CN115057437B - SnO (tin oxide) 2 NiO/graphene ternary composite material and preparation method and application thereof - Google Patents
SnO (tin oxide) 2 NiO/graphene ternary composite material and preparation method and application thereof Download PDFInfo
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- CN115057437B CN115057437B CN202210601290.XA CN202210601290A CN115057437B CN 115057437 B CN115057437 B CN 115057437B CN 202210601290 A CN202210601290 A CN 202210601290A CN 115057437 B CN115057437 B CN 115057437B
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- 239000011206 ternary composite Substances 0.000 title claims abstract description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 62
- 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 abstract description 8
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 8
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 88
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000000137 annealing Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 90
- 239000000243 solution Substances 0.000 claims description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- 239000002244 precipitate Substances 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 239000002077 nanosphere Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 239000002057 nanoflower Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001514 detection method Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene 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
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 238000010306 acid treatment Methods 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 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 claims description 3
- 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 claims description 3
- 229960000999 sodium citrate dihydrate Drugs 0.000 claims description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims 9
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims 2
- 239000012466 permeate Substances 0.000 claims 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims 2
- 230000004044 response Effects 0.000 abstract description 42
- 238000012360 testing method Methods 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 18
- 239000002131 composite material Substances 0.000 abstract description 14
- 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 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 229910000480 nickel 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
- 230000035945 sensitivity Effects 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000004729 solvothermal method Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- 238000000502 dialysis Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910021382 natural graphite Inorganic materials 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
- 230000005476 size effect Effects 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
- 239000011165 3D composite Substances 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 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
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 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
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 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
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process 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
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical class [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination 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
- 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
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method 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
- 230000005641 tunneling Effects 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
Classifications
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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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 NiO/graphene ternary composite material, preparation method and application thereof, and based on Graphene Oxide (GO) prepared by Hummers method and surface control type semiconductor sensitive material, tin oxide/nickel oxide/reduced graphene oxide nano sieve (SnO) is obtained by solvothermal, oxidation etching, high-temperature annealing and other methods 2 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 composite and structure regulation of graphene and metal oxide, and realizes NO 2 Is used for designing, preparing and NO of multi-element composite material 2 The gas-sensitive test has a good guiding effect.
Description
Technical Field
The invention belongs to the technology of gas-sensitive materials, in particular to SnO 2 NiO/graphene ternary three-dimensional composite material, and preparation method and application thereof.
Background
Because of the aggravation of environmental pollution and the demands of production and living, the design and preparation of the gas sensor with high sensitivity, high response speed, good stability, portability and low cost are important problems. The gas-sensitive material determines the quality of the sensor and is the key of sensor research. Wherein, the graphene has higher electron mobility and larger electron mobilityIs of great interest. However, graphene sensitive materials have bottlenecks such as low response sensitivity, slow response, poor selectivity and the like. In general, the formation of heterostructures by the recombination of graphene and metal oxides is one of the effective approaches to solve this problem. To meet the actual NO 2 The requirements of low detection limit, low power consumption, high sensitivity and the like of the sensor can be met, and the gas sensing performance can be improved from the strategy of designing different novel structures. As common knowledge, a single graphene or metal oxide gas sensor has the defects of low gas-sensitive response, high working temperature and the like, and is often improved by compounding graphene and metal oxide, so that the gas-sensitive response performance of the conventional compound gas-sensitive material is required to be improved.
Disclosure of Invention
The invention passes MnO 2 Etching GO under an acidic condition to prepare graphene oxide nano-screen HGO, and obtaining SnO 2 NiO/HrGO ternary composite material exhibiting excellent NO 2 Gas sensitive properties. Through AFM test, the morphology structures of GO and HGO are compared, and besides the HGO has a porous structure, the sheet diameter is slightly smaller than GO. Reference to SnO 2 NiO/rGO for SnO 2 The same test and characterization method was used for NiO/HrGO. SnO at room temperature 2 NiO/HrGO ternary composite material vs. 1 ppm NO 2 The response of the sensor is 23.4 percent, which is obviously improved compared with the prior compound sensor.
The invention adopts the following technical scheme:
SnO (tin oxide) 2 Ternary composite material of NiO/graphene comprising nano SnO 2 Nano NiO and porous graphene; specifically, nano SnO 2 Mixing, grinding and calcining the nano NiO and the graphene oxide nano sieve to obtain SnO 2 NiO/graphene ternary composite material.
A gas sensor comprises interdigital electrodes and a gas-sensitive material, wherein the gas-sensitive material is the SnO 2 NiO/graphene ternary composite material; as common knowledge, the invention also comprises leads, a base and the like, and the invention is characterized in that the SnO is 2 The NiO/graphene ternary composite material is a gas-sensitive material, and other elements used for devices are all existingAnd (5) a product.
In the invention, nano NiO solution, graphene oxide nano sieve solution and nano SnO are mixed together 2 Stirring and mixing the solution, centrifuging, collecting precipitate, drying, grinding, and calcining to obtain SnO 2 NiO/graphene ternary composite material. Preferably, the nano NiO solution and the graphene oxide nano sieve solution are sequentially added into nano SnO 2 In the solution, stirring and mixing, centrifuging, collecting precipitate, drying, grinding, and calcining to obtain SnO 2 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 to 1, such as 10:2:1 and 5:2:1. Calcining in air at 180-220 deg.c for 1.5-3 hr.
In the invention, potassium permanganate and graphene oxide solution are mixed, then microwave heating is carried out, and the graphene oxide nano sieve is obtained after hydrochloric acid treatment; the power of microwave heating is 500-1000W, the time is 3-6 minutes, the preferable power of microwave heating is 600-800W, and the time is 4-5 minutes; when hydrochloric acid is treated, the temperature is 60-80 ℃ and the time is 2-4 h.
In the invention, nickel salt and citrate are used as raw materials, and the nano NiO is obtained by drying and calcining after hydrothermal reaction; preferably, the hydrothermal reaction is carried out for 15-18 hours at 170-190 ℃; 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 nano SnO is obtained by drying and calcining after solvothermal reaction 2 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the solvothermal reaction is carried out for 2 to 4 hours at the temperature of 170 to 190 ℃; calcining at 470-520 deg.c for 1-3 hr.
The invention adopts the oxidation etching method to prepare the graphene oxide nano-screen HGO, and constructs a two-dimensional reduction graphene oxide nano-screen HrGO supported metal oxide SnO 2 Ternary composite structure of nanospheres and NiO nanoflowers. Based on this structure, the SnO is studied deeply 2 NiO/HrGO ternary composite material sensor pair NO 2 And with SnO 2 And comparing and analyzing the test result of the NiO/rGO ternary composite material. SnO (SnO) 2 The gas-sensitive response of the NiO/HrGO ternary composite material device is obviously improved. The invention discloses the SnO 2 Application of NiO/graphene ternary composite material or gas sensor in nitrogen dioxide detection, or SnO 2 Application of NiO/graphene ternary composite material in preparation of nitrogen dioxide detection gas-sensitive material.
Currently, there are a great deal of research reports on graphene binary composites, but few reports on ternary composites. The graphene-based ternary composite heterostructure is constructed, the gas-sensitive characteristic under the action of a ternary composite interface is studied, and the method has important significance on the gas-sensitive mechanism of the li-qing graphene multi-element composite heterostructure. The invention is based on a Hummers method for preparing Graphene Oxide (GO) and a surface control type semiconductor sensitive material, and adopts methods such as solvothermal method, oxidation etching method, high-temperature annealing method and the like to obtain the tin oxide/nickel oxide/reduced graphene oxide nano-screen (SnO) 2 NiO/HrGO) ternary composite material and studied its pair of NO 2 The specific research results are as follows: obtaining a ternary composite material with a novel reduced graphene oxide nano sieve (HrGO) as a substrate and loaded with nickel oxide nanoflower and tin oxide nanospheres through structure regulation and control, and carrying out NO 2 The gas exhibits more excellent gas-sensitive properties. And preparing the graphene oxide nano sieve (HGO) by adopting an oxidation etching method. Then high-temperature annealing and reduction are carried out to obtain SnO 2 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%, and the highest response value is SnO respectively 2 1.7, 2 and 3.2 times that of HrGO binary composite, niO/HrGO binary composite and single HrGO. Along with SnO 2 Mass ratio with NiO is increased, snO 2 The gas-sensitive response of/NiO/HrGO increases and decreases. In addition, the response value of the HrGO series products is higher than that of the rGO series products.
Drawings
Fig. 1 is an SEM image of NiO nanoflower.
FIG. 2 is SnO 2 SEM image of nanospheres.
FIG. 3 is an AFM image of HGO.
FIG. 4 shows HGO and ternary composite material SnO 2 XRD pattern of NiO/HrGO.
FIG. 5 shows XPS (a) full spectrum and (b) C1 s fine spectrum of HGO.
FIG. 6 is a ternary composite material SnO 2 XPS fine spectrogram of NiO/HrGO: (a) C1 s; (b) O1 s; (c) Ni 2p; (d) Sn 3d.
FIG. 7 is SnO 2 /NiO/HrGO、SnO 2 HrGO, niO/HrGO vs. 1 ppm NO 2 Is a gas-sensitive response curve of (2).
FIG. 8 is SnO 2 NiO/HrGO ternary composite material sensor for NO with different concentrations 2 Is a gas-sensitive response curve of (2).
FIG. 9 shows different mass ratios of (a) SnO 2 NiO/HrGO vs. 1 ppm NO 2 Is a real-time gas-sensitive response curve of (2).
FIG. 10 is SnO 2 NiO/rGO and SnO 2 Gas-sensitive response value line graph of NiO/HrGO.
FIG. 11 is SnO 2 NiO/rGO ternary composite material sensor for NO with different concentrations 2 Is a gas-sensitive response curve of (2).
FIG. 12 is SnO 2 Gas-sensitive response value bar graph of the NiO/HrGO ternary composite sensor for different gases.
Detailed Description
The invention adopts the three-dimensional graphene and the metal oxide with two unique shapes of sphere and flower to combine to form the ternary composite structure model of the P-N-P heterojunction, and the NO of the ternary composite material is obviously improved by utilizing the heterostructure of the contact surface 2 Gas sensing properties. The combination of three morphologies of nanospheres, nanoflower and nanoplatelets enables SnO to be formed 2 Nanospheres and NiO nanoflower are dispersed between graphene sheets, so that stacking of graphene sheets is effectively reduced, an electron transport channel is established between composite materials, gas adsorption sites are increased, and the sensitivity of the composite materials to target gas can be improved due to rich oxygen defects. The reduced dimensions or reduced dimensional structure of the composite material may manifest particular properties such as surface and interface effects, small size effects, quantum size effects, dielectric propertiesA confinement effect and a macroscopic quantum tunneling effect. The invention prepares SnO 2 And (3) the NiO/graphene ternary composite material and excellent gas-sensitive response characteristics are obtained.
The invention adopts an annealing reduction mode to prepare SnO 2 NiO/HrGO ternary composite material. First, snO is respectively treated with 2 And adding the NiO powder into ethanol to obtain a uniform solution. With conventional stirring, the milky SnO is then stirred 2 Dropwise adding the solution into a green NiO solution, dropwise adding an HGO solution, conventionally stirring and mixing, centrifugally collecting a product, and drying in a 60 ℃ oven; grinding the solid to obtain SnO 2 The NiO/HGO powder is put into a tube furnace and calcined for 2 hours at 200 ℃ in air for reduction, and finally the SnO is obtained 2 NiO/HrGO ternary composite material. Adopting an atomic force microscope to perform morphology scanning on HrGO and performing morphology scanning on the composite material SnO 2 The general characterization of XRD, raman, XPS, FTIR is carried out on NiO/HrGO.
All raw materials of the invention are commercial products, and the specific preparation operation and room temperature gas-sensitive test are all conventional test operations such as stirring, washing and the like. The graphene oxide is prepared by referring to a conventional Hummers method, the principle is that natural graphite flakes are subjected to oxidation intercalation by using a strong acid and strong oxidant, the interlayer spacing of the graphite flakes is increased, the interlayer spacing is further increased by using a thermal expansion method, the graphite flakes 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 is as follows:
1) Weighing 2g natural graphite (500 meshes), mixing with 50 ml concentrated sulfuric acid in a 250 ml beaker, and stirring for 30 min conventionally; adding 1g sodium nitrate, and stirring under ice bath for 2 h; adding 7.3 g potassium permanganate in three batches, and stirring the reaction solution in a water bath at 35 ℃ to react for 2h to further complete the oxidation intercalation; adding 150 ml deionized water into the mixed solution, stirring for 30 min to release heat, and further increasing interlayer spacing by thermal expansion; then dropwise adding a 55 ml 4% hydrogen peroxide solution into the mixed solution and stirring for 30 min to further oxidize and consume excessive potassium permanganate, and obtaining a brown-yellow GO suspension after stirring;
2) The brown yellow suspension solution is subjected to suction filtration, washed by dilute hydrochloric acid (3 percent, 100 percent and ml) for three times and centrifuged for three times, then is dissolved by deionized water and put into a dialysis bag for dialysis for one week, and is put into a baking oven for drying at 40 ℃ after the dialysis is finished, and finally, graphene Oxide (GO) is obtained and dispersed in the deionized water.
Example-preparation of NiO nanoflower
The NiO nanoflower is prepared by adopting a solvothermal method, and the specific operation flow is sequentially as follows:
(1) 1.5. 1.5 g nickel nitrate hexahydrate (Ni (NO) 3 ) 2 . 6H 2 O) adding 30 mL deionized water into a beaker to obtain a solution A; weigh 0.5 g sodium citrate dihydrate (Na 3 C 6 H 5 O 7 . 2H 2 O), adding 30 mL 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 autoclave, and reacting for 16 hours at 180 ℃; after the reaction liquid is cooled to room temperature, taking out the green precipitate, and centrifugally washing with deionized water and absolute ethyl alcohol, wherein the centrifugal speed is 6000 rpm; placing the washed product in a 60 ℃ oven for drying for 12 hours to obtain precursor powder;
(3) And placing the precursor powder into a tube furnace, calcining in air at 400 ℃ for 3 hours to obtain the NiO nanoflower. Fig. 1 is an SEM image of NiO nanoflowers with particle size of about 3 μm and complete, uniform flower shape, free of impurity particles.
Example two SnO 2 Preparation of nanospheres
The SnO with the particle size of about 500 nm is obtained by adopting a solvothermal method and combining a high-temperature annealing mode 2 A nanosphere. The specific preparation method is carried out as follows:
(1) 0.5. 0.5 g polyvinylpyrrolidone (PVP), 0.25. 0.25 g tin tetrachloride pentahydrate (SnCl) 4 . 5H 2 0) Adding 60-mL methanol into polytetrafluoroethylene autoclave, heating in 180 deg.C oven3 hours;
(2) After the reaction is completed, cooling the reaction kettle to room temperature, taking out white precipitate at the bottom, centrifuging at 4000 rpm, collecting the precipitate, repeatedly centrifuging and washing with ethanol for 3 times, and drying in an oven to obtain a precursor;
(3) Grinding the precursor into powder, then placing the powder into a tube furnace, and annealing the powder at 500 ℃ for 2 hours in an air atmosphere to obtain SnO 2 A nanosphere. FIG. 2 is SnO 2 SEM image of nanospheres, snO 2 The diameter of the spheres was about 0.5 μm and SnO 2 The nano-particles have uniform particle size, complete morphology and no impurity particles.
Example preparation of graphene oxide nanosieve (HGO)
The preparation of the graphene oxide nano sieve is based on MnO under acidic conditions 2 The etching of GO is carried out sequentially as follows:
(1) Weigh 0.2 g KMnO 4 Adding into 100 ml GO aqueous solution with the concentration of 1 mg/ml, and magnetically stirring for 20min to obtain deep purple solution;
(2) Transferring the deep purple solution into a conventional household microwave oven (700W), and heating with high fire for 5 min;
(3) Naturally cooling the product after microwave reaction to room temperature, taking out, and centrifugally washing with deionized water for 5 times;
(4) Transferring the cleaned precipitate into a round bottom flask, adding hydrochloric acid (37 wt%) to the product, and then placing the product into a water bath container to perform water bath treatment at 70 ℃ for 3h, wherein magnetic stirring is continuously performed during the period;
(5) And centrifuging the product after hydrochloric acid treatment, collecting precipitate, washing until the washing solution is neutral, and drying to obtain HGO. FIG. 3 is an AFM image of HGO, with the holes in the HGO sheets not being of a regular circular structure and being of different sizes.
Example four SnO 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. Preparing SnO by adopting an annealing reduction mode 2 NiO/HrGO ternary composite material. First, divideWeighing 0.1g SnO 2 Nanospheres, 0.02g of NiO nanoflower are placed in a beaker and 50 ml ethanol is added respectively to obtain milky SnO 2 Solution, green NiO solution; subsequently, milky SnO 2 Dropwise adding the solution into the NiO solution, then dropwise adding 10 ml HGO water solution with the concentration of 1 mg/ml into the mixed solution, and stirring for 15 minutes conventionally; centrifuging at 4000 rpm, collecting precipitate, drying in oven at 60deg.C to obtain solid, and grinding to obtain SnO 2 The NiO/HGO powder is put into a tube furnace and calcined for 2 hours at 200 ℃ in air for reduction, and finally the SnO is obtained 2 NiO/HrGO ternary composite material.
SnO 2 XRD spectra of the/NiO/HrGO ternary composite material and HGO are shown in FIG. 4. The individual diffraction planes have been marked, in which no characteristic peaks of impurities are observed, nor are other phases associated with nickel, tin or tin-nickel compounds, which indicate SnO 2 And (3) successfully synthesizing the NiO/HrGO ternary composite material. The (001), (004) diffraction planes at 12.23 ° and 42.59 ° are reported to belong to graphene oxide, and the (002) peak at 20 ° belongs to reduced graphene oxide; the ternary composite contains the (002) peak of reduced graphene oxide, an important change that indicates successful reduction of the composite.
FIG. 5 shows XPS full spectrum and C1 s fine spectrum of graphene oxide nano-sieves. In the full spectrum, the corresponding peak of C, O was clearly observed and no other impurity peaks were seen. In the fine spectrum of C1 s, it can be seen that a plurality of functional groups such as c= C, C-O, C =o exist in HGO, wherein the ratio of oxygen-containing functional groups is large.
FIG. 6 is SnO under narrow scan 2 C1 s, O1 s, ni 2p and Sn 3d fine spectra of the NiO/HrGO ternary composite material. SnO was analyzed by XPS characterization 2 Surface chemical element composition and electronic state of the NiO/HrGO ternary composite material. First, HGO is compared with SnO 2 C1 s of NiO/HrGO is not difficult to find, snO 2 The content and peak value of oxygen-containing functional groups in the NiO/HrGO are obviously reduced, which indicates that the composite material is successfully reduced. Second, O1 s consists of three components of different chemical states: o (O) Lattice 、O V 、O- x。
0.1g SnO is weighed 2 Adding 50 ml ethanol into nanospheres to obtain milky SnO 2 A solution; then, adding the HGO aqueous solution with the concentration of 1 mg/ml into the milky SnO by dripping 10 ml 2 Stirring the solution for 15 minutes conventionally; centrifuging at 4000 rpm, collecting precipitate, drying in oven at 60deg.C to obtain solid, and grinding to obtain SnO 2 HGO powder is put into a tube furnace and calcined for 2 hours at 200 ℃ in air to be reduced, and finally SnO is obtained 2 HrGO composite material.
Weighing 0.02g of NiO nanoflower, and adding 50 ml ethanol into a beaker to obtain a green NiO solution; then, dropwise adding 10 ml HGO water solution with the concentration of 1 mg/ml into the green NiO solution, and stirring for 15 minutes conventionally; and then centrifuging at 4000 rpm, collecting the precipitate, drying in a 60 ℃ oven to obtain a solid, grinding the solid to obtain NiO/HGO powder, placing the NiO/HGO powder in a tubular furnace, calcining at 200 ℃ for 2 hours in air for reduction, and finally obtaining the NiO/HrGO composite material.
Example five preparation of gas sensor
(1) Preparation of interdigital electrode
In gas sensitive testing, the interdigitated electrodes may act as physical carrier elements, supplying a voltage to the attached and conductive 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 micro-processing process, and the preparation process comprises the following steps: placing the cleaned silicon wafer into a concentration H 2 SO 4 And H is 2 O 2 Treating for half an hour at 90 ℃ to obtain a silicon wafer substrate with hydrophilic surface, spin-coating photoresist on the surface after washing and drying, putting a conventional interdigital mask plate for exposure and development, then sputtering gold on the substrate, and finally ultrasonically stripping the photoresist to obtain interdigital electrodes, wherein the prepared interdigital electrodes have the spacing of 10 microns, 10 microns wide and 600 microns long.
(2) Drop coating of gas sensitive materials
First, 2. Mu.L of SnO having a concentration of 0.5. 0.5 mg/mL was collected using a micropipette 2 The ethanol solution of the NiO/HrGO ternary composite material is dripped on the effective contact area of the interdigital electrode, so thatThe gas-sensitive material is connected with the two poles of the interdigital electrode to form a conductive channel, and the conductive channel is dried naturally and then is put into a drying oven at 60 ℃. And connecting the interdigital electrode with the copper base through a lead wire to obtain the gas sensor.
Based on the preparation method of the device, the gas-sensitive material is changed as a control:
SnO is prepared 2 Modification of NiO/HrGO ternary composite material into SnO 2 NiO/HGO powder, the rest is unchanged, and SnO is obtained 2 NiO/HGO gas sensor.
SnO is prepared 2 The NiO/HrGO ternary composite material is changed into a NiO/HrGO composite material, and the rest is unchanged, so that the NiO/HGO gas sensor is obtained.
SnO is prepared 2 Modification of NiO/HrGO ternary composite material into SnO 2 HrGO composite material, the rest is unchanged, and SnO is obtained 2 HGO gas sensor.
And (3) dropwise adding 2 mu L of HGO aqueous solution with the concentration of 1 mg/ml into an effective contact area of the interdigital electrode, naturally drying the solution, then placing the dried solution into a tube furnace, calcining the dried solution in air at 200 ℃ for 2 hours, and reducing the calcined solution to finally obtain the HrGO gas sensor.
Example six gas sensitive sensing test
According to the prior art, an Agilent B1500A semiconductor tester was used to build a gas sensitive test system. The test system comprises two parts, namely air supply and data acquisition; the air supply system takes compressed air as background gas, NO 2 The two gases are fully mixed in the mixing cavity and then are introduced into the testing cavity where the device is positioned.
And placing the gas sensor into a test cavity, and connecting the two pins with the Agilent tester. Before testing, switching to an I-V mode of the tester to check whether the device is on or not. Then, a background gas is introduced for a period of time to remove residual NO 2 The gas is continuously introduced into the background gas, the test mode is adjusted to be I/V-T, the voltage is set to be 0.5V, and then the dynamic curve of the resistance of the device can be observed. After obtaining a stable baseline, introducing target gas NO 2 By regulating NO 2 Flow rate F n Flow rate of background gas F a Determining the required NO 2 Concentration C n . To be treatedAfter the resistance is stable and the proper time is allowed to elapse, all gases can be shut down, and a complete cycle of gas response is obtained when the gas-sensitive curve reaches stability again. The percentage response is the ratio of the resistance change to the initial resistance calculated as follows:
the improved graphene nano sieve is in a small-piece structure and has a porous structure. To reflect the modified HGO and the two oxides combined to NO 2 Influence of sensing characteristics and implementation of SnO 2 NiO/HrGO and SnO 2 Sensitivity comparison of the two materials of NiO/HGO, the section tests SnO 2 NO of NiO/HrGO 2 Gas sensitive properties.
FIG. 7 shows SnO 2 /NiO/HrGO、SnO 2 HrGO, niO/HrGO vs. 1 ppm NO 2 Is a 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 (SnO) 2 The gas-sensitive response of the NiO/HrGO ternary composite material is obviously higher than that of SnO 2 The invention has the advantages of high response speed, stable response state and strong recovery capability. In addition, the existing SnO 2 CuO/rGO sensor vs. 5ppm NO 2 The response of (2) is only 18%; devices of metal oxide alone are substantially unresponsive at room temperature.
FIG. 8 shows SnO 2 NiO/HrGO ternary composite sensor pair 200 ppb, 500 ppb, 1 ppm NO 2 The gas response values of (2) were 16.9%, 18.9% and 23.4%, respectively. The concentration responses varied significantly, indicating SnO 2 NiO/HrGO pair low concentration NO 2 Has excellent resolving power, and is suitable for NO 2 And when the concentration detection limit is low.
Example seven
Based on the preparation method of the fourth embodiment, snO is changed 2 Feeding of/NiO/HrGO, i.e. protectionThe dosage of the HGO water solution is unchanged, and SnO is changed 2 The amount of NiO is unchanged, and SnO with different raw material proportions is obtained 2 Gas test of example six was performed on a NiO/HrGO ternary composite material, and FIG. 9 explores different composite ratios versus SnO 2 Impact of NiO/HrGO ternary composite sensor performance. Also according to SnO 2 NiO: HGO sequentially takes 5 mass ratios (keeping the dosage of HGO aqueous solution unchanged) of 1:20:1, 2:5:1, 5:2:1, 10:2:1 and 20:1:1, and the amount of HGO is fixed in the experiment and passes through SnO 2 Observation of SnO with changes in the content of two oxides of NiO 2 Trend of response value change of NiO/HrGO, NO 2 The concentrations were 1 ppm.
Example eight
Firstly, 0.1g SnO is weighed respectively 2 Nanospheres, 0.02g of NiO nanoflower are placed in a beaker and 50 ml ethanol is added respectively to obtain milky SnO 2 Solution, green NiO solution; subsequently, milky SnO 2 Dropwise adding the solution into the NiO solution, then dropwise adding 10 ml 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 oven at 60deg.C to obtain solid, and grinding to obtain SnO 2 The NiO/GO powder is put into a tube furnace and calcined for 2 hours at 200 ℃ in air for reduction, and finally SnO is obtained 2 NiO/rGO ternary composite material. And then according to the method of the fifth embodiment, snO is obtained 2 Gas testing of the NiO/rGO gas device was performed as described in example six, FIG. 10 is SnO 2 NiO/HrGO and SnO 2 Gas-sensitive response comparison graph of NiO/rGO, NO 2 The concentrations were 1 ppm. It can be observed that with SnO 2 Mass ratio with NiO is increased, snO 2 The gas sensitivity value of NiO/HrGO is increased and then decreased, when SnO 2 NiO-HGO is at a ratio of 10:2:1, the response is maximized, and the change is similar to SnO 2 The same applies to NiO/rGO. In all proportions, however, snO 2 Response value ratio of NiO/HrGO SnO 2 the/NiO/rGO ratio is much higher. SnO, in particular at a ratio of 10:2:1 2 Response value of NiO/HrGO is 23.4% compared with SnO 2 The NiO/rGO is 7.2 percent higher.
FIG. 11 shows different NO 2 SnO at a concentration of 2 Gas-sensitive response curve of a NiO/rGO ternary composite sensor. With NO 2 Concentration increases, NO 2 The coverage area of the gas on the surface of the material is increased, so that the surface reaction is aggravated, and the gas-sensitive response is improved. As shown in the figure, snO 2 NiO/rGO pair of 200 ppb, 500 ppb, 1 ppmNO 2 The gas-sensitive response values of (2) were 10.9%, 13.7% and 16.2%, respectively.
Example nine
FIG. 12 shows SnO in different gaseous environments 2 Gas-sensitive response histogram of NiO/HrGO ternary composite (example four) gas sensor for different gases. SnO (SnO) 2 NiO/HrGO vs. NO 2 Response values of formaldehyde, ethanol, acetone, chloroform and ethyl acetate are 23.4, 2.5%, 1.2%, 3.0%, 2.3% and 1.7%, respectively, and the ternary composite material is corresponding to NO 2 Is much more responsive than other gases.
Summarizing:
the research focus of the invention is to prepare a ternary composite material SnO of reduced graphene oxide nano-screen supported tin oxide and nickel oxide 2 NiO/HrGO and analyzed for NO 2 Is a gas-sensitive property of (2). Firstly, an oxidation etching method is adopted to realize improvement of graphene oxide, and the graphene oxide nano sieve is prepared. Then adopting a high-temperature annealing reduction mode to obtain SnO 2 The NiO/HrGO ternary composite material is finally dripped onto the interdigital electrode to obtain SnO 2 A NiO/HrGO ternary composite material sensor is provided, and is subjected to gas sensitivity test.
SnO 2 Compared with SnO in gas-sensitive test of materials with different composite proportions, niO/HrGO device 2 NiO/rGO shows extremely fast response speed, excellent environmental stability and good selectivity, especially in terms of response value, snO 2 Higher NiO/HrGO. In summary, the present invention successfully developed a simpler, sensitive, reliable SnO-based solution 2 NO of NiO/HrGO 2 A gas sensor.
Claims (8)
1. SnO (tin oxide) 2 The NiO/graphene ternary composite material is characterized in that,the SnO 2 The preparation method of the NiO/graphene ternary composite material comprises the steps of weighing 0.1g of SnO respectively 2 Nanospheres, 0.02g of NiO nanoflower are placed in a beaker and 50 ml ethanol is added respectively to obtain milky SnO 2 Solution, green NiO solution; subsequently, milky SnO 2 The solution was added dropwise to the NiO solution, and then 10 ml aqueous HGO solution with a concentration of 1 mg/ml was added dropwise to the mixed solution, followed by conventional stirring for 15 minutes; centrifuging at 4000 rpm, collecting precipitate, drying in oven at 60deg.C to obtain solid, and grinding to obtain SnO 2 The NiO/HGO powder is put into a tube furnace and calcined for 2 hours at 200 ℃ in air for reduction, and finally the SnO is obtained 2 NiO/HrGO ternary composite material.
2. The SnO of claim 1 2 The preparation method of the NiO/graphene ternary composite material is characterized by comprising the following steps of:
(1) Weighing 1.5. 1.5 g of nickel nitrate hexahydrate in a beaker, and adding 30. 30 mL of deionized water to obtain a solution A; weighing 0.5 g sodium citrate dihydrate, and adding 30 mL 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 autoclave, and reacting for 16 hours at 180 ℃; after the reaction liquid is cooled to room temperature, taking out the green precipitate, and centrifugally washing with deionized water and absolute ethyl alcohol, wherein the centrifugal speed is 6000 rpm; placing the washed product in a 60 ℃ oven for drying for 12 hours to obtain precursor powder;
(3) Placing the precursor powder into a tube furnace, calcining in air at 400 ℃ for 3 hours to obtain NiO nanoflower;
the SnO 2 The preparation method of the nanospheres comprises the following steps:
(1) Adding 0.5 g polyvinylpyrrolidone, 0.25 g penta-water stannic chloride and 60 mL methanol into a polytetrafluoroethylene autoclave, and heating in an oven at 180 ℃ for 3 hours;
(2) After the reaction is completed, cooling the reaction kettle to room temperature, taking out white precipitate at the bottom, centrifuging at 4000 rpm, collecting the precipitate, repeatedly centrifuging and washing with ethanol for 3 times, and drying in an oven to obtain a precursor;
(3) Grinding the precursor into powder, then placing the powder into a tube furnace, and annealing the powder for 2 hours at 500 ℃ in an air atmosphere to obtain SnO 2 A nanosphere;
the preparation method of the HGO comprises the following steps:
(1) Weigh 0.2 g KMnO 4 Adding into 100 ml GO aqueous solution with the concentration of 1 mg/ml, and magnetically stirring for 20min to obtain deep purple solution;
(2) Transferring the deep purple solution into a conventional household microwave oven, and heating with 700W high fire for 5 min;
(3) Naturally cooling the product after microwave reaction to room temperature, taking out, and centrifugally washing with deionized water for 5 times;
(4) Transferring the cleaned precipitate into a round bottom flask, adding 37wt% hydrochloric acid to permeate the product, and then placing the product into a water bath container to be treated in a water bath at 70 ℃ for 3h, wherein magnetic stirring is continuously carried out during the period;
(5) And centrifuging the product after hydrochloric acid treatment, collecting precipitate, washing until the washing solution is neutral, and drying to obtain HGO.
3. The SnO of claim 1 2 Preparation method of NiO/graphene ternary composite material is characterized by weighing 0.1g SnO respectively 2 Nanospheres, 0.02g of NiO nanoflower are placed in a beaker and 50 ml ethanol is added respectively to obtain milky SnO 2 Solution, green NiO solution; subsequently, milky SnO 2 Dropwise adding the solution into the NiO solution, then dropwise adding 10 ml HGO water solution with the concentration of 1 mg/ml into the mixed solution, and stirring for 15 minutes conventionally; centrifuging at 4000 rpm, collecting precipitate, drying in oven at 60deg.C to obtain solid, and grinding to obtain SnO 2 The NiO/HGO powder is put into a tube furnace and calcined for 2 hours at 200 ℃ in air for reduction, and finally the SnO is obtained 2 NiO/HrGO ternary composite material.
4. Root of Chinese characterThe SnO of claim 3 2 The preparation method of the NiO/graphene ternary composite material is characterized by comprising the following steps of:
(1) Weighing 1.5. 1.5 g of nickel nitrate hexahydrate in a beaker, and adding 30. 30 mL of deionized water to obtain a solution A; weighing 0.5 g sodium citrate dihydrate, and adding 30 mL 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 autoclave, and reacting for 16 hours at 180 ℃; after the reaction liquid is cooled to room temperature, taking out the green precipitate, and centrifugally washing with deionized water and absolute ethyl alcohol, wherein the centrifugal speed is 6000 rpm; placing the washed product in a 60 ℃ oven for drying for 12 hours to obtain precursor powder;
(3) Placing the precursor powder into a tube furnace, calcining in air at 400 ℃ for 3 hours to obtain NiO nanoflower;
the SnO 2 The preparation method of the nanospheres comprises the following steps:
(1) Adding 0.5 g polyvinylpyrrolidone, 0.25 g penta-water stannic chloride and 60 mL methanol into a polytetrafluoroethylene autoclave, and heating in an oven at 180 ℃ for 3 hours;
(2) After the reaction is completed, cooling the reaction kettle to room temperature, taking out white precipitate at the bottom, centrifuging at 4000 rpm, collecting the precipitate, repeatedly centrifuging and washing with ethanol for 3 times, and drying in an oven to obtain a precursor;
(3) Grinding the precursor into powder, then placing the powder into a tube furnace, and annealing the powder for 2 hours at 500 ℃ in an air atmosphere to obtain SnO 2 A nanosphere;
the preparation method of the HGO comprises the following steps:
(1) Weigh 0.2 g KMnO 4 Adding into 100 ml GO aqueous solution with the concentration of 1 mg/ml, and magnetically stirring for 20min to obtain deep purple solution;
(2) Transferring the deep purple solution into a conventional household microwave oven, and heating with 700W high fire for 5 min;
(3) Naturally cooling the product after microwave reaction to room temperature, taking out, and centrifugally washing with deionized water for 5 times;
(4) Transferring the cleaned precipitate into a round bottom flask, adding 37wt% hydrochloric acid to permeate the product, and then placing the product into a water bath container to be treated in a water bath at 70 ℃ for 3h, wherein magnetic stirring is continuously carried out during the period;
(5) And centrifuging the product after hydrochloric acid treatment, collecting precipitate, washing until the washing solution is neutral, and drying to obtain HGO.
5. A gas sensor comprising interdigital electrodes and a gas-sensitive material, wherein the gas-sensitive material is SnO as claimed in claim 1 2 NiO/graphene ternary composite material.
6. A nitrogen oxide gas detection method, wherein the gas sensor of claim 5 is placed in an environment containing nitrogen oxide gas to complete the detection of nitrogen oxide gas.
7. The SnO of claim 1 2 Application of the NiO/graphene ternary composite material in nitrogen dioxide detection or in preparation of nitrogen dioxide detection gas-sensitive material.
8. Use of the gas sensor device according to claim 5 for nitrogen dioxide detection.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210601290.XA CN115057437B (en) | 2022-05-30 | 2022-05-30 | SnO (tin oxide) 2 NiO/graphene ternary composite material and preparation method and application thereof |
| PCT/CN2022/114144 WO2023231191A1 (en) | 2022-05-30 | 2022-08-23 | Sno2/nio/graphene ternary composite material, and preparation method therefor and application thereof |
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| CN104803376A (en) * | 2015-03-27 | 2015-07-29 | 天津工业大学 | Efficient preparation process of graphene oxide nanosheets |
| CN105092646A (en) * | 2015-08-19 | 2015-11-25 | 电子科技大学 | Graphene/metal oxide composite film gas sensor and preparation method |
| CN106970119A (en) * | 2017-04-26 | 2017-07-21 | 成都聚立汇信科技有限公司 | A kind of graphene gas sensor |
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| CN103663438B (en) * | 2013-11-18 | 2016-01-27 | 南京久和纳米科技有限公司 | A kind of preparation method of porous graphene |
| CN106290489A (en) * | 2016-10-27 | 2017-01-04 | 苏州大学 | A kind of porous graphene gas sensor and preparation method thereof |
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| CN104803376A (en) * | 2015-03-27 | 2015-07-29 | 天津工业大学 | Efficient preparation process of graphene oxide nanosheets |
| CN105092646A (en) * | 2015-08-19 | 2015-11-25 | 电子科技大学 | Graphene/metal oxide composite film gas sensor and preparation method |
| CN106970119A (en) * | 2017-04-26 | 2017-07-21 | 成都聚立汇信科技有限公司 | A kind of graphene gas sensor |
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