained by the preparation method of any one of claims 1 to 8, has the characteristics of a zeolite imidazole ester structure material, and has the advantages that microscopic particles are octahedron or dodecahedron, the particle size is 1-4 μm, holes are distributed on the surface of the particles, and the mass percentage of tin dioxide is 5-30%.
10. The use of the micron-sized cobaltosic oxide/tin dioxide voc sensing material of claim 9, wherein: the material is used for detecting volatile organic compounds.
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