CN102220622A - Method for synthesizing polypyrrole-chitosan-metal nanoparticle composite film on surface of cathode by one-step process - Google Patents
Method for synthesizing polypyrrole-chitosan-metal nanoparticle composite film on surface of cathode by one-step process Download PDFInfo
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- CN102220622A CN102220622A CN 201110101342 CN201110101342A CN102220622A CN 102220622 A CN102220622 A CN 102220622A CN 201110101342 CN201110101342 CN 201110101342 CN 201110101342 A CN201110101342 A CN 201110101342A CN 102220622 A CN102220622 A CN 102220622A
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Abstract
The invention relates to a method for preparing a polypyrrole-chitosan-metal nanoparticle composite film, which comprises the following steps: 1) dissolving the chitosan in 0.01 to 1 mol/L nitric acid solution to obtain solution A, wherein the mass percentage concentration of the chitosan in the solution A is 0.5 to 5 percent; 2) adding a pyrrole monomer and a divalent metal salt into the solution A to obtain solution B, wherein the concentration of the pyrrole monomer in the solution B is 0.1 to 0.4mol/L and the concentration of the divalent metal salt in the solution B is 0.1 to 0.3 mol/L; and 3) placing the cathode into the solution B, energizing under protection of nitrogen, performing electrochemical synthesis to synthesize the composite film on the surface of the cathode by a one-step process. In the invention, the reaction conditions are mild, the process is simple, the cost of large-scale production is low, the thickness of the composite film and the component content in the composite film can be controlled, and the method has a bright application prospect in the field of film materials.
Description
Technical field
The present invention relates to the synthetic of polymer/metal nanoparticle composite membrane, the preparation method of especially a kind of polypyrrole-chitosan-metallic nanoparticle composite membrane.
Background technology
The metal nanoparticle specific surface area is big, the reactive behavior height, make it in that fields such as the electrocatalysis of organic substance, modified electrode, transmitter have been shown tempting application prospect, become the research field that becomes increasingly active that material subject, analytical chemistry subject and biological medicine subject interpenetrate intersection.The metal nanoparticle that processability is good has and important significance for theories and practical value.But metal nanoparticle is very easily reunited, and limits its widespread use.How effectively stoping metal nanoparticle to be reunited is a challenging task.
Discover that the material that macromolecular material and metal nanoparticle are obtained after compound can keep the dispersiveness of metal nanoparticle preferably, has both had the photoelectric properties of metal nanoparticle uniqueness, has high stability again.Conducting polymer has special structure and excellent physical chemistry has a wide range of applications it on transmitter, electromagnetic shielding, anti-corrosion of metal and photoelectric device.In various conducting polymers, polypyrrole is one of more system of research.Polypyrrole can pass through chemistry or electrochemical production, and wherein electrochemical polymerization can directly obtain polymeric film on working electrode.And chitosan is the straight chain biomacromolecule polysaccharide that the natural polysaccharide chitin obtains by the connection of β-1,4 glycosidic link through partially deacetylated back.The chitosan source is abundant, is the environment renewable resources, has excellent biological compatibility.Active aminos a large amount of in the chitosan molecule can be protonated under sour environment, makes it be dissolved in acidic solution.
The method that generally prepares the polymer/metal nanoparticle composite membrane at present all is a two-step approach, promptly earlier obtain polymeric membrane by chemistry or electrochemical method, to contain metal ion solution then and contact, thereby add reductive agent or electrochemical reduction obtain being dispersed with metal nanoparticle in polymer composite membrane at last with polymeric membrane.But polymer/metal nanoparticle-enzyme modified electrode preparation technology is generally complicated in the prior art, and preparation cycle is long, and cost is higher.
Summary of the invention
Problem to be solved by this invention is the method for the synthetic polypyrrole-chitosan of a kind of cathode surface single stage method of proposing at above-mentioned existing deficiency-metallic nanoparticle composite membrane, and its technology is simple, and cost is lower, controllable film thickness.
The present invention for the solution that problem adopts of the above-mentioned proposition of solution is: the cathode surface single stage method is synthesized the method for polypyrrole-chitosan-metallic nanoparticle composite membrane, may further comprise the steps:
1) chitosan is dissolved in the 0.01-1mol/L salpeter solution, obtains solution A, the mass percent concentration of chitosan is 0.5-5% in the solution A;
2) behind adding pyrrole monomer and the divalent metal salt, obtain solution B in solution A, the concentration of pyrrole monomer in solution B is 0.1-0.4mol/L, and the concentration of divalent metal salt in solution B is 0.1-0.3mol/L;
3) negative electrode is placed solution B, electrochemical synthesis is carried out in energising under nitrogen protection, obtains polypyrrole-chitosan-metallic nanoparticle composite membrane in the cathode surface single stage method.
Press such scheme, described negative electrode is metallic nickel, indium tin oxide-coated glass or glass-carbon electrode;
Press such scheme, during the described electrochemical synthesis of step 3) cathode potential be-0.5～-2V;
Press such scheme, the generated time of the described electrochemical synthesis of step 3) is 1-30 minute;
Press such scheme, described divalent metal salt is copper sulfate, cupric chloride, cupric nitrate, tin protochloride, the inferior tin of nitric acid or stannous sulfate.
Insert electrifying electrodes in the mixing solutions of chitosan, pyrrole monomer and divalent metal salt after, nitrate ion in the solution and hydrogen ion get electron reaction and generate NO near cathode electrodes
+Ion.NO
+Ion has strong oxidizing property, and then the oxidation pyrrole monomer becomes polypyrrole and is deposited on cathode surface; Meanwhile, near the pH value the negative electrode is consumed along with hydrogen ion and raises, and causes chitosan to become insoluble state and also is deposited on cathode surface; Divalent-metal ion in the solution also obtains electronics and is reduced on negative electrode, thereby single stage method has obtained the composite membrane of polypyrrole-chitosan-metal nanoparticle.
The present invention with respect to the advantage that prior art exists is: 1) on the preparation method, the galvanic deposit of the negative electrode polymerization of polypyrrole, chitosan is equipped with metal nanoparticle with the electroreduction legal system combines, single stage method has obtained polypyrrole-chitosan-metallic nanoparticle composite membrane at cathode surface; 2) compare with the method that routine prepares the polymer/metal nanoparticle composite membrane, reaction conditions gentleness of the present invention, technology is simple, and the scale operation cost is low, and may command composite membrane thickness and each component concentration, in the mould material field application promise in clinical practice is arranged.
Description of drawings
Fig. 1 is the sem photograph of the polypyrrole-chitosan-metallic nanoparticle composite membrane of the inventive method preparation.
Embodiment
For a better understanding of the present invention, further illustrate content of the present invention, but content of the present invention not only is confined to the following examples below in conjunction with embodiment.
Embodiment 1:
1) chitosan is dissolved in the 0.1mol/L salpeter solution, obtains solution A, the mass percent concentration of chitosan is 1% in the solution A;
2) behind adding pyrrole monomer and the copper sulfate, obtain solution B in solution A, the concentration of pyrrole monomer in solution B is 0.1mol/L, and the concentration of copper sulfate in solution B is 0.2mol/L;
3) the nickel bar is placed solution B as negative electrode, electrochemical synthesis is carried out in energising under nitrogen protection, and current potential is-0.8V that electrodeposition time is 10 minutes, obtains polypyrrole-chitosan-metallic copper nano particle composite membrane in the cathode surface single stage method.
Observe the surface with scan electrode, contain the copper nano-particle that is evenly distributed in polypyrrole-chitosan-metallic copper nano particle composite membrane.
Embodiment 2:
1) with the step 1 among the embodiment 1;
2) with the step 2 among the embodiment 1;
3) indium tin oxide-coated glass is placed solution B as negative electrode, electrochemical synthesis is carried out in energising under nitrogen protection, and current potential is-1.2V that electrodeposition time is 20 minutes, obtains polypyrrole-chitosan-metallic copper nano particle composite membrane in the cathode surface single stage method.
Observe the surface with scan electrode, contain the copper nano-particle that is evenly distributed in polypyrrole-chitosan-metallic copper nano particle composite membrane.
Embodiment 3:
1) with the step 1 among the embodiment 1;
2) behind adding pyrrole monomer and the cupric nitrate, obtain solution B in solution A, the concentration of pyrrole monomer in solution B is 0.2mol/L, and the concentration of copper sulfate in solution B is 0.3mol/L;
3) with the step 3 among the embodiment 1.
Embodiment 4:
1) with the step 1 among the embodiment 1;
2) behind adding pyrrole monomer and the cupric chloride, obtain solution B in solution A, the concentration of pyrrole monomer in solution B is 0.4mol/L, and the concentration of cupric chloride in solution B is 0.3mol/L;
3) glass-carbon electrode is placed solution B as negative electrode, electrochemical synthesis is carried out in energising under nitrogen protection, and current potential is-1.5V that electrodeposition time is 15 minutes, obtains polypyrrole-chitosan-metallic copper nano particle composite membrane in the cathode surface single stage method.
Observe the surface with scan electrode, contain the copper nano-particle that is evenly distributed in polypyrrole-chitosan-metallic copper nano particle composite membrane.
Embodiment 5:
1) chitosan is dissolved in the 0.5mol/L salpeter solution, obtains solution A, the mass percent concentration of chitosan is 2% in the solution A;
2) behind the inferior tin of adding pyrrole monomer and nitric acid, obtain solution B in solution A, the concentration of pyrrole monomer in solution B is 0.2mol/L, and the concentration of the inferior tin of nitric acid in solution B is 0.1mol/L;
3) indium tin oxide-coated glass is placed solution B as negative electrode, electrochemical synthesis is carried out in energising under nitrogen protection, and current potential is-0.7V that electrodeposition time is 20 minutes, obtains polypyrrole-chitosan-metallic tin nanoparticle composite membrane in the cathode surface single stage method.
Observe the surface with scan electrode, contain the sijna rice corpuscles that is evenly distributed in polypyrrole-chitosan-metallic tin nanoparticle composite membrane.
Embodiment 6:
1) with the step 1 among the embodiment 5;
2) behind the inferior tin of adding pyrrole monomer and nitric acid, obtain solution B in solution A, the concentration of pyrrole monomer in solution B is 0.3mol/L, and the concentration of tin protochloride in solution B is 0.2mol/L;
3) with the step 3 among the embodiment 5.
Embodiment 7:
1) chitosan is dissolved in the 0.05mol/L salpeter solution, obtains solution A, the mass percent concentration of chitosan is 4% in the solution A;
2) behind adding pyrrole monomer and the stannous sulfate, obtain solution B in solution A, the concentration of pyrrole monomer in solution B is 0.3mol/L, and the concentration of stannous sulfate in solution B is 0.2mol/L;
3) with the step 3 among the embodiment 5.
Embodiment 8:
1) with the step 1 among the embodiment 5;
2) with the step 2 among the embodiment 5;
3) the nickel bar is placed solution B as negative electrode, electrochemical synthesis is carried out in energising under nitrogen protection, and current potential is-0.8V that electrodeposition time is 15 minutes, obtains polypyrrole-chitosan-metallic tin nanoparticle composite membrane in the cathode surface single stage method.
Observe the surface with scan electrode, contain the sijna rice corpuscles that is evenly distributed in polypyrrole-chitosan-metallic tin nanoparticle composite membrane.
Each cited raw material of the present invention can both be realized the present invention, and the bound value of each raw material, interval value can both realize the present invention; Do not enumerate embodiment one by one at this.Bound value, the interval value of processing parameter of the present invention (as temperature, time etc.) can both be realized the present invention, do not enumerate embodiment one by one at this.
Claims (5)
1. the cathode surface single stage method is synthesized the method for polypyrrole-chitosan-metallic nanoparticle composite membrane, may further comprise the steps:
1) chitosan is dissolved in the 0.01-1mol/L salpeter solution, obtains solution A, the mass percent concentration of chitosan is 0.5-5% in the solution A;
2) behind adding pyrrole monomer and the divalent metal salt, obtain solution B in solution A, the concentration of pyrrole monomer in solution B is 0.1-0.4mol/L, and the concentration of divalent metal salt in solution B is 0.1-0.3mol/L;
3) negative electrode is placed solution B, electrochemical synthesis is carried out in energising under nitrogen protection, obtains polypyrrole-chitosan-metallic nanoparticle composite membrane in the cathode surface single stage method.
2. by the method for the synthetic polypyrrole-chitosan of the described cathode surface single stage method of claim 1-metallic nanoparticle composite membrane, it is characterized in that described negative electrode is metallic nickel, indium tin oxide-coated glass or glass-carbon electrode.
3. by the method for the synthetic polypyrrole-chitosan of claim 1 or 2 described cathode surface single stage method-metallic nanoparticle composite membrane, when it is characterized in that the described electrochemical synthesis of step 3) cathode potential be-0.5～-2V.
4. by the method for the synthetic polypyrrole-chitosan of the described cathode surface single stage method of claim 3-metallic nanoparticle composite membrane, the generated time that it is characterized in that the described electrochemical synthesis of step 3) is 1-30 minute.
5. by the method for claim 1 or the synthetic polypyrrole-chitosan of 2 described cathode surface single stage method-metallic nanoparticle composite membrane, it is characterized in that described divalent metal salt is copper sulfate, cupric chloride, cupric nitrate, tin protochloride, the inferior tin of nitric acid or stannous sulfate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105645523A (en) * | 2016-01-07 | 2016-06-08 | 西安建筑科技大学 | Method for preparing polypyrrole/chitosan composite electrode |
| CN105692812A (en) * | 2016-04-22 | 2016-06-22 | 西安建筑科技大学 | Method for applying polypyrrole/chitosan combined electrode to heavy metal ion adsorption |
| CN112588278A (en) * | 2020-11-06 | 2021-04-02 | 兰州城市学院 | Method for adsorbing Cu (II) by using efficient polymer functionalized stirring rod SS/PPy/CS |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760226A (en) * | 2005-09-30 | 2006-04-19 | 西安交通大学 | Method for preparing composite conductive high molecular electrode material in use for super capacitor |
| CN101492545A (en) * | 2009-02-17 | 2009-07-29 | 武汉工程大学 | Method of preparing poly-pyrrole/polythiofuran derivative composite conductive macromolecule material for super electrical condenser |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760226A (en) * | 2005-09-30 | 2006-04-19 | 西安交通大学 | Method for preparing composite conductive high molecular electrode material in use for super capacitor |
| CN101492545A (en) * | 2009-02-17 | 2009-07-29 | 武汉工程大学 | Method of preparing poly-pyrrole/polythiofuran derivative composite conductive macromolecule material for super electrical condenser |
Non-Patent Citations (1)
| Title |
|---|
| 《Carbohydrate Polymers》 20091031 S.Yalcinkaya,et al. Electrochemical synthesis and characterization of polypyrrole/chitosan composite on platinum electrode: Its electrochemical and thermal behaviors 全文 1-5 第79卷, * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105645523A (en) * | 2016-01-07 | 2016-06-08 | 西安建筑科技大学 | Method for preparing polypyrrole/chitosan composite electrode |
| CN105645523B (en) * | 2016-01-07 | 2018-05-11 | 西安建筑科技大学 | A kind of method for preparing polypyrrole/chitosan combination electrode |
| CN105692812A (en) * | 2016-04-22 | 2016-06-22 | 西安建筑科技大学 | Method for applying polypyrrole/chitosan combined electrode to heavy metal ion adsorption |
| CN105692812B (en) * | 2016-04-22 | 2018-03-30 | 西安建筑科技大学 | Polypyrrole/chitosan combination electrode is applied to heavy metal ion adsorbed method |
| CN112588278A (en) * | 2020-11-06 | 2021-04-02 | 兰州城市学院 | Method for adsorbing Cu (II) by using efficient polymer functionalized stirring rod SS/PPy/CS |
| CN112588278B (en) * | 2020-11-06 | 2022-12-13 | 兰州城市学院 | Method for adsorbing Cu (II) by using efficient polymer functionalized stirring rod SS/PPy/CS |
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