CN115196694B - NiS/rGO composite material, preparation method thereof and application thereof in gas sensitive material - Google Patents
NiS/rGO composite material, preparation method thereof and application thereof in gas sensitive material Download PDFInfo
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- CN115196694B CN115196694B CN202210543195.9A CN202210543195A CN115196694B CN 115196694 B CN115196694 B CN 115196694B CN 202210543195 A CN202210543195 A CN 202210543195A CN 115196694 B CN115196694 B CN 115196694B
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- 239000002131 composite material Substances 0.000 title claims abstract description 117
- 239000000463 material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002070 nanowire Substances 0.000 claims abstract description 69
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000000137 annealing Methods 0.000 claims abstract description 19
- 238000005342 ion exchange Methods 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims description 127
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 16
- 238000006722 reduction reaction Methods 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 3
- 239000005416 organic matter Substances 0.000 claims 2
- 230000004044 response Effects 0.000 abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 34
- 229910021389 graphene Inorganic materials 0.000 abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 230000009467 reduction Effects 0.000 abstract description 8
- 229910052976 metal sulfide Inorganic materials 0.000 abstract description 5
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 26
- 238000001228 spectrum Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000001237 Raman spectrum Methods 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 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 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000011540 sensing material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 2
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000000903 blocking effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229940079101 sodium sulfide Drugs 0.000 description 1
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010897 surface acoustic wave method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/11—Sulfides
-
- 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
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- 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
- C01B32/194—After-treatment
-
- 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
-
- 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
-
- 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
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
Abstract
The invention discloses a NiS/rGO composite material, a preparation method thereof and application thereof in gas sensitive materials. The invention prepares Ni nano wire through high temperature water bath under the assistance of magnetic field, prepares NiO nano wire through high temperature annealing, prepares NiS nano wire through ion exchange reaction, and composites the NiS nano wire with GO, builds a multi-stage heterostructure based on NiS/rGO composite material through high temperature reduction, and prepares a gas sensor, explores NO of the device at normal temperature 2 Gas-sensitive response characteristics of the gas. The nickel sulfide (NiS)/reduced graphene oxide (rGO) composite material gas sensor follows a surface charge control model, the composite material formed by the reduced graphene oxide and the metal sulfide integrally shows semiconductor characteristics, electrons are captured, so that the concentration of electrons in the material is reduced, the concentration of holes is increased, and the gas sensor is of a hole conduction type, so that the conductivity of the sensor is increased, and the resistance is reduced.
Description
Technical Field
The invention belongs to the technology of gas sensors, and particularly relates to a NiS/rGO composite material, a preparation method thereof and application thereof in gas sensitive materials.
Background
Graphene has a large specific surface area, excellent charge carrier mobility and an energy band structure with zero band gap due to its unique two-dimensional structure, shows ideal gas sensing characteristics, and compared with graphene alone, graphene derivatives such as reduced graphene oxide (rGO) show excellent sensing performance due to huge surface vacancies and surface oxygen-containing functional groups. In the prior art, graphene oxide dispersion liquid is mixed with zinc oxide to obtain a mixed solution; the mass percentage of graphene oxide and zinc oxide in the graphene oxide dispersion liquid is more than 5%; passing the mixed solution through hydrothermal treatmentReacting to obtain a precipitate; and centrifugally washing and drying the precipitate to obtain the zinc oxide-based sensing material. The prior art discloses a high-sensitivity surface acoustic wave nitrogen dioxide sensor which sequentially comprises a piezoelectric substrate, an electrode layer and a sensor body from bottom to top, wherein NO is carried out through ultraviolet irradiation 2 A three-dimensional porous structure composite sensitive layer of the reduced graphene oxide-polypyrrole doped with the sensing silver nano particles; the 3D porous sensitive material rGO-PPy/Ag is adopted as a sensitive film, ag nano particles are adopted to dope so as to improve the repeatability of the sensor, and ultraviolet light is adopted to irradiate the sensitive film to assist NO 2 And (5) sensing. The prior art discloses a nitrogen dioxide sensor based on a composite material blocking effect and a preparation method thereof, and relates to the technical field of gas sensors and composite nano materials. The prior art has less research on gas sensors composed of metal sulfides and reduced graphene oxide.
Disclosure of Invention
In the invention, a nickel sulfide (NiS)/reduced graphene oxide (rGO) composite material gas sensor follows a surface charge control model, the composite material formed by reduced graphene oxide and metal sulfide integrally shows semiconductor characteristics, electrons are captured so that the concentration of electrons in the material is reduced, the concentration of holes is increased, and the material is of a hole conduction type, so that the conductivity of the sensor is increased, and the resistance is reduced.
The invention adopts the following technical scheme:
the preparation method of the NiS/rGO composite material comprises the steps of compounding GO and NiS nanowires to prepare the NiS/GO composite material; and then heating to prepare the NiS/rGO composite material. Preferably, the mass ratio of the NiS nanowires to the GO is (0.2-20) to 1, and preferably (2-10) to 1.
In the invention, a nickel source is subjected to reduction reaction under alkaline conditions in the presence of a reducing agent and under the assistance of a magnetic field to obtain Ni nanowires; then annealing at high temperature to obtain NiO nanowires; and then preparing the NiS nanowire through ion exchange reaction.
In the invention, water-soluble nickel salt is used as a nickel source, and nickel chloride hexahydrate and the like can be selected; organic reducing agent is used as reducing agent, hydrazine hydrate and the like can be selected; inorganic base is used as alkaline condition.
In the invention, the temperature of the reduction reaction is 60-80 ℃ and the time is 30-60 minutes; the high-temperature annealing temperature is 450-550 ℃ and the time is 100-150 minutes.
In the invention, sodium sulfide and NiO nanowires are used as raw materials to carry out ion exchange reaction to prepare the NiS nanowires. Preferably, the ion exchange reaction is carried out at 150-170 ℃ for 5-10 h.
In the invention, mixing NiS nanowire dispersion liquid and GO dispersion liquid, then centrifuging, and collecting precipitate to obtain a NiS/GO composite material; the temperature of the heating treatment is 180-250 ℃ and the time is 70-110 minutes.
The invention discloses a gas sensor made of a NiS/rGO composite material, which takes the NiS/rGO composite material as a gas-sensitive material. And (3) dripping the NiS/rGO composite material solution on the interdigital electrode, drying to form a film to obtain a gas sensing electrode, and conducting the electrode conventionally to obtain the NiS/rGO composite material gas sensor. The invention is creatively mainly to take the NiS/rGO composite material as a gas-sensitive material.
The invention discloses a nitrogen oxide gas detection method, which comprises the steps of placing a NiS/rGO composite material gas sensor in an environment containing nitrogen oxide gas to finish nitrogen oxide gas detection; preferably, the nitrogen oxide is nitrogen dioxide.
The response sensitivity of the gas sensor is closely related to the surface morphology, state and components of the sensing material, the nickel sulfide/reduced graphene oxide composite material provides a large specific surface area for adsorption of gas molecules, and meanwhile, the high mobility of the nickel sulfide/reduced graphene oxide composite material also becomes a rapid carrier transmission channel, so that the migration rate of carriers is enhanced. The nano heterostructure constructed by the composite material can effectively slow down aggregation and accumulation of graphene nano sheets and metal sulfides, is beneficial to expanding the effective contact area of the sensing material on gas molecules, and the constructed heterojunction can further improve the gas sensitivity of the composite material.
The invention uses hexahydrate nickel chloride as nickel source in alkaline by chemical oxidation-reduction methodUnder the condition that hydrazine hydrate is used as a reducing agent, under the assistance of a magnetic field, preparing the Ni nanowire through high-temperature water bath; and annealing 2h at 500 ℃ to prepare NiO nanowires, and preparing the NiS nanowires through ion exchange reaction. The NiS/GO composite material with different mass ratios is prepared by compounding GO and NiS nanowires with different proportions, the NiS/rGO composite material is prepared by further annealing at a high temperature of 200 ℃, and the composite material is assembled on an interdigital electrode to prepare the gas sensor of the NiS/rGO composite material, and the NO of the sensor is explored at room temperature 2 Response characteristics of the gas. The composite material can provide more adsorption sites for gas adsorption and improve gas-sensitive response. In general, the micro-nano structure is regulated and controlled through various strategies such as controllable synthesis of a novel nano structure, construction of a heterojunction, regulation and control of composite material components and the like, and the gas-sensitive performance of the micro-nano structure is improved.
Drawings
Fig. 1 is an SEM image of Ni nanowires.
Fig. 2 is an XRD pattern of Ni and NiO after annealing.
Fig. 3 is an SEM image of different samples: (a) NiO; (b) NiS; (c) NiS/GO; (d) NiS/rGO.
FIG. 4 is a Raman spectrum of NiO, niS, GO and NiS/rGO.
FIG. 5 is an XRD pattern for NiS and NiS/rGO.
FIG. 6 is an X-ray photoelectron spectrum of GO and NiS/rGO composites: (a) a full spectrum of GO; (b) the C1 s energy spectrum of GO; (c) a full spectrum of NiS/rGO; fine spectra of NiS/rGO: (d) C1S energy spectrum, (e) Ni 2p energy spectrum, and (f) S2 p energy spectrum.
FIG. 7 is a graph of NiO, niS, rGO and NiS/rGO composites versus 1ppm NO 2 Is a gas-sensitive response curve of (2).
FIG. 8 is a performance test of NiS/rGO composites of different graphene content.
FIG. 9 is a graph of NO at lower concentrations for a NiS/rGO-4 composite gas sensor 2 A gas-sensitive response test was performed under gas.
FIG. 10 is a NiS/rGO-4 composite sensor pair 1ppm NO 2 Repeatability ofGas-sensitive response curve.
FIG. 11 is a selectivity test of a NiS/rGO-4 composite sensor.
Detailed Description
According to the invention, the Ni nanowire is prepared by a chemical oxidation-reduction method, the NiO nanowire is prepared by high-temperature annealing, the NiS nanowire is further prepared by an ion exchange method, and the NiS/rGO heterostructure with different mass ratios of NiS and GO is prepared by adding different contents of graphene. Observing the surface morphology and the material crystal phase of the prepared composite material through the characterization means such as SEM, XRD, raman, FTIR, XPS and the like; and preparing the NiS/rGO composite materials with different mass ratios into a gas sensor for NO 2 The gas-sensitive test was performed with the following specific test results:
(1) NiS/rGO composite gas sensor pair with different mass ratios of 1ppm NO 2 The gas is tested, and the gas-sensitive test result shows that when the mass ratio of the NiS to the GO is 5:1, the response of the NiS/rGO composite material gas sensor is best, and the response reaches 29.7 percent, and compared with the graphene gas sensor, the response is improved by 2.3 times.
(2) Different concentrations of NO are carried out on the NiS/rGO composite material gas sensor 2 The results of the test of (2) show that the composite material gas sensor has NO concentration of 100 ppm 2 The gas response reaches 46.4%, and the NO with low concentration of 50 ppb 2 The gas response was still 10.1%. At the same time, the composite material gas sensor is subjected to repeatability test of four response recovery cycles, and experimental results show that the device has NO response of 1ppm 2 The gas has excellent repeatability; the composite material gas sensor is subjected to ten-period stability test and also shows good stability; meanwhile, the selectivity test is carried out on the composite material gas sensor, and the response of the device to organic gases such as ammonia gas, methanol and the like is very low, which indicates that the NiS/rGO composite material gas sensor has excellent selectivity.
The raw materials adopted by the invention are all existing products, and the specific preparation operation and the testing method are all conventional technologies.
Synthesis example
The graphene oxide is prepared by an optimized 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 2 g natural graphite (500 meshes), mixing with 50 ml concentrated sulfuric acid in a 250 ml beaker, and stirring for 30 min conventionally; adding 1 g 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, stirring for 30 min, further oxidizing and consuming 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 1
Ni nanowires are prepared by a chemical oxidation-reduction method, nickel chloride hexahydrate is used as a nickel source, hydrazine hydrate is used as a reducing agent under an alkaline condition, and the Ni nanowires are prepared under a high-temperature water bath condition by magnetic field assistance, wherein the specific preparation process is as follows:
(1) Weighing 0.7 g of nickel chloride hexahydrate and 2 g of sodium hydroxide, placing the nickel chloride hexahydrate and the sodium hydroxide into two beakers, respectively weighing 100 ml of ethylene glycol solution into the beakers by using a dosage cylinder, and magnetically stirring for 40 min to form a uniform solution;
(2) Mixing the above solutions, magnetically stirring for 3 min, weighing 20 ml hydrazine hydrate solution (85%) and adding into the above mixed solution, and continuously stirring for 5 min to form uniform mixed solution;
(3) Transferring the mixed solution into a flask, placing the flask into a water bath kettle with the temperature of 70 ℃, placing two magnets (the length is the same as the bottom diameter of the flask, the height is half of the height of the flask, and the thickness is 1 cm) on two sides of the flask, and keeping the flask for 40 min, wherein a black product floats on the surface of the solution; the product was collected by centrifugation, washed with deionized water, acetone and absolute ethanol, and dried at 60 ℃ for 5 h to obtain the Ni nanowires, and the SEM test chart is shown in fig. 1.
(4) Preparation of NiO nanowires:
the Ni nanowire is weighed to be placed on a clean silicon wafer, the clean silicon wafer is placed on a quartz boat, the quartz boat is placed in an annealing furnace, the temperature is raised to 500 ℃ at the heating rate of 10 ℃/min, and the NiO nanowire is prepared by keeping the temperature of 2 h.
(5) Preparation of the NiS nanowires:
the nickel sulfide nanowire is prepared through ion exchange reaction. Weighing 1.2. 1.2 g sodium sulfide nonahydrate, dissolving in 50 ml deionized water, and magnetically stirring for 30 min to form uniform sodium sulfide nonahydrate solution with the concentration of 0.1M; weighing 0.1 g of NiO nanowire powder, adding the powder into the solution, and performing ultrasonic dispersion for 10 min; transferring the mixed solution into a 100 ml reaction kettle, placing the mixed solution into an oven, and reacting at 160 ℃ for 8 h; and naturally cooling the solution after the reaction to room temperature, centrifugally collecting a reaction product, washing the reaction product with deionized water and absolute ethyl alcohol for several times, and drying the reaction product in a baking oven at 60 ℃ for 3 h to obtain the NiS nanowire.
(6) Weighing 0.01 g of NiS nanowires, dispersing the NiS nanowires in 2 ml absolute ethyl alcohol in an ultrasonic manner to form a dispersion liquid of 5 mg/ml, dispersing a GO solution with the concentration of 0.2 ml of 10 mg/ml in 50 ml deionized water in an ultrasonic manner to form a GO solution of 0.04 mg/ml, dripping the NiS dispersion liquid into the GO solution in a stirring state, continuing to magnetically stir for 3 h, centrifugally collecting the solution, taking a bottom precipitate, and drying in an oven at 60 ℃ to obtain the NiS/GO composite material. Finally, the obtained NiS/GO composite material is subjected to heat preservation in a baking oven at 200 ℃ for 90 min to obtain the NiS/rGO composite material, which is named as NiS/rGO-4.
According to the preparation method, the mass ratio of the NiS to the GO is changed, the NiS/GO composite materials with different mass ratios are prepared, and the NiS/rGO composite materials are prepared after the same high-temperature reduction. The mass ratio of the NiS to the GO is 1:5, 1:2, 2:1, 5:1, 10:1 and 20:1, and the NiS/rGO composite materials are respectively named as NiS/rGO-1, niS/rGO-2, niS/rGO-3, niS/rGO-4, niS/rGO-5 and NiS/rGO-6 after high-temperature reduction.
Fig. 1 is an SEM test chart of a Ni nanowire, and it can be seen that the entire nanowire has a linear shape, the diameter of the nanowire is about 300 a nm a, and the surface of the nanowire has thorn-shaped protrusions.
Fig. 2 is an XRD pattern of Ni and NiO after annealing, and it was found that the diffraction peak of Ni completely disappeared and only the diffraction peak of NiO, indicating that the Ni nanowires were completely oxidized to NiO nanowires, after annealing at 500 ℃.
Fig. 3 is an SEM image of different samples: (a) NiO; (b) NiS; (c) NiS/GO; (d) The NiS/rGO can be seen that the diameter distribution of the nanowires is relatively uniform, both are about 300 and nm, and both have good linear morphology. The diameter of the NiS nanowire prepared by ion exchange is not changed too much, the linear morphology is still maintained, and the nanowire can be clearly seen to be in a hollow structure; compounding GO and NiS through magnetic stirring, and attaching a certain amount of film-like graphene on the surface of a NiS nanowire to prepare a NiS/GO composite material; the morphology structure of the NiS/rGO composite material prepared by high-temperature reduction is not greatly changed with that of the NiS/GO composite material, and the graphene can be well attached to the surface of the nanowire, and the graphene is tightly attached to the nanowire after high temperature.
FIG. 4 is a Raman spectrum of NiO, niS, GO and NiS/rGO. In the Raman spectrum of NiO, the NiO can be obtained at 512 and 512 cm -1 Characteristic peaks corresponding to Ni-O bonds in NiO were observed. In the Raman spectrum of NiS, the fluorescence can be obtained at 512 and 512 cm -1 Characteristic peaks corresponding to Ni-S bonds in NiS are observed. Meanwhile, in the Raman spectrum of the NiS/rGO composite material, characteristic peaks belonging to NiS can be observed, and compared with the Raman spectrum of GO, the characteristic peaks can be both detected at 1337 and 1337 cm -1 Here and in 1587 cm -1 Two distinct characteristic peaks were observed, a D peak and a G peak, which are characteristic of carbon materials. From the Raman spectrum, GO I D /I G About 1.025, after 200℃reduction, I in CoS/rGO composites D /I G About 1.263 of the total number of the samples,the increase of the ratio of the D peak to the G peak indicates that oxygen-containing functional groups on the surface of GO are removed in a large amount, the integrity of graphene sheets is affected, the overall defects are increased, the degree of disorder is increased, and GO is successfully reduced to rGO.
Fig. 5 is an XRD pattern of NiS and NiS/rGO, showing diffraction peaks at 2θ=18.4°,30.3 °,32.2 °,35.7 °,37.3 °,40.5 °,48.8 °,50.1 °,52.6 °,56.3 °,57.4 °,59.7 °,67.4 °,72.6 ° and 75.6 °, corresponding to (110), (101), (300), (021), (220), (211), (131), (410), (401), (321), (330), (012), (600), (312) and (042) crystal planes, respectively, substantially conforming to diffraction peaks of the standard spectrum (JCPDS: 12-0041). In the XRD spectrum of the NiS/rGO composite, the corresponding diffraction peak of NiS can be found, and a characteristic peak of reduced graphene oxide appears near 2θ=24°, indicating successful preparation of the NiS/rGO composite.
To further analyze the chemical composition of the composite, the GO and NiS/rGO composites were subjected to test characterization by X-ray photoelectron spectroscopy (XPS), and fig. 6 is an X-ray photoelectron spectroscopy of the GO and NiS/rGO composites: (a) a full spectrum of GO; (b) the C1 s energy spectrum of GO; (c) a full spectrum of NiS/rGO; fine spectra of NiS/rGO: (d) C1S energy spectrum, (e) Ni 2p energy spectrum, and (f) S2 p energy spectrum. Two elements, C and O, can be observed; the C1 s spectrum of GO can give 3 peaks by curve fitting, a C-C bond at 284.8 eV, a C-O bond at 286.8 eV, and a c=o bond at 288.7 eV, respectively. Four elements of Ni, S, C and O can be observed in the full spectrum of the NiS/rGO composite material, and no other elements are present. The C1S spectrum of the NiS/rGO composite material can observe C-C bonds at 284.7 eV, C-S bonds at 285.6 eV, C-O bonds at 286.9 eV, c=o bonds at 287.9 eV, and COOH bonds at 289.1 eV, with more C-S bonds in the C1S spectrum of the NiS/rGO composite material compared to the C1S fine spectrum of GO, with reduced intensities of the C-O, C =o and COOH bonds, particularly with greatly reduced intensities of the C-O, indicating a reduction in oxygen-containing groups in the composite material, with successful reduction of GO. The fine spectrum of Ni 2p for the NiS/rGO composite can be seen with two occurrences at 853.5 eV and 856.6 eVCharacteristic peaks, which are attributed to Ni 2+ Ni 2p of (2) 3/2 The characteristic peaks at 870.8 eV and 874.2 eV are attributed to Ni 2+ Ni 2p of (2) 1/2 The spin-orbit splitting values of the 2p doublets were 17.3 eV and 17.6 eV, and the characteristic peaks at 861.8 eV and 879.6 eV were assigned to their satellite peaks. The fine spectrum of S2 p of the NiS/rGO composite material can be seen with two characteristic peaks at 161.8 eV and 162.9 eV, corresponding to S 2- S2 p of (2) 3/2 And S2 p 1/2 Furthermore, the peak at 164.8 eV is attributed to the S-C bond and the characteristic peak at 168.7 eV is primarily due to oxidation of the composite material and oxygen formation in the air.
Example two
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.
And washing the prepared interdigital electrode with acetone and deionized water, drying, fixing the interdigital electrode on a metal base by using glue, and connecting two ends of the interdigital electrode with the metal base by using gold wires. Dispersing the prepared NiS/rGO composite material into an ethanol solution to prepare a solution of 0.1mg/ml, uniformly dripping 2 microlitres of the solution on an interdigital electrode by using a micropipette, placing the interdigital electrode into an oven for drying, and conducting the electrode conventionally, thereby preparing the NiS/rGO composite material gas sensor.
The method for preparing the device by using the rest materials as the gas sensitive layer is consistent with the method, and only the gas sensitive material is replaced, so that the gas sensor with the corresponding gas sensitive material is obtained.
0.1 And (3) taking 2 microliters of the GO aqueous solution of mg/ml by using a micropipette, uniformly dripping the solution on the interdigital electrode, and annealing the solution in an annealing furnace at 200 ℃ for 2 hours to prepare the rGO sensing device.
Example three gas sensitive property study of NiS/rGO composite
The gas sensing test system is an existing method and is completed through a conventional gas path, and the whole test system consists of dry compressed air, gas to be tested, a gas pipe, a flow controller, a switch, a gas mixing cavity, a test cavity, a filter and an Agilent semiconductor device analyzer. The test system has two gas paths capable of passing through the test cavity to form background gas and gas to be tested, wherein the background gas is dry compressed air, and the gas to be tested is NO 2 And diluting with dry compressed air.
And preparing the prepared NiO, niS/rGO composite material and other samples into a gas sensing device, and performing gas-sensitive test on the gas sensing device. NiO, niS, rGO and NiS/rGO composite (NiS/rGO-4) gas sensor pair 1ppm NO at room temperature 2 The gas-sensitive response test was performed, as shown in FIG. 7, with a response time and recovery time of 150 s for the device, and as can be seen from the graph, niO, niS, rGO and NiS/rGO composite gas sensor pair NO 2 Exhibits response characteristics, device vs. 1ppm NO 2 The responses of the gas sensor are 3.2%, 9.5%, 10.8% and 29.7%, respectively, and the gas sensor made of the NiS/rGO composite material shows more excellent gas-sensitive performance relative to the single material; and it can be seen from the figure that the device can be restored to baseline, indicating that it has good restorability.
The sensing performance of the composite material is affected to a certain extent by the addition amount of the graphene, and NiS/rGO-1, niS/rGO-2, niS/rGO-3, niS/rGO-4, niS/rGO-5 and NiS/rGO-6 are prepared, and NiS/rGO composite material sensors with different graphene contents are used for measuring 1ppm NO 2 Gas sensitive performance tests were performed. As shown in FIG. 8, the gas sensor pairs of the NiS/rGO-1, niS/rGO-2, niS/rGO-3, niS/rGO-4, niS/rGO-5 and NiS/rGO-6 composite materials were 1ppm NO 2 The responses of (a) were 13.6%, 18.3%, 23.4%, 29.7%, 24.6% and 17.6%, respectively. It can be seen that the NiS/rGO composite material pair NO 2 Has good gas-sensitive response, and when the mass ratio of the NiS to the GO is 5:1, the sensing performance of the NiS/rGO composite material is best, and reachesUp to 29.7%, a nearly 3-fold improvement over graphene.
NO at lower concentration for NiS/rGO-4 composite gas sensor 2 The gas-sensitive response test was carried out under the gas, as shown in FIG. 9, for NO at the concentrations of 50 ppb, 100 ppb, 200 ppb and 500 ppb, respectively 2 Gas sensitive tests were performed with response values of 10.1%, 15.0%, 19.5% and 24.3%, respectively. It can be seen that even at lower concentrations of NO 2 The lower sensor has a certain response, which indicates that the NiS/rGO composite material has NO effect on NO 2 Has good adsorption effect, shows higher gas-sensitive response, and is used for detecting NO 2 An excellent gas-sensitive material.
Reusable is an important performance indicator of gas sensors. For a gas sensor of a NiS/rGO-4 composite material, the concentration of NO in the gas sensor is 1ppm 2 In the following, four cycles of repeatability test were performed with 300 s as one cycle, and as shown in fig. 10, the responses of the four cycles are 29.5%, 29.7%, 29.9% and 29.8%, respectively, and it can be seen that the fluctuation of the response value is not large, and is always kept at a very stable level, and the gas sensor of the NiS/rGO-4 composite material still has good response recovery characteristics after four cycles, which indicates that the gas sensor has excellent repeatability.
In the practical application process of the sensor, the selectivity is an important index for determining the performance of the sensor. Different gas response tests are carried out on the NiS/rGO-4 composite material gas sensor, mainly saturated steam gas (diluted gas is compressed air) with concentration of 1% is selected, and the saturated steam gas contains ammonia, methanol, isopropanol, ethanol, ethylene glycol and ethyl acetate, and is mixed with 1ppm NO 2 The response values of the gases are used as a comparison. As shown in FIG. 11, it can be seen that the NiS/rGO-4 composite gas sensor pair was 1ppm NO 2 The response of (2) is far higher than that of other organic gases, and the highest response of the comparative organic gases is to ammonia, the response value reaches 3.6%, but the response value is to 1ppm of NO 2 The response value was also far different than 29.7% and the concentration was also far above 1 ppm. The test result shows that the gas sensor of the NiS/rGO-4 composite material has good selectivity.
The invention comprises the steps of ultrasonically dispersing NiS/rGO composite materials containing GO with different mass in ethanol solution, using a micropipette to obtain a proper amount of dispersion, dripping the dispersion on an interdigital electrode, drying to form a film, and obtaining the film by using a micro-pipette to obtain the film of 1ppm NO 2 The gas-sensitive test of the gas shows that when the mass ratio of the NiS to the GO is 5:1, the response of the NiS/rGO composite material gas sensor can reach 29.7%, and the device has NO with different concentrations 2 The gas test also showed good response. At high concentration of NO 2 Under gas, the device was free of NO at 1ppm, 10 ppm, 50 ppm and 100 ppm 2 Response values of 29.5%, 36.1%, 42.0% and 46.4%, respectively, device pairs were low concentration NO of 50 ppb, 100 ppb, 200 ppb and 500 ppb 2 Response values were 10.1%, 15.0%, 19.5% and 24.3%, respectively. Meanwhile, the gas sensor made of the NiS/rGO composite material has good repeatability, stability and selectivity.
Summary
The invention prepares Ni nanowire through high temperature water bath under the assistance of magnetic field, prepares NiO nanowire through high temperature annealing, prepares NiO nanowire through ion exchange reaction, and composites the NiO nanowire with GO, builds a multi-stage heterostructure based on NiS/rGO composite material through high temperature reduction, and prepares a gas sensor, and explores NO at normal temperature 2 Gas-sensitive response characteristics of the gas. The main innovation points are as follows:
(1) Preparing NiS nanowires by taking NiO nanowires as templates through ion exchange reaction, compositing the NiS nanowires with graphene oxide, and constructing a multi-stage heterostructure based on a NiS/rGO composite material through high-temperature reduction; and the graphene and sulfide materials are compounded to provide more adsorption sites for detecting gas, and meanwhile, heterojunction can be formed between the composite materials, so that the migration rate of carriers is improved, and the gas-sensitive response is improved.
(2) The invention discloses a gas sensor pair NO based on a multi-level heterostructure of a NiS/rGO composite material 2 The gas has good response, and 1ppm NO at normal temperature 2 The maximum response value is reached through 150 s under the gas, and the initial value can be recovered through 150 s, so that the gas has good response recovery characteristics. At the same time the sensor pair NO 2 The gas has excellent repeatability, stability and selectionSex.
(3) The ion exchange reaction is an effective and low-cost nano material chemical conversion method; the preparation of metal sulfides based on ion exchange reactions can avoid the disadvantages of high temperature, high pressure and toxic precursor sources, while significantly reducing costs.
Claims (3)
1. The method for detecting nitrogen oxide gas is characterized in that a NiS/rGO composite material gas sensor is placed in an environment containing nitrogen oxide gas to complete nitrogen oxide gas detection, and the preparation method of the NiS/rGO composite material is characterized in that water-soluble nickel salt is subjected to reduction reaction under alkaline conditions in the presence of an organic matter reducing agent and under the assistance of a magnetic field to obtain Ni nanowires; then annealing at high temperature to obtain NiO nanowires; then, carrying out ion exchange reaction by taking sodium sulfide and NiO nanowires as raw materials to prepare NiS nanowires; mixing the NiS nanowire dispersion liquid and the GO dispersion liquid, then centrifuging, and collecting precipitate to obtain a NiS/GO composite material; then heating to prepare a NiS/rGO composite material; the NiS/rGO composite material gas sensor takes a NiS/rGO composite material as a gas-sensitive material; the mass ratio of the NiS nanowire to the GO is (0.2-20) to 1; inorganic base is used as alkaline condition; the temperature of the reduction reaction is 60-80 ℃ and the time is 30-60 minutes; the high-temperature annealing temperature is 450-550 ℃ and the time is 100-150 minutes; the ion exchange reaction is carried out for 5 to 10 hours at the temperature of 150 to 170 ℃; the temperature of the heating treatment is 180-250 ℃ and the time is 70-110 minutes.
2. The method for detecting nitrogen oxide gas is characterized in that a NiS/rGO composite material gas sensor is placed in an environment containing nitrogen oxide gas to complete nitrogen oxide gas detection, and the preparation method of the NiS/rGO composite material is characterized in that water-soluble nickel salt is subjected to reduction reaction under alkaline conditions in the presence of an organic matter reducing agent and under the assistance of a magnetic field to obtain Ni nanowires; then annealing at high temperature to obtain NiO nanowires; then, carrying out ion exchange reaction by taking sodium sulfide and NiO nanowires as raw materials to prepare NiS nanowires; mixing the NiS nanowire dispersion liquid and the GO dispersion liquid, then centrifuging, and collecting precipitate to obtain a NiS/GO composite material; then heating to prepare a NiS/rGO composite material; the NiS/rGO composite material gas sensor takes a NiS/rGO composite material as a gas-sensitive material; the mass ratio of the NiS nanowire to the GO is (0.2-20) to 1; inorganic base is used as alkaline condition; the temperature of the reduction reaction is 60-80 ℃ and the time is 30-60 minutes; the high-temperature annealing temperature is 450-550 ℃ and the time is 100-150 minutes; the ion exchange reaction is carried out for 5 to 10 hours at the temperature of 150 to 170 ℃; the temperature of the heating treatment is 180-250 ℃ and the time is 70-110 minutes.
3. The application of the NiS/rGO composite material in preparing the nitrogen oxide gas sensor is characterized in that the preparation method of the NiS/rGO composite material comprises the steps of carrying out reduction reaction on water-soluble nickel salt under alkaline conditions in the presence of an organic reducing agent and under the assistance of a magnetic field to obtain Ni nanowires; then annealing at high temperature to obtain NiO nanowires; then, carrying out ion exchange reaction by taking sodium sulfide and NiO nanowires as raw materials to prepare NiS nanowires; mixing the NiS nanowire dispersion liquid and the GO dispersion liquid, then centrifuging, and collecting precipitate to obtain a NiS/GO composite material; then heating to prepare a NiS/rGO composite material; the NiS/rGO composite material gas sensor takes a NiS/rGO composite material as a gas-sensitive material; the mass ratio of the NiS nanowire to the GO is (0.2-20) to 1; inorganic base is used as alkaline condition; the temperature of the reduction reaction is 60-80 ℃ and the time is 30-60 minutes; the high-temperature annealing temperature is 450-550 ℃ and the time is 100-150 minutes; the ion exchange reaction is carried out for 5 to 10 hours at the temperature of 150 to 170 ℃; the temperature of the heating treatment is 180-250 ℃ and the time is 70-110 minutes.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101736377A (en) * | 2009-12-08 | 2010-06-16 | 郑州大学 | Method for preparing nickel sulfide nano-wire array |
| WO2018019921A1 (en) * | 2016-07-29 | 2018-02-01 | Trinamix Gmbh | Optical sensor and detector for optical detection |
| CN109970108A (en) * | 2019-04-15 | 2019-07-05 | 青岛大学 | A kind of gas sensor and preparation method thereof based on nanometer nickel sulfide composite material |
| CN110243881A (en) * | 2019-07-16 | 2019-09-17 | 东北大学 | One kind being based on rGO-SnO2The NO of nanocomposite2Gas sensor and preparation method thereof |
| CN112903761A (en) * | 2021-01-19 | 2021-06-04 | 重庆大学 | Molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material and preparation method and application thereof |
-
2022
- 2022-05-19 CN CN202210543195.9A patent/CN115196694B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101736377A (en) * | 2009-12-08 | 2010-06-16 | 郑州大学 | Method for preparing nickel sulfide nano-wire array |
| WO2018019921A1 (en) * | 2016-07-29 | 2018-02-01 | Trinamix Gmbh | Optical sensor and detector for optical detection |
| CN109970108A (en) * | 2019-04-15 | 2019-07-05 | 青岛大学 | A kind of gas sensor and preparation method thereof based on nanometer nickel sulfide composite material |
| CN110243881A (en) * | 2019-07-16 | 2019-09-17 | 东北大学 | One kind being based on rGO-SnO2The NO of nanocomposite2Gas sensor and preparation method thereof |
| CN112903761A (en) * | 2021-01-19 | 2021-06-04 | 重庆大学 | Molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Deyi Zhang等.Facile solid-phase synthesis of layered NiS/rGO nanocomposite for high-performance hybrid supercapacitor.Journal of Power Sources.2021,第1-10页. * |
| Facile solid-phase synthesis of layered NiS/rGO nanocomposite for high-performance hybrid supercapacitor;Deyi Zhang等;Journal of Power Sources;第1-10页 * |
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