CN105585729A - Method for in-situ growth of polyaniline array on surface of polymer film - Google Patents

Method for in-situ growth of polyaniline array on surface of polymer film Download PDF

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CN105585729A
CN105585729A CN201510970169.4A CN201510970169A CN105585729A CN 105585729 A CN105585729 A CN 105585729A CN 201510970169 A CN201510970169 A CN 201510970169A CN 105585729 A CN105585729 A CN 105585729A
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polymer film
film surface
thin polymer
situ growth
polyaniline array
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CN105585729B (en
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袁定胜
张海宁
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Guangdong Nanhai Puruisi Science & Technology Co Ltd
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Guangdong Nanhai Puruisi Science & Technology Co Ltd
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Abstract

The invention discloses a method for in-situ growth of a polyaniline array on the surface of a polymer film. According to the method, the surface of a polymer/aminated inorganic nano-oxide composite film is matched with gold nanoparticles, then an aniline monomer is self-assembled in a directed mode, condensation polymerization is conducted through chemical reaction under mild conditions, and the polyaniline array grows in situ on the surface of the polymer film. The array material prepared through the method is anchored on the surface of the polymer film, and can be effectively compounded with ion conductive membranes in electrochemical sensors, fuel batteries and other electrochemical devices. The interface resistance is reduced, ordering membrane electrodes are easy to prepare, and performance of the electrochemical devices is improved.

Description

A kind of method of thin polymer film surface in situ growth polyaniline array
Technical field
The invention belongs to field of new, be specifically related to a kind of side of thin polymer film surface in situ growth polyaniline arrayMethod.
Background technology
Electrode material electrochemical reaction and the device based on electrochemical reaction as electrochemical sensor, fuel cell,The fields such as brine electrolysis are widely used. At present, be generally conductive material load for electrochemical reaction device electrode used therein materialNoble metal catalyst. For example, in electrochemical sensor and fuel cell, generally adopt carbon to carry platinum as electrode material. But,Noble metal is as the scarcity of resources such as platinum, expensive. Performance and life-span at base metal electrocatalyst materials fail to meet electrificationLearn in the situation of requirement on devices, noble metal electrocatalyst remains the first-selection of electrochemical device electrocatalysis material. Therefore, protectingUnder card performance and the prerequisite in life-span, reducing the consumption of noble metal catalyst in electrochemical device is one of these field research and development at presentIndividual important directions. By by the ordering of electrode material being comparatively effective method of reduction noble metal catalyst consumption.
Theoretical calculating shows (Sunetal., FuelCells, 2015,15,456): adopt orderly electrode passableElectrocatalytic reaction efficiency while effectively improving the operation of electrochemical reaction device, reduces concentration polarization, can ensure device performanceUnder the condition meeting the demands, effectively reduce the consumption of noble metal catalyst. Therefore, the research and development of orderly electrode have been received and have been paid close attention to and getObtained certain effect: Minnesota Mining and Manufacturing Company applies for and disclose a kind of patent of ordering platinum electrode at first(US2006039543W), it is processed and is made to dye by high vacuum, high temperature distillation mainly taking the little molecule of organic dyestuff as initiation materialMaterial molecular ordered arrangement forms orderly carrier, then precious metals pt catalyst deposit is prepared with to formed orderly carrierOrder electrode, realizes the significantly reduction of noble metal carrying capacity, and this patented technology obtains in Proton Exchange Membrane Fuel CellsApplication; Chinese invention patent (CN101682034A, CN102769140A) discloses respectively the orderly electrode of fuel cellDesign and preparation patent, it mainly, by noble metal catalyst nano particle is deposited to magnetic material surface, is done at high-intensity magnetic fieldWith under make magnetic material ordered arrangement and then prepare orderly electrode; Chinese invention patent application (CN104716340A) discloses oneKind adopt the technology path of template synthesis orderly electrode, by noble metal catalyst the deposition of pre-prepared template and withAfter removal mould plate technique preparation there is the orderly electrode of self-supporting ability. The technical scheme that foregoing invention patent is mentioned not onlyNeed special special equipment (high vacuum sublimation apparatus, high-intensity magnetic field etc.), and the electronic conduction ability of its orderly carrier is poor,Thereby be difficult to generally apply.
Polyaniline is a kind of macromolecule of the electric conductivity with conjugated structure, therefore can be used as the carrier of catalyst and answersFor the electrode material of electrochemical reaction device. At present, the polyaniline array of ordering be mainly adopt template (Wang Zhen etc.,SCI, 2002,23,721 etc.) and electrochemical polymerization (high gorgeous new etc., electrochemistry, 2012,18,51 etc.)Be prepared. Adopt the shortcoming of template to be that technique is loaded down with trivial details, and how polyaniline array is effectively shifted after removing templateStable maintenance to polymer dielectric film surface and array structure has very large uncontrollability; Employing electrochemical polymerizationMain inferior position is that polyaniline array must be in the preparation of conductive material surface, and prepares the fluctuation that voltage is small and can have influence on institutePrepare the repeatability of material, thereby limited its extensive use.
Summary of the invention
For solving the shortcoming and defect part of prior art, the object of the present invention is to provide a kind of poly-by directed chemistryBe combined in the method for polymer surfaces in-situ preparation of poly aniline array.
For achieving the above object, the present invention adopts following technical scheme: a kind of thin polymer film surface in situ growthThe method of polyaniline array, comprises the following steps:
(1) preparation of aminated polymer matrix material: in polymer solution, add aminated inorganic oxide nanoparticles,Double teeming film forming after ultrasonic being uniformly dispersed, makes aminated polymer matrix material;
(2) the aminated matrix surface preparation that nanogold particle is modified: aminated polymer matrix material prepared by step (1)Be placed in nano gold sol solution and flood, make nanogold particle deposition certain hour, take out matrix material, careful by deionized waterClean, remove not and the nm of gold ion of amido coordination, obtain the aminated matrix that nanogold particle is modified;
(3) the directed self assembly of aniline monomer on decorated by nano-gold matrix: nanogold particle prepared step (2) is modifiedAminated matrix impregnated in 4-amido in the ethanolic solution of benzenethiol (4-ATP), dip time is no less than 8h, makes 4-ATP fully reacts with nanogold particle, takes out subsequently matrix, carefully cleans with ethanol, removes not the 4-ATP with golden coordination;
(4) preparation of polyaniline array modified polymer film: under normal temperature, the prepared matrix of step (3) is placed in to aniline and wineIn the mixed solution of stone acid, drip and the isopyknic ammonium persulfate aqueous solution of mixed solution gradually, drip rear maintenance one timingBetween, obtain thin polymer film surface in situ growth polyaniline array.
Described in the inventive method, thin polymer film comprises anionic polymer film, as Nafion film, sulfonated polyether-ether-ketone film,Polymethyl sorrels etc., or neutral polymer film, as the one in polymethyl methacrylate, polyvinyl alcohol etc. StepSuddenly (1) described polymer solution can be commercial polymer solution, and as Nafion solution, described polymer solution is also passableBe to obtain after will polymer thin-film material directly dissolving, in methanol solution, obtain poly-methyl as polymethyl methacrylate is dissolved inThe methanol solution of methyl acrylate.
Further, described aminated inorganic oxide can be aminated silica, titanium dioxide, titanium dioxideOne in zirconium, aluminium oxide. The mass ratio of the polymer in described inorganic oxide nanoparticles and polymer solution is preferably10：90～50：50。
Further, in described nano gold sol, gold ion is of a size of 8 ± 2nm, and described nano gold sol concentration is1mg/ml ~ 20mg/ml, described sedimentation time is 5min ~ 1h.
Further, described 4-amido is 0.2mg/ml ~ 2mg/ml to the concentration of benzenethiol.
Further, in described mixed solution, the concentration of aniline is 0.02mM ~ 0.2mM, the concentration of tartaric acid and anilineThan being 1:2, the concentration ratio of ammonium persulfate and aniline is 1:1, and the retention time after dropwising is 20min ~ 4h.
The present invention passes through to coordinate with nanogold particle on polymer/aminated inorganic nanometer oxide laminated film surface,And then directed self assembly aniline monomer, carry out polycondensation by chemical reaction under temperate condition, raw at thin polymer film surface in situLong polyaniline array. Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) because the electrode of electrochemical device is need to be with ion-conductive membranes compound and then be prepared into membrane electrode to meet wanting of performanceAsk, be therefore easier to compound with polymer dielectric film and then fall at the polyaniline array ratio of thin polymer film surface in situ growthLow interface resistance, even can prepare polyaniline array, Jin Erti at the required ion-conductive membranes surface in situ of electrochemical deviceHigh device chemical property;
(2) whole preparation technology's engineering is all carried out under normal temperature, condition of normal pressure, and not affected by environment, is easy to realize;
(3) in the thickness of prepared polyaniline array, unit volume, the density of polyaniline nano-line can be by changing from groupDress condition and polymeric reaction condition are controlled, thereby can meet demand prepared by different electrode of electrochemical device.
Brief description of the drawings
Fig. 1 is the projection electromicroscopic photograph of nano gold sol used in the embodiment of the present invention 1.
Fig. 2 is the atomic force of the aminated Nafion film modified of nanogold particle prepared in the embodiment of the present invention 1Microphotograph.
Fig. 3 is that the atomic force of the aminated Nafion film modified of aniline monomer prepared in the embodiment of the present invention 1 is aobviousMicro mirror photo.
Fig. 4 is the surface sweeping electromicroscopic photograph of the polyaniline array of growing on Nafion film prepared in the embodiment of the present invention 1.
Detailed description of the invention
Below by embodiment, the present invention is described in further details, these embodiment are only used for illustrating the present invention, andDo not limit the scope of the invention.
Embodiment 1 adopts following steps to realize the present invention.
1, the preparation of aminated Nafion compound matrix material: the Nafion solution that is 5% by 80ml mass content is concentrated intoAfter 40ml, the nano SiO 2 particle that adds 0.4g amine propyl-triethoxysilicane to modify, ultrasonic again after magnetic agitation 30minDisperse 10min, subsequently above-mentioned dispersion liquid is placed in to polytetrafluoroethylene (PTFE) culture dish, 60oIn C vacuum drying oven, solvent is waved completelySend out, subsequently temperature is brought up to 120oC keeps 1h, obtains aminated Nafion compound matrix material.
The preparation of the Nafion compound matrix material that 2, nanogold particle is modified: by the prepared matrix material of step (1)Be immersed in the nano gold sol that pre-prepared concentration is 10mg/ml, make nano Au particle deposition 20min, take out matrix material,Clean 3 times with deionized water is careful, remove not and the nanogold particle of amido coordination, obtain that nanogold particle modifiesNafion compound matrix material.
Accompanying drawing 1 is the projection electromicroscopic photograph of nano gold sol used, and as can be seen from the figure, nanogold particle size exists8nm left and right, and size is comparatively even respectively; Accompanying drawing 2 is atomic forces of the Nafion compound matrix material of nanogold particle modificationMicrophotograph, in figure, bright spot is nanogold particle, as can be seen from the figure, nanogold particle only in specific region (amido) deposit, the consistent size in its size and colloidal sol, illustrates that nanogold particle does not occur agglomeration in modification matrix material process.
3, the directed self assembly of aniline monomer on decorated by nano-gold Nafion matrix material: by prepared step (2)It is that the 4-amido of 1mg/ml is to benzenethiol (4-that the Nafion compound matrix material that nanogold particle is modified impregnated in 50ml concentrationATP) in ethanolic solution, after 12h, take out, clean 3 times with absolute ethyl alcohol is careful, wash away the 4-not reacting with nanogold particleATP, obtains the sample of the directed self assembly of aniline monomer on decorated by nano-gold Nafion matrix material.
Accompanying drawing 3 is atomic force microscopies of sample, and in figure, bright spot is the nanogold particle that 4-ATP modifies, from figureCan find out, accompanying drawing 2 is compared in the brightness of bright spot to be increased to some extent, and reason is that the increase of the height after 4-ATP modifies causes.
4, the preparation of Nafion film that polyaniline array is modified: by the prepared sample of step (3) be placed in 20ml aniline andIn tartaric mixed solution, wherein the concentration of aniline is that 0.1mM, tartaric concentration are 0.05mM, in above-mentioned system byBe added dropwise to the ammonium persulfate aqueous solution that 20ml concentration is 0.1mM, dropwise rear room temperature and keep 2h, obtain polyaniline array and repairThe Nafion film of decorations. Accompanying drawing 4 is surface sweeping electromicroscopic photographs of the Nafion film modified of prepared polyaniline array, can from figureThe clear pattern of finding out polyaniline array, the thickness of prepared polyaniline array is about 9.7 microns.
Embodiment 2 implementation steps are identical with embodiment 1, and difference is to adopt 0.05g amido to modify in step (1)Titania nanoparticles mix (quality of Nafion is 0.45g), prepared polyaniline array with Nafion solutionThickness is about 8.6 microns.
Embodiment 3 implementation steps are identical with embodiment 1, and difference is the nm of gold at 20mg/ml in step (2)In colloidal sol, deposit 5min, the 4-ATP concentration in step (3) is 2mg/ml, and it is 6.3 micro-that the thickness of prepared polyaniline array is aboutRice.
Embodiment 4 implementation steps are identical with embodiment 1, and difference is that in step (4), concentration of aniline used is0.2mM, tartaric acid concentration is 0.1mM, and ammonium persulfate concentration is 0.2mM, and the retention time is 4h, prepared polyaniline arrayThickness is about 11.2 microns.
Embodiment 5 implementation steps are identical with embodiment 1, difference with step (1) in adopt 0.4g polymethylAcid methyl esters is dissolved in 40ml methanol solution and replaces Nafion solution, and the thickness of prepared polyaniline array is about 9.1 microns.
Embodiment 6 implementation steps are identical with embodiment 5, and difference is the concentration of the nano gold sol in step (2)For 1mg/ml, sedimentation time is 1h, and the thickness of prepared polyaniline array is about 6.2 microns.
Embodiment 7 implementation steps are identical with embodiment 5, and difference is that the 4-ATP concentration in step (3) is0.2mg/ml, the thickness of prepared polyaniline array is about 3.4 microns.
Embodiment 8 experimental procedures are identical with embodiment 5, and difference is that the concentration of aniline in step (4) is0.02mM, tartaric acid concentration is 0.01mM, and ammonium persulfate concentration is 0.02mM, and the thickness of prepared polyaniline array is about1.9 micron.
Above-described embodiment is preferably embodiment of the present invention, but embodiments of the present invention are not subject to above-described embodimentRestriction, other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplification,All should be equivalent substitute mode, within being included in protection scope of the present invention.

Claims (10)

1. a method for thin polymer film surface in situ growth polyaniline array, is characterized in that: comprise the following steps:
(1) preparation of aminated polymer matrix material: in polymer solution, add aminated inorganic oxide nanoparticles,Double teeming film forming after ultrasonic being uniformly dispersed, makes aminated polymer matrix material;
(2) the aminated matrix surface preparation that nanogold particle is modified: aminated polymer matrix material prepared by step (1)Be placed in nano gold sol solution and flood, make nanogold particle deposition, take out matrix material, carefully clean by deionized water, goExcept not with the nm of gold ion of amido coordination, obtain the aminated matrix that nanogold particle is modified;
(3) the directed self assembly of aniline monomer on decorated by nano-gold matrix: nanogold particle prepared step (2) is modifiedAminated matrix impregnated in 4-amido in the ethanolic solution of benzenethiol, dip time is no less than 8h, makes 4-amido to benzeneThiophenol fully reacts with nanogold particle, takes out subsequently matrix, carefully cleans with ethanol, removes not the 4-amido pair with golden coordinationBenzenethiol;
(4) preparation of polyaniline array modified polymer film: under normal temperature, the prepared matrix of step (3) is placed in to aniline and wineIn the mixed solution of stone acid, drip and the isopyknic ammonium persulfate aqueous solution of mixed solution gradually, drip rear maintenance one timingBetween, obtain thin polymer film surface in situ growth polyaniline array.
2. the method for a kind of thin polymer film surface in situ growth polyaniline array according to claim 1, its feature existsIn: the method is for the polyaniline array of growing at described thin polymer film surface in situ, and described thin polymer film refers to anionOne in thin polymer film or neutral polymer film.
3. the method for a kind of thin polymer film surface in situ growth polyaniline array according to claim 1 and 2, its featureBe: described polymer is in polymethyl methacrylate, polyvinyl alcohol, Nafion, sulfonated polyether-ether-ketone, polymethylacrylic acidOne.
4. the method for a kind of thin polymer film surface in situ growth polyaniline array according to claim 1, its feature existsIn: the described inorganic oxide of step (1) is the one in silica, titanium dioxide, zirconium dioxide, aluminium oxide.
5. the method for a kind of thin polymer film surface in situ growth polyaniline array according to claim 1, its feature existsIn: the mass ratio of the described inorganic oxide nanoparticles of step (1) and polymer is 10:90～50:50.
6. the method for a kind of thin polymer film surface in situ growth polyaniline array according to claim 1, its feature existsIn: the described nano gold sol concentration of step (2) is 1mg/ml ~ 20mg/ml; Described sedimentation time is 5min ~ 1h.
7. the method for a kind of thin polymer film surface in situ growth polyaniline array according to claim 1, its feature existsIn the 4-amido: step (3) described to the ethanolic solution of benzenethiol in, 4-amido to the concentration of benzenethiol be 0.2mg/ml ~2mg/ml。
8. the method for a kind of thin polymer film surface in situ growth polyaniline array according to claim 1, its feature existsIn: in the mixed solution described in step (4), the concentration of aniline is 0.02mM ~ 0.2mM, and the concentration ratio of tartaric acid and aniline is 1:2。
9. according to the method for a kind of thin polymer film surface in situ growth polyaniline array claimed in claim 1, it is characterized in that:The concentration ratio of the described ammonium persulfate of step (4) and aniline is 1:1.
10. according to the method for a kind of thin polymer film surface in situ growth polyaniline array claimed in claim 1, its feature existsIn: the retention time after dropwising described in step (4) is 20min ~ 4h.
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