CN108303449A - The quick element of room temperature high sensitivity ammonia based on tungsten oxide-polypyrrole core sheath nano wire - Google Patents
The quick element of room temperature high sensitivity ammonia based on tungsten oxide-polypyrrole core sheath nano wire Download PDFInfo
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- CN108303449A CN108303449A CN201710017563.5A CN201710017563A CN108303449A CN 108303449 A CN108303449 A CN 108303449A CN 201710017563 A CN201710017563 A CN 201710017563A CN 108303449 A CN108303449 A CN 108303449A
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- 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
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- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
Abstract
The present invention discloses the quick element of room temperature high sensitivity ammonia based on tungsten oxide-polypyrrole core sheath nano wire, neopelex is dissolved in deionized water, obtain neopelex solution, pyrrole monomer is dissolved in absolute ethyl alcohol, it instills in neopelex solution dropwise after mixing, tungsten oxide nano solution is instilled dropwise in above-mentioned mixed solution after continuing stirring, it is 14 by the way that concentrated hydrochloric acid is added dropwise to adjust mixed solution pH, obtain polymerisation reaction solution, ammonium persulfate solution is added dropwise dropwise in polymerisation reaction solution again, eccentric cleaning；By above-mentioned polymerizate W18O49@PPy core sheath nano wires absolute ethyl alcohols, which fully dilute, to be disperseed and is spin-coated in electrode basement.It forms polypyrrole sheaths and covers the uniform and regulatable one-dimensional W of sheaths pattern18O49@PPy core sheath heterojunction nanowires construct sensor sensing member, obtain a kind of quick gas sensor element of ammonia with room temperature high sensitivity and quick response recovery characteristics.
Description
Technical field
The invention belongs to inorganic/organic heterogeneous nanocomposite technical fields of one-dimentional structure to be more particularly related to
One kind being based on the quick element of room temperature high sensitivity ammonia of tungsten oxide-polypyrrole core sheath nano wire.
Background technology
Currently, non-renewable energy is increasingly reduced, and atmospheric environment runs down.Increasingly in face of energy shortage and atmosphere pollution
Seriously, the development and utilization of regenerative resource, the reliable detection of toxic and harmful gas have become increasingly urgent.With material science
Development, low-dimension nano material obtains extensive concern and application with its exclusive characteristic in energy and environment field.
Low-dimension nano material includes zero dimension, a peacekeeping two-dimensional material.Due to its special low-dimensional nano structure, low-dimensional materials
With the specific physicals chemical property such as apparent volume, skin effect.For example, low-dimensional materials have large specific surface area, active site
Feature more than position, therefore can be applied to material energy storage and gas detection；Using one-dimensional carbon fiber as electrode material of lithium battery, tool
There are lithium ion diffusion rate height, the big advantage of specific capacity；It, not only can be effective using tungsten oxide nano as gas sensitive material
Senor operating temperature is reduced, and has good response special part toxic and harmful gas due to its strong skin effect
Property.
But there are apparent performance offices when applied to energy storage or gas sensing for the low-dimensional functional material of one-component
Limit：Powder phenomenon-tion can occur as electrode energy storage material, lead to poor circulation；It is sensitive at room temperature as gas sensitive material
Spend that low, gas-selectively is poor.In order to improve these performance shortcomings, low-dimensional inorganic nano material, shape are coated using conducting polymer
It is a kind of effective way at low-dimensional organic and inorganic core-shell structure, the preparation method of organic polymer shell usually has liquid phase
Chemical oxidative polymerization, saturated vapor polymerization and electrochemically oxidative polymerization method.Wherein, saturated vapor polymerization and electrochemical polymerization
Although method can prepare the Core-shell structure material that thickness is uniform, clad ratio is high, complex process is of high cost, the polymerization item of high temperature
Part can also reduce the stability and functional characteristic of shell conducting polymer, comparatively, liquid phase chemical oxidation polymerization has system
Standby process safety, advantage easy to operate at low cost is a kind of technique side for preparing organic polymer shell having dynamogenetic value
Method.But it polymerize the polymeric shell layer shape to be formed in one-dimensional inorganic nanowire surface using current liquid phase chemical oxidative polymerization method
Looks poor controllability, shell thickness is uneven and is difficult to form the uniform cladding to nano wire, to influence organic and inorganic nucleocapsid
The physical and chemical performance of structure.
Invention content
The present invention overcomes deficiencies in the prior art, provide one kind and being based on tungsten oxide-polypyrrole core sheath nano wire
The quick element of room temperature high sensitivity ammonia realizes pyrroles in the uniform of one-dimensional nano line surface by a kind of pyrroles's polymerization technique of optimization
Polymerization, to prepare, the covering of polypyrrole shell is uniform and the regulatable one-dimensional tungsten oxide/polypyrrole nucleocapsid of shell pattern is heterogeneous
Structure nanometer wire, overcome Traditional liquid phase polymerization prepare polymer shell layer film caused by morphology controllable difference nucleocapsid material
Expect the unstable problem of performance.
The purpose of the present invention is achieved by following technical proposals.
The quick element of room temperature high sensitivity ammonia based on tungsten oxide-polypyrrole core sheath nano wire, in aluminium oxide ceramics substrate
Platinum interdigital electrode is set, tungsten oxide-polypyrrole nucleocapsid heterogeneous structural nano line coating is set in platinum interdigital electrode.
Tungsten oxide-polypyrrole nucleocapsid heterogeneous structural nano line, carries out as steps described below：
Tungsten oxide nano suspension is instilled in pyrroles's polymerization liquid, and hydrochloric acid is added dropwise thereto, so that mixture
Be pH it is 1-4, while is uniformly dispersed to mixed system；Then it under conditions of lasting dispersion, is added dropwise into mixed system
To cause pyrrole monomer on tungsten oxide nano surface the uniform shell that polymerisation forms polypyrrole occurs for ammonium persulfate aqueous solution
Layer forms tungsten oxide-polypyrrole nucleocapsid heterogeneous structural nano line.
In the above-mentioned technical solutions, detached, cleaned and dried after reacting, after polymerisation, respectively according to
It is secondary that obtained solid is reacted 2-4 times using deionized water and washes of absolute alcohol；The condition of the drying is：Drying temperature is 40-
60 DEG C, drying time 10-15h.
In the above-mentioned technical solutions, in ammonium persulfate aqueous solution, a concentration of 0.005-0.04mol/L of ammonium persulfate.
In the above-mentioned technical solutions, hydrochloric acid is the aqueous solution of the hydrogen chloride of mass percent 20-30%.
In the above-mentioned technical solutions, when adjusting mixed system pH value, carried out using magnetic agitation evenly dispersed, the time is
0.5-3h, preferably 1-2h, mixing speed are 200-300 turns per minute.
In the above-mentioned technical solutions, when adjusting mixed system pH value, mixed system pH is 2-3.
In the above-mentioned technical solutions, in initiated polymerization, evenly dispersed, mixing time is carried out using magnetic agitation
1-5 hours, preferably 2-4h, mixing speed are 200-300 turns per minute.
The tungsten oxide nano suspension is prepared as steps described below：Tungsten hexachloride powder is added to cyclohexanol
In, after magnetic agitation 10-40min, tungsten hexachloride homogeneous solution is obtained, the hexamethylene alcoholic solution of above-mentioned tungsten hexachloride is sealed anti-
Answer, reaction temperature be 180-220 DEG C, preferably 200 DEG C, reaction time 6-9h, by above-mentioned reaction solution cooled to room temperature
It 20-25 DEG C, centrifuges, centrifugal rotational speed 4000-6000r/min, preferably 5000r/min, obtained solid uses anhydrous successively
After ethyl alcohol and deionized water cleaning, then centrifugation obtained solid is transferred in deionized water after ultrasound 10-15min to get to oxygen
Change tungsten nanowires suspension.
Pyrroles's polymerization liquid is prepared as steps described below：Neopelex (SDBS) is added to
In deionized water, magnetic agitation 3-7min, preferably 5min are to get to neopelex solution, by pyrrole monomer (Py)
Predissolve is dispersed in absolute ethyl alcohol, obtains pyrrole monomer solution after mixing, under conditions of magnetic agitation, by pyrroles's list
Liquid solution is instilled dropwise in neopelex solution, continues magnetic agitation 20-30min, forms uniform pyrroles's polymerization
The molar ratio of reaction solution, neopelex and pyrrole monomer is (1-1.2)：3, neopelex and over cure
The molar ratio of sour ammonium is 4：(1—1.5).
It is 700-800nm according to nanowire length prepared by above-mentioned technical proposal, polypyrrole shell thickness is 5-20nm,
(preferably nanowire length is 720-760nm to a diameter of 70-80nm of tungsten oxide nano, and polypyrrole shell thickness is 10-
15nm, a diameter of 75-80nm of tungsten oxide nano).
When platinum interdigital electrode is arranged, the metal platinum target used is with quality purity for quality purity 99.95%
99.999% argon gas is as working gas, background vacuum 4~6 × 10-4Pa is prepared using radio-frequency magnetron sputter method, sputtering
2-5min, 80~120nm of film thickness.
When tungsten oxide-polypyrrole nucleocapsid heterogeneous structural nano line coating is arranged, dispersion oxidation is diluted using absolute ethyl alcohol
Tungsten-polypyrrole nucleocapsid heterogeneous structural nano line is simultaneously spin-coated in the platinum interdigital electrode of aluminium oxide ceramics substrate, is done at 40~60 DEG C
The quick test of the dry laggard promoting the circulation of qi of 10~15h.
It is 700-800nm according to nanowire length prepared by above-mentioned technical proposal, polypyrrole shell thickness is 5-20nm,
(preferably nanowire length is 720-760nm to a diameter of 70-80nm of tungsten oxide nano, and polypyrrole shell thickness is 10-
15nm, a diameter of 75-80nm of tungsten oxide nano).Shell is prepared by pyrroles's polymerization technique of optimization the present invention provides a kind of
Layer dense uniform, shell morphology controllable the heterogeneous core-shell nano line of one-dimensional tungsten oxide/polypyrrole preparation method, overcome tradition
Liquid polymerization is difficult to organic/nothing caused by one-dimensional nano line surface forms the organic polymer blanket films of morphology controllable
The unstable problem of movement sheath nanowire properties.The inventive method prepares polymer using the liquid phase chemical oxidative polymerization method of optimization
Shell has equipment simple, and easy to operate, technological parameter is easily controllable, cost extremely cheap the advantages that can be mass-produced.It is logical
Ethyl alcohol pre-dispersion is crossed to form the polymerization liquid of high uniformity that one-dimensional inorganic tungsten oxide nano surface may be implemented is organic
The uniform fold of polymer；Critical concentration by regulating and controlling polymerization reactant in liquid-phase polymerization liquid can effectively change nucleocapsid
Structure nanometer wire shell pattern.Shell pyrroles organic matter can be made to be formed on tungsten oxide nano surface using the preparation method
Even polymerization, high quality tungsten oxide/polypyrrole nucleocapsid heterojunction nanowire of formation has the heterogeneous interface of maximization, so as to fill
Distribution is waved hetero-junctions and is acted on the Effective Regulation of heterojunction structure nano material performance, in researchs such as gas sensor, battery energy storages
Have great importance in field.
Description of the drawings
Fig. 1 is the electron scanning micrograph and transmission electron microscope of the tungsten oxide nano prepared by embodiment 1
Photo.
Fig. 2 is that the scanning electron microscope of the heterogeneous nuclear shell structure nano line of tungsten oxide/polypyrrole prepared by embodiment 1 is shone
Piece and transmission electron microscope photo.
Fig. 3 is that the scanning electron microscope of the heterogeneous nuclear shell structure nano line of tungsten oxide/polypyrrole prepared by embodiment 2 is shone
Piece and transmission electron microscope photo.
Fig. 4 is that the scanning electron microscope of the heterogeneous nuclear shell structure nano line of tungsten oxide/polypyrrole prepared by embodiment 2 is shone
Piece and EDS spectrograms.
Fig. 5 be the present invention prepare the heterogeneous nuclear shell structure nano line of tungsten oxide/polypyrrole, polypyrrole and tungsten oxide XRD
Spectrum, wherein (a) is the heterogeneous nuclear shell structure nano line of tungsten oxide/polypyrrole, (b) is polypyrrole polymers, (c) is tungsten oxide
Nano wire.
Fig. 6 is the air-sensitive test device structural schematic diagram that the present invention uses.
Fig. 7 is the W prepared using the present invention18O49The gas-sensitive sensing element structural schematic diagram of@PPy core sheath nano wires composition.
Fig. 8 is W prepared by the present invention18O49@PPy core sheath nano wire gas-sensitive sensing elements to 1ppm, 3ppm, 5ppm,
The dynamic response curve of 10ppm, 20ppm, 50ppm, 100ppm, 200ppm ammonia.
Fig. 9 is W prepared by the present invention18O49Selective schematic diagram of the@PPy core sheath nano wire gas sensors to gas with various.
Specific implementation mode
Technical scheme of the present invention is further described below by specific embodiment.
Embodiment 1
(1) solvent-thermal method prepares tungsten oxide nano
Tungsten hexachloride powder is added in 60ml cyclohexanol, magnetic agitation 20min makes tungsten hexachloride powder be completely dissolved, obtains
Obtain the homogeneous solution of a concentration of 0.005mol/L of tungsten hexachloride.It is poly- four that the hexamethylene alcoholic solution of the tungsten hexachloride, which is transferred to liner,
Reaction kettle is placed in heating in baking oven in the autoclave of vinyl fluoride, after sealing and carries out solvent thermal reaction, baking oven operating temperature
It is 200 DEG C, heating time 6h.
(2) cleaning of tungsten oxide nano
Solvent thermal reaction terminates to make autoclave Temperature fall to room temperature, reaction kettle is taken out, by the blue in reaction kettle
Solid-liquid reaction object centrifuges, and centrifuge speed is set as 5000r/min.It centrifuges obtained solid priority absolute ethyl alcohol and goes
Ionized water distinguishes eccentric cleaning 2 times.Finally the centrifugation product after cleaning is transferred in 10ml deionized waters, ultrasonic 15min is obtained
Obtain evenly dispersed tungsten oxide nano suspension.
(3) pyrroles's polymerization liquid is configured
0.2mmol neopelexes (SDBS) are weighed, 80ml deionized waters are added, at a slow speed magnetic agitation 5min,
Obtain neopelex solution.Weigh 0.6mmol pyrrole monomers (Py) and by its predissolve in 1ml absolute ethyl alcohols,
Pyrrole monomer solution is formed after mixing.In the condition of magnetic agitation, pyrrole monomer solution instilled into dodecyl dropwise
In benzene sulfonic acid sodium salt solution, continues magnetic agitation 30min, form uniform pyrroles's polymerization liquid.
(4) polymerisation forms polypyrrole shell
Under conditions of continuing magnetic force stirs, the tungsten oxide nano suspension that step (2) obtains is instilled into step dropwise
(3) in the pyrroles's polymerization liquid obtained, it is 2-3 that concentrated hydrochloric acid, which is added dropwise, and adjusts the PH of mixed liquor.Continue magnetic agitation 1-2h.Then
Ammonium persulfate (APS) oxidizing agent solution of a concentration of 0.005M of 10ml is added dropwise dropwise, continues to stir 4h, pyrrole monomer is made to aoxidize
The uniform shell that polymerisation forms polypyrrole occurs for tungsten nanowires surface.Polymerisation terminates, and suspension centrifuges, gained
Solid uses deionized water and absolute ethyl alcohol eccentric cleaning twice respectively, and wet sample dry 10h under the conditions of 50 DEG C is aoxidized
The heterogeneous nuclear shell structure nano line sample of tungsten/polypyrrole.
Scanning electron microscope analysis result such as Fig. 1 of the tungsten oxide nano pattern obtained after 1 step of embodiment (2) is left
Shown in figure, tem study result such as Fig. 1 right figures.Pure zirconia tungsten nanowires average diameter is about 70nm, and length is about
For 800nm.The scanning electron microscopy of the tungsten oxide that 1 step of embodiment (4) is prepared afterwards/polypyrrole nucleocapsid heterojunction nano-wire pattern
Mirror analysis result is as shown in Fig. 2 left figures, and pattern, size and pure zirconia tungsten nanowires are without too big difference；Transmission electron microscope
Analysis result such as Fig. 1 right figures, it is observed that polypyrrole coats kernel tungsten oxide nano completely, shell thickness average out to 5nm,
It is evenly distributed and fine and close, surface is relatively smooth.
Embodiment 2
(1) solvent-thermal method prepares tungsten oxide nano
Tungsten hexachloride powder is added in 60ml cyclohexanol, magnetic agitation 10min makes tungsten hexachloride powder be completely dissolved, obtains
Obtain the homogeneous solution of a concentration of 0.005mol/L of tungsten hexachloride.It is poly- four that the hexamethylene alcoholic solution of the tungsten hexachloride, which is transferred to liner,
Reaction kettle is placed in heating in baking oven in the autoclave of vinyl fluoride, after sealing and carries out solvent thermal reaction, baking oven operating temperature
It is 180 DEG C, heating time 9h.
(2) cleaning of tungsten oxide nano
Solvent thermal reaction terminates to make autoclave Temperature fall to room temperature, reaction kettle is taken out, by the blue in reaction kettle
Solid-liquid reaction object centrifuges, and centrifuge speed is set as 4000r/min.It centrifuges obtained solid priority absolute ethyl alcohol and goes
Ionized water distinguishes eccentric cleaning 2 times.Finally the centrifugation product after cleaning is transferred in 10ml deionized waters, ultrasonic 10min is obtained
Obtain evenly dispersed tungsten oxide nano suspension.
(3) pyrroles's polymerization liquid is configured
0.8mmol neopelexes (SDBS) are weighed, 80ml deionized waters are added, at a slow speed magnetic agitation 3min,
Obtain neopelex solution.Weigh 2.4mmol pyrrole monomers (Py) and by its predissolve in 1ml absolute ethyl alcohols,
Pyrrole monomer solution is formed after mixing.In the condition of magnetic agitation, pyrrole monomer solution instilled into dodecyl dropwise
In benzene sulfonic acid sodium salt solution, continues magnetic agitation 20min, form uniform pyrroles's polymerization liquid.
(4) polymerisation forms polypyrrole shell
Under conditions of continuing magnetic force stirs, the tungsten oxide nano suspension that step (2) obtains is instilled into step dropwise
(3) in the pyrroles's polymerization liquid obtained, it is 1-2 that concentrated hydrochloric acid, which is added dropwise, and adjusts the PH of mixed liquor.Continue magnetic agitation 2-4h.Then
Ammonium persulfate (APS) oxidizing agent solution of a concentration of 0.04M of 10ml is added dropwise dropwise, continues to stir 5h, pyrrole monomer is made to aoxidize
The uniform shell that polymerisation forms polypyrrole occurs for tungsten nanowires surface.Polymerisation terminates, and suspension centrifuges, gained
Solid uses deionized water and absolute ethyl alcohol eccentric cleaning four times, wet sample dry 15h under the conditions of 40 DEG C to be aoxidized respectively
The heterogeneous nuclear shell structure nano line sample of tungsten/polypyrrole.
The scanning electron microscope analysis result of tungsten oxide/tungsten oxide heterojunction nano-wire pattern prepared by embodiment 2 is such as
Shown in Fig. 3 left figures, it can be found that with the increase of polymerisation object amount, nucleocapsid radial dimension significantly increases, and approaches
100nm, rough surface；Tem study result such as Fig. 3 right figures, polypyrrole shell average thickness are about 15nm, mistake
More polymeric reaction products causes shell layer surface to generate protrusion.Element detection is carried out it is found that containing nano wire in region with EDS again
Middle multiple element C, N, O, W, as shown in the table：
| Element | Weight percent | Atomic percent |
| C K | 6.38 | 23.01 |
| N K | 4.38 | 4.27 |
| O K | 20.62 | 55.85 |
| W M | 71.62 | 16.88 |
| Total amount | 100.00 |
Embodiment 3
(1) solvent-thermal method prepares tungsten oxide nano
Tungsten hexachloride powder is added in 60ml cyclohexanol, magnetic agitation 40min makes tungsten hexachloride powder be completely dissolved, obtains
Obtain the homogeneous solution of a concentration of 0.005mol/L of tungsten hexachloride.It is poly- four that the hexamethylene alcoholic solution of the tungsten hexachloride, which is transferred to liner,
Reaction kettle is placed in heating in baking oven in the autoclave of vinyl fluoride, after sealing and carries out solvent thermal reaction, baking oven operating temperature
It is 220 DEG C, heating time 7h.
(2) cleaning of tungsten oxide nano
Solvent thermal reaction terminates to make autoclave Temperature fall to room temperature, reaction kettle is taken out, by the blue in reaction kettle
Solid-liquid reaction object centrifuges, and centrifuge speed is set as 6000r/min.It centrifuges obtained solid priority absolute ethyl alcohol and goes
Ionized water distinguishes eccentric cleaning 2 times.Finally the centrifugation product after cleaning is transferred in 10ml deionized waters, ultrasonic 12min is obtained
Obtain evenly dispersed tungsten oxide nano suspension.
(3) pyrroles's polymerization liquid is configured
0.8mmol neopelexes (SDBS) are weighed, 80ml deionized waters are added, at a slow speed magnetic agitation 7min,
Obtain neopelex solution.Weigh 2.4mmol pyrrole monomers (Py) and by its predissolve in 1ml absolute ethyl alcohols,
Pyrrole monomer solution is formed after mixing.In the condition of magnetic agitation, pyrrole monomer solution instilled into dodecyl dropwise
In benzene sulfonic acid sodium salt solution, continues magnetic agitation 30min, form uniform pyrroles's polymerization liquid.
(4) polymerisation forms polypyrrole shell
Under conditions of continuing magnetic force stirs, the tungsten oxide nano suspension that step (2) obtains is instilled into step dropwise
(3) in the pyrroles's polymerization liquid obtained, it is 3-4 that concentrated hydrochloric acid, which is added dropwise, and adjusts the PH of mixed liquor.Continue magnetic agitation 0.5-2h.So
Ammonium persulfate (APS) oxidizing agent solution of a concentration of 0.02M of 10ml is added dropwise dropwise afterwards, continues to stir 3h, makes pyrrole monomer in oxygen
Change tungsten nanowires surface and the uniform shell that polymerisation forms polypyrrole occurs.Polymerisation terminates, and suspension centrifuges, institute
It obtains solid and uses deionized water and absolute ethyl alcohol eccentric cleaning three times respectively, wet sample dry 12h under the conditions of 60 DEG C obtains oxygen
Change the heterogeneous nuclear shell structure nano line sample of tungsten/polypyrrole.
The heterogeneous nuclear shell structure nano line of tungsten oxide/polypyrrole, polypyrrole and tungsten oxide nano prepared by the present invention is (i.e. not
Carry out polypyrrole it is compound) XRD spectrums, by compare it is found that in 23.2 ° of monoclinic system Ws corresponding with 47.4 °18O49(010) and
(020) crystal face exists in tungsten oxide nano and heterogeneous nuclear shell structure nano line, at the same polypyrrole characteristic peak be also presented in it is different
In matter nuclear shell structure nano line.
Heterogeneous nuclear shell structure nano line is configured to gas sensor, the preparation of electrode basement is carried out first, aluminium oxide is made pottery
Tile is successively placed in ultrasound in acetone solvent, absolute ethyl alcohol, deionized water and is respectively washed 5-10min, remove surface and oil contaminant and
Organic impurities are placed in infrared baking oven and thoroughly dry.It is interdigital in aluminium oxide ceramics on piece formation platinum by the help of template
Electrode, as shown in Fig. 7, a 22mm, b 1.2mm, c 1.5mm.The metal platinum target used for quality purity 99.95%,
Using the argon gas that quality purity is 99.999% as working gas, background vacuum 4~6 × 10-4Pa, using rf magnetron sputtering
Prepared by method, sputter 2min, 80~120nm of film thickness.Then the heterogeneous nuclear shell structure nano line (W prepared by the present invention18O49@
PPy core sheaths nano wire) with being spin-coated in the electrode basement prepared after the dilution of 5ml absolute ethyl alcohols, it is carried out after dry 10h at 60 DEG C
Air-sensitive is tested.As shown in Fig. 6, the air-sensitive test device that the present invention uses, 1 is air admission hole, enters survey by micro injectant
The tested gas of examination amount；2 be gas sensor element, is connected with platinum electrode by probe, is connect with external detection equipment；3 are
It can heat and keep to the platform for needing temperature；4 be to take the test sealing container made, and is 30L capacity；5 be mini fan, side
Gas diffusion is helped, gas is made to be dispersed in cube container；6 be gas outlet；7 be the brain box of controllable adjustment temperature
Device；8 be the UT70D resistance detection equipment of excellent Leadd B.V, the resistance value of real-time display probe junction, and exports to computer and set
It is standby；9 be the computer terminal that the resistance variations measured are recorded as to table and display；The air admission hole being arranged by sealing container top to
Micro injection is tested gas in sealing container, passes through mini fan and the collective effect of gas outlet so that tested gas is close
It further spreads, makes in tested gas diffusion to the gas sensor element being placed on heating platform, electronics control in envelope container
Instrument processed by the temperature of temperature pilot real-time control heating platform, gas sensor element by sensing element conducting wire with
The UT70D resistance detection equipment of excellent Leadd B.V is connected, to the resistance value of real-time display probe junction, and will corresponding electricity
Resistance test number is transmitted to computer terminal, by computer terminal by whole resistance test numerical value summary records at table.
As shown in figs. 8 and 9, W18O49@PPy core sheath nano wire gas sensors show selectivity well to ammonia and (survey
Strip part：18 DEG C of temperature, humidity 16%), the W of preparation18O49@PPy core sheath nano wire gas-sensitive sensing elements to 1ppm, 3ppm,
Dynamic response curve (the test condition of 5ppm, 10ppm, 20ppm, 50ppm, 100ppm, 200ppm ammonia：14 DEG C of temperature, humidity
20%), sensitivity is respectively：1.021,1.121,1.7,2.76,4.106,5.64,6.192,6.49, wherein 1ppm are minimum
Detecting concentration, the W prepared based on the method for the present invention18O49The gas sensor of@PPy core sheath heterojunction nanowires at 14 DEG C to 1~
The sensitivity (S=Rg/Ra) of 200ppm ammonias is up to 6.49, and most short response time is about 4s, and the quick performance of the ammonia is substantially better than
The performance data for the quick element of the ammonia based on same type of material reported.
The present invention provides one kind being based on W18O49The preparation side of the quick element of room temperature high sensitivity ammonia of@PPy core sheath nano wires
Method.The covering of polypyrrole sheaths may be implemented uniformly and the regulatable one-dimensional W of sheaths pattern by open one kind18O49@PPy core sheaths
Heterojunction nanowire sensing element preparation process realizes the efficient quick detection of room temperature of ammonia gas.The present invention solves one-dimensional
It is poly- on one-dimensional nano line surface to be difficult to uniform, controllable for organic sheaths in the compound ammonia-sensitive material preparation process of structural inorganic/organic core sheath
The problem of conjunction, the high activity that the quick element of ammonia prepared using the method for the present invention is had by the one-dimensional characteristic of heterojunction nanowire
Gas absorption surface area, meanwhile, maximization heterogeneous interface possessed by the uniform core sheath heterojunction structure of organic/inorganic has efficient
Heterogeneous collaboration coupling performance, so as to the quick performance of ammonia of Effective Regulation element.With existing saturated vapor polymerization, electrochemistry
The methods of oxidative polymerization method is compared, uniform using pyrroles's liquid phase chemical oxidation polymerization preparation structure of optimization disclosed by the invention
W18O49There is the method for@PPy core sheath nano wire ammonia-sensitive materials product uniformity consistency higher and equipment to be simple and convenient to operate, work
Skill parameter is easily controllable, cost extremely cheap the advantages that can be mass-produced.The W prepared based on the method for the present invention18O49@PPy cores
The gas sensor of sheath heterojunction nanowire is up to 6.49 to the sensitivity (S=Rg/Ra) of 1~200ppm ammonias at 14 DEG C, most
Short response time is 4-5s, and the quick performance of the ammonia is substantially better than the performance data for the quick element of the ammonia based on same type of material reported.
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (9)
1. the quick element of room temperature high sensitivity ammonia based on tungsten oxide-polypyrrole core sheath nano wire, which is characterized in that in aluminium oxide
Platinum interdigital electrode is set in ceramic bases, tungsten oxide-polypyrrole nucleocapsid heterogeneous structural nano line is set in platinum interdigital electrode and is applied
Layer, wherein：Tungsten oxide-polypyrrole nucleocapsid heterogeneous structural nano line, carries out as steps described below：Tungsten oxide nano is suspended
Drop enters in pyrroles's polymerization liquid, and hydrochloric acid is added dropwise thereto so that mixed system pH be 1-4, while to mixed system into
Row is uniformly dispersed；Then under conditions of lasting dispersion, ammonium persulfate aqueous solution is added dropwise into mixed system, to cause pyrroles's list
On tungsten oxide nano surface the uniform shell that polymerisation forms polypyrrole occurs for body, and it is different to form tungsten oxide-polypyrrole nucleocapsid
Matter structure nanometer wire, nanowire length are 700-800nm, and polypyrrole shell thickness is 5-20nm, tungsten oxide nanometer linear diameter
For 70-80nm；It is up to 6.49 to the sensitivity of 1~200ppm ammonias at 14 DEG C, most short response time is 4-5s.
2. the room temperature high sensitivity ammonia quick element according to claim 1 based on tungsten oxide-polypyrrole core sheath nano wire,
It is characterized in that, when platinum interdigital electrode is arranged, the metal platinum target used is with quality purity for quality purity 99.95%
99.999% argon gas is as working gas, background vacuum 4~6 × 10-4Pa is prepared using radio-frequency magnetron sputter method, sputtering
2-5min, 80~120nm of film thickness.
3. the room temperature high sensitivity ammonia quick element according to claim 1 based on tungsten oxide-polypyrrole core sheath nano wire,
It is characterized in that, when tungsten oxide-polypyrrole nucleocapsid heterogeneous structural nano line coating is arranged, is diluted and disperseed using absolute ethyl alcohol
Tungsten oxide-polypyrrole nucleocapsid heterogeneous structural nano line is simultaneously spin-coated in the platinum interdigital electrode of aluminium oxide ceramics substrate.
4. the room temperature high sensitivity ammonia quick element according to claim 1 based on tungsten oxide-polypyrrole core sheath nano wire,
It is characterized in that, nanowire length is 720-760nm, polypyrrole shell thickness is 10-15nm, and tungsten oxide nano is a diameter of
75—80nm。
5. the room temperature high sensitivity ammonia quick element according to claim 1 based on tungsten oxide-polypyrrole core sheath nano wire,
It is characterized in that, in ammonium persulfate aqueous solution, a concentration of 0.005-0.04mol/L of ammonium persulfate；Hydrochloric acid is quality percentage
The aqueous solution of the hydrogen chloride of number 20-30%.
6. the room temperature high sensitivity ammonia quick element according to claim 1 based on tungsten oxide-polypyrrole core sheath nano wire,
It is characterized in that, when adjusting mixed system pH value, carried out using magnetic agitation evenly dispersed, the time is 0.5-3h, preferably
1-2h, mixing speed are 200-300 turns per minute, and mixed system pH is 2-3.
7. the room temperature high sensitivity ammonia quick element according to claim 1 based on tungsten oxide-polypyrrole core sheath nano wire,
It is characterized in that, in initiated polymerization, evenly dispersed, mixing time 1-5 hours, preferably 2- are carried out using magnetic agitation
4h, mixing speed are 200-300 turns per minute.
8. the room temperature high sensitivity ammonia quick element according to claim 1 based on tungsten oxide-polypyrrole core sheath nano wire,
It is characterized in that, the tungsten oxide nano suspension is prepared as steps described below：Tungsten hexachloride powder is added to ring
In hexanol, after magnetic agitation 10-40min, tungsten hexachloride homogeneous solution is obtained, the hexamethylene alcoholic solution of above-mentioned tungsten hexachloride is sealed
Reaction, reaction temperature are 180-220 DEG C, and preferably 200 DEG C, above-mentioned reaction solution is naturally cooled to room by reaction time 6-9h
It warm 20-25 DEG C, centrifuges, centrifugal rotational speed 4000-6000r/min, preferably 5000r/min, obtained solid uses nothing successively
Water-ethanol and deionized water cleaning after, then will centrifugation obtained solid be transferred in deionized water after ultrasound 10-15min to get to
Tungsten oxide nano suspension.
9. the room temperature high sensitivity ammonia quick element according to claim 1 based on tungsten oxide-polypyrrole core sheath nano wire,
It is characterized in that, pyrroles's polymerization liquid is prepared as steps described below：Neopelex (SDBS) is added
Enter into deionized water, magnetic agitation 3-7min, preferably 5min are to get to neopelex solution, by pyrrole monomer
(Py) predissolve is dispersed in absolute ethyl alcohol, obtains pyrrole monomer solution after mixing, under conditions of magnetic agitation, by pyrrole
It coughs up monomer solution to instill dropwise in neopelex solution, continues magnetic agitation 20-30min, form uniform pyrroles
The molar ratio of polymerization liquid, neopelex and pyrrole monomer is (1-1.2)：3, neopelex and
The molar ratio of ammonium persulfate is 4：(1—1.5).
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