CN113655097B - SnO (tin oxide) 2 Preparation method and application of ZIF-8 composite gas-sensitive material - Google Patents
SnO (tin oxide) 2 Preparation method and application of ZIF-8 composite gas-sensitive material Download PDFInfo
- Publication number
- CN113655097B CN113655097B CN202110999604.1A CN202110999604A CN113655097B CN 113655097 B CN113655097 B CN 113655097B CN 202110999604 A CN202110999604 A CN 202110999604A CN 113655097 B CN113655097 B CN 113655097B
- Authority
- CN
- China
- Prior art keywords
- sno
- zif
- methanol
- composite
- gas
- 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.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 55
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims description 14
- 229910001887 tin oxide Inorganic materials 0.000 title claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 98
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 53
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 235000019253 formic acid Nutrition 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 27
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 27
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 22
- 239000000725 suspension Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 13
- IZAPCPZNEWXCRP-UHFFFAOYSA-N (2-methylimidazol-2-yl)methanol Chemical compound OCC1(C)N=CC=N1 IZAPCPZNEWXCRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000013049 sediment Substances 0.000 claims abstract description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 38
- 239000000919 ceramic Substances 0.000 claims description 26
- 230000035945 sensitivity Effects 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- 238000001514 detection method Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 claims description 8
- 235000011837 pasties Nutrition 0.000 claims description 8
- 239000011265 semifinished product Substances 0.000 claims description 8
- 238000003466 welding Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000035515 penetration Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 111
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 10
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 5
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000013110 organic ligand Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- -1 formaldehyde, hydrogen Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 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
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
-
- 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
-
- 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
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Pathology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Engineering & Computer Science (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention discloses SnO 2 The preparation method and application of the ZIF-8 composite gas-sensitive material comprise the following steps: (1) SnO (SnO) 2 Pretreatment: according to (0.1-0.15) g:40mL solid to liquid ratio will be nano SnO 2 Adding into methanol, performing ultrasonic dispersion, and adding polyvinylpyrrolidone into the obtained SnO 2 Magnetically stirring for 24 hr, centrifuging, washing, drying, and preparing into 2mg/mL SnO 2 -methanol suspension for use; (2) Preparation of SnO 2 ZIF-8 composite: zn (NO) 3 ) 2 Adding SnO into methanol solution and 2-methylimidazole-methanol solution 2 After the methanol suspension reacts for 24 hours by magnetic stirring, the obtained milky white solution is centrifugally separated, the lower sediment is washed for 3-4 times by absolute ethyl alcohol, and white products are collected; and (3) drying the product. The invention adopts ZIF-8 to nano SnO for the first time 2 The material is doped and modified, and the ZIF-8 surface has a large number of active reaction sites, can be specifically combined with formic acid, and simultaneously can make the material perform nano SnO 2 The method has stronger loading capacity and improves the composite stability.
Description
Technical Field
The invention relates to the technical field of functional nano material preparation, also relates to the technical field of gas sensing detection, and in particular relates to SnO 2 Preparation method and application of ZIF-8 composite gas-sensitive material.
Background
Along with the rapid development of modern industrial production, the sensor and the sensing technology enter every corner in the life of people, and the gas sensor is a detection device, is an important tool for people to know the world, and provides a lot of convenience for the life of people. In the industry, various toxic and harmful gases are produced, and the gases are directly or indirectly put into the living environment of people, so that the health of people is seriously endangered. With the increasing of ecological civilization construction force, people have higher requirements on the living environment of the people, and the existence of toxic gases polluting the environment is difficult to allow. It is therefore highly desirable to be able to easily detect these toxic gases in a simple and convenient manner. Therefore, development and research of more accurate and convenient gas sensing devices and sensing technologies are also urgent. Because the gas-sensitive material with single type can not meet the actual production application requirements at some time, the methods of changing different materials, controlling and changing the morphology of the materials, adding different substances to modify the materials, or researching porous novel materials and the like are required to be researched, and all detection performances of the sensor are improved from the aspects of specific surface area of the materials, area of sensing gas during testing, manufacturing cost and the like, such as prolonging the service life, reducing the lower limit of detection concentration, enhancing the selectivity, reducing the response/recovery time and the like. In addition, the gas sensor developed at present is mainly applied to gases such as ethanol, formaldehyde, hydrogen, carbon monoxide, sulfur dioxide, acetone, volatile benzene and the like, but related reports on research on a formic acid gas sensitive material are rare. Therefore, the development of a composite gas-sensitive material and a sensor for selectively detecting formic acid is a technical problem to be solved urgently, and is one of the important research subjects at present.
The Metal Organic Frameworks (MOFs) are made of inorganic metal ions (e.g. Zn 2+ 、Zr 4+ 、Cu 2+ 、Fe 3+ 、Ln 4+ 、Co 4 + Etc.) or a porous compound having a network structure formed by coordination of metal ion clusters with organic ligands. Because MOFs has very high specific surface area, a large number of holes and abundant metal sites, the MOFs has adjustable structure and flexibility and diversity ] The method has the characteristics of diversity in use functions, and is widely applied to the fields of catalysts, gas separation, biology and medicine, ion exchange, energy storage, solar cells, sensors and the like, has great feasibility in the aspect of sensing materials, and is one of the hot spots for the research on the performance of new materials at present. The zeolite-like imidazole skeleton structure material (ZIFs) is one branch of MOFs material and is formed by open crystalsA new material which is displayed according to a certain rule. ZIFs take Zn or Co as a metal center and coordinate with a para-nitrogen heterocyclic connector to form a tetrahedral three-dimensional structure. ZIFs materials have many advantages: firstly, the gas diffusion device comprises a plurality of pore canals which are uniform in size and shape and are used for gas diffusion, so that the gas diffusion device has a good screening effect on some gas molecules with smaller sizes; secondly, the structure is relatively simple, and various ZIFs materials with different special performances can be synthesized by changing the types of metal ions or organic ligands in the reaction; finally, the organic ligand imidazole forms an anion ligand with stronger alkalinity and metal ion coordination, so the organic ligand imidazole has higher mechanical property. The ZIFs have self-assembly characteristics of solvents and ligands in the synthesis process, the structure of the ZIFs is multifunctional, and the surface of the ZIFs can be flexibly regulated and controlled, so that the ZIFs have wide application prospects in the aspects of adsorbents (gas separation and storage), ion exchangers (ion removal and water softening), catalysts, sensors and the like. Currently, the preparation of functionalized ZIFs materials by modification is also one of the hot spots of this direction of research.
Tin dioxide powder is generally white, but also somewhat pale grey and pale yellow, and is an inorganic compound. The melting point of the tin dioxide is 1600 ℃, the boiling point is 1800-1900 ℃, and the molar mass and the density are 150.72g/mol and 6.94g/cm respectively 3 Is an amphoteric oxide, insoluble or poorly soluble in polar solvents such as water and alcohols, but soluble in hot strong bases and hot strong acids. SnO (SnO) 2 The unit cell of the crystal is a body center orthorhombic parallelepiped, is of a rutile structure, has a forbidden band width of 3.54eV, and belongs to wide forbidden band metal oxides. People are measuring SnO 2 After the conductivity and the Hall coefficient of the tin oxide semiconductor are determined to be N-type conductivity, the main reason for researching the N-type semiconductor defect of the tin dioxide is that the structure contains oxygen gaps and tin gap atoms. SnO (SnO) 2 Was first discovered in 1962 that Pd and Pt doped SnO was available from Ferand Corp 2 After commercialization of the gas sensor, snO is used as a material for the gas sensor 2 The research of the gas sensor is carried out, and the types of the gas sensor are also increasing. SnO (SnO) 2 The gas sensor mainly comprises a sintering type gas sensor and a thick film type gas sensor: 1) The sintering type is the research of the gas sensor at presentThe most mature of the materials is that sintering type needs to be heated during testing, and the heating modes include direct heating type and side heating type. Wherein, the direct heating type is to use a heating wire buried in the gas sensitive material to provide the working temperature required by the element test, and to measure the wire to test the change of the element resistance value; the side heating type is to provide the working temperature by passing through the heating wire inside the ceramic tube with the surface coated with the gas sensitive material, the heating wire is only used for providing the temperature, and the measuring wire is fixed on the ceramic tube, is not influenced by the heating wire when the measuring resistance value changes, and has higher stability. 2) The thick film type sensor is generally manufactured by adopting a screen printing process, the screen printing process is simpler than that of a thin film type sensor, the cost is low, the mechanical strength of the element is improved, and compared with a sintered element, the consistency is good. However, the single pure tin dioxide is used as the semiconductor gas-sensitive material, and the problems of higher working temperature, poorer selectivity, longer response and recovery time and the like in the gas-sensitive test process still exist.
Based on the above, the invention provides a method for preparing the catalyst for SnO by utilizing the characteristics of porous screening, large specific surface area, high thermal stability and the like of a zeolite imidazole ester framework material ZIF-8 2 Doping modification of nano material, compared with pure SnO 2 Modified SnO 2 The gas-sensitive performance of (2) is further optimized and improved greatly, and is used for high-sensitivity and high-selectivity detection of formic acid.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a SnO 2 Preparation method and application of ZIF-8 composite gas-sensitive material.
The technical scheme of the invention is summarized as follows:
SnO (tin oxide) 2 The preparation method of the ZIF-8 composite gas-sensitive material comprises the following steps:
(1)SnO 2 pretreatment: according to (0.1-0.15) g:40mL solid to liquid ratio will be nano SnO 2 Adding into methanol, performing ultrasonic dispersion, and adding polyvinylpyrrolidone into the obtained SnO 2 Controlling nano SnO in the suspension 2 The mass ratio of the polyvinylpyrrolidone is (1-2) (0-2), and the polyvinylpyrrolidone is magnetically stirred for 24 hoursCentrifuging, washing, drying, and preparing into 2mg/mL SnO 2 -methanol suspension for use;
(2) Preparation of SnO 2 ZIF-8 composite:
zn (NO) was added at a solid-to-liquid ratio of (1.6-2.0) g/38 mL 3 ) 2 ·6H 2 O is dissolved in methanol to obtain Zn (NO) 3 ) 2 -a methanol solution;
dissolving 2-methylimidazole in methanol according to the solid-to-liquid ratio of (1.6-2.0) g to 38mL to obtain 2-methylimidazole-methanol solution;
zn (NO) 3 ) 2 Adding SnO into methanol solution and 2-methylimidazole-methanol solution 2 After the methanol suspension reacts for 24 hours by magnetic stirring, the obtained milky white solution is centrifugally separated, the lower sediment is washed for 3-4 times by absolute ethyl alcohol, and white products are collected;
(3) And (3) drying a product: drying the obtained white product at 80deg.C for 12 hr to obtain white powdered SnO 2 ZIF-8 composite gas-sensitive material.
Preferably, the nano SnO 2 The preparation method of (2) comprises the following steps: snCl is added 4 ·5H 2 O, naOH adding solution and polyvinylpyrrolidone into deionized water, magnetically stirring until the solution is clear, transferring to a reaction kettle, performing hydrothermal reaction at constant temperature of 200 ℃ for 24 hours, cooling to obtain precipitate, respectively performing cross washing with deionized water and ethanol for 3 times, drying at 300 ℃ for 2 hours, removing ethanol, water and unreacted polyvinylpyrrolidone, grinding and crushing to obtain white powdery product, namely the nano SnO 2 And (5) storing for later use.
Preferably, the SnCl 4 ·5H 2 O, naOH solution, polyvinylpyrrolidone and deionized water in the weight ratio of (2-2.5) g (8-10) mL to 50mL.
Preferably, the concentration of the NaOH solution is 6mol/L.
Preferably, the Zn (NO 3 ) 2 -methanol solution, 2-methylimidazole-methanol solution, snO 2 The volume ratio of the methanol suspension is (3.5-4): 5.
SnO 2 ZIF-8 composite gas-sensitive materialThe application in the preparation of the selective formic acid gas sensor.
Preferably, the specific application method comprises the following steps:
(1) Preparing slurry: the SnO is treated with 2 Grinding the ZIF-8 composite gas-sensitive material for 30min, adding deionized water according to the feed liquid ratio of 1g (0.6-1.2) mL, and continuously mixing and grinding for 30min to prepare uniform pasty slurry;
(2) And (3) assembling: at Al 2 O 3 The outer surface of the ceramic tube is sleeved with two mutually parallel annular gold electrodes, two mutually opposite platinum wire leads are welded on two sides of the annular gold electrodes, and the composite Al is assembled 2 O 3 A ceramic tube;
(3) Coating: uniformly coating the obtained pasty slurry on composite Al 2 O 3 Drying the surface of the ceramic tube at 80 ℃ for 5 hours to obtain the composite gas-sensitive Al 2 O 3 A ceramic tube;
(3) Welding: penetration of nickel-chromium alloy wire for controlling heating temperature into composite gas-sensitive Al 2 O 3 After the ceramic tube is internally filled, respectively welding two ends of the nickel-chromium alloy wire and four platinum wires on the outer side of the ceramic tube on a base to obtain a semi-finished product of the gas sensor;
(4) Aging: aging the semi-finished product of the gas sensor at 300 ℃ for 3d to obtain the bypass type selective formic acid gas sensor.
Preferably, the operating temperature of the bypass type selective formic acid gas sensor is 175-325 ℃, and when the operating temperature is 260 ℃, the detection sensitivity value of 10ppm formic acid reaches 20.314, and the detection sensitivity value of 100ppm formic acid reaches 372.5.
The invention has the beneficial effects that:
1. the invention adopts the zeolite imidazole ester framework material ZIF-8 to nano SnO for the first time 2 The material is doped and modified, ZIF-8 has the characteristics of porous screening, high specific surface area, strong thermal stability and the like, and the surface has a large number of active reaction sites which can be specifically combined with formic acid, so that the sensitivity of the gas-sensitive material to formic acid is improved, and meanwhile, the nano SnO is also enabled to be subjected to the high specific surface area and the large number of active sites 2 Provides the SnO modified by ZIF-8 with stronger loading capacity and improved composite stability 2 The gas-sensitive performance of (2) is further optimized and improved greatly, and is used for high-sensitivity and high-selectivity detection of formic acid.
2. SnO prepared by the invention 2 The ZIF-8 composite gas-sensitive material has high sensitivity and strong selectivity to formic acid, and simultaneously has higher stability and can be recycled.
Drawings
FIG. 1 is SnO of comparative example 1 2 Gas-sensitive material and SnO produced in examples 1-4 2 XRD pattern of ZIF-8 composite gas-sensitive material;
FIG. 2 shows SnO obtained in example 1 2 SEM image of ZIF-8 composite gas-sensitive material;
FIG. 3 shows SnO obtained in comparative example 2 2 Gas sensor and SnO produced in example 5 2 A sensitivity change chart of detecting 100ppm formic acid at different temperatures by the ZIF-8 gas sensor;
FIG. 4 shows SnO obtained in comparative example 2 2 Gas sensor and SnO produced in example 5 2 A sensitivity change chart of detecting formic acid with different concentrations at 260 ℃ by the ZIF-8 gas sensor;
FIG. 5 shows SnO obtained in example 5 2 Sensitivity bar graph of ZIF-8 gas sensor for detecting 10ppm different gas at 260 ℃;
FIG. 6 shows SnO obtained in example 5 2 A ZIF-8 gas sensor product diagram;
FIG. 7 shows SnO of the present invention 2 A flow chart of a preparation method of the ZIF-8 composite gas-sensitive material.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
The invention provides SnO of an embodiment 2 The preparation method of the ZIF-8 composite gas-sensitive material comprises the following steps:
(1) Preparation of nano SnO 2 : snCl is added 4 ·5H 2 Adding O, 6mol/L NaOH solution and polyvinylpyrrolidone into deionized water, magnetically stirring until the solution is clear, transferring into a reaction kettle, performing hydrothermal reaction at constant temperature of 200 ℃ for 24 hours,after the precipitate is cooled to obtain a precipitate, respectively carrying out cross washing with deionized water and ethanol for 3 times, drying at 300 ℃ for 2 hours, removing ethanol, water and polyvinylpyrrolidone which is not completely reacted, grinding and crushing to obtain a white powdery product, namely the nano SnO 2 Storing for later use; the SnCl 4 ·5H 2 O, naOH solution, polyvinylpyrrolidone and deionized water in the weight ratio of (2-2.5) g (8-10) to 50mL;
(2)SnO 2 pretreatment: according to (0.1-0.15) g:40mL solid to liquid ratio will be nano SnO 2 Adding into methanol, performing ultrasonic dispersion, and adding polyvinylpyrrolidone into the obtained SnO 2 Controlling nano SnO in the suspension 2 The mass ratio of polyvinylpyrrolidone is (1-2) (0-2), magnetic stirring is carried out for 24 hours, and after centrifugation, washing and drying, 2mg/mL SnO is prepared 2 -methanol suspension for use;
(3) Preparation of SnO 2 ZIF-8 composite:
zn (NO) was added at a solid-to-liquid ratio of (1.6-2.0) g/38 mL 3 ) 2 ·6H 2 O is dissolved in methanol to obtain Zn (NO) 3 ) 2 -a methanol solution;
dissolving 2-methylimidazole in methanol according to the solid-to-liquid ratio of (1.6-2.0) g to 38mL to obtain 2-methylimidazole-methanol solution;
zn (NO) 3 ) 2 Adding SnO into methanol solution and 2-methylimidazole-methanol solution 2 After the methanol suspension reacts for 24 hours by magnetic stirring, the obtained milky white solution is centrifugally separated, the lower sediment is washed for 3-4 times by absolute ethyl alcohol, and white products are collected; the Zn (NO) 3 ) 2 -methanol solution, 2-methylimidazole-methanol solution, snO 2 The volume ratio of the methanol suspension is (3.5-4): 5;
(4) And (3) drying a product: drying the obtained white product at 80deg.C for 12 hr to obtain white powdered SnO 2 ZIF-8 composite gas-sensitive material.
SnO produced in this example 2 The application of the ZIF-8 composite gas-sensitive material in the preparation of the selective formic acid gas-sensitive element comprises the following specific application methods:
(1) Preparation ofAnd (3) sizing: the SnO is treated with 2 Grinding the ZIF-8 composite gas-sensitive material for 30min, adding deionized water according to the feed liquid ratio of 1g (0.6-1.2) mL, and continuously mixing and grinding for 30min to prepare uniform pasty slurry;
(2) And (3) assembling: at Al 2 O 3 The outer surface of the ceramic tube is sleeved with two mutually parallel annular gold electrodes, two mutually opposite platinum wire leads are welded on two sides of the annular gold electrodes, and the composite Al is assembled 2 O 3 A ceramic tube;
(3) Coating: uniformly coating the obtained pasty slurry on composite Al 2 O 3 Drying the surface of the ceramic tube at 80 ℃ for 5 hours to obtain the composite gas-sensitive Al 2 O 3 A ceramic tube;
(3) Welding: penetration of nickel-chromium alloy wire for controlling heating temperature into composite gas-sensitive Al 2 O 3 After the ceramic tube is internally filled, respectively welding two ends of the nickel-chromium alloy wire and four platinum wires on the outer side of the ceramic tube on a base to obtain a semi-finished product of the gas sensor;
(4) Aging: aging the semi-finished product of the gas sensor at 300 ℃ for 3d to obtain the bypass type selective formic acid gas sensor.
And (3) performing sensitivity test on the bypass type selective formic acid gas sensor: and inserting the obtained gas sensor into a gas-sensitive tester, adding formic acid with different concentrations or gases with different types by adopting a static gas distribution method, opening a testing system for testing, and calculating the sensitivity by using an S=Ra/Rg formula after the resistance value is stable.
Example 1
SnO (tin oxide) 2 The preparation method of the ZIF-8 composite gas-sensitive material comprises the following steps:
(1) Preparation of nano SnO 2 : 2.2275g SnCl 4 ·5H 2 Adding O, 8mL of 6mol/L NaOH solution and 2.1173g of polyvinylpyrrolidone (PVP, mr=30000) into 50mL of deionized water, magnetically stirring until the solution is clear, transferring into a reaction kettle, performing hydrothermal reaction at constant temperature of 200 ℃ for 24 hours, cooling to obtain precipitate, respectively performing cross washing with deionized water and ethanol for 3 times, drying at 300 ℃ for 2 hours, removing ethanol, water and unreacted polyvinylpyrrolidone, grinding and crushing to obtain white powderThe final product is the nano SnO 2 Storing for later use;
(2)SnO 2 pretreatment: 0.1152g of nano SnO 2 Adding into 40mL of methanol, performing ultrasonic dispersion, and adding 0.1152g of polyvinylpyrrolidone (PVP, mr=30000) into the obtained SnO 2 Controlling nano SnO in the suspension 2 The mass ratio of polyvinylpyrrolidone is 1:1, magnetically stirring for 24 hours, centrifuging, washing, drying, and preparing 50mL of 2mg/mL SnO 2 -methanol suspension for use;
(3) Preparation of SnO 2 ZIF-8 composite:
1.8563g Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 38mL of methanol to give Zn (NO) 3 ) 2 -a methanol solution;
1.7940g of 2-methylimidazole was dissolved in 38mL of methanol to obtain a 2-methylimidazole-methanol solution;
38mL of Zn (NO) 3 ) 2 50mL of SnO was added to 38mL of 2-methylimidazole-methanol solution 2 After the reaction of the methanol suspension for 24 hours by magnetic stirring, the obtained milky white solution is centrifugally separated, the lower sediment is washed for 3 times by absolute ethyl alcohol, and the white product is collected;
(4) And (3) drying a product: drying the obtained white product at 80deg.C for 12 hr to obtain white powdered SnO 2 ZIF-8 composite gas-sensitive material.
Example 2 is identical to example 1, except that: nano SnO in example 2 2 The mass ratio of polyvinylpyrrolidone is 1:0.
example 3 is identical to example 1, except that: example 3 nanometer SnO 2 The mass ratio of polyvinylpyrrolidone is 1:2.
example 4 is identical to example 1, except that: example 3 nanometer SnO 2 The mass ratio of polyvinylpyrrolidone is 2:1.
comparative example 1: nano SnO 2 The preparation method is the same as in the step (1) in the example 1.
SnO was prepared in examples 1 to 4 2 ZIF-8 composite gas-sensitive material and comparative exampleSnO of 1 2 The gas sensitive material is subjected to X-ray diffraction characterization:
FIG. 1 is comparative example 1SnO 2 Gas-sensitive material and SnO produced in examples 1-4 2 XRD pattern of ZIF-8 composite gas-sensitive material: as shown in the figure, the prepared SnO 2 One-to-one comparison is carried out with a standard JCPDS card (JCPDS card No. 41-1445), and all diffraction peaks correspond to and are matched with the standard card. SnO from the figure 2 The spectrum line of the obtained product is relatively smooth, the peak shape is obviously sharp, and the coordinate base lines are relatively consistent, which shows that the grain growth of the sample prepared in the experiment is relatively complete, the crystallization performance is better, and the amorphous and noncrystalline structures are almost not existed. In addition, no other impurity diffraction peaks appear in the graph, namely SnO 2 The sample is not carried with impurities in the process of manufacturing, and the obtained SnO 2 The purity of the product is higher. Meanwhile, it can be seen from the figure that when PVP and SnO 2 The mass ratio of (2) is 1: the peak value is higher in 1, the full width at half maximum is larger, which indicates that the crystallization is stronger and the crystal grain is smaller, namely the crystal grain of the composite material prepared in the embodiment 1 is more complete.
For SnO prepared in example 1 2 SEM characterization of the ZIF-8 composite gas-sensitive material: as can be seen from FIG. 2, in SnO 2 After the ZIF-8 is compounded, the sample of the example 1 comprises irregular flower-shaped aggregates formed by loading tiny particles on spherical components, the surface is smooth although stacking and agglomeration occur, and the size of each nanoparticle is relatively uniform, which proves that SnO is successfully prepared 2 ZIF-8 composite material.
Example 5 preparation of Selective formic acid gas sensor
(1) Preparing slurry: 1.5g of SnO prepared in example 1 2 Grinding the ZIF-8 composite gas-sensitive material for 30min, adding 1.2mL of deionized water, and continuously mixing and grinding for 30min to prepare uniform pasty slurry;
(2) And (3) assembling: at Al 2 O 3 The outer surface of the ceramic tube is sleeved with two mutually parallel annular gold electrodes, two mutually opposite platinum wire leads are welded on two sides of the annular gold electrodes, and the composite Al is assembled 2 O 3 A ceramic tube;
(3) Coating: uniformly coating the obtained pasty slurry on composite Al 2 O 3 Drying the surface of the ceramic tube at 80 ℃ for 5 hours to obtain the composite gas-sensitive Al 2 O 3 A ceramic tube;
(3) Welding: penetration of nickel-chromium alloy wire for controlling heating temperature into composite gas-sensitive Al 2 O 3 After the ceramic tube is internally filled, respectively welding two ends of the nickel-chromium alloy wire and four platinum wires on the outer side of the ceramic tube on a base to obtain a semi-finished product of the gas sensor;
(4) Aging: aging the semi-finished product of the gas sensor at 300 ℃ for 3d to obtain the bypass type selective formic acid gas sensor.
Comparative example 2 is the same as example 5, except that: snO is prepared 2 The ZIF-8 composite gas-sensitive material is replaced by nano SnO of comparative example 1 2 。
Sensitivity test was performed on the bypass type selective formic acid gas sensor prepared in example 5 and comparative example 2: and inserting the obtained gas sensor into a gas-sensitive tester, adding formic acid with different concentrations or gases with different types by adopting a static gas distribution method, opening a testing system for testing, and calculating the sensitivity by using an S=Ra/Rg formula after the resistance value is stable.
FIG. 3 shows SnO of comparative example 2 at different temperatures 2 And SnO of example 5 2 Sensitivity curve of ZIF-8 gas sensor for detecting formic acid: as can be seen from FIG. 3, 260℃is SnO 2 And SnO 2 ZIF-8 gas sensor tested formic acid optimum operating temperature and SnO in example 5 at 200-260℃ 2 The sensitivity of the ZIF-8 gas sensor increases rapidly, reaching a maximum sensitivity 372.5 at 260℃and SnO alone 2 The sensitivity of the gas sensor to formic acid is only 27.3, which proves that the ZIF-8 doping modification can obviously improve SnO 2 The gas-sensitive properties of the material.
FIG. 4 is SnO of comparative example 2 2 And SnO of example 5 2 Sensitivity curve of ZIF-8 gas sensor for detecting formic acid with different concentration: as shown in FIG. 4, snO in example 5 2 The sensitivity of the ZIF-8 gas sensor to formic acid gas increases rapidly in the range of 60-200ppm, because the reaction rate of formic acid gas with oxygen adsorbed on the surface of the material increases continuously, and the response value to 10ppm formic acid is 8.5, illustrating the SnO prepared in example 5 2 The ZIF-8 composite gas sensor has a lower detection limit which is lower than 10ppm.
FIG. 5 is SnO of example 5 2 Sensitivity of ZIF-8 gas sensor for detecting different gases, shown as SnO in the figure 2 The response values of the ZIF-8 gas sensor to 10ppm of methanol, ethanol, formic acid, ammonia, acetone, n-propanol and 1, 2-propanediol at 260 ℃ are respectively 1.978, 1.975, 20.314, 1.189, 0.925, 0.979 and 10.632, and the sensitivity of the gas sensor to formic acid is far higher than that of other gases to be tested by sensitivity comparison, so that SnO prepared in example 5 2 The ZIF-8 gas sensor has the best selectivity to formic acid, which shows that the prepared gas sensor has better selectivity.
Stability test was performed on the side heating type selective formic acid gas sensor prepared in example 5: the product prepared in example 5 was exposed to air, and after leaving for 10d and 20d, the formic acid detection sensitivity value reached 99.86% of the 1d sensitivity value at 10d and 92.83% of the 1d sensitivity value at 20 d.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (5)
1. SnO (tin oxide) 2 The preparation method of the ZIF-8 composite gas-sensitive material is characterized by comprising the following steps of:
(1)SnO 2 pretreatment: according to (0.1-0.15) g:40mL solid to liquid ratio will be nano SnO 2 Adding into methanol, performing ultrasonic dispersion, and adding polyvinylpyrrolidone into the obtained SnO 2 Controlling nano SnO in the suspension 2 The mass ratio of polyvinylpyrrolidone is (1-2) (0-2), magnetic stirring is carried out for 24 hours, and after centrifugation, washing and drying, 2mg/mL SnO is prepared 2 -methanol suspension for use;
the nanometer SnO 2 The preparation method of (2) comprises the following steps: snCl is added 4 ·5H 2 O, naOH adding solution and polyvinylpyrrolidone into deionized water, magnetically stirring until the solution is clear, transferring to a reaction kettle, performing hydrothermal reaction at constant temperature of 200 ℃ for 24 hours, cooling to obtain precipitate, respectively performing cross washing with deionized water and ethanol for 3 times, drying at 300 ℃ for 2 hours, removing ethanol, water and unreacted polyvinylpyrrolidone, grinding and crushing to obtain white powdery product, namely the nano SnO 2 Storing for later use; the SnCl 4 ·5H 2 O, naOH solution, polyvinylpyrrolidone and deionized water in the weight ratio of (2-2.5) g (8-10) to 50mL; the concentration of the NaOH solution is 6mol/L;
(2) Preparation of SnO 2 ZIF-8 composite:
zn (NO) was added at a solid-to-liquid ratio of (1.6-2.0) g/38 mL 3 ) 2 ·6H 2 O is dissolved in methanol to obtain Zn (NO) 3 ) 2 -a methanol solution;
dissolving 2-methylimidazole in methanol according to the solid-to-liquid ratio of (1.6-2.0) g to 38mL to obtain 2-methylimidazole-methanol solution;
zn (NO) 3 ) 2 Adding SnO into methanol solution and 2-methylimidazole-methanol solution 2 After the methanol suspension reacts for 24 hours by magnetic stirring, the obtained milky white solution is centrifugally separated, the lower sediment is washed for 3-4 times by absolute ethyl alcohol, and white products are collected;
(3) And (3) drying a product: drying the obtained white product at 80deg.C for 12 hr to obtain white powdered SnO 2 ZIF-8 composite gas-sensitive material.
2. A SnO according to claim 1 2 A preparation method of the ZIF-8 composite gas-sensitive material is characterized in that Zn (NO 3 ) 2 -methanol solution, 2-methylimidazole-methanol solution, snO 2 The volume ratio of the methanol suspension is (3.5-4): 5.
3. SnO produced by the process of claim 1 or 2 2 /ZIThe F-8 composite gas-sensitive material is applied to the preparation of a selective formic acid gas-sensitive element.
4. The application according to claim 3, wherein the specific application method is:
(1) Preparing slurry: the SnO is treated with 2 Grinding the ZIF-8 composite gas-sensitive material for 30min, adding deionized water according to the feed liquid ratio of 1g (0.6-1.2) mL, and continuously mixing and grinding for 30min to prepare uniform pasty slurry;
(2) And (3) assembling: at Al 2 O 3 The outer surface of the ceramic tube is sleeved with two mutually parallel annular gold electrodes, two mutually opposite platinum wire leads are welded on two sides of the annular gold electrodes, and the composite Al is assembled 2 O 3 A ceramic tube;
(3) Coating: uniformly coating the obtained pasty slurry on composite Al 2 O 3 Drying the surface of the ceramic tube at 80 ℃ for 5 hours to obtain the composite gas-sensitive Al 2 O 3 A ceramic tube;
(3) Welding: penetration of nickel-chromium alloy wire for controlling heating temperature into composite gas-sensitive Al 2 O 3 After the ceramic tube is internally filled, respectively welding two ends of the nickel-chromium alloy wire and four platinum wires on the outer side of the ceramic tube on a base to obtain a semi-finished product of the gas sensor;
(4) Aging: aging the semi-finished product of the gas sensor at 300 ℃ for 3d to obtain the bypass type selective formic acid gas sensor.
5. The use according to claim 4, wherein the operation temperature of the bypass type selective formic acid gas sensor is 175-325 ℃, and the detection sensitivity of 10ppm formic acid is 20.314 and the detection sensitivity of 100ppm formic acid is 372.5 when the operation temperature is 260 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110999604.1A CN113655097B (en) | 2021-08-29 | 2021-08-29 | SnO (tin oxide) 2 Preparation method and application of ZIF-8 composite gas-sensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110999604.1A CN113655097B (en) | 2021-08-29 | 2021-08-29 | SnO (tin oxide) 2 Preparation method and application of ZIF-8 composite gas-sensitive material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113655097A CN113655097A (en) | 2021-11-16 |
| CN113655097B true CN113655097B (en) | 2024-01-23 |
Family
ID=78482294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110999604.1A Active CN113655097B (en) | 2021-08-29 | 2021-08-29 | SnO (tin oxide) 2 Preparation method and application of ZIF-8 composite gas-sensitive material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113655097B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104990961A (en) * | 2015-07-23 | 2015-10-21 | 吉林大学 | Ethanol gas sensor based on Al-doped NiO nano rod-flower material and preparation method thereof |
| CN105628748A (en) * | 2015-12-24 | 2016-06-01 | 东北师范大学 | Platinum-loaded tin dioxide nanofiber gas-sensitive material and gas-sensitive element made from same |
| CN107315035A (en) * | 2017-05-24 | 2017-11-03 | 江苏时瑞电子科技有限公司 | A kind of preparation method of tin oxide molybdenum oxide composite gas sensor |
| CN107991350A (en) * | 2017-11-17 | 2018-05-04 | 济南大学 | The preparation of bar-shaped ZnO/ZIF-8 a kind of and its low temperature H2Sensitlzing effect |
| CN109970355A (en) * | 2019-04-04 | 2019-07-05 | 重庆大学 | Prepare method, ZnO ZIF-8 compound and the gas sensor of ZnO ZIF-8 compound |
| CN110044971A (en) * | 2019-04-16 | 2019-07-23 | 蚌埠学院 | A kind of gas sensitive, preparation method and its application in gas sensor |
| CN110396006A (en) * | 2019-07-16 | 2019-11-01 | 济南大学 | A kind of ZIF-8 film cladding SnO2Composite air-sensitive material and its preparation method and application |
| CN110577236A (en) * | 2019-10-09 | 2019-12-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of NiO modified tin dioxide nano material for gas sensor, product and application thereof |
| CN111056566A (en) * | 2019-12-20 | 2020-04-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of tin dioxide nano material, product and application thereof |
| CN112221358A (en) * | 2020-09-14 | 2021-01-15 | 湖北工程学院 | Polyether-ether-ketone composite membrane of modified carbon nanotube and metal organic framework composite material and preparation method and application thereof |
-
2021
- 2021-08-29 CN CN202110999604.1A patent/CN113655097B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104990961A (en) * | 2015-07-23 | 2015-10-21 | 吉林大学 | Ethanol gas sensor based on Al-doped NiO nano rod-flower material and preparation method thereof |
| CN105628748A (en) * | 2015-12-24 | 2016-06-01 | 东北师范大学 | Platinum-loaded tin dioxide nanofiber gas-sensitive material and gas-sensitive element made from same |
| CN107315035A (en) * | 2017-05-24 | 2017-11-03 | 江苏时瑞电子科技有限公司 | A kind of preparation method of tin oxide molybdenum oxide composite gas sensor |
| CN107991350A (en) * | 2017-11-17 | 2018-05-04 | 济南大学 | The preparation of bar-shaped ZnO/ZIF-8 a kind of and its low temperature H2Sensitlzing effect |
| CN109970355A (en) * | 2019-04-04 | 2019-07-05 | 重庆大学 | Prepare method, ZnO ZIF-8 compound and the gas sensor of ZnO ZIF-8 compound |
| CN110044971A (en) * | 2019-04-16 | 2019-07-23 | 蚌埠学院 | A kind of gas sensitive, preparation method and its application in gas sensor |
| CN110396006A (en) * | 2019-07-16 | 2019-11-01 | 济南大学 | A kind of ZIF-8 film cladding SnO2Composite air-sensitive material and its preparation method and application |
| CN110577236A (en) * | 2019-10-09 | 2019-12-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of NiO modified tin dioxide nano material for gas sensor, product and application thereof |
| CN111056566A (en) * | 2019-12-20 | 2020-04-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of tin dioxide nano material, product and application thereof |
| CN112221358A (en) * | 2020-09-14 | 2021-01-15 | 湖北工程学院 | Polyether-ether-ketone composite membrane of modified carbon nanotube and metal organic framework composite material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 皮肤美容化妆品制剂手册;马振友;皮肤美容化妆品制剂手册;第470页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113655097A (en) | 2021-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Triethylamine gas sensor based on Pt-functionalized hierarchical ZnO microspheres | |
| Zhang et al. | Highly-sensitivity acetone sensors based on spinel-type oxide (NiFe2O4) through optimization of porous structure | |
| Liu et al. | Highly sensitive and low detection limit of ethanol gas sensor based on hollow ZnO/SnO2 spheres composite material | |
| Zhang et al. | Highly sensitive detection of acetone using mesoporous In2O3 nanospheres decorated with Au nanoparticles | |
| Zhang et al. | Facile approach to prepare hierarchical Au-loaded In2O3 porous nanocubes and their enhanced sensing performance towards formaldehyde | |
| Zhang et al. | Self-assembled hierarchical Au-loaded In2O3 hollow microspheres with superior ethanol sensing properties | |
| Yang et al. | PtO2-nanoparticles functionalized CuO polyhedrons for n-butanol gas sensor application | |
| Lv et al. | Sb-doped three-dimensional ZnFe2O4 macroporous spheres for N-butanol chemiresistive gas sensors | |
| CN1329338C (en) | Gas-sensing material with noble metal doped composite metal oxide and its production | |
| Wang et al. | MOF-derived polyhedral NiMoO4@ NiO pp heterostructure as an effective bridge for regulating carriers enhanced sensitivity and selectivity to trimethylamine | |
| Wang et al. | Enhanced triethylamine sensing performance of metal–organic framework derived nest-type Fe-doped NiO nanostructure | |
| Yang et al. | Coral-like ZnFe 2 O 4–ZnO mesoporous heterojunction architectures: synthesis and enhanced sensing properties for triethylamine | |
| Xu et al. | MOF-derived Co3O4/Fe2O3 pn hollow cubes for improved acetone sensing characteristics | |
| Hou et al. | Enhanced triethylamine-sensing properties of hierarchical molybdenum trioxide nanostructures derived by oxidizing molybdenum disulfide nanosheets | |
| Sun et al. | Annealing temperature-dependent porous ZnFe2O4 olives derived from bimetallic organic frameworks for high-performance ethanol gas sensing | |
| Peng et al. | In2O3/ZnO S-scheme heterojunction nanocomposite hollow microtubes with highly sensitive response to formaldehyde | |
| Feng et al. | Ionic liquid-assisted synthesis of 2D porous lotus root slice-shaped NiO nanomaterials for selective and highly sensitive detection of N2H4 | |
| CN113830753A (en) | Pd-doped rGO/ZnO-SnO2Heterojunction quaternary composite material, preparation method and application thereof | |
| Chen et al. | High-response of NiO-modified self-assembled nanosheets formed with ZnO nanoparticles for n-butanol detection | |
| Cai et al. | A fast responsive triethylamine gas sensor based on heterostructured YVO4/V2O5 composites | |
| Shao et al. | Insight into Au functionalization on core-shell LaFeO3 spheres for high-response and selectivity n-butanol gas sensors with DFT study | |
| Wang et al. | MOF-derived NiWO4@ NiO pp heterostructure for distinguish detection of TEA and xylene by temperature regulation | |
| Du et al. | Designed synthesis of yolk-shell WO3 microspheres for enhanced phenylamine sensing performance at room temperature | |
| Tan et al. | Co3O4 nanoboxes with abundant porestructure boosted ultrasensitive toluene gas sensors | |
| CN108440767A (en) | It is a kind of that nanometer Au is combined to the new method for preparing Au@MOF composite materials with porous MOF |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |