CN102731781A - Method for preparing polypyrrole-zinc oxide nano-grade composite material - Google Patents
Method for preparing polypyrrole-zinc oxide nano-grade composite material Download PDFInfo
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- CN102731781A CN102731781A CN2012101902583A CN201210190258A CN102731781A CN 102731781 A CN102731781 A CN 102731781A CN 2012101902583 A CN2012101902583 A CN 2012101902583A CN 201210190258 A CN201210190258 A CN 201210190258A CN 102731781 A CN102731781 A CN 102731781A
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Abstract
The invention relates to a method for preparing a polypyrrole-zinc oxide nano-grade composite material. The method comprises the steps that: (1) an oxalic acid solution and dodecylbenzene sulfonic acid are adopted as electrolytes, and an oxalic acid electrolyte is prepared; (2) nano-grade zinc oxide powder is added to the oxalic acid electrolyte; the mixture is subjected to ultrasonic treatment and magnetic stirring, such that a uniformly dispersed mixed liquid is formed; pyrrole monomers are added to the mixed liquid; the mixture is well mixed by magnetic stirring, and is stood; and (3) polymerization is carried out by using an electrochemical method, and is carried out on a conductive substrate, such that a polypyrrole-zinc oxide nano-grade composite material sample is obtained; the sample is washed by using anhydrous ethanol and distilled water, and is naturally dried in air. The method provided by the invention is advantaged in simple conditions, controllable operation processes, short time, and low cost. The prepared polypyrrole-zinc oxide nano-grade composite material has good electrochemical properties and corrosion resistance.
Description
Technical field
The present invention relates to a kind of preparation method of polypyrrole-zinc oxide nanometer composite material, particularly make ionogen, form a kind of method of polypyrrole-zinc oxide nanometer composite material through electrochemical polymerization with macroanion tensio-active agent Witco 1298 Soft Acid.
Background technology
The conducting polymer composite polypyrrole that contains conjugated double bond has higher relatively specific conductivity, good environmental stability and is easy to adopt characteristics such as chemistry or electrochemical synthesis, is considered to have one of conducting polymer composite of commercial promise most.These performances of polypyrrole make it at [the Surajit K that has a wide range of applications aspect electrode, battery material, biomedicine, transmitter, molecular device, electrochromism demonstration, the anticorrosive; Swapan K D; Materials Chemistry and Physics; 2010,124:738; Lin X W, Xin G L, Yu L Y, Reactive & Funct. Polym., 2001,47:125-139; Han M J, Chu Y, Han D X, Liu Y J, Colloid Int. Sci., 2006,296:110 – 117].Nano zine oxide (ZnO) is a kind of Multifunction inorganic materials, and physicochemical property are stable, and oxidation activity is high and cheap and easy to get; Be at present a lot of hot research fields; ZnO has surface effects, volume effect, quantum size effect and macroscopical tunnel effect etc., shows many exceptional functions at aspects such as catalysis, optics, magnetic and mechanics, has important effect in a lot of fields such as chemical industry, electronics, optics; Make it become important research object and be used widely [Zhao J et al; J. Polym. Sci. Part A-Polymer Chem., 2009,47:746-753; Kudol Y, Tsuchiya S, Kojima T, M Fukuyama, Yoshlmura S, Synth. Met., 1991,1133:41-43; Yang X T, Xu L, Nanotechnology, 2003,14:624 – 629; Zhu J H, Wei S Y, J. Phys. Chem. C 2010,114:16335].Through mixing organic or mineral compound; The electronics of electric polypyrrole and optical property can obtain changing; So just can obtain the matrix material of excellent property, because the property of composite organic-inorganic material, this material plays more and more important effect in the industry in modern times.The present invention proposes a kind of preparation method of polypyrrole-zinc oxide nanometer composite material.
At present on the preparation method of polypyrrole-zinc oxide nanometer composite material, mainly contain two kinds: chemical oxidization method and electricity polymerization.People [Aditee J, Aswal D K, Gupta S K such as Aditee J; Applied Physics Letters; 2009,94:103115] adopt chemical oxidation method, will contain pyrroles, ammonium persulphate, ZnO nano wire and alcoholic acid colloidal solution and mix; Promptly prepared the Pt/Polypyrrole composite material that the ZnO nano wire is modified, wherein ZnO is present in the mixture with the form of nano wire.People [Rooma D such as Rooma D; Manish T, Pundir C S, Biosensors and Bioelectronics; 2011,26:3420-3426] utilized electrochemical production based on the current mode xanthine biosensor of Zinc oxide nanoparticle and polypyrrole laminated film.The ZnO nano particle joined contain NaClO
4In the solution of pyrrole monomer, utilize electrochemical method polymerization on platinum electrode to obtain Zinc oxide nanoparticle and polypyrrole laminated film, wherein polypyrrole does not exist with typical cauliflower form form of film.People [Dong U L, Debabrata P, Rola M, Chem. Mater, 2010,22:218-225] such as Dong U L utilize electrochemical deposition method on film of poly pyrrole, to prepare nano zine oxide.With Zn (NO
3)
2With the KCl mixing solutions be electrolytic solution, adopt electrochemical method, electrochemical deposition obtains nano zine oxide on the polypyrrole coating.Wherein, ZnO with different nanometer shapes like (nano-pillar, nanometer sheet and flower-like structure) form attached to above the film of poly pyrrole.People [Hosseini M G such as Hosseini M G; Bagheri R; Najjar R, Journal of Applied Polymer Science, Vol. 2011; 121:3159-3166] be electrolytic solution with the mixing solutions of the oxalic acid, Witco 1298 Soft Acid and the pyrrole monomer that contain nano-ZnO, the polypyrrole-zinc oxide nanometer composite material that utilized electrochemical production.Wherein, ZnO is present in the film of poly pyrrole with the form of nanometer rod.
Deliver the preparation method who has proposed polypyrrole and nano zine oxide duplicature in the document in addition in addition.People [Mitsutoshi O, Kiminori I, Eiji K, and kira F, J. Appl. Phys., 1987,62:2143] such as Mitsutoshi O adopt electrochemical method at SiO
2Deposit the layer of ZnO film in the substrate, on ZnO, deposited one deck film of poly pyrrole again, thereby prepared polypyrrole/nano zine oxide double membrane structure.
Polypyrrole-the zinc oxide nanometer composite material of method for preparing; The doping level of zinc oxide is lower, and nano zine oxide not well with doped polypyrrole together, the form with matrix material does not exist; But exist alone with the form of minute amorph; Perhaps exist with double-deck form, do not demonstrate fully the property of matrix material, electroconductibility and electrochemistry are all poor.This patent utilizes electrochemical method, based on multiple conductive electrode, and the polypyrrole of preparation-zinc oxide nanometer composite material film; Matrix material has high electrochemical performance; Good anti-corrosion protection performance is utilized the electrochemical method growth, can be used as the decorative material of electrode.
Summary of the invention
Technical problem:The present invention seeks to solve the problem of the low and matrix material antiseptic property difference of nano-zinc oxide doped degree, propose a kind of method for preparing polypyrrole-zinc oxide nanometer composite material.The present invention is an ionogen with oxalic acid and Witco 1298 Soft Acid, adopts electrochemical production polypyrrole-zinc oxide nanometer composite material.Processing condition of the present invention are simple, and operating process is controlled, and the time is short, and the polypyrrole of preparation-zinc oxide nanometer composite material chemical property is good, can be applied in the electronics of transmitter.
Technical scheme:The present invention prepare polypyrrole-zinc oxide nanometer composite material method preparation technology order as follows:
(1) be ionogen with oxalic acid and Witco 1298 Soft Acid, preparation oxalic acid electrolytic solution.
(2) in above-mentioned oxalic acid electrolytic solution, add nano zine oxide powder (ZnO), ultrasonic and magnetic agitation forms homodisperse mixing solutions.Add pyrrole monomer then, magnetic agitation after solution to be mixed is even, leaves standstill it.
(3) adopt the electrochemical method polymerization, polymerization obtains polypyrrole-zinc oxide nanometer composite material sample on conductive substrates, and the gained sample cleans the back with absolute ethyl alcohol, zero(ppm) water and dries naturally.
Oxalic acid solution in said preparing method's the step (1), its concentration range are 0.1mol/L ~ 1mol/L, and wherein Witco 1298 Soft Acid and oxalic acid molar concentration rate are 1:3.
The pyrrole monomer in said preparing method's the step (2) and the mass percent of ZnO powder are 90% ~ 70%:10% ~ 30%.
Electrochemical method in said preparing method's the step (3) can be chronoamperometry, timing coulometry and cyclic voltammetry, and the polymerization voltage range of said chronoamperometry is 0.7V ~ 1.5V, and the range of current of timing coulometry is 1mA/cm
2~ 10 mA/cm
2, the voltage range of cyclic voltammetry is-1V ~ 1V.
Conductive substrates in said preparing method's the step (3) is nickel sheet, stainless (steel) wire, carbon cloth, carbon-point or gac.
Polymerization time in said preparing method's the step (3) is 3min ~ 60min.
Beneficial effect:Processing condition of the present invention are simple, and operating process is controlled, and the time is short; Cost is low; Polypyrrole-zinc oxide nanometer composite material the chemical property of preparation is good, can be widely used in aspects such as impregnating material, electromagnetic shielding, has expanded the range of application of polypyrrole-zinc oxide nanometer composite material.
Description of drawings
Fig. 1 is the ESEM picture based on nickel sheet polymeric polypyrrole-zinc oxide nanometer composite material (90%:10%) of instance 1 of the present invention;
Fig. 2 is the X-ray diffractogram based on nickel sheet polymeric polypyrrole-zinc oxide nanometer composite material (90%:10%) of instance 1 of the present invention;
Fig. 3 is the Fourier transform infrared spectroscopy figure based on nickel sheet polymeric polypyrrole-zinc oxide nanometer composite material (90%:10%) of instance 1 of the present invention
Fig. 4 be instance 1 of the present invention based on the Ta Feier curve of nickel sheet polymeric polypyrrole-zinc oxide nanometer composite material (90%:10%) in 0.1mol/L KCl solution;
Fig. 5 be instance 1 of the present invention based on the electrochemical impedance spectral curve of nickel sheet polymeric polypyrrole-zinc oxide nanometer composite material (90%:10%) in 0.1mol/L KCl solution, its hollow core curve is the nyquist curve, solid-line curve is matched curve.
Fig. 6 be instance 2 of the present invention based on the Ta Feier curve of nickel sheet polymeric polypyrrole-zinc oxide nanometer composite material (80%:20%) in 0.1mol/L KCl solution;
Fig. 7 be instance 2 of the present invention based on the electrochemical impedance spectral curve of nickel sheet polymeric polypyrrole-zinc oxide nanometer composite material (80%:20%) in 0.1mol/L KCl solution, its hollow core curve is the nyquist curve, solid-line curve is matched curve.
Fig. 8 be instance 3 of the present invention based on the Ta Feier curve of carbon cloth polymeric polypyrrole-zinc oxide nanometer composite material in 0.1mol/L KCl solution;
Fig. 9 be instance 3 of the present invention based on the electrochemical impedance spectral curve of carbon cloth polymeric polypyrrole-zinc oxide nanometer composite material in 0.1mol/L KCl solution, its hollow core curve is the nyquist curve, solid-line curve is matched curve.
Figure 10 be instance 4 of the present invention based on the Ta Feier curve of stainless (steel) wire polymeric polypyrrole-zinc oxide nanometer composite material in 0.1mol/L KCl solution;
Figure 11 be instance 4 of the present invention based on the electrochemical impedance spectral curve of stainless (steel) wire polymeric polypyrrole-zinc oxide nanometer composite material in 0.1mol/L KCl solution, its hollow core curve is the nyquist curve, solid-line curve is matched curve.
Embodiment
(1) be ionogen with oxalic acid and Witco 1298 Soft Acid, the oxalic acid electrolytic solution of preparation 0.1mol/L ~ 1mol/L, wherein Witco 1298 Soft Acid and oxalic acid molar concentration rate are 1:3, and be even with magnetic stirrer.
(2) in above-mentioned oxalic acid electrolytic solution, add nano zine oxide powder (ZnO), ultrasonic 1 hour, magnetic agitation 2 hours formed homodisperse mixing solutions.Add pyrrole monomer then, magnetic agitation 1 hour after solution to be mixed is even, leaves standstill it.The pyrrole monomer among the said preparation method and the mass percent of ZnO powder are 90% ~ 70%:10% ~ 30%.
(3) adopt electrochemical method (chronoamperometry, timing coulometry or cyclic voltammetry); Polyase 13 min ~ 60min; Polymerization obtains polypyrrole-zinc oxide nanometer composite material sample on conductive substrates, and the gained sample cleans the back with absolute ethyl alcohol, zero(ppm) water and dries naturally.Conductive substrates among the said preparation method is nickel sheet, stainless (steel) wire, carbon cloth, carbon-point or gac; The shape of substrate can be a sheet, netted or block; The material of substrate can be electro-conductive materials such as gold and silver, nickel, platinum, carbon, stainless steel.
Embodiment 1
(1) preparing electrolyte: take by weighing 1.26g oxalic acid and 1mL Witco 1298 Soft Acid, add the 100mL deionized water, use magnetic stirrer 30min, be mixed with 0.1mol/L oxalic acid electrolytic solution.Ratio according to the mass ratio 90%:10% of pyrrole monomer and ZnO adds 0.065gZnO in electrolytic solution, and ultrasonic 1 hour, magnetic agitation 2 hours.After treating that solution evenly, in electrolytic solution, add 0.65g pyrrole monomer, magnetic agitation 1 hour.Obtain polymer electrolyte liquid.
(2) preparation polypyrrole-zinc oxide nanometer composite material: polymerization experiment is carried out in electrochemical workstation, adopts three-electrode system, is working electrode with the nickel sheet, and stainless (steel) wire is a counter electrode, and SCE is a reference electrode, and experiment is carried out at ambient temperature.Adopt chronoamperometry, polymerization voltage is 1V, and polymerization time is 5min.Polypyrrole-the zinc oxide nanometer composite material that on the nickel sheet, obtains, gained sample dry after with absolute ethyl alcohol, distilled water wash naturally.
(3) cyclic voltammetry curve of polypyrrole-zinc oxide nanometer composite material test: preparation 0.1mol/L KCl solution; In the three-electrode system of electrochemical workstation control; Adopt cyclic voltammetry, the TV scope is-1V ~ 1V that scanning speed is 0.01mV/s.
(4) the anti-test of the Tafel curve of polypyrrole-zinc oxide nanometer composite material: preparation 0.1mol/L KCl solution; The electrode that is coated with matrix material is soaked 30min in solution, adopt three-electrode system, select Ta Feierfa; The TV scope is-1V ~ 1V that scanning speed is 0.01mV/s.
(5) electrochemical impedance of polypyrrole-zinc oxide nanometer composite material test: preparation 0.1mol/L KCl solution; The electrode that is coated with matrix material is soaked 30min in solution; Adopt three-electrode system; Select the electrochemical impedance method, the starting voltage parameter is set to 0V, and the test frequency scope is 1Hz ~ 10KHz.
Embodiment 2
(1) preparing electrolyte: take by weighing 1.26g oxalic acid and 1mL Witco 1298 Soft Acid, add the 100mL deionized water, use magnetic stirrer 30min, be mixed with 0.1mol/L oxalic acid electrolytic solution.Ratio according to the mass ratio 80%:20% of pyrrole monomer and ZnO adds 0.13gZnO in electrolytic solution, and ultrasonic 1 hour, magnetic agitation 2 hours.After treating that solution evenly, in electrolytic solution, add 0.65g pyrrole monomer, magnetic agitation 1 hour.Obtain polymer electrolyte liquid.
(2) preparation polypyrrole-zinc oxide nanometer composite material: polymerization experiment is carried out in electrochemical workstation, adopts three-electrode system, is working electrode with the nickel sheet, and stainless (steel) wire is a counter electrode, and SCE is a reference electrode, and experiment is carried out at ambient temperature.Adopt chronoamperometry, polymerization voltage is 1V, and polymerization time is 5min.Polypyrrole-the zinc oxide nanometer composite material that on the nickel sheet, obtains, gained sample dry after with absolute ethyl alcohol, distilled water wash naturally.
(3) cyclic voltammetry curve of polypyrrole-zinc oxide nanometer composite material test: preparation 0.1mol/L KCl solution; In the three-electrode system of electrochemical workstation control; Adopt cyclic voltammetry, the TV scope is-1V ~ 1V that scanning speed is 0.01mV/s.
(4) electrochemical impedance of polypyrrole-zinc oxide nanometer composite material test: preparation 0.1mol/L KCl solution; The electrode that is coated with matrix material is soaked 30min in solution; Adopt three-electrode system; Select the electrochemical impedance method, the starting voltage parameter is set to 0V, and the test frequency scope is 1Hz ~ 10KHz.
(1) preparing electrolyte: take by weighing 1.26g oxalic acid and 1mL Witco 1298 Soft Acid, add the 100mL deionized water, use magnetic stirrer 30min, be mixed with 0.1mol/L oxalic acid electrolytic solution.Ratio according to the mass ratio 70%:30% of pyrrole monomer and ZnO adds 0.195gZnO in electrolytic solution, and ultrasonic 1 hour, magnetic agitation 2 hours.After treating that solution evenly, in electrolytic solution, add 0.65g pyrrole monomer, magnetic agitation 1 hour.Obtain polymer electrolyte liquid.
(2) preparation polypyrrole-zinc oxide nanometer composite material: polymerization experiment is carried out in electrochemical workstation, adopts three-electrode system, is working electrode with the carbon cloth, and stainless (steel) wire is a counter electrode, and SCE is a reference electrode, and experiment is carried out at ambient temperature.Adopt chronoamperometry, polymerization voltage is 1V, and polymerization time is 5min.Polypyrrole-the zinc oxide nanometer composite material that on carbon cloth, obtains, gained sample dry after with absolute ethyl alcohol, distilled water wash naturally.
(3) cyclic voltammetry curve of polypyrrole-zinc oxide nanometer composite material test: preparation 0.1mol/L KCl solution; In the three-electrode system of electrochemical workstation control; Adopt cyclic voltammetry, the TV scope is-1V ~ 1V that scanning speed is 0.01mV/s.
(4) electrochemical impedance of polypyrrole-zinc oxide nanometer composite material test: preparation 0.1mol/L KCl solution; The electrode that is coated with matrix material is soaked 30min in solution; Adopt three-electrode system; Select the electrochemical impedance method, the starting voltage parameter is set to 0V, and the test frequency scope is 1Hz ~ 10KHz.
(1) preparing electrolyte: take by weighing 1.26g oxalic acid and 1mL Witco 1298 Soft Acid, add the 100mL deionized water, use magnetic stirrer 30min, be mixed with 0.1mol/L oxalic acid electrolytic solution.Ratio according to the mass ratio 70%:30% of pyrrole monomer and ZnO adds 0.065gZnO in electrolytic solution, and ultrasonic 1 hour, magnetic agitation 2 hours.After treating that solution evenly, in electrolytic solution, add 0.65g pyrrole monomer, magnetic agitation 1 hour.Obtain polymer electrolyte liquid.
(2) preparation polypyrrole-zinc oxide nanometer composite material: polymerization experiment is carried out in electrochemical workstation, adopts three-electrode system, is working electrode and counter electrode with the stainless (steel) wire, and SCE is a reference electrode, and experiment is carried out at ambient temperature.Adopt chronoamperometry, polymerization voltage is 1V, and polymerization time is 5min.Polypyrrole-the zinc oxide nanometer composite material that on stainless (steel) wire, obtains, gained sample dry after with absolute ethyl alcohol, distilled water wash naturally.
(3) cyclic voltammetry curve of polypyrrole-zinc oxide nanometer composite material test: preparation 0.1mol/L KCl solution; In the three-electrode system of electrochemical workstation control; Adopt cyclic voltammetry, the TV scope is-1V ~ 1V that scanning speed is 0.01mV/s.
(4) the anti-test of the Tafel curve of polypyrrole-zinc oxide nanometer composite material: preparation 0.1mol/L KCl solution; The electrode that is coated with matrix material is soaked 30min in solution, adopt three-electrode system, select Ta Feierfa; The TV scope is-1V ~ 1V that scanning speed is 0.01mV/s.
(5) electrochemical impedance of polypyrrole-zinc oxide nanometer composite material test: preparation 0.1mol/L KCl solution; The electrode that is coated with matrix material is soaked 30min in solution; Adopt three-electrode system; Select the electrochemical impedance method, the starting voltage parameter is set to 0V, and the test frequency scope is 1Hz ~ 10KHz.
Claims (6)
1. method for preparing polypyrrole-zinc oxide nanometer composite material is characterized in that this preparing method's sequence of process steps is following:
1). with oxalic acid solution and Witco 1298 Soft Acid is ionogen, preparation oxalic acid electrolytic solution;
2). in above-mentioned oxalic acid electrolytic solution, add the nano zine oxide powder, ultrasonic and magnetic agitation forms homodisperse mixing solutions; Add pyrrole monomer then, after magnetic agitation is even, it is left standstill;
3). adopt the electrochemical method polymerization, polymerization obtains polypyrrole-zinc oxide nanometer composite material sample on conductive substrates, and the gained sample cleans the back with absolute ethyl alcohol, zero(ppm) water and dries naturally.
2. the preparation method of polypyrrole-zinc oxide nanometer composite material according to claim 1; It is characterized in that: the oxalic acid solution in said preparing method's the step 1); Its concentration 0.1mol/L ~ 1mol/L, wherein Witco 1298 Soft Acid and oxalic acid molar concentration rate are 1:3.
3. the preparation method of polypyrrole-zinc oxide nanometer composite material according to claim 1, it is characterized in that: the pyrrole monomer said preparing method's step 2) and the mass percent of ZnO powder are 90% ~ 70%:10% ~ 30%.
4. the preparation method of polypyrrole-zinc oxide nanometer composite material according to claim 1; It is characterized in that: the electrochemical method in said preparing method's the step 3) is chronoamperometry, timing coulometry or cyclic voltammetry; The polymerization voltage range of said chronoamperometry is 0.7V ~ 1.5V, and the range of current of timing coulometry is 1mA/cm
2~ 10 mA/cm
2, the voltage range of cyclic voltammetry is-1V ~ 1V.
5. the preparation method of polypyrrole-zinc oxide nanometer composite material according to claim 1, it is characterized in that: the conductive substrates in said preparing method's the step 3) is nickel sheet, stainless (steel) wire, carbon cloth, carbon-point or gac.
6. the preparation method of polypyrrole-zinc oxide nanometer composite material according to claim 1, it is characterized in that: the polymerization time in said preparing method's the step 3) is 3min ~ 60min.
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| CN103713019A (en) * | 2013-12-23 | 2014-04-09 | 浙江大学 | Zinc oxide/polypyrrole nano composite resistance-type film gas sensor and production method thereof |
| CN105820358A (en) * | 2016-03-24 | 2016-08-03 | 太原理工大学 | Method for preparing organic/inorganic hybrid electroactivity ion exchange membrane in microgravity environment |
| CN107275611A (en) * | 2017-06-19 | 2017-10-20 | 南昌航空大学 | The spherical zinc oxide material of nanometer and preparation method of a kind of polypyrrole cladding |
| CN111044595A (en) * | 2018-10-14 | 2020-04-21 | 天津大学 | Three-dimensional ZnO array polypyrrole molecularly imprinted electrochemical sensor and preparation method and application thereof |
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| CN103713019A (en) * | 2013-12-23 | 2014-04-09 | 浙江大学 | Zinc oxide/polypyrrole nano composite resistance-type film gas sensor and production method thereof |
| CN103713019B (en) * | 2013-12-23 | 2015-09-16 | 浙江大学 | Nano combined resistance type thin film gas sensor of zinc paste/polypyrrole and preparation method thereof |
| CN105820358A (en) * | 2016-03-24 | 2016-08-03 | 太原理工大学 | Method for preparing organic/inorganic hybrid electroactivity ion exchange membrane in microgravity environment |
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| CN107275611B (en) * | 2017-06-19 | 2019-11-29 | 南昌航空大学 | A kind of spherical zinc oxide material of nanometer and preparation method of polypyrrole cladding |
| CN111044595A (en) * | 2018-10-14 | 2020-04-21 | 天津大学 | Three-dimensional ZnO array polypyrrole molecularly imprinted electrochemical sensor and preparation method and application thereof |
| CN112795033A (en) * | 2020-12-30 | 2021-05-14 | 苏州中科先进技术研究院有限公司 | Nano zero-valent iron-loaded porous polypyrrole nano film and preparation method and application thereof |
| CN112795033B (en) * | 2020-12-30 | 2023-08-15 | 苏州中科先进技术研究院有限公司 | Porous polypyrrole nano film loaded with nano zero-valent iron, and preparation method and application thereof |
| CN113500189A (en) * | 2021-08-10 | 2021-10-15 | 复旦大学 | Zinc microsphere-polypyrrole degradable composite material and interface super-assembly preparation method thereof |
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