CN113552180A - NiO/SnO2Composite nanowire and preparation method and application thereof - Google Patents
NiO/SnO2Composite nanowire and preparation method and application thereof Download PDFInfo
- Publication number
- CN113552180A CN113552180A CN202110752640.8A CN202110752640A CN113552180A CN 113552180 A CN113552180 A CN 113552180A CN 202110752640 A CN202110752640 A CN 202110752640A CN 113552180 A CN113552180 A CN 113552180A
- Authority
- CN
- China
- Prior art keywords
- sno
- nio
- gas
- nanowire
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002070 nanowire Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 102
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 91
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000002131 composite material Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 33
- 239000006260 foam Substances 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 238000001514 detection method Methods 0.000 claims abstract description 24
- 238000002207 thermal evaporation Methods 0.000 claims abstract description 19
- 239000007789 gas Substances 0.000 claims description 68
- 239000010931 gold Substances 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 230000003647 oxidation Effects 0.000 claims description 20
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 238000004140 cleaning Methods 0.000 claims description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 17
- 229910052737 gold Inorganic materials 0.000 claims description 17
- 239000002105 nanoparticle Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 238000013329 compounding Methods 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000005516 engineering process Methods 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 238000004544 sputter deposition Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000000861 blow drying Methods 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000009966 trimming Methods 0.000 claims description 2
- 235000012149 noodles Nutrition 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 201000004569 Blindness Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 229910002647 NiO–SnO2 Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 208000028990 Skin injury Diseases 0.000 description 1
- 206010058679 Skin oedema Diseases 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011217 control strategy Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention belongs to the field of triethylamine gas detection sensors, and particularly relates to NiO/SnO2Composite nano-wire and its preparation method and application. The NiO/SnO2The composite nano-wire has the atomic ratio of Ni to Sn of 1:1-1:3, the diameter of the nano-wire is 100-500nm, and the length of the nano-wire is more than 10 mu m. The invention uses porous foam metal nickel applied in large scale in industry as a template, and prepares NiO/SnO by using a thermal evaporation method2The composite nanowire is used for triethylamine gas detection, has the characteristics of high sensitivity, low detection limit and low working temperature, is simple and controllable in preparation method, can realize large-scale preparation, and has a good practical application prospect.
Description
Technical Field
The invention belongs to the field of triethylamine gas detection sensors, and particularly relates to NiO/SnO2Composite nano-wire and its preparation method and application.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Triethylamine is an industrial gas with toxicity, pungent smell and easy explosion, and is widely applied to the fields of corrosion prevention, catalysis, organic solvents and the like. Generally, if the concentration of triethylamine gas is more than 10ppm, symptoms such as headache, skin injury, edema and the like can be caused. When exposed to this gas for a long period of time, it may even cause serious consequences such as blindness, death, etc. Therefore, the method has strong practical application value for realizing the low-concentration and high-precision rapid detection of the triethylamine gas.
In recent years, the metal oxide nano structure has the characteristics of stable physical and chemical properties, simple preparation, low cost, high specific surface area and the like, and is widely applied to aspects of gas sensors, photoelectric devices, solar devices, battery electrodes and the like. Among them, metal oxide composite materials based on nano-structuring are attracting much attention for the detection of triethylamine gas.
The prior literature discloses various methods for preparing gas-sensitive materials based on metal oxides. Such as: SnO (stannic oxide) -based2The invention discloses a toluene gas sensor of a modified NiO nano-structure composite material and a preparation method thereof, and the invention patent utilizes N-type SnO2The P-type NiO semiconductor material is modified by the semiconductor material, the detection capability of toluene gas is improved in a P-n type heterojunction construction mode, and the sensor has excellent selectivity sensitivity and moisture resistance. NiO-SnO2The preparation method of the flower-shaped structure composite material is used for detecting ethanol gas, and the sensor has the characteristics of high sensitivity, high selectivity, quick response and recovery characteristics, good stability and the like. NiO/SnO2A process for preparing nano-class composite gas-sensitive material from oxalate as sacrificial template and SnCl2Separating precipitate after forming mixed solution, and decomposing to generate CO in high temperature calcination process2Preparing porous NiO/SnO by the characteristics of pore forming of the material2The composite material is used for gas detection.
At present, for a traditional gas-sensitive composite material system, the performance of a gas-sensitive device can be effectively improved by specifically assembling a p-n type heterojunction structure and utilizing a synergistic effect, the response time is shortened, and the application prospect is wide. The prior art discloses a NiO/Fe-based method2O3A triethylamine gas sensor made of a heterostructure composite material. The NiO/Fe is prepared by combining a hydrothermal method and high-temperature annealing treatment2O3Composite material using NiO/Fe2O3The heterostructure formed by the two steps improves the detection capability of triethylamine, but the inventor finds that the gas-sensitive performance and stable working repeatability at a lower working temperature are not mentioned, and the specific performance of the gas-sensitive performance and stable working repeatability cannot be judged. Moreover, the existing p-n junction type heterojunction regulation and control strategy for improving the gas-sensitive property becomes an effective technical path, the preparation methods are various, but most preparation methods are completed through a hydrothermal synthesis method, and the repeatability of material preparation needs to be further improved.
Therefore, the method for preparing the composite material by utilizing the simple and controllable method has important scientific value and practical application significance for completing the low-temperature high-sensitivity detection of the specific gas through reasonable device structure design.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide NiO/SnO2The invention relates to a composite nano wire and a preparation method and application thereof, wherein porous foam metal nickel applied in large scale in industry is used as a template, and a thermal evaporation method is used for preparing NiO/SnO2The composite nanowire is used for triethylamine gas detection, has the characteristics of high sensitivity, low detection limit and low working temperature, is simple and controllable in preparation method, can realize large-scale preparation, and has a good practical application prospect.
In order to achieve the above object, the first aspect of the present invention provides a NiO/SnO2The composite nanowire has the atomic ratio of Ni to Sn in the nanowire of 1:1-1:3, the diameter of the nanowire is 100-500nm, and the length of the nanowire is more than 10 mu m.
The second aspect of the invention provides the NiO/SnO2The preparation method of the composite nanowire comprises the following steps:
oxidizing the surface of the porous foam metal Ni, and depositing Au nano particles on the surface of the foam metal Ni by adopting a direct-current magnetron sputtering technology to form Au particlesThe film is used as a template, and a thermal evaporation method is utilized to prepare NiO/SnO by taking a Sn and SnO mixture as a raw material2And (4) compounding the nano-wires.
In a third aspect, the invention provides a gas sensor, wherein the gas sensitive material in the sensor is NiO/SnO2Compounding nanometer lines;
further, the gas sensor is a triethylamine gas sensor.
The fourth aspect of the present invention provides a method for preparing the gas sensor, specifically, the method comprises: first NiO/SnO2And stripping the composite nanowire, and transferring the composite nanowire to a silicon-based interdigital electrode deposited with a Ti electrode and an Au electrode.
The fifth aspect of the invention provides an application of the triethylamine gas sensor in the fields of industrial detection and environmental detection.
One or more embodiments of the present invention have at least the following advantageous effects:
(1) the invention utilizes the foam nickel as a template and combines the magnetron sputtering technology with the thermal evaporation method to prepare NiO/SnO2The composite nanowire is made of NiO and SnO2The nanowire composition can establish an effectively combined p-n type heterojunction, fully play the advantages of high specific surface area of the nanowire material and regulation and sensitization of the p-n type heterojunction, enhance the adsorption capacity of gas, improve the response sensitivity of a device and reduce the detection limit of the gas.
(2) The invention carries out oxidation pretreatment on the surface of the foamed nickel, and can effectively improve the single crystal crystallization quality of the nanowire. NiO exhibits p-type semiconductor characteristics, and SnO2The nanowire forms a pn junction heterojunction, has the advantages of high sensitivity, good repeatability, low detection limit and the like at the working temperature of 100 ℃, and has great application prospect.
(3) The technical process is simple and repeatable, the advantages of the traditional gas sensitive material are fully utilized by means of reasonable device structure design, the p-n type heterojunction is constructed, the high-sensitivity triethylamine sensitive device is obtained, and the high-sensitivity triethylamine sensitive device has a high application value.
(4) The triethylamine gas sensor provided by the invention can also be expanded to form a gas sensor array, so that the application value is further expanded.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is an SEM image and an EDS spectrum of a gas sensitive material prepared in example 1 of the present invention.
FIG. 2 is a graph showing the gas-sensitive properties of the gas-sensitive material prepared in example 1 of the present invention at a concentration ranging from 500ppb to 200ppm, with respect to triethylamine.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background art, the existing gas-sensitive material with the p-n type heterojunction structure has the key problems to be solved, such as high working temperature, poor stability and the like, most of the preparation methods are completed through a hydrothermal synthesis method, and the repeatability of the material preparation is not high.
In order to solve the technical problems, the first aspect of the invention provides NiO/SnO2The composite nanowire has the atomic ratio of Ni to Sn in the nanowire of 1:1-1:3, the diameter of the nanowire is 100-500nm, and the length of the nanowire is more than 10 mu m.
The nano wire is made of NiO and SnO2The nanowire composition can establish an effectively combined p-n type heterojunction and fully exert the high ratio of the nanowire materialThe surface area and the regulation and control sensitization advantage of the p-n type heterojunction enhance the adsorption capacity of the gas, and the application of the method in the triethylamine gas sensor is beneficial to improving the response sensitivity of the sensor and reducing the detection limit of the gas. Furthermore, the NiO/SnO2The composite nanowire can detect triethylamine gas at low temperature (200 ℃), has lower working temperature and good stability compared with the similar sensors (the detection temperature is 240-400 ℃), and can realize high-sensitivity detection of toxic and explosive gas triethylamine.
The second aspect of the invention provides the NiO/SnO2The preparation method of the composite nanowire comprises the following steps:
oxidizing the surface of porous foam metal Ni, depositing Au nanoparticles on the surface of the foam metal Ni by adopting a direct-current magnetron sputtering technology to form an Au particle film, and preparing NiO/SnO by taking a Sn and SnO mixture as a raw material by using the Au particle film as a template and utilizing a thermal evaporation method2And (4) compounding the nano-wires.
The NiO/SnO is prepared by taking porous foam metal nickel as a template and utilizing a thermal evaporation method2The thermal evaporation method is a material growth method which vaporizes a source material by controlling temperature, then utilizes carrier gas to transport, and deposits, nucleates and grows on a substrate material. The advantages of using thermal evaporation methods are mainly: the inherent rule that hydrothermal synthesis is commonly adopted in the prior art is eliminated, the problem of low repeatability of a hydrothermal method for material preparation is further avoided, and the stable repeatability of the material is favorably realized. In addition, the thermal evaporation method takes the mixture of Sn and SnO as raw materials, and compared with the pure Sn powder and SnO powder, the shape of the material prepared by adopting the mixed material is more controllable.
Wherein, the Au particles are used as nucleation sites of the nanowires to guide the generation of the nanowires, if Au particle films are not deposited on the surface of the porous foam metal Ni, the Au particle films are directly subjected to thermal evaporation treatment, are not easy to grow into a nanowire structure, and are not beneficial to NiO and SnO2The load of (2).
The aim of the preoxidation treatment of the foam metal Ni is to provide a source of enough oxygen for the growth of the nanowire, and the single crystal crystallization quality of the nanowire can be effectively improved. As a preferred embodiment, the mode of performing oxidation pretreatment on the porous foam metal Ni surface is as follows: and respectively putting the foamed nickel into acetone, ethanol and deionized water for ultrasonic cleaning, taking out the foamed nickel, putting the foamed nickel into an acid solution for soaking and cleaning, then ultrasonically cleaning in the deionized water, blow-drying by nitrogen, and finally trimming the foamed nickel into a proper size for drying and oxidation treatment.
The porous foam metal Ni is respectively put into acetone, ethanol and deionized water for cleaning, so that impurities on the surface are removed, and ultrasonic cleaning is 10-15min, preferably 10 min.
The acid solution is used for further removing impurities on the surface of the porous metal foam nickel, and as a preferred embodiment, the acid solution is hydrochloric acid, sulfuric acid or nitric acid solution, the concentration is 3mol/L, and the soaking time is 30-40 min.
Further, after soaking in the acid solution, ultrasonically cleaning in deionized water for 30-40 min.
The drying temperature and the heat preservation time influence the oxidation degree of the foam Ni surface and provide a source of oxygen elements in the subsequently grown nanowire, and in order to improve the crystallization quality of the nanowire, the drying and oxidation treatment temperature is set to be 150 ℃ and 250 ℃ for 6-24h, and the temperature rise rate is 5 ℃/min.
Preferably, the drying temperature is 200 ℃ and the holding time is 12 h.
The nickel foam is suitably trimmed to further facilitate the dry oxidation of the nickel foam, and as a preferred embodiment, is cut into 5cm x 5cm squares.
In one or more embodiments of the present invention, the thickness of the Au particle film is 5nm to 100nm, and the Au particle film is in a (111) preferred orientation. The thickness of the Au particle film cannot be too thick, and if the film is too thick, the diameter of the nanowire becomes large or a case where the nanowire cannot be generated occurs.
In one or more embodiments of the present invention, the technical parameters of the dc magnetron sputtering are as follows: sputtering power is 20-50W, pressure is 0.5-1.5Pa, argon flow is 20-50 SCCM;
the direct current magnetron sputtering deposition time determines the size of the gold particles, and if the deposition time is too long, the gold particles exist in the form of a particle film, so that the activity of the catalyst is reduced, and the growth of the nanowires at the later stage is not facilitated. As a preferred embodiment, the deposition time is 3s-1 min; preferably 5s to 30s, more preferably 30 s.
Preferably, the sputtering technical parameters of the gold nanoparticle film are as follows: the power is 20W, the pressure is 1Pa, and the time is 30 s. And the information such as the size, the shape and the like of the designed metal nano-particles is obtained by strictly controlling sputtering parameters.
In one or more embodiments of the present invention, the mass ratio of Sn to SnO in the raw material during thermal evaporation is 1:2 to 1: 5.
Further, the preparation parameters are as follows: the temperature is controlled at 650-1000 ℃, the holding time is 10-60 min, the pressure is 10Pa, the carrier gas is argon, and the argon flow is 20-50 sccm.
Preferably, the temperature is 850 ℃, the time is 30min, and the argon flow is 20 sccm.
In a third aspect, the invention provides a gas sensor, wherein the gas sensitive material in the sensor is NiO/SnO2And (4) compounding the nano-wires.
The fourth aspect of the present invention provides a method for preparing the gas sensor, specifically, the method comprises:
first NiO/SnO2And stripping the composite nanowire, and transferring the composite nanowire to a silicon-based interdigital electrode deposited with a Ti electrode and an Au electrode. Among them, the use of metal Ti is intended to improve the bonding force between the gold electrode and the substrate.
The stripping process comprises the following steps: carefully treating the surface flocculent substance by using a doctor blade, then placing the flocculent substance into an absolute ethanol solution for ultrasonic treatment for 1-1.5h, taking supernatant fluid, and then keeping the supernatant fluid for 10-15min by using a centrifuge with the rotation speed of 4000 plus 5000rpm to obtain colloid white sticky matter, namely NiO/SnO2And (4) compounding the nano-wires.
The parameters of the silicon-based interdigital electrode are as follows: the external dimension is 4mm 6mm 0.5mm, the line width is 20 μm, the line distance is 20 μm, and the logarithm is 20; the substrate is coated with 1 μm SiO2Monocrystalline silicon of the insulating layer.
Further, the gas sensor is a triethylamine gas sensor.
The material is used for preparing a unit device for detecting triethylamine gas, the triethylamine sensor is a resistance type semiconductor gas-sensitive sensor, and the main action principle is that the relation between gas concentration and resistance is represented by detecting the change of resistance before and after the sensitive unit adsorbs the triethylamine gas.
The fifth aspect of the invention provides an application of the triethylamine gas sensor in the fields of industrial detection and environmental detection.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
NiO/SnO2The preparation method of the composite nanowire material pn heterojunction type triethylamine gas sensitive material comprises the following steps:
1) porous foam metal Ni oxidation pretreatment: and respectively putting the foamed nickel into acetone, ethanol and deionized water, ultrasonically cleaning for 10min, taking out, putting into a 3mol hydrochloric acid solution, soaking and cleaning for 30min, ultrasonically cleaning in deionized water for 30min, and drying by nitrogen. Then the foamed nickel is cut into 5cm multiplied by 5cm square blocks, and then is put into a drying oven for oxidation treatment for 12h at 200 ℃, so that the superficial layer oxidation treatment of the porous foamed metal nickel is completed, and other foamed metals such as copper foam can use similar oxidation treatment. The aim of the preoxidation treatment of the foam metal Ni is to provide a sufficient oxygen source for the later growth of the nano wire, thereby being beneficial to the synthesis of the metal oxide nano wire.
2) Depositing an Au nanoparticle film on the surface of the foam metal Ni layer: depositing Au on the surface of the foamed nickel in the step 1) by using a direct current magnetron sputtering technology, wherein the sputtering time is 30s, the power is 20W, the argon flow is 20sccm, and uniformly distributed gold nanoparticle films are obtained, and the thickness of the sputtered gold nanoparticle films is about 10 nm. And the nucleation points are provided for the growth of the nanowires at the later stage.
3)NiO/SnO2Preparing the composite nanowire: preparing NiO/SnO by taking the foamed nickel coated with the gold nanoparticles obtained in the step 2) as a template and using a Sn and SnO mixture (the mass ratio of Sn to SnO is 1:3) as a raw material by using a thermal evaporation method2Composite nanowire, thermal evaporationThe temperature of the method is 850 ℃, the time is 30min, and the argon flow is 20 sccm.
4)NiO/SnO2The stripping technology of the composite nanowire comprises the following steps: taking the prepared NiO/SnO2And compounding the nanowires, treating floccule substances on the surface by using a doctor blade, putting the floccule substances into an absolute ethanol solution, ultrasonically cleaning for 1h, taking supernatant, and keeping for 10min by using a centrifugal machine at 5000rpm to obtain colloidal white sticky substances for later use.
5) Preparing a gas sensitive device: the white floccule NiO/SnO obtained in the step 4)2And transferring the composite nanowire to the silicon-based interdigital electrode. The parameters of the silicon-based interdigital electrode are as follows: external dimensions 4mm 6mm 0.5mm, line width 20 μm, line spacing 20 μm, log 20. The substrate is coated with 1 μm SiO2Monocrystalline silicon of the insulating layer.
Example 2
NiO/SnO2The preparation method of the p-n heterojunction type triethylamine gas-sensitive material of the composite nanowire material comprises the following steps:
1) porous foam metal Ni oxidation pretreatment: and respectively putting the foamed nickel into acetone, ethanol and deionized water, ultrasonically cleaning for 10min, taking out, putting into a 3mol hydrochloric acid solution, soaking and cleaning for 30min, ultrasonically cleaning in deionized water for 30min, and drying by nitrogen. Then the foamed nickel is cut into 5cm multiplied by 5cm square blocks, and then is put into a drying oven for oxidation treatment for 12h at 200 ℃, so that the superficial layer oxidation treatment of the porous foamed metal nickel is completed, and other foamed metals such as copper foam can use similar oxidation treatment. The aim of the preoxidation treatment of the foam metal Ni is to provide a sufficient oxygen source for the later growth of the nano wire, thereby being beneficial to the synthesis of the metal oxide nano wire.
2) Depositing an Au nanoparticle film on the surface of the foam metal Ni layer: depositing Au on the surface of the foamed nickel in the step 1) by using a direct current magnetron sputtering technology, wherein the sputtering time is 60s, the power is 20W, and the argon flow is 20sccm, so that a uniformly distributed gold nanoparticle film is obtained, and the thickness of the gold nanoparticle film is about 20 nm. The presence of gold provides nucleation sites for the growth of nanowires.
3)NiO/SnO2Preparing the composite nanowire: using the foamed nickel covered with gold nanoparticles obtained in the step 2) as a moldA board, which is prepared by using a thermal evaporation method and using a Sn and SnO mixture (the mass ratio of Sn to SnO is 1:3) as a raw material2The temperature of the thermal evaporation method is set to 850 ℃, the time is 30min, and the argon flow is 20 sccm.
4)NiO/SnO2The stripping technology of the composite nanowire comprises the following steps: taking the prepared NiO/SnO2And compounding the nanowires, treating floccule substances on the surface by using a doctor blade, putting the floccule substances into an absolute ethanol solution, ultrasonically cleaning for 1h, taking supernatant, and keeping for 10min by using a centrifugal machine at 5000rpm to obtain colloidal white sticky substances for later use.
5) Preparing a gas sensitive device: the white floccule NiO/SnO obtained in the step 4)2And transferring the composite nanowire to the silicon-based interdigital electrode. The parameters of the silicon-based interdigital electrode are as follows: external dimensions 4mm 6mm 0.5mm, line width 20 μm, line spacing 20 μm, log 20. The substrate is coated with 1 μm SiO2Monocrystalline silicon of the insulating layer.
Example 3
NiO/SnO2The preparation method of the p-n heterojunction type triethylamine gas-sensitive material of the composite nanowire material comprises the following steps:
1) porous foam metal Ni oxidation pretreatment: and respectively putting the foamed nickel into acetone, ethanol and deionized water, ultrasonically cleaning for 10min, taking out, putting into a 3mol hydrochloric acid solution, soaking and cleaning for 30min, ultrasonically cleaning in deionized water for 30min, and drying by nitrogen. Then the foamed nickel is cut into 5cm multiplied by 5cm square blocks, and then is put into a drying oven for oxidation treatment for 12h at 200 ℃, so that the superficial layer oxidation treatment of the porous foamed metal nickel is completed, and other foamed metals such as copper foam can use similar oxidation treatment. The aim of the preoxidation treatment of the foam metal Ni is to provide a sufficient oxygen source for the later growth of the nano-wire, thereby being beneficial to the synthesis of the nano-wire.
2) Depositing an Au nanoparticle film on the surface of the foam metal Ni layer: depositing Au on the surface of the foamed nickel in the step 1) by using a direct current magnetron sputtering technology, wherein the sputtering time is 10s, the power is 20W, and the argon flow is 20sccm, so that a uniformly distributed gold nanoparticle film is obtained, and the thickness of the sputtered gold nanoparticle film is about 5nm, so that a nucleation point is provided for the growth of the nanowire.
3)NiO/SnO2Preparing the composite nanowire: preparing NiO/SnO by taking the foamed nickel coated with the gold nanoparticles obtained in the step 2) as a template and using a Sn and SnO mixture (the mass ratio of Sn to SnO is 1:3) as a raw material by using a thermal evaporation method2And (4) compounding the nano-wires. The temperature setting for the thermal evaporation method was 950 ℃ for 60min with an argon flow of 20 sccm.
4)NiO/SnO2The stripping technology of the composite nanowire comprises the following steps: taking the prepared NiO/SnO with foam nickel as a template2And compounding the nanowires, treating floccule substances on the surface by using a doctor blade, putting the floccule substances into an absolute ethanol solution, ultrasonically cleaning for 1h, taking supernatant, and keeping for 15min by using a centrifugal machine at 5000rpm to obtain colloidal white sticky substances for later use.
5) Preparing a gas sensitive device: the white floccule NiO/SnO obtained in the step 4)2And transferring the composite nanowire to the silicon-based interdigital electrode. The parameters of the silicon-based interdigital electrode are as follows: external dimensions 4mm 6mm 0.5mm, line width 20 μm, line spacing 20 μm, log 20. The substrate is coated with 1 μm SiO2Monocrystalline silicon of the insulating layer.
And (3) performance testing:
fig. 2 is a gas-sensitive characteristic test chart of the gas-sensitive material prepared in embodiment 1 of the present invention for triethylamine, the working temperature is 200 ℃, and the triethylamine concentration is 1ppm to 200ppm, and it can be seen from the chart that, at a concentration of 200ppm, the gas-sensitive response sensitivity of the sensor prepared in the present invention for triethylamine reaches 5, the minimum detected concentration value can reach 500ppb, and compared with the similar sensors, the device has the advantages of low working temperature and good stability, and can realize high-sensitivity detection for the toxic and explosive gas triethylamine.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. NiO/SnO2A composite nanowire characterized by: the atomic ratio of Ni to Sn is 1:1-1:3, NaThe diameter of the rice-flour noodle is 100-500nm, and the length is more than 10 μm.
2. The NiO/SnO of claim 12The preparation method of the composite nanowire is characterized by comprising the following steps: oxidizing the surface of porous foam metal Ni, depositing Au nanoparticles on the surface of the foam metal Ni by adopting a direct-current magnetron sputtering technology to form an Au particle film, and preparing NiO/SnO by taking a Sn and SnO mixture as a raw material by using the Au particle film as a template and utilizing a thermal evaporation method2And (4) compounding the nano-wires.
3. The method of claim 2, wherein: the oxidation pretreatment mode of the porous foam metal Ni surface is as follows: respectively putting the foamed nickel into acetone, ethanol and deionized water for ultrasonic cleaning, taking out the foamed nickel, putting the foamed nickel into an acid solution for soaking and cleaning, then ultrasonically cleaning in the deionized water, blow-drying by nitrogen, and finally trimming the foamed nickel into a proper size for drying and oxidizing treatment;
further, the acetone, the ethanol and the deionized water are respectively put into the acetone, the ethanol and the deionized water for ultrasonic cleaning for 10-15min, preferably 10 min;
further, the acid solution is hydrochloric acid, sulfuric acid or nitric acid solution, the concentration is 3mol/L, and the soaking time is 30-40 min;
further, after soaking in the acid solution, ultrasonically cleaning in deionized water for 30-40 min.
4. The method of claim 3, wherein: the drying and oxidation treatment temperature is 150-;
preferably, the drying temperature is 200 ℃, and the holding time is 12 h;
or, the nickel foam is cut into 5cm × 5cm squares;
or the thickness of the gold particle film is 5nm-100nm, and the Au particle film is in (111) preferred orientation.
5. The method of claim 2, wherein: the parameters of the direct current magnetron sputtering technology are as follows: sputtering power is 20-50W, pressure is 0.5-1.5Pa, argon flow is 20-50 SCCM;
further, the deposition time is 3s-1min, preferably 5s-30s, and more preferably 30 s;
preferably, the sputtering technical parameters of the gold nanoparticle film are as follows: the power is 20W, the pressure is 1Pa, and the time is 30 s.
6. The method of claim 2, wherein: in the raw materials in the thermal evaporation process, the mass ratio of Sn to SnO is 1:2-1: 5;
further, the preparation parameters of the thermal evaporation method are as follows: the temperature is controlled at 650-1000 ℃, the holding time is 10-60 min, the pressure is 10Pa, the carrier gas is argon, and the argon flow is 20-50 sccm;
preferably, the temperature is 850 ℃, the time is 30min, and the argon flow is 20 sccm.
7. A gas sensor, characterized in that: the gas-sensitive material in the sensor is NiO/SnO defined by claim 12And (4) compounding the nano-wires.
8. A method for preparing the gas sensor according to claim 7, wherein: the method specifically comprises the following steps:
first NiO/SnO2And stripping the composite nanowire, and transferring the composite nanowire to a silicon-based interdigital electrode deposited with a Ti electrode and an Au electrode. Among them, the use of metal Ti is intended to improve the bonding force between the gold electrode and the substrate.
9. The method of claim 8, wherein: the stripping process comprises the following steps: carefully treating the surface flocculent substance by using a doctor blade, then placing the flocculent substance into an absolute ethanol solution for ultrasonic treatment for 1-1.5h, taking supernatant fluid, and then keeping the supernatant fluid for 10-15min by using a centrifuge with the rotation speed of 4000 plus 5000rpm to obtain colloid white sticky matter, namely NiO/SnO2Compounding nanometer lines;
further, the parameters of the silicon-based interdigital electrode are as follows: external dimension 4mm 6mm 0.5mm, line width 20 mum, line spacing 20 μm, log 20; the substrate is coated with 1 μm SiO2Monocrystalline silicon of the insulating layer;
further, the gas sensor is a triethylamine gas sensor.
10. The triethylamine gas sensor as claimed in claim 9, wherein the triethylamine gas sensor is applied to the fields of industrial detection and environmental detection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110752640.8A CN113552180A (en) | 2021-07-02 | 2021-07-02 | NiO/SnO2Composite nanowire and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110752640.8A CN113552180A (en) | 2021-07-02 | 2021-07-02 | NiO/SnO2Composite nanowire and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113552180A true CN113552180A (en) | 2021-10-26 |
Family
ID=78131292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110752640.8A Pending CN113552180A (en) | 2021-07-02 | 2021-07-02 | NiO/SnO2Composite nanowire and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113552180A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010091116A2 (en) * | 2009-02-03 | 2010-08-12 | The Florida International University Board Of Trustees | Method of forming an anode material for a lithium ion battery |
| CN103728342A (en) * | 2014-01-06 | 2014-04-16 | 吉林大学 | Gas sensitive material with ultrahigh sensitivity |
| CN107321358A (en) * | 2017-07-12 | 2017-11-07 | 三峡大学 | A kind of sea cucumber shape SnO2/ NiO composite nano-tube materials and preparation method and application |
| CN111170357A (en) * | 2020-01-13 | 2020-05-19 | 云南大学 | SnO sensitive to formaldehyde gas2Preparation and application of nanorod array/reduced graphene oxide composite nanomaterial |
-
2021
- 2021-07-02 CN CN202110752640.8A patent/CN113552180A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010091116A2 (en) * | 2009-02-03 | 2010-08-12 | The Florida International University Board Of Trustees | Method of forming an anode material for a lithium ion battery |
| CN103728342A (en) * | 2014-01-06 | 2014-04-16 | 吉林大学 | Gas sensitive material with ultrahigh sensitivity |
| CN107321358A (en) * | 2017-07-12 | 2017-11-07 | 三峡大学 | A kind of sea cucumber shape SnO2/ NiO composite nano-tube materials and preparation method and application |
| CN111170357A (en) * | 2020-01-13 | 2020-05-19 | 云南大学 | SnO sensitive to formaldehyde gas2Preparation and application of nanorod array/reduced graphene oxide composite nanomaterial |
Non-Patent Citations (2)
| Title |
|---|
| TIANYU LIU 等: "Gas sensor based on Ni foam: SnO2-decorated NiO for Toluene detection", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
| 孙阳硕 等: "泡沫镍衬底上生长二氧化锡纳米线的生长行为及光致发光性能研究", 《人工晶体学报》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | Graphene-enhanced metal oxide gas sensors at room temperature: A review | |
| Sun et al. | Rapid synthesis of ZnO nano-rods by one-step, room-temperature, solid-state reaction and their gas-sensing properties | |
| Shen et al. | In-situ growth of mesoporous In2O3 nanorod arrays on a porous ceramic substrate for ppb-level NO2 detection at room temperature | |
| Park et al. | Enhanced H2S gas sensing performance of networked CuO-ZnO composite nanoparticle sensor | |
| Qin et al. | Microstructure characterization and NO2-sensing properties of tungsten oxide nanostructures | |
| Öztürk et al. | Fabrication of ZnO nanorods for NO2 sensor applications: effect of dimensions and electrode position | |
| Van Hieu | Comparative study of gas sensor performance of SnO2 nanowires and their hierarchical nanostructures | |
| CN109709160B (en) | Electronic conductive metal organic framework film and preparation method and application thereof | |
| Zhang et al. | Synthesis of the cactus-like silicon nanowires/tungsten oxide nanowires composite for room-temperature NO2 gas sensor | |
| KR101498157B1 (en) | ZnO-SnO2 nanofiber-nanowire stem-branch heterostructure material and preparation method thereof and gas sensor containing the material | |
| Li et al. | In situ decoration of Zn2SnO4 nanoparticles on reduced graphene oxide for high performance ethanol sensor | |
| Sun et al. | An integrating photoanode consisting of BiVO 4, rGO and LDH for photoelectrochemical water splitting | |
| Shruthi et al. | Ultrasensitive sensor based on Y2O3-In2O3 nanocomposites for the detection of methanol at room temperature | |
| WO2021232503A1 (en) | Gallium oxide nanostructure device, preparation method therefor and use thereof | |
| Huang et al. | Fabrication of rigid and flexible SrGe 4 O 9 nanotube-based sensors for room-temperature ammonia detection | |
| KR20140134174A (en) | Hydrogen sensor based on zinc oxide and method of fabricating the same | |
| Wang et al. | Enhanced nitrogen oxide sensing performance based on tin-doped tungsten oxide nanoplates by a hydrothermal method | |
| Wang et al. | Effect of solvothermal reaction temperature on the morphology of WO3 nanocrystals and their low-temperature NO2-sensing properties | |
| Shruthi et al. | Synthesis of Y2O3-ZnO nanocomposites for the enhancement of room temperature 2-methoxyethanol gas sensing performance | |
| Hyun et al. | Ethanol gas sensing using a networked PbO-decorated SnO2 nanowires | |
| Zeng et al. | A novel room temperature SO2 gas sensor based on TiO2/rGO buried-gate FET | |
| Shen et al. | Synthesis of rGO-SnO2 nanocomposites using GO as an alkali-resistant substrate for high-performance detection of NO2 | |
| CN108931559B (en) | Boron-doped graphene-modified Au @ ZnO core-shell heterojunction type triethylamine gas sensor and preparation method thereof | |
| Wang et al. | Chemiresistive n-butanol gas sensors based on Co3O4@ ZnO hollow-sphere-array thin films prepared by template-assisted magnetron sputtering | |
| CN107402242B (en) | Surface-modified titanium dioxide film gas sensor and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211026 |
|
| RJ01 | Rejection of invention patent application after publication |