CN110057875A - Polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick and its preparation method and application of Argent grain modification - Google Patents
Polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick and its preparation method and application of Argent grain modification Download PDFInfo
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- CN110057875A CN110057875A CN201810051179.1A CN201810051179A CN110057875A CN 110057875 A CN110057875 A CN 110057875A CN 201810051179 A CN201810051179 A CN 201810051179A CN 110057875 A CN110057875 A CN 110057875A
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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- 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
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- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
Abstract
The present invention discloses polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick and its preparation method and application of Argent grain modification, through liquid phase polymerization technique while polypyrrole shell homogeneous polymerization is realized on one-dimensional tungsten oxide nanometer stick surface, it is synchronous to realize the modification of polypyrrole-tungsten oxide nucleocapsid heterojunction structure Argent grain, to prepare with polypyrrole shell uniform fold and there are the nucleocapsid heterogeneous structural nano sticks of metallic silver particles modification.Gas sensor based on nanometer rods of the present invention is up to 6.15 to the sensitivity of 100ppb~50ppm ammonia at 25 DEG C, and most short response time is 10-13s, and the quick performance of the ammonia is substantially better than the performance of the reported quick element of the ammonia based on same type of material.
Description
Technical field
The invention belongs to surface Argent grain modification one-dimensional organic-inorganic heterojunction structure nanocomposite technical field,
More particularly, it is related to a kind of one-dimensional polypyrrole@tungsten oxide nucleocapsid heterojunction structure prepared with Argent grain surface modification to receive
Rice stick and preparation method thereof.
Background technique
The structure of gas sensing materials largely determines the practical application value of gas sensor.Structure is excellent
The gas sensor that gas sensitive prepares has high sensitivity, and response resume speed is fast, and stability is strong and can be in room temperature work
The features such as making.In current material system combination and composite structure preparation research, there are two research direction always by
To extensive concern: first, the combination of organic conductive polymer and inorganic, metal oxide semiconductor, especially conducting polymer
Coated metal oxide is formed by low-dimensional Core-shell structure material, and have while air-sensitive performance can be remarkably reinforced has room again
The good characteristic of temperature work；Second, surface modification and improvement of the noble metal for low-dimensional gas sensitive, for example, metallic silver particles with
A series of interactions can occur for the contact of low dimension semiconductor gas sensitive, and electronics transfer and spilling effect can significantly improve phase
Sensitivity of the low-dimensional materials for test gas is answered, detection limit is extended, promotes the stability of gas sensitive.The two are studied
Direction combines, and can largely realize the optimization of air-sensitive performance, before air-sensitive field has very big development
Scape.
Summary of the invention
It is an object of the invention to overcome deficiency in the prior art, a kind of polypyrrole@oxygen for modifying Argent grain is provided
Change tungsten nucleocapsid heterogeneous structural nano stick and its preparation method and application, is received by the liquid phase polymerization technique of innovation in one-dimensional tungsten oxide
While polypyrrole shell homogeneous polymerization is realized on rice stick surface, the synchronous silver for realizing polypyrrole@tungsten oxide nucleocapsid heterojunction structure
Grain surface modification, thus prepare with polypyrrole shell uniform fold and there are metallic silver particles modification nucleocapsid heterojunction structure
Nanometer rods.The present invention introduces surface modified by silver for the compound nucleocapsid low-dimensional materials of all organic/inorganics and provides a simple and reality
Technical thought and scheme.
Technical purpose of the invention is achieved by following technical proposals:
Polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick and preparation method thereof of Argent grain modification, as steps described below
It carries out:
Tungsten oxide nanometer stick suspension is instilled in pyrroles's polymerization liquid, and nitric acid is added dropwise thereto, so that mixture
Be pH it is 1.5-3, while is uniformly dispersed to mixed system；Then it under conditions of lasting dispersion, is dripped into mixed system
Add silver nitrate aqueous solution, forms uniform poly- pyrrole to cause pyrrole monomer in tungsten oxide nanometer stick surface generation oxidative polymerization
Shell is coughed up, meanwhile, silver ion is reduced into metallic silver particles by pyrrole monomer and is attached to nuclear shell structure nano rod surface, forms surface
Polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick of Argent grain modification.
In the above-mentioned technical solutions, separated, cleaned and dried after reacting, after polymerization reaction, respectively according to
It is secondary to be reacted obtained solid 2-4 times using deionized water and washes of absolute alcohol；The condition of the drying are as follows: drying temperature 40-
60 DEG C, drying time 10-15h.
In the above-mentioned technical solutions, in the aqueous solution of silver nitrate, the concentration of silver nitrate is 0.005-0.05mol/L.
In the above-mentioned technical solutions, nitric acid is the aqueous solution of the nitric acid of mass percent 5-8wt%.
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 200-300r 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
48-60h, preferably 48h, mixing speed are 200-300r per minute.
The tungsten oxide nanometer stick 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-
It answers, reaction temperature is 180-240 DEG C, and preferably 200-220 DEG C, reaction time 6-9h naturally cools to above-mentioned reaction solution
20-25 DEG C of room temperature, centrifuge separation, centrifugal rotational speed 4000-6000r/min, preferably 5000-5500r/min, obtained solid according to
It is secondary using dehydrated alcohol and deionized water cleaning after, then by centrifugation obtained solid be transferred to ultrasound 10-15min in deionized water
Afterwards to get arrive tungsten oxide nanometer stick suspension.
Pyrroles's polymerization liquid is prepared as steps described below: neopelex (SDBS) is added to
In deionized water, magnetic agitation 3-10min, preferably 5-8min are to get neopelex solution is arrived, by pyrrole monomer
(Py) predissolve is dispersed in dehydrated 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 be (1-1.5): 3, neopelex and
The molar ratio of silver nitrate is 4:(1-1.5).
Nanorod length according to above-mentioned technical proposal preparation is 700-800nm, and polypyrrole shell thickness is 8-15nm,
Tungsten oxide nanometer stick diameter be 70-80nm (preferably nanorod length is 740-760nm, and polypyrrole shell thickness is 10-15nm,
Tungsten oxide nanometer stick diameter is 75-80nm).Polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick table of surface Argent grain modification
Pattern performance in face is more coarse, and a large amount of random protrusions occurs in shell；Observe a large amount of particles (silver of average 15-20nm diameters
Particle) it is mixed between polypyrrole shell and tungsten oxide kernel, the attachment of polypyrrole shell is uniform and smooth, and average thickness is 8-
10nm or so.
Polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick of above-mentioned Argent grain modification is in preparation room temperature high sensitivity ammonia
Platinum interdigital electrode is arranged in application in quick element in aluminium oxide ceramics substrate, and surface Argent grain is arranged in platinum interdigital electrode
The polypyrrole of modification-tungsten oxide nucleocapsid heterogeneous structural nano stick coating.
It is up to 6.15 to the sensitivity of 100ppb~50ppm ammonia at 25 DEG C, most short response time is 10-13s,
The quick performance of the ammonia is substantially better than the performance of the reported quick element of the ammonia based on same type of material.The PPy@W of Argent grain modification18O49
Nanometer rods and pure PPy@W18O49The air-sensitive performance of nanometer rods gas sensor is compared and is obviously improved.This can be attributed to the fact that
The catalysis behavior of silver, energy needed for silver can be effectively reduced reaction as catalyst promote oxygen and ammonia in PPy@W18O49
Absorption, dissociation and the reaction of nanorod surfaces, that is, everybody so-called spills-over effects.Spills-over effects make PPy@W18O49It receives
There are more negative oxygen ions to participate in reaction on rice stick surface, so that air-sensitive response greatly promotes.
The present invention provide a kind of pyrroles's polymerization technique by optimization prepare shell dense uniform, shell morphology controllable one
Tie up the heterogeneous core-shell nanometer rod of tungsten oxide/polypyrrole and the synchronous method for introducing Argent grain surface modification.It is provided based on the invention
Method can innovatively realize uniform polymeric shell and Argent grain surface modification on the basis of Traditional liquid phase polymerization
Synchronous (step) obtains, that is, shell pyrroles organic matter can be made to be formed on tungsten oxide nanometer stick surface using the preparation method
Homogeneous polymerization simultaneously synchronizes to form Argent grain surface modification.The inventive method has equipment simple, and easy to operate, technological parameter is easy to
Control, cost extremely cheap the advantages that can be mass-produced.Pass through regulation liquid-phase polymerization time or the pass of polymerization reactant
Key concentration can effectively change the shell pattern of modified by silver nuclear shell structure nano rod.The poly- pyrrole of high-quality surface modified by silver of formation
Cough up heterogeneous interface and significant heterojunction structure performance regulation effect that@tungsten oxide nucleocapsid heterogeneous structural nano stick not only has maximization
Fruit, and the synchronous surface Argent grain modification introduced can make material obtain gas sensitive property further to be promoted.Therefore, of the invention
Achievement has great importance in the research fields such as gas sensor and directive function.
Detailed description of the invention
Fig. 1 is the electron scanning micrograph and transmission electron microscope of tungsten oxide nanometer stick prepared by embodiment 1
Photo.
Fig. 2 is the scanning of the polypyrrole@tungsten oxide nucleocapsid heterogeneous structural nano stick of the modification of Argent grain prepared by embodiment 1
Electron micrograph and transmission electron microscope photo.
Fig. 3 is the scanning of the polypyrrole@tungsten oxide nucleocapsid heterogeneous structural nano stick of the modification of Argent grain prepared by embodiment 2
Electron micrograph and transmission electron microscope photo.
Fig. 4 is the FTIR of the polypyrrole@tungsten oxide nucleocapsid heterogeneous structural nano stick of the modification of Argent grain prepared by embodiment 2
Spectrogram, wherein the polypyrrole@oxidation that (a) is tungsten oxide nanometer stick, (b) is polypyrrole polymers, (c) is the modification of surface Argent grain
Tungsten nucleocapsid heterogeneous structural nano stick.
Fig. 5 be the polypyrrole@tungsten oxide nucleocapsid heterogeneous structural nano stick of Argent grain prepared by the present invention modification, polypyrrole and
The XRD spectrum of tungsten oxide nanometer stick, wherein (a) is tungsten oxide nanometer stick, (b) is polypyrrole polymers, (c) is surface silver
The polypyrrole@tungsten oxide nucleocapsid heterogeneous structural nano stick of grain modification.
Fig. 6 is (Ag-PPy)@W prepared by the present invention18O49Dynamic of the nanometer rods gas sensor to ppb concentration rank ammonia
Respond schematic diagram.
Fig. 7 is (Ag-PPy)@W prepared by the present invention18O49Dynamic of the nanometer rods gas sensor to ppm concentration rank ammonia
Respond schematic diagram.
Specific embodiment
Below by specific embodiment, further description of the technical solution of the present invention.
Embodiment 1
(1) solvent-thermal method prepares tungsten oxide nanometer stick
Tungsten hexachloride powder is added in 60ml cyclohexanol, magnetic agitation 20min is completely dissolved tungsten hexachloride powder, obtains
Obtain the homogeneous solution that tungsten hexachloride concentration is 0.005mol/L.It is poly- four that the hexamethylene alcoholic solution of the tungsten hexachloride, which is transferred to liner,
In the autoclave of vinyl fluoride, reaction kettle is placed in heating in baking oven 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 nanometer stick
Solvent thermal reaction terminates to make autoclave Temperature fall to room temperature, reaction kettle is taken out, by the blue in reaction kettle
The centrifuge separation of solid-liquid reaction object, centrifuge speed are set as 5000r/min.The solid that centrifugation obtains successively with dehydrated alcohol and is gone
Ionized water is centrifuged clear 2 times respectively.Finally the centrifugation product after cleaning is transferred in 10ml deionized water, ultrasonic 15min, is obtained
Evenly dispersed tungsten oxide nanometer stick suspension.
(3) pyrroles's polymerization liquid is configured
It weighs 0.2mmol neopelex (SDBS), 80ml deionized water is added, at a slow speed magnetic agitation 5min,
Obtain neopelex solution.Weigh 0.6mmol pyrrole monomer (Py) and by its predissolve in 1ml dehydrated alcohol,
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) polymerization reaction forms polypyrrole shell
Under conditions of continuing magnetic force stirring, the tungsten oxide nanometer stick suspension that step (2) obtains is instilled into step dropwise
(3) in the pyrroles's polymerization liquid obtained, it is 2-3 that dust technology (mass percent 5wt%), which is added dropwise, and adjusts the pH of mixed liquor.Continue
Magnetic agitation 1-2h.Then silver nitrate (the AgNO that 10ml concentration is 0.005M is added dropwise dropwise3) oxidizing agent solution, continue to stir
60h makes pyrrole monomer that the uniform shell that polymerization reaction forms polypyrrole occur on tungsten oxide nanometer stick surface.Polymerization reaction knot
Beam, suspension centrifuge separation, obtained solid use deionized water and dehydrated alcohol eccentric cleaning twice respectively, and wet sample is in 50 DEG C of items
Dry 10h is the polypyrrole@tungsten oxide nucleocapsid heterogeneous structural nano stick sample for obtaining silver surface modification under part.
Scanning electron microscope analysis result such as Fig. 1 of the tungsten oxide nanometer stick looks obtained after 1 step of embodiment (2) is left
Shown in figure, tem study result such as Fig. 1 right figure.Pure zirconia tungsten nanometer rods average diameter is about 70nm, and length is about
For 800nm.(Ag-PPy) the@W that 1 step of embodiment (4) is prepared afterwards18O49The scanning electron microscope analysis knot of nanometer rods pattern
Fruit is as shown in Fig. 2 left figure, and size and pure zirconia tungsten nanometer rods are without too many differences, but surface topography is more coarse, and shell goes out
Now a large amount of random protrusions；Tem study result such as Fig. 2 right figure, it can be observed that a large amount of particles (average 18-
20nm diameter) it is mixed between polypyrrole shell and tungsten oxide kernel, the attachment of polypyrrole shell is uniform and smooth, and average thickness exists
8-10nm or so.
Embodiment 2
(1) solvent-thermal method prepares tungsten oxide nanometer stick
Tungsten hexachloride powder is added in 60ml cyclohexanol, magnetic agitation 10min is completely dissolved tungsten hexachloride powder, obtains
Obtain the homogeneous solution that tungsten hexachloride concentration is 0.005mol/L.It is poly- four that the hexamethylene alcoholic solution of the tungsten hexachloride, which is transferred to liner,
In the autoclave of vinyl fluoride, reaction kettle is placed in heating in baking oven 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 nanometer stick
Solvent thermal reaction terminates to make autoclave Temperature fall to room temperature, reaction kettle is taken out, by the blue in reaction kettle
The centrifuge separation of solid-liquid reaction object, centrifuge speed are set as 4000r/min.The solid that centrifugation obtains successively with dehydrated alcohol and is gone
Ionized water is distinguished eccentric cleaning 2 times.Finally the centrifugation product after cleaning is transferred in 10ml deionized water, ultrasonic 10min is obtained
Obtain evenly dispersed tungsten oxide nanometer stick suspension.
(3) pyrroles's polymerization liquid is configured
It weighs 0.8mmol neopelex (SDBS), 80ml deionized water is added, at a slow speed magnetic agitation 3min,
Obtain neopelex solution.Weigh 2.4mmol pyrrole monomer (Py) and by its predissolve in 1ml dehydrated alcohol,
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) polymerization reaction forms polypyrrole shell
Under conditions of continuing magnetic force stirring, the tungsten oxide nanometer stick suspension that step (2) obtains is instilled into step dropwise
(3) in the pyrroles's polymerization liquid obtained, it is 1-2 that dust technology (5wt%), which is added dropwise, and adjusts the pH of mixed liquor.Continue magnetic agitation 2-
4h.Then silver nitrate (the AgNO that 10ml concentration is 0.005M is added dropwise dropwise3) oxidizing agent solution, continue to stir 48h, keeps pyrroles single
On tungsten oxide nanometer stick surface the uniform shell that polymerization reaction forms polypyrrole occurs for body.Polymerization reaction terminates, suspension centrifugation
Separation, obtained solid use deionized water and dehydrated alcohol eccentric cleaning four times respectively, and wet sample dry 15h under the conditions of 40 DEG C is
Obtain polypyrrole@tungsten oxide nucleocapsid heterogeneous structural nano stick sample.
(Ag-PPy) the@W that 2 step of embodiment (4) is prepared afterwards18O49The scanning electron microscope analysis knot of nanometer rods pattern
Fruit is as shown in Fig. 3 left figure, and compared with gained sample after embodiment 1, surface particles volume is obviously reduced；Corresponding transmitted electron is aobvious
Micro mirror analyzes result such as Fig. 3 right figure, it can be observed that the little particle (average diameter is 10-15nm) of dispersion is mixed in polypyrrole
Between shell and tungsten oxide kernel.Integrated embodiment 1 and example 2 can be obtained through control whipping process (oxidation polymerization pyrroles, reduction
Silver) time, can be with Effective Regulation Argent grain size.
(Ag-PPy)@W prepared by the present invention18O49Nucleocapsid heterogeneous structural nano stick, polypyrrole and tungsten oxide nanometer stick are (i.e.
It is compound without polypyrrole) FTIR spectrogram as shown in figure 4,659,738 and 819cm-1For W18O49Characteristic absorption peak, 919,
1041,1201,1298,1460,1551 and 1703cm-1For polypyrrole characteristic absorption peak, W18O49With the characteristic absorption peak of polypyrrole
It exists simultaneously in (Ag-PPy)@W18O49In the FTIR map of nucleocapsid heterogeneous structural nano stick.
(Ag-PPy)@W prepared by the present invention18O49Nucleocapsid heterogeneous structural nano stick, polypyrrole and tungsten oxide nanometer stick are (i.e.
It is compound without polypyrrole) XRD spectra as shown in figure 5, by compare it is found that in 23.2 ° of monoclinic system Ws corresponding with 47.4 °18O49
(010) and (020) crystal face, it is brilliant in (111), (200), (220) and (311) of 38 °, 44 °, 64 ° and 77 ° corresponding metallic silvers
Face, in (Ag-PPy)@W18O49Monoclinic system W is existed simultaneously in nucleocapsid heterogeneous structural nano stick18O49, metallic silver and polypyrrole spy
Levy peak.
Heterogeneous nuclear shell structure nano rod is configured to gas sensor.The preparation for carrying out electrode basement first, aluminium oxide is made pottery
Tile is successively placed in that acetone solvent, dehydrated alcohol, ultrasound is respectively washed 5-10min in deionized water, 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.The metal platinum target used is quality purity 99.95%, using the argon gas that quality purity is 99.999% as work gas
Body, background vacuum 4~6 × 10-4Pa is prepared using radio-frequency magnetron sputter method, sputters 2min, 80~120nm of film thickness.So
Afterwards by heterogeneous nuclear shell structure nano rod (W prepared by the present invention18O49@PPy core sheath nanometer rods) use 5ml dehydrated alcohol to dilute back spin
It is coated in the electrode basement prepared, the dry quick test of the laggard promoting the circulation of qi of 10h at 60 DEG C.
(Ag-PPy)@W18O49Nanometer rods gas sensor shows excellent detection performance (test condition: temperature to ammonia
25 DEG C, humidity 40%), (Ag-PPy) the@W of preparation18O49Nanometer rods gas-sensitive sensing element to 100ppb, 130ppb, 160ppb and
The dynamic response curve (test condition: 25 DEG C of temperature, humidity 40%) of 1ppm, 5ppm, 20ppm, 50ppm ammonia such as attached drawing 6 and 7
Shown, sensitivity is respectively as follows: 1.05,1.07,1.1 and 1.52,2.02,4.24,6.15, and wherein 100ppb is that minimum detection is dense
Degree, (Ag-PPy) the@W based on the method for the present invention preparation18O49The gas sensor of nanometer rods is at 25 DEG C to 100ppb~50ppm
The sensitivity (S=Rg/Ra) of ammonia is up to 6.15, and most short response time is 10-13s, and the quick performance of the ammonia, which is substantially better than, have been reported
The performance of the quick element of ammonia based on same type of material in road.
Content carries out the adjustment of technological parameter according to the present invention, and preparation and the table of nanometer rods and its gas sensor can be achieved
Reveal the performance almost the same with embodiment.Illustrative description is done to the present invention above, it should which explanation is not departing from
In the case where core of the invention, any simple deformation, modification or other skilled in the art can not spend creation
Property labour equivalent replacement each fall within protection scope of the present invention.
Claims (10)
1. Argent grain modification polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick, which is characterized in that as steps described below into
Row: tungsten oxide nanometer stick suspension is instilled in pyrroles's polymerization liquid, and nitric acid is added dropwise thereto, so that mixed system pH is
1.5-3, while being uniformly dispersed to mixed system；Then under conditions of lasting dispersion, nitric acid is added dropwise into mixed system
Silver-colored aqueous solution forms uniform polypyrrole shell to cause pyrrole monomer in tungsten oxide nanometer stick surface generation oxidative polymerization
Layer, meanwhile, silver ion is reduced into metallic silver particles by pyrrole monomer and is attached to nuclear shell structure nano rod surface, forms surface silver
Polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick of grain modification；Nanorod length is 700-800nm, polypyrrole shell thickness
For 8-15nm, tungsten oxide nanometer stick diameter is 70-80nm, and Argent grain average diameter is 15-20nm, and preferably nanorod length is
740-760nm, polypyrrole shell thickness are 10-15nm, and tungsten oxide nanometer stick diameter is 75-80nm.
2. polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick of Argent grain modification according to claim 1, feature
It is, in the aqueous solution of silver nitrate, the concentration of silver nitrate is 0.005-0.05mol/L；Nitric acid is mass percent 5-
The aqueous solution of the nitric acid of 8wt%；When adjusting mixed system pH value, evenly dispersed, time 0.5- is carried out using magnetic agitation
3h, preferably 1-2h, mixing speed are 200-300r per minute, and mixed system pH is 2-3；In initiated polymerization, magnetic is used
Power stirring carries out evenly dispersed, mixing time 48-60h, preferably 48h, and mixing speed is 200-300r per minute.
3. polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick of Argent grain modification according to claim 1, feature
It is, the tungsten oxide nanometer stick suspension is prepared as steps described below: tungsten hexachloride powder is added in cyclohexanol,
After magnetic agitation 10-40min, tungsten hexachloride homogeneous solution is obtained, the hexamethylene alcoholic solution of above-mentioned tungsten hexachloride is sealed into reaction, instead
Answer temperature be 180-240 DEG C, preferably 200-220 DEG C, reaction time 6-9h, by above-mentioned reaction solution cooled to room temperature
20-25 DEG C, centrifuge separation, centrifugal rotational speed 4000-6000r/min, preferably 5000-5500r/min, obtained solid are successively adopted
After being cleaned with dehydrated alcohol and deionized water, then by centrifugation obtained solid be transferred in deionized water after ultrasound 10-15min, i.e.,
Obtain tungsten oxide nanometer stick suspension.
4. polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick of Argent grain modification according to claim 1, feature
It is, pyrroles's polymerization liquid is prepared as steps described below: neopelex (SDBS) is added to
In ionized water, magnetic agitation 3-10min, preferably 5-8min are to get neopelex solution is arrived, by pyrrole monomer
(Py) predissolve is dispersed in dehydrated 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 be (1-1.5): 3, neopelex and
The molar ratio of silver nitrate is 4:(1-1.5).
5. polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick preparation method of Argent grain modification, which is characterized in that according to
Following step carries out: tungsten oxide nanometer stick suspension being instilled in pyrroles's polymerization liquid, and nitric acid is added dropwise thereto, so that mixed
Zoarium system pH is 1.5-3, while being uniformly dispersed to mixed system；Then under conditions of lasting dispersion, to mixed system
Middle dropwise addition silver nitrate aqueous solution is formed uniformly with causing pyrrole monomer in tungsten oxide nanometer stick surface generation oxidative polymerization
Polypyrrole shell, meanwhile, silver ion is reduced into metallic silver particles by pyrrole monomer and is attached to nuclear shell structure nano rod surface, is formed
Polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick of surface Argent grain modification.
6. polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick preparation side of Argent grain modification according to claim 5
Method, which is characterized in that in the aqueous solution of silver nitrate, the concentration of silver nitrate is 0.005-0.05mol/L；Nitric acid is quality hundred
The aqueous solution of the nitric acid of score 5-8wt%；When adjusting mixed system pH value, evenly dispersed, the time is carried out using magnetic agitation
For 0.5-3h, preferably 1-2h, mixing speed is 200-300r per minute, and mixed system pH is 2-3；In initiated polymerization,
Evenly dispersed, mixing time 48-60h, preferably 48h are carried out using magnetic agitation, mixing speed is 200-300r per minute.
7. polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick preparation side of Argent grain modification according to claim 5
Method, which is characterized in that the tungsten oxide nanometer stick suspension is prepared as steps described below: tungsten hexachloride powder is added to
In cyclohexanol, after magnetic agitation 10-40min, tungsten hexachloride homogeneous solution is obtained, the hexamethylene alcoholic solution of above-mentioned tungsten hexachloride is close
Envelope reaction, reaction temperature is 180-240 DEG C, preferably 200-220 DEG C, reaction time 6-9h, above-mentioned reaction solution is naturally cold
But to 20-25 DEG C of room temperature, centrifuge separation, centrifugal rotational speed 4000-6000r/min, preferably 5000-5500r/min, gained are solid
After body successively uses dehydrated alcohol and deionized water to clean, then centrifugation obtained solid is transferred to ultrasound 10- in deionized water
After 15min to get arrive tungsten oxide nanometer stick suspension.
8. polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick preparation side of Argent grain modification according to claim 5
Method, which is characterized in that pyrroles's polymerization liquid is prepared as steps described below: by neopelex (SDBS)
It is add to deionized water, magnetic agitation 3-10min, preferably 5-8min are to get neopelex solution is arrived, by pyrrole
It coughs up monomer (Py) predissolve to be dispersed in dehydrated alcohol, pyrrole monomer solution is obtained after mixing, in the condition of magnetic agitation
Under, pyrrole monomer solution is instilled dropwise in neopelex solution, magnetic agitation 20-30min is continued, is formed uniform
Pyrroles's polymerization liquid, the molar ratio of neopelex and pyrrole monomer is (1-1.5): 3, detergent alkylate sulphur
The molar ratio of sour sodium and silver nitrate is 4:(1-1.5).
9. polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick of Argent grain modification as described in claim 1 is in preparation room temperature
Application in the highly sensitive quick element of ammonia, which is characterized in that platinum interdigital electrode is set in aluminium oxide ceramics substrate, it is interdigital in platinum
Polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick coating that surface Argent grain is modified is set on electrode.
10. application according to claim 9, which is characterized in that the sensitivity of 100ppb~50ppm ammonia at 25 DEG C
Up to 6.15, most short response time is 10-13s.
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