CN105585729B - A kind of method of polymeric film surface growth in situ polyaniline array - Google Patents

A kind of method of polymeric film surface growth in situ polyaniline array Download PDF

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CN105585729B
CN105585729B CN201510970169.4A CN201510970169A CN105585729B CN 105585729 B CN105585729 B CN 105585729B CN 201510970169 A CN201510970169 A CN 201510970169A CN 105585729 B CN105585729 B CN 105585729B
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film surface
polymeric film
surface growth
polyaniline array
situ
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CN105585729A (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 kind of method of polymeric film surface growth in situ polyaniline array.This method on polymer/aminated inorganic nanometer oxide laminated film surface and nanogold particle mainly by coordinating, and then orient self assembly aniline monomer, polycondensation is carried out by being chemically reacted under temperate condition, so that in polymeric film surface growth in situ polyaniline array.Array material prepared by the method for the present invention is anchored at polymer film surface, can be effectively compound with the ion-conductive membranes in the electrochemical devices such as electrochemical sensor, fuel cell, interface resistance is reduced, realizes the simple preparation of ordering membrane electrode, improves the performance of electrochemical device.

Description

A kind of method of polymeric film surface growth in situ polyaniline array
Technical field
The invention belongs to field of new materials, and in particular to a kind of side of polymeric film surface growth in situ polyaniline array Method.
Background technology
Electrode material electrochemical reaction and device based on electrochemical reaction for example electrochemical sensor, fuel cell, The fields such as electrolysis water are widely used.At present, it is usually conductive material load for electrochemical reaction device electrode used therein material Noble metal catalyst.For example, generally using pallium-on-carbon as electrode material in electrochemical sensor and fuel cell.However, It is the scarcity of resources such as noble metal such as platinum, expensive.Fail to meet electrification in the performance of base metal electrocatalyst materials and service life In the case of learning requirement on devices, noble metal electrocatalyst is still the first choice of electrochemical device electrocatalysis material.Therefore, protecting Demonstrate,prove performance and on the premise of the service life, reduce dosage of the noble metal catalyst in electrochemical device is current field research and development one A important directions.And by being then to reduce noble metal catalyst dosage more effective method by the ordering of electrode material.
Theoretical calculation shows（Sun et al., Fuel Cells, 2015, 15, 456）:Use orderly electrode can be with The electrocatalytic reaction efficiency during operation of electrochemical reaction device is effectively improved, reduces concentration polarization, can ensure device performance The dosage of noble metal catalyst is effectively reduced under conditions of meeting the requirements.Therefore, the research and development of orderly electrode, which have received, pays close attention to and takes Obtained certain effect：Minnesota Mining and Manufacturing Company applies and discloses a kind of patent of ordering platinum electrode at first （US2006039543W）, it makes dye mainly using organic dyestuff small molecule as starting material, by high vacuum, high temperature distillation processing Material molecular ordered arrangement forms orderly carrier, then has being prepared on precious metals pt catalyst deposit to the orderly carrier formed Sequence electrode, realizes being greatly lowered for noble metal carrying capacity, this patented technology obtains in Proton Exchange Membrane Fuel Cells Application；Chinese invention patent（CN101682034A、CN102769140A）Fuel cell is individually disclosed with orderly electrode Design and preparation patent, it makees mainly by the way that noble metal catalyst nano-particle is deposited to magnetic material surface in high-intensity magnetic field Make magnetic material ordered arrangement under and then prepare orderly electrode；Chinese invention patent application（CN104716340A）Disclose one Kind the technology path of orderly electrode is prepared using template, i.e., by noble metal catalyst the deposition of pre-prepared template and with The mould plate technique that removes afterwards prepares the orderly electrode with self-supporting ability.The technical solution that foregoing invention patent is previously mentioned is not only Need special special equipment（High vacuum sublimation apparatus, high-intensity magnetic field etc.）, and the electronic conduction ability of its orderly carrier is poor, Thus it is difficult to commonly used.
Polyaniline is a kind of macromolecule of the electric conductivity with conjugated structure, therefore can be answered as the carrier of catalyst Electrode material for electrochemical reaction device.At present, the polyaniline array of ordering mainly uses template（Wang Zhen etc., Chemical Journal of Chinese Universities, 2002,23,721 etc.）And electrochemical polymerization（It is high gorgeous new etc., electrochemistry, 2012,18,51 etc.） Prepared.It is that technique is cumbersome using the shortcomings that template, and how is effectively shifted polyaniline array after removing removing template Keep that there is very big uncontrollability to polymer dielectric film surface and stablizing for array structure；Using electrochemical polymerization Main drawback is that polyaniline array must be prepared in conductive material surface, and prepares the small fluctuation of voltage and influence whether institute The repeatability of material is prepared, thus limits its extensive use.
The content of the invention
The shortcomings that to solve the prior art and shortcoming, are gathered it is an object of the invention to provide one kind by directed chemical Close the method that polyaniline array is prepared in situ in polymer surfaces.
For achieving the above object, the present invention adopts the following technical scheme that：A kind of polymeric film surface growth in situ The method of polyaniline array, comprises the following steps：
（1）The preparation of amino fluidized polymer basis material：The inorganic oxygen of aminoization is added into polymer solution Compound nano particle, uniformly rear double teeming forms a film ultrasonic disperse, and amination polymeric matrix material is made；
（2）It is prepared by the amination matrix surface of nanogold particle modification：By step（1）The amination polymeric matrix of preparation Material, which is placed in nano gold sol solution, to be impregnated, and nanogold particle is deposited certain time, is taken out basis material, is used deionized water Careful cleaning, removes the nanometer gold ion not with amino coordination, obtains the amination matrix of nanogold particle modification；
（3）Orientation self assembly of the aniline monomer on decorated by nano-gold matrix：By step（2）Prepared nanogold particle The amination matrix of modification is impregnated in 4- amino to benzenethiol（4-ATP）Ethanol solution in, dip time is no less than 8 h, makes Obtain 4-ATP fully to react with nanogold particle, then take out matrix, carefully cleaned with ethanol, remove the 4- not with gold coordination ATP；
（4）The preparation of polyaniline array modified polymer film：Under room temperature, by step（3）Prepared matrix is placed in aniline In the mixed solution of tartaric acid, gradually dropwise addition and the isometric ammonium persulfate aqueous solution of mixed solution, one is kept after dripping Fix time, that is, obtain polymeric film surface growth in situ polyaniline array.
Thin polymer film described in the method for the present invention includes anionic polymer film, as Nafion membrane, sulfonated polyether-ether-ketone film, One kind in polymethyl sorrel etc., or neutral polymer film, such as polymethyl methacrylate, polyvinyl alcohol.Step Suddenly（1）The polymer solution can be the polymer solution of commercialization, such as Nafion solution, and the polymer solution can also It is to be obtained after polymer thin-film material is directly dissolved, such as polymethyl methacrylate is dissolved in methanol solution and obtains poly- methyl The methanol solution of methyl acrylate.
Further, the amination inorganic oxide can be amidized silica, titanium dioxide, titanium dioxide One kind in zirconium, aluminium oxide.The inorganic oxide nanoparticles and the mass ratio of the polymer in polymer solution are preferably 10：90~50：50.
Further, the size of gold ion is 8 ± 2nm in the nano gold sol, and the nano gold sol concentration is 1mg/ml ~ 20mg/ml, the sedimentation time are 5min ~ 1h.
Further, the 4- amino is 0.2 mg/ml ~ 2mg/ml to the concentration of benzenethiol.
Further, in the mixed solution concentration of aniline be 0.02mM ~ 0.2mM, tartaric acid and aniline concentration Than for 1：2, the concentration ratio of ammonium persulfate and aniline is 1：1, the retention time after being added dropwise is 20min ~ 4h.
The present invention by coordinating in polymer/amination inorganic nanometer oxide laminated film surface and nanogold particle, And then self assembly aniline monomer is oriented, and polycondensation is carried out by being chemically reacted under temperate condition, it is in situ raw in polymeric film surface Long polyaniline array.Compared with prior art, the present invention has the following advantages and beneficial effect：
（1）Since the electrode of electrochemical device needs compound with ion-conductive membranes and then is prepared into membrane electrode to meet performance Requirement, therefore polymeric film surface growth in situ polyaniline array be easier with polymer dielectric film it is compound into And reduce interface resistance, it might even be possible to polyaniline array is prepared in the ion-conductive membranes surface in situ needed for electrochemical device, into And improve device chemical property；
（2）Whole preparation process engineering carries out under room temperature, condition of normal pressure, and not affected by environment, it is easy to accomplish；
（3）The density of polyaniline nano-line can be by varying in the thickness of prepared polyaniline array, unit volume Self assembly condition and polymeric reaction condition are controlled, thus can meet the needs of 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 amination Nafion films of nanogold particle modification prepared in the embodiment of the present invention 1 Microphotograph.
Fig. 3 is that the atomic force of the amination Nafion films of aniline monomer modification prepared in the embodiment of the present invention 1 is shown Micro mirror photo.
Fig. 4 is the surface sweeping electromicroscopic photograph of the polyaniline array grown on Nafion membrane prepared in the embodiment of the present invention 1.
Embodiment
The present invention is described in further details below by embodiment, these embodiments are only used for illustrating the present invention, and Do not limit the scope of the invention.
Embodiment 1 realizes the present invention using following steps.
1st, the preparation of amination Nafion compound matrix materials：The Nafion solution that 80ml mass contents are 5% is concentrated into After 40ml, the nano SiO 2 particle of 0.4g amine propyl-triethoxysilicane modification is added, it is ultrasonic again after magnetic agitation 30min Scattered 10min, is then placed in polytetrafluoroethylene (PTFE) culture dish, 60 by above-mentioned dispersion liquidoSolvent is waved completely in C vacuum drying ovens Hair, then brings up to 120 by temperatureoC keeps 1h, that is, obtains amidized Nafion compound matrix materials.
2nd, the preparation of the Nafion compound matrix materials of nanogold particle modification：By step（1）Prepared basis material It is immersed in the nano gold sol that pre-prepared concentration is 10mg/ml, nano Au particle is deposited 20min, takes out basis material, Carefully cleaned with deionized water 3 times, remove the nanogold particle not with amino coordination, that is, obtain nanogold particle modification Nafion compound matrix materials.
Attached drawing 1 is the projection electromicroscopic photograph of nano gold sol used, it can be seen from the figure that nanogold particle size exists 8nm or so, and size is more uniform respectively；Attached drawing 2 is the atomic force of the Nafion compound matrix materials of nanogold particle modification Microphotograph, bright spot is nanogold particle in figure, it can be seen from the figure that nanogold particle is only in specific region（Amino）Deposit Its size is consistent with the size in colloidal sol, illustrates that nanogold particle does not occur agglomeration during basis material is modified.
3rd, orientation self assembly of the aniline monomer on decorated by nano-gold Nafion basis materials：By step（2）Prepared The Nafion compound matrix materials of nanogold particle modification are impregnated in 4- amino of the 50ml concentration for 1mg/ml to benzenethiol（4- ATP）Ethanol solution in, take out, carefully cleaned with absolute ethyl alcohol 3 times after 12h, wash away not with nanogold particle reaction 4- ATP, that is, obtain the sample of orientation self assembly of the aniline monomer on decorated by nano-gold Nafion basis materials.
Attached drawing 3 is the atomic force microscopy of sample, and bright spot is the nanogold particle of 4-ATP modifications in figure, from figure As can be seen that the brightness of bright spot increased compared to attached drawing 2, reason is caused by the increase of the height after 4-ATP modifications.
4th, the preparation of the Nafion membrane of polyaniline array modification：By step（3）Prepared sample be placed in 20ml aniline and In the mixed solution of tartaric acid, the concentration of wherein aniline is 0.1mM, the concentration of tartaric acid is 0.05mM, into above-mentioned system by The ammonium persulfate aqueous solution that 20ml concentration is 0.1mM is added dropwise to, rear room temperature is added dropwise and keeps 2h, that is, obtains polyaniline array and repaiies The Nafion membrane of decorations.Attached drawing 4 is the surface sweeping electromicroscopic photograph of the Nafion membrane of prepared polyaniline array modification, can be with from figure The pattern of polyaniline array is clearly seen, the thickness of prepared polyaniline array is about 9.7 microns.
2 implementation steps of embodiment are same as Example 1, and difference is step（1）It is middle amido modified using 0.05g Titania nanoparticles mixed with Nafion solution（The quality of Nafion is 0.45g）, prepared polyaniline array Thickness is about 8.6 microns.
3 implementation steps of embodiment are same as Example 1, and difference is step（2）In 20mg/ml nanogold 5min, step are deposited in colloidal sol（3）In 4-ATP concentration be 2mg/ml, the thickness of prepared polyaniline array is about 6.3 micro- Rice.
4 implementation steps of embodiment are same as Example 1, and difference is step（4）In concentration of aniline used be 0.2mM, tartaric acid concentration 0.1mM, ammonium persulfate concentrations 0.2mM, retention time 4h, prepared polyaniline array Thickness is about 11.2 microns.
5 implementation steps of embodiment are same as Example 1, difference with step（1）It is middle to use 0.4g polymethyls Sour methyl esters is dissolved in 40ml methanol solutions and replaces Nafion solution, and the thickness of prepared polyaniline array is about 9.1 microns.
6 implementation steps of embodiment are same as Example 5, and difference is step（2）In nano gold sol concentration For 1mg/ml, sedimentation time 1h, the thickness of prepared polyaniline array is about 6.2 microns.
7 implementation steps of embodiment are same as Example 5, and difference is step（3）In 4-ATP concentration be 0.2mg/ml, the thickness of prepared polyaniline array is about 3.4 microns.
8 experimental procedure of embodiment is same as Example 5, and difference is step（4）The concentration of middle aniline is 0.02mM, tartaric acid concentration 0.01mM, ammonium persulfate concentrations 0.02mM, the thickness of prepared polyaniline array are about 1.9 micron.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (10)

  1. A kind of 1. method of polymeric film surface growth in situ polyaniline array, it is characterised in that：Comprise the following steps：
    （1）The preparation of amination polymeric matrix material：Amination inorganic oxide nanoparticles are added into polymer solution, Uniformly rear double teeming forms a film ultrasonic disperse, and amination polymeric matrix material is made；
    （2）It is prepared by the amination matrix surface of nanogold particle modification：By step（1）The amination polymeric matrix material of preparation It is placed in nano gold sol solution and impregnates, deposit nanogold particle, takes out basis material, carefully cleaned, gone with deionized water Except the nanometer gold ion not being coordinated with amino, the amination matrix that nanogold particle is modified is obtained；
    （3）Orientation self assembly of the aniline monomer on decorated by nano-gold matrix：By step（2）Prepared nanogold particle modification Amination matrix be impregnated in 4- amino in the ethanol solution of benzenethiol, dip time is no less than 8 h so that 4- amino is to benzene Thiophenol is fully reacted with nanogold particle, then takes out matrix, is carefully cleaned with ethanol, removes the 4- amino pair not with gold coordination Benzenethiol；
    （4）The preparation of polyaniline array modified polymer film：Under room temperature, by step（3）Prepared matrix is placed in aniline and wine In the mixed solution of stone acid, gradually it is added dropwise with the isometric ammonium persulfate aqueous solution of mixed solution, the timing of holding one after dripping Between, that is, obtain polymeric film surface growth in situ polyaniline array.
  2. 2. a kind of method of polymeric film surface growth in situ polyaniline array according to claim 1, its feature exist In：This method is used to refer to anion in the polymeric film surface growth in situ polyaniline array, the thin polymer film One kind in thin polymer film or neutral polymer film.
  3. 3. a kind of method of polymeric film surface growth in situ polyaniline array according to claim 1 or 2, its feature It is：The polymer is in polymethyl methacrylate, polyvinyl alcohol, Nafion, sulfonated polyether-ether-ketone, polymethylacrylic acid One kind.
  4. 4. a kind of method of polymeric film surface growth in situ polyaniline array according to claim 1, its feature exist In：Step（1）The inorganic oxide is one kind in silica, titanium dioxide, zirconium dioxide, aluminium oxide.
  5. 5. a kind of method of polymeric film surface growth in situ polyaniline array according to claim 1, its feature exist In：Step（1）The mass ratio of the inorganic oxide nanoparticles and polymer is 10：90~50：50.
  6. 6. a kind of method of polymeric film surface growth in situ polyaniline array according to claim 1, its feature exist In：Step（2）The nano gold sol concentration is 1mg/ml ~ 20mg/ml；The sedimentation time is 5min ~ 1h.
  7. 7. a kind of method of polymeric film surface growth in situ polyaniline array according to claim 1, its feature exist In：Step（3）The 4- amino in the ethanol solution of benzenethiol, 4- amino to the concentration of benzenethiol for 0.2 mg/ml ~ 2mg/ml。
  8. 8. a kind of method of polymeric film surface growth in situ polyaniline array according to claim 1, its feature exist In：Step（4）The concentration of aniline is 0.02mM ~ 0.2mM in the mixed solution, and the concentration ratio of tartaric acid and aniline is 1： 2。
  9. 9. according to a kind of method of polymeric film surface growth in situ polyaniline array described in claim 1, it is characterised in that： Step（4）The concentration ratio of the ammonium persulfate and aniline is 1：1.
  10. 10. according to a kind of method of polymeric film surface growth in situ polyaniline array described in claim 1, its feature exists In：Step（4）It is described be added dropwise after retention time be 20min ~ 4h.
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