CN115057437A - SnO (stannic oxide) 2 /NiO/graphene ternary composite material and preparation method and application thereof - Google Patents
SnO (stannic oxide) 2 /NiO/graphene ternary composite material and preparation method and application thereof Download PDFInfo
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 104
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 71
- 239000011206 ternary composite Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 98
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000001514 detection method Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 94
- 238000001035 drying Methods 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 19
- 239000002244 precipitate Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 5
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 238000004729 solvothermal method Methods 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 238000010306 acid treatment Methods 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims 9
- 150000001336 alkenes Chemical class 0.000 claims 2
- 230000004044 response Effects 0.000 abstract description 43
- 238000012360 testing method Methods 0.000 abstract description 19
- 239000002131 composite material Substances 0.000 abstract description 18
- 238000000137 annealing Methods 0.000 abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 8
- 150000004706 metal oxides Chemical class 0.000 abstract description 8
- 238000005530 etching Methods 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 229910000480 nickel oxide Inorganic materials 0.000 abstract description 4
- 229910001887 tin oxide Inorganic materials 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 230000033228 biological regulation Effects 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000013461 design Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 25
- 239000002077 nanosphere Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000002057 nanoflower Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 230000009467 reduction Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 9
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- 238000001228 spectrum Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- 230000008859 change Effects 0.000 description 6
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- 230000000694 effects Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011218 binary composite Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
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- 230000002378 acidificating effect Effects 0.000 description 2
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- 238000000502 dialysis Methods 0.000 description 2
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- 239000002135 nanosheet Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000011165 3D composite Substances 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical class [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- 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
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- 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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- C01P2004/32—Spheres
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses SnO 2 A preparation method and application of a/NiO/graphene ternary composite material are provided, wherein a method for preparing a Graphene Oxide (GO) and a surface control type semiconductor sensitive material by a Hummers method is used as a basis, and a method for preparing a tin oxide/nickel oxide/reduced graphene oxide nano-sieve (SnO) is adopted by solvothermal, oxidation etching, high-temperature annealing and the like 2 the/NiO/HrGO) ternary composite material successfully overcomes the defects of low gas-sensitive response, high working temperature and the like of a single graphene and metal oxide gas sensor by ternary compounding and structure regulation of graphene and metal oxide, and realizes NO treatment 2 High response room temperature detection, design and manufacture of multi-component composite materialPrepared and NO 2 The gas-sensitive test has good guiding function.
Description
Technical Field
The invention belongs to the gas-sensitive material technology, and particularly relates to SnO 2 a/NiO/graphene ternary three-dimensional composite material, and a preparation method and application thereof.
Background
Due to the aggravation of environmental pollution and the requirements of production and living, designing and preparing the gas sensor with high sensitivity, high response speed, good stability, portability and low cost is an important subject. The gas sensitive material determines the quality of the sensor and is the key to the research of the sensor. Among them, graphene has attracted much attention because of its extremely high electron mobility and large specific surface area. However, the graphene sensitive material has bottlenecks such as low response sensitivity, slow response, poor selectivity and the like. In general, it is one of effective approaches to solve this problem to compound graphene and a metal oxide to form a heterostructure. To satisfy actual NO 2 The sensor has the advantages of low detection limit, low power consumption, high sensitivity and the like, and the gas sensing performance can be improved by designing a different novel structure. As a common sense, a single graphene or metal oxide gas sensor has the defects of low gas-sensitive response, high working temperature and the like, and is usually improved by compounding graphene and metal oxide, and the gas-sensitive response performance of the existing composite gas-sensitive material needs to be improved.
Disclosure of Invention
The invention passes MnO 2 Etching GO under acidic condition to obtain graphene oxide nano-sieve HGO and SnO 2 ternary/NiO/HrGO composites exhibiting excellent NO 2 Gas-sensitive properties. Through AFM test, the appearance structure of GO and HGO has been compared, and except that HGO has porous structure, the sheet diameter is also slightly less than GO. Reference SnO 2 NiO/rGO, para SnO 2 The same testing and characterization method is adopted for the/NiO/HrGO. SnO at room temperature 2 the/NiO/HrGO ternary composite material is opposite to NO of 1 ppm 2 The response of the composite sensor is 23.4 percent, which is obviously improved by a lot compared with the existing composite sensor.
The invention adopts the following technical scheme:
SnO (stannic oxide) 2 the/NiO/graphene ternary composite material comprises nano SnO 2 Nano NiO and porous graphene; specifically, nano SnO 2 Mixing the nano NiO and the graphene oxide nano sieve, grinding and calcining to obtain SnO 2 the/NiO/graphene ternary composite material.
Gas sensorComprises interdigital electrodes and a gas-sensitive material, wherein the gas-sensitive material is the SnO 2 a/NiO/graphene ternary composite material; the invention is characterized in that the SnO is the general knowledge 2 the/NiO/graphene ternary composite material is a gas sensitive material, and other elements used for devices are existing products.
In the invention, a nano NiO solution, a graphene oxide nano-sieve solution and nano SnO 2 The solution is stirred, mixed and then centrifuged, the precipitate is collected, dried, ground and then calcined to obtain SnO 2 the/NiO/graphene ternary composite material. Preferably, the nano NiO solution and the graphene oxide nano-sieve solution are sequentially added into the nano SnO 2 Stirring and mixing the solution, centrifuging the solution, collecting precipitates, drying, grinding, and calcining the precipitates to obtain SnO 2 the/NiO/graphene ternary composite material. Nano SnO 2 The mass ratio of the nano NiO to the graphene oxide nano sieve is (1-20) to 1, preferably (2-10) to (2-5) to 1, and more preferably (5-10) to 2:1, such as 10:2:1 and 5:2: 1. The calcination is carried out in air, and the mixture is heated for 1.5 to 3 hours at the temperature of 180 to 220 ℃.
In the invention, potassium permanganate is mixed with a graphene oxide solution, then microwave heating is carried out, and the mixture is treated by hydrochloric acid to obtain a graphene oxide nano-sieve; the microwave heating power is 500-1000W, the time is 3-6 minutes, the preferred microwave heating power is 600-800W, and the time is 4-5 minutes; the temperature is 60-80 ℃ and the time is 2-4 h when hydrochloric acid is used for treatment.
According to the method, nickel salt and citrate are used as raw materials, and are subjected to hydrothermal reaction, drying and calcining to obtain nano NiO; preferably, the hydrothermal reaction is carried out for 15-18 hours at 170-190 ℃; the calcination is carried out for 2 to 4 hours at the temperature of 370 to 420 ℃.
In the invention, polyvinylpyrrolidone and tin salt are used as raw materials, and the nanometer SnO is obtained by drying and calcining after the thermal reaction of a solvent 2 (ii) a Preferably, the solvothermal reaction is carried out at 170-190 ℃ for 2-4 hours; the calcination is carried out for 1 to 3 hours at the temperature of 470 to 520 ℃.
The invention adopts an oxidation etching methodPreparing to obtain graphene oxide nano-sieve HGO, and constructing a two-dimensional reduced graphene oxide nano-sieve HrGO-loaded metal oxide SnO 2 The ternary composite structure of the nanospheres and the NiO nanoflower. Deep research SnO based on structure 2 NO pair of/NiO/HrGO ternary composite material sensor 2 And with SnO 2 And carrying out comparative analysis on the test result of the/NiO/rGO ternary composite material. SnO 2 The gas-sensitive response of the/NiO/HrGO ternary composite material device is obviously improved. The invention discloses the above SnO 2 Application of/NiO/graphene ternary composite material or gas sensing device in nitrogen dioxide detection, or SnO 2 The application of the/NiO/graphene ternary composite material in preparing a nitrogen dioxide detection gas-sensitive material.
At present, a great deal of research reports are available on graphene binary composite materials, and reports on ternary composite materials are few. The method has the advantages that the graphene-based ternary composite heterostructure is constructed, the gas-sensitive characteristic under the action of the ternary composite interface is researched, and the method has important significance for the gas-sensitive mechanism of the centimeter-clean graphene multi-element composite heterostructure. The invention obtains the tin oxide/nickel oxide/reduced graphene oxide nano-sieve (SnO) by adopting methods such as solvothermal, oxidation etching, high-temperature annealing and the like on the basis of preparing Graphene Oxide (GO) and a surface control type semiconductor sensitive material by a Hummers method 2 /NiO/HrGO) ternary composite material and research on NO 2 The specific research results of the room temperature gas-sensitive performance of (1) are as follows: the ternary composite material which takes a novel reduced graphene oxide nano sieve (HrGO) as a substrate and loads nickel oxide nanoflowers and tin oxide nanospheres is obtained through structure regulation and control, and NO is treated 2 The gas shows more excellent gas-sensitive performance. And preparing a graphene oxide nano sieve (HGO) by adopting an oxidation etching method. Then obtaining SnO by high-temperature annealing reduction 2 the/NiO/HrGO ternary composite material. The gas-sensitive test result shows that SnO 2 The highest response value of the/NiO/HrGO ternary composite material to 1 ppm is 23.4 percent, and the highest response value is SnO 2 the/HrGO binary composite material, the NiO/HrGO binary composite material and the single HrGO are 1.7 times, 2 times and 3.2 times. With SnO 2 Increased mass ratio to NiO, SnO 2 Gas sensitive response early increase of/NiO/HrGOAnd decreases after increasing. In addition, the response values of the HrGO series products are higher than those of the rGO series.
Drawings
Fig. 1 is an SEM image of NiO nanoflowers.
FIG. 2 is SnO 2 SEM image of nanospheres.
FIG. 3 is an AFM image of an HGO.
FIG. 4 shows HGO and ternary composite SnO 2 XRD pattern of/NiO/HrGO.
FIG. 5 shows XPS (a) full spectrum and (b) C1 s fine spectrum of HGO.
FIG. 6 shows ternary composite SnO 2 XPS fine spectrum of/NiO/HrGO: (a) c1 s; (b) o1 s; (c) ni 2 p; (d) sn 3 d.
FIG. 7 is SnO 2 /NiO/HrGO、SnO 2 /HrGO, NiO/HrGO and HrGO to 1 ppm NO 2 Gas sensitive response curve of (2).
FIG. 8 is SnO 2 the/NiO/HrGO ternary composite material sensor can measure NO with different concentrations 2 Gas sensitive response curve of (2).
FIG. 9 shows different mass ratios of (a) SnO 2 NiO/HrGO to 1 ppm NO 2 Real-time gas sensitive response curve.
FIG. 10 is SnO 2 NiO/rGO and SnO 2 A gas sensitive response value line graph of/NiO/HrGO.
FIG. 11 shows SnO 2 the/NiO/rGO ternary composite material sensor can measure NO with different concentrations 2 Gas sensitive response curve of (2).
FIG. 12 is SnO 2 And (3) a gas-sensitive response value histogram of the/NiO/HrGO ternary composite material sensor to different gases.
Detailed Description
The invention adopts two-dimensional graphene and spherical and flower-shaped metal oxides to form a ternary composite structure model of a P-N-P heterojunction, and the NO of the ternary composite material is obviously improved by utilizing the heterostructure of a contact surface 2 Gas sensing performance. The combination of three shapes of nanospheres, nanoflowers and nanosheets enables SnO 2 The nanospheres and the NiO nanoflowers are dispersed among graphene sheet layers, so that stacking of graphene nanosheets is effectively reduced, and the stacking is repeatedAn electron transport channel is established between the composite materials, gas adsorption sites are increased, and the sensitivity of the composite material to target gas can be improved due to abundant oxygen defects. The reduction in the dimensions or the reduction in the dimensional structure of the composite material can have particular properties, such as surface and interface effects, small-scale effects, quantum-size effects, dielectric confinement effects, macroscopic quantum tunneling effects. SnO prepared by the invention 2 the/NiO/graphene ternary composite material has excellent gas-sensitive response characteristics.
The invention adopts a mode of annealing reduction to prepare SnO 2 the/NiO/HrGO ternary composite material. First, SnO is separately prepared 2 And adding NiO powder into ethanol to obtain a uniform solution. With conventional stirring, followed by a milky SnO 2 Dropwise adding the solution into a green NiO solution, then dropwise adding an HGO solution, conventionally stirring and mixing, centrifuging and collecting a product, and drying in an oven at 60 ℃; grinding the solid to obtain SnO 2 Putting the/NiO/HGO powder into a tube furnace, calcining in air at 200 ℃ for 2 hours for reduction to finally obtain SnO 2 the/NiO/HrGO ternary composite material. Adopting an atomic force microscope to perform morphology scanning on HrGO and carrying out SnO treatment on the composite material 2 the/NiO/HrGO is subjected to conventional characterization such as XRD, Raman, XPS, FTIR and the like.
All the raw materials of the invention are commercial products, the specific preparation operation and the room temperature gas-sensitive test are the prior art, and the conventional test operations such as stirring, washing and the like are performed. The graphene oxide is prepared by referring to a conventional Hummers method, the principle is that a strong acid strong oxidant is used for oxidizing and intercalating natural graphite flakes, the interlayer spacing of graphite flake layers is increased, the interlayer spacing is further increased by using a thermal expansion method, the graphite flake layers are separated by combining a mechanical stirring and ultrasonic stripping method in the process of increasing the interlayer spacing, and finally, the Graphene Oxide (GO) is successfully prepared, wherein the preparation process comprises the following steps:
1) weighing 2g of natural graphite (500 meshes), mixing the natural graphite with 50 ml of concentrated sulfuric acid in a 250 ml beaker, and conventionally stirring for 30 min; then adding 1g of sodium nitrate, and conventionally stirring for 2 hours in ice bath; adding 7.3 g of potassium permanganate into the solution in three batches, and then stirring the reaction solution in a water bath at the temperature of 35 ℃ for 2 hours to further complete oxidation intercalation; adding 150 ml of deionized water into the mixed solution, stirring for 30 min to release heat of the solution, and further increasing the interlayer spacing by utilizing thermal expansion; then, 55 ml of 4% hydrogen peroxide solution is dripped into the mixed solution and stirred for 30 min, so that redundant potassium permanganate is further oxidized and consumed, and a brown-yellow GO suspension is obtained after stirring is finished;
2) and (3) carrying out suction filtration on the brown yellow suspension solution, washing with dilute hydrochloric acid (3%, 100 ml) for three times, centrifuging for three times, dissolving with deionized water, dialyzing in a dialysis bag for one week, drying in an oven at 40 ℃ after dialysis, and finally obtaining Graphene Oxide (GO) which is dispersed in deionized water.
EXAMPLE preparation of NiO nanoflowers
The preparation method of the NiO nanoflower by adopting a solvothermal method comprises the following specific operation processes in sequence:
(1) 1.5 g of nickel nitrate hexahydrate (Ni (NO) was weighed 3 ) 2 . 6H 2 O) adding 30 mL of deionized water into a beaker to obtain a solution A; 0.5 g of sodium citrate dihydrate (Na) is weighed 3 C 6 H 5 O 7 . 2H 2 O), adding 30 mL of deionized water to obtain a solution B;
(2) dropwise adding the solution B into the stirred solution A to obtain a transparent light green mixed solution, transferring the transparent light green mixed solution into a polytetrafluoroethylene lining high-pressure kettle, and reacting for 16 hours at 180 ℃; cooling the reaction liquid to room temperature, taking out the green precipitate, and centrifugally washing the green precipitate by using deionized water and absolute ethyl alcohol at the centrifugal rate of 6000 revolutions per minute; drying the washed product in a 60 ℃ drying oven for 12 hours to obtain precursor powder;
(3) and putting the precursor powder into a tube furnace, calcining in the air for 3 hours at the temperature of 400 ℃ to obtain the NiO nanoflower. FIG. 1 is an SEM image of NiO nanoflower, with a grain size of about 3 μm and a complete, uniform, impurity-free flower shape.
EXAMPLE two SnO 2 Preparation of nanospheres
SnO with the particle size of about 500 nm is obtained by adopting a solvothermal method and combining a high-temperature annealing mode 2 Nanosphere. The specific preparation method comprises the following steps of:
(1) 0.5 g of polyvinylpyrrolidone (PVP) and 0.25 g of stannic chloride pentahydrate (SnCl) 4 . 5H 2 0) Adding 60 mL of methanol into a polytetrafluoroethylene high-pressure kettle, and heating in a drying oven at 180 ℃ for 3 hours;
(2) after the reaction is finished, cooling the reaction kettle to room temperature, taking out white precipitate at the bottom, centrifuging at 4000 revolutions per minute, collecting the precipitate, repeatedly centrifuging and washing the precipitate for 3 times by using ethanol, and drying in an oven to obtain a precursor;
(3) grinding the precursor into powder, putting the powder into a tube furnace, and annealing for 2 hours at 500 ℃ in the air atmosphere to obtain SnO 2 Nanospheres. FIG. 2 is SnO 2 SEM image of nanospheres, SnO 2 The diameter of the spheres is about 0.5 μm, SnO 2 The nanospheres have uniform particle size, complete appearance and no impurity particles.
Examples preparation of graphene oxide nanosieve (HGO)
The preparation of the graphene oxide nano-sieve is based on MnO under acidic condition 2 The specific preparation method for etching GO is as follows:
(1) weigh 0.2 g KMnO 4 Adding into 100 ml of 1 mg/ml GO water solution, and magnetically stirring for 20 min to obtain a dark purple solution;
(2) transferring the dark purple solution into a conventional household microwave oven (700W), and heating with high fire for 5 min;
(3) naturally cooling the product after the microwave reaction to room temperature, taking out, and centrifugally washing for 5 times by using deionized water;
(4) transferring the cleaned precipitate into a round-bottom flask, adding hydrochloric acid (37 wt%) to submerge the product, and then placing into a water bath container to perform water bath treatment at 70 ℃ for 3h, wherein magnetic stirring is continuously performed;
(5) and centrifuging the product after hydrochloric acid treatment, collecting precipitate, washing until the washing solution is neutral, and drying to obtain the HGO. FIG. 3 is an AFM image of HGOs with pores on the HGO lamellae that are not regularly circular structures and are of varying sizes.
Example TetraSnO 2 Preparation of/NiO/HrGO ternary composite material
The response speed and sensitivity of the sensing device are closely related to the structural size, specific surface area and heterogeneity of the active material. SnO preparation by adopting annealing reduction mode 2 the/NiO/HrGO ternary composite material. First, 0.1g SnO was weighed separately 2 Putting the nanospheres and 0.02g of NiO nanoflower into a beaker, and respectively adding 50 ml of ethanol to obtain milky SnO 2 Solution, green NiO solution; followed by the formation of opalescent SnO 2 Dropwise adding the solution into the NiO solution, then dropwise adding 10 ml of HGO aqueous solution with the concentration of 1 mg/ml into the mixed solution, and conventionally stirring for 15 minutes; centrifuging at 4000 rpm, collecting precipitate, drying in 60 deg.C oven to obtain solid, and grinding to obtain SnO 2 Putting the/NiO/HGO powder into a tube furnace, calcining in air at 200 ℃ for 2 hours for reduction to finally obtain SnO 2 the/NiO/HrGO ternary composite material.
SnO 2 The XRD spectra of the/NiO/HrGO ternary composite material and the HGO are shown in figure 4. The individual diffraction planes are marked in the figure without any characteristic peaks of impurities and without other phases associated with nickel, tin or tin-nickel compounds being observed, which indicates SnO 2 The ternary composite material of/NiO/HrGO is successfully synthesized. It is reported that the (001), (004) diffraction planes at 12.23 ° and 42.59 ° belong to graphene oxide, and the (002) peak at 20 ° belongs to reduced graphene oxide; the ternary composite material contains a (002) peak of reduced graphene oxide, and the important change indicates that the composite material is successfully reduced.
FIG. 5 shows XPS survey spectra and C1 s fine spectra of graphene oxide nanosieves. In the full spectrum, the corresponding peak of C, O was clearly observed and no other impurity peaks were seen. In the C1 s fine spectrum, it can be seen that multiple functional groups such as C = C, C-O, C = O exist in the HGO, wherein the proportion of the oxygen-containing functional groups is large.
FIG. 6 is SnO under narrow scan 2 C1 s, O1 s, Ni 2p and Sn 3d fine spectrums of the/NiO/HrGO ternary composite material. SnO was analyzed by XPS characterization 2 The chemical element composition and the electronic state of the surface of the/NiO/HrGO ternary composite material. First, HGO was compared with SnO 2 C1 s of/NiO/HrGO can be easily found, SnO 2 The content and peak value of the oxygen-containing functional group in the/NiO/HrGO are obviously reduced, which indicates that the composite material is successfully reduced. Second, O1 s consists of three components in different chemical states: o is Lattice 、O V 、O- x。
0.1g SnO was weighed 2 Adding 50 ml ethanol into the nanospheres to obtain milky SnO 2 A solution; then 10 ml of HGO aqueous solution with the concentration of 1 mg/ml is taken and dripped into the milky SnO 2 In the solution, stirring for 15 minutes conventionally; centrifuging at 4000 rpm, collecting precipitate, drying in 60 deg.C oven to obtain solid, and grinding to obtain SnO 2 Putting the/HGO powder into a tubular furnace, calcining in air at 200 ℃ for 2 hours for reduction to finally obtain SnO 2 a/HrGO composite material.
Weighing 0.02g of NiO nanoflower, adding 50 ml of ethanol into a beaker to obtain a green NiO solution; then 10 ml of HGO aqueous solution with the concentration of 1 mg/ml is dropwise added into the green NiO solution, and the mixture is stirred for 15 minutes conventionally; and then centrifuging at 4000 rpm, collecting the precipitate, drying in an oven at 60 ℃ to obtain a solid, grinding the solid to obtain NiO/HGO powder, putting the NiO/HGO powder into a tubular furnace, calcining in the air at 200 ℃ for 2 hours, and reducing to finally obtain the NiO/HrGO composite material.
EXAMPLE five gas sensor preparation
(1) Preparation of interdigital electrode
In the gas-sensitive test, the interdigital electrode can be used as a physical carrier element to supply voltage for the attached and conducted gas-sensitive material. The interdigital electrode of the gas sensor is an existing product, is manufactured based on a silicon process and is manufactured by adopting a traditional micromachining process, and the preparation process comprises the following steps: putting the cleaned silicon wafer into concentrated H 2 SO 4 And H 2 O 2 Processing the mixed solution at 90 ℃ for half an hour to obtain a silicon wafer substrate with a hydrophilic surface, washing and drying the silicon wafer substrate, then spin-coating photoresist on the surface, placing a conventional interdigital mask for exposure and development, then sputtering gold on the substrate, and finally ultrasonically stripping the photoresist to prepare the interdigital electrodes, wherein the prepared interdigital electrodes have the pitch of 10 microns, the width of 10 microns and the length of 600 microns.
(2) Drop coating of gas sensitive material
First, 2. mu.L of SnO with a concentration of 0.5 mg/mL using a micropipette 2 And (3) dripping ethanol solution of the/NiO/HrGO ternary composite material on an effective contact area of the interdigital electrode, so that the gas sensitive material is connected with two poles of the interdigital electrode to form a conductive channel, and naturally drying the conductive channel, and then putting the conductive channel into a 60-DEG C drying oven for drying. And then the interdigital electrode is connected with the copper base through a lead wire to obtain the gas sensor.
On the basis of the preparation method of the device, the gas-sensitive material is changed as a contrast:
SnO 2 changing/NiO/HrGO ternary composite material into SnO 2 the/NiO/HGO powder, the rest being unchanged, to give SnO 2 the/NiO/HGO gas sensor.
SnO 2 And changing the/NiO/HrGO ternary composite material into a NiO/HrGO composite material, and keeping the balance unchanged to obtain the NiO/HGO gas sensor.
SnO 2 changing/NiO/HrGO ternary composite material into SnO 2 The rest of the/HrGO composite material is unchanged to obtain SnO 2 A/HGO gas sensor.
And (3) dropwise adding 2 mu L of HGO aqueous solution with the concentration of 1 mg/ml to an effective contact area of the interdigital electrode, naturally drying the HGO aqueous solution, then placing the HGO aqueous solution into a tubular furnace, calcining the HGO aqueous solution for 2 hours at 200 ℃ in the air, and reducing the HGO aqueous solution to finally obtain the HrGO gas sensor.
Example six gas sensing test
According to the prior art, a gas sensitive test system is built by using an Agilent B1500A semiconductor tester. The test system comprises two parts of gas supply and data acquisition; the air supply system uses compressed air as background gas, NO 2 The two gases are fully mixed in the mixing chamber and then enter the testing chamber where the device is located.
The gas sensor is placed in the test cavity, and the two pins are connected with the Agilent tester. Before testing, the I-V mode of the tester is switched to check whether the device is conducted. Then, a background gas is introduced for a period of time to remove residual NO 2 Gas, continuously introducing background gas, adjusting the test mode to I/V-T, setting the voltage to 0.5V, and observing the device electricityDynamic curve of resistance. After a stable baseline is obtained, the target gas NO is introduced 2 By regulating NO 2 Flow rate F n Background gas flow rate F a Determination of the required NO 2 Concentration C n . All gases can be closed after the resistance is stable and lasts for a proper time, and a gas response of a complete period is obtained when the gas-sensitive curve is stable again. The percent response is the ratio of the change in resistance to the initial resistance and is calculated as follows:
the improved graphene nano-sieve is mostly in a small-piece structure and has a porous structure. To reflect the improved HGO and NO after the two oxides are compounded 2 Influence of sensing characteristics and realization of SnO 2 /NiO/HrGO and SnO 2 The sensitivity of/NiO/HGO two materials is compared, and SnO is tested in this section 2 NO of/NiO/HrGO 2 Gas-sensitive performance.
FIG. 7 shows SnO 2 /NiO/HrGO、SnO 2 HrGO, NiO/HrGO and HrGO to 1 ppm NO 2 Gas sensitive response curve of (2). SnO in the figure 2 /NiO/HrGO、SnO 2 The gas-sensitive response values of the/HrGO, the NiO/HrGO and the HrGO are 23.4%, 13.9%, 11.8% and 7.4% respectively. SnO 2 The gas-sensitive response of the/NiO/HrGO ternary composite material is obviously higher than that of SnO 2 The material has the advantages of high response speed, stable response state and strong recovery capability. In addition, existing SnO 2 -CuO/rGO sensor vs 5ppm NO 2 Response of (a) is only 18%; devices of metal oxide alone are essentially unresponsive at room temperature.
FIG. 8 shows SnO 2 200 ppb, 500 ppb and 1 ppm NO of/NiO/HrGO ternary composite material sensor pair 2 The gas response values of the gas response curves are 16.9%, 18.9% and 23.4%, respectively. There was a significant change in each concentration response, indicating SnO 2 /NiO/HrGO to low concentration NO 2 Has excellent resolving power and is suitable for NO 2 And (5) on the occasion of lower concentration detection limit.
EXAMPLE seven
On the basis of the preparation method of example four, SnO is changed 2 charging/NiO/HrGO, i.e. keeping the dosage of HGO aqueous solution unchanged and changing SnO 2 The amount of the/NiO is not changed, and SnO with different raw material ratios is obtained 2 The gas test of example six was performed on the/NiO/HrGO ternary composite, and FIG. 9 explores different composite ratios versus SnO 2 Influence of the performance of the/NiO/HrGO ternary composite material sensor. Likewise in accordance with SnO 2 NiO and HGO are mixed in the order of 1:20:1, 2:5:1, 5:2:1, 10:2:1 and 20:1:1 to 5 mass ratios (keeping the amount of the HGO aqueous solution unchanged), and the amount of the HGO is fixed in the experiment by SnO 2 SnO observation of content change of two oxides with NiO 2 Trend of response value change of/NiO/HrGO, NO 2 The concentrations were all 1 ppm.
Example eight
First, 0.1g SnO was weighed separately 2 Putting the nanospheres and 0.02g of NiO nanoflower into a beaker, and respectively adding 50 ml of ethanol to obtain milky SnO 2 Solution, green NiO solution; followed by the formation of opalescent SnO 2 Dropwise adding the solution into the NiO solution, then dropwise adding 10 ml of GO aqueous solution with the concentration of 1 mg/ml into the mixed solution, and conventionally stirring for 15 minutes; centrifuging at 4000 rpm, collecting precipitate, drying in 60 deg.C oven to obtain solid, and grinding to obtain SnO 2 Putting the/NiO/GO powder into a tubular furnace, calcining the powder in the air at 200 ℃ for 2 hours for reduction to finally obtain SnO 2 the/NiO/rGO ternary composite material. SnO was prepared according to the method of example five 2 a/NiO/rGO gas device, gas testing was performed according to the method of example six, and FIG. 10 is SnO 2 /NiO/HrGO and SnO 2 Gas sensitive response contrast plot of/NiO/rGO, NO 2 The concentrations were all 1 ppm. It can be observed that with SnO 2 Mass ratio to NiO is increased, SnO 2 The gas-sensitive value of/NiO/HrGO is increased and then reduced, when SnO 2 The response of NiO and HGO is 10:2:1, and the change and SnO are achieved 2 the/NiO/rGO is the same. Except that in all ratios, SnO 2 of/NiO/HrGOResponse value ratio SnO 2 the/NiO/rGO is much higher. In particular, SnO at a ratio of 10:2:1 2 The response value of/NiO/HrGO is 23.4 percent, specific SnO 2 the/NiO/rGO is 7.2 percent higher.
FIG. 11 shows the difference NO 2 SnO at concentration 2 And the gas-sensitive response curve of the/NiO/rGO ternary composite material sensor. With NO 2 Increased concentration of NO 2 The coverage of gas on the surface of the material is enlarged, so that the surface reaction is intensified, and the gas-sensitive response is improved. As shown, SnO 2 NiO/rGO pair 200 ppb, 500 ppb, 1 ppmNO 2 The gas sensitivity response values of (1) were 10.9%, 13.7%, and 16.2%, respectively.
Example nine
FIG. 12 shows SnO in different gas environments 2 Gas sensor gas sensitive response bar chart of/NiO/HrGO ternary composite (example four) to different gases. SnO 2 NiO/HrGO pair NO 2 The response values of formaldehyde, ethanol, acetone, trichloromethane and ethyl acetate are 23.4, 2.5%, 1.2%, 3.0%, 2.3% and 1.7%, respectively, and the ternary composite material has NO 2 Much more than other gases.
To summarize:
the research of the invention is mainly to prepare the ternary composite material SnO of the reduced graphene oxide nano-sieve loaded tin oxide and nickel oxide 2 NiO/HrGO and analyzed for NO 2 Gas-sensitive properties of (2). Firstly, an oxidation etching method is adopted to realize the improvement of the graphene oxide, and the graphene oxide nano-sieve is prepared. Then SnO is obtained by adopting a high-temperature annealing reduction mode 2 the/NiO/HrGO ternary composite material is finally dripped on the interdigital electrode to obtain SnO 2 And carrying out gas-sensitive test on the/NiO/HrGO ternary composite material sensor.
SnO 2 Compared with SnO in gas-sensitive test of materials with different composite proportions, the/NiO/HrGO device 2 the/NiO/rGO shows extremely fast response speed, excellent environmental stability and good selectivity, particularly, SnO in response value 2 higher/NiO/HrGO. In conclusion, the present invention successfully develops a simpler, sensitive and reliable SnO-based catalyst 2 NO of/NiO/HrGO 2 A gas sensor.
Claims (10)
1. SnO (stannic oxide) 2 the/NiO/graphene ternary composite material is characterized by comprising nano SnO 2 Nano NiO and porous graphene.
2. The SnO of claim 1 2 The preparation method of the/NiO/graphene ternary composite material is characterized in that nano SnO is added 2 Mixing the nano NiO and the graphene oxide nano sieve, grinding and calcining to obtain SnO 2 the/NiO/graphene ternary composite material.
3. A SnO according to claim 2 2 The preparation method of the/NiO/graphene ternary composite material is characterized in that a nano NiO solution, a graphene oxide nano-sieve solution and nano SnO are added 2 The solution is stirred, mixed and then centrifuged, the precipitate is collected, dried, ground and then calcined to obtain SnO 2 the/NiO/graphene ternary composite material.
4. A SnO according to claim 2 2 The preparation method of the/NiO/graphene ternary composite material is characterized in that the nano SnO 2 The mass ratio of the nano NiO to the graphene oxide nano sieve is (1-20) to 1.
5. A SnO according to claim 2 2 The preparation method of the/NiO/graphene ternary composite material is characterized in that potassium permanganate and a graphene oxide solution are mixed, then microwave heating is carried out, and hydrochloric acid treatment is carried out to obtain a graphene oxide nano-sieve; taking nickel salt and citrate as raw materials, carrying out hydrothermal reaction, drying and calcining to obtain nano NiO; taking polyvinylpyrrolidone and tin salt as raw materials, carrying out thermal reaction of a solvent, drying and calcining to obtain nano SnO 2 。
6. A SnO according to claim 5 2 The preparation method of the/NiO/graphene ternary composite material is characterized by preparing graphite oxideWhen the alkene is sieved by the nano sieve, the microwave heating power is 600-800W, the time is 4-5 minutes, and when the alkene is treated by hydrochloric acid, the temperature is 60-80 ℃, and the time is 2-4 hours; when the nano NiO is prepared, the solvothermal reaction is carried out for 2-4 hours at the temperature of 170-190 ℃, and the calcination is carried out for 1-3 hours at the temperature of 470-520 ℃; nano SnO in preparation 2 Carrying out hydrothermal reaction at 170-190 ℃ for 15-18 hours; the calcination is carried out for 2 to 4 hours at the temperature of 370 to 420 ℃.
7. A gas sensor device comprising interdigital electrodes and a gas-sensitive material, wherein the gas-sensitive material is the SnO of claim 1 2 the/NiO/graphene ternary composite material.
8. A method for detecting a nitrogen oxide gas, comprising placing the gas sensor according to claim 7 in an environment containing a nitrogen oxide gas to perform detection of a nitrogen oxide gas.
9. The SnO of claim 1 2 The application of the/NiO/graphene ternary composite material in nitrogen dioxide detection or the preparation of a nitrogen dioxide detection gas-sensitive material.
10. Use of the gas sensor device according to claim 7 for the detection of nitrogen dioxide.
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