CN100523088C - Hybridization material of Nano fiber of titanium oxide / polyaniline, and preparation method - Google Patents
Hybridization material of Nano fiber of titanium oxide / polyaniline, and preparation method Download PDFInfo
- Publication number
- CN100523088C CN100523088C CN 200710011078 CN200710011078A CN100523088C CN 100523088 C CN100523088 C CN 100523088C CN 200710011078 CN200710011078 CN 200710011078 CN 200710011078 A CN200710011078 A CN 200710011078A CN 100523088 C CN100523088 C CN 100523088C
- Authority
- CN
- China
- Prior art keywords
- titanium oxide
- polyaniline
- hybrid material
- nano fiber
- hour
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
This invention relates to a method for preparing TiO2/polyaniline nanofiber hybrid material. The hybrid material is composite nanoparticles composed of 20-70 wt. % one-dimensional TiO2 nanorods and polyaniline nanofibers. The hybrid material is prepared by combination of template-induced polymerization and hydrothermal method from TiO2 and aniline with HCl as the dopant, ammonium persulfate as the initiator, and poly (vinyl pyrrolidone) as the surfactant. The ratio of polyaniline to ammonium persulfate is 4:1. The hybrid material has such advantages as high thermal stability, good mechanical properties, low cost, abundant and cheap raw materials, no toxicity, no harm, simple process, and controllable composition and properties.
Description
Technical field
The present invention relates to a kind of nano-hybrid material and technology of preparing thereof, particularly a kind of titanium oxide/polyaniline nano fiber hybrid material and preparation method thereof.
Background technology
But organic/inorganic composite material not only combines elasticity, the toughness processed-type of organic materials, combines rigidity, dimensional stability and the thermostability of inorganic materials again.And the organic/inorganic composite material of low-dimensional is further combined with the advantage of nano material, and mixture has stronger synergistic effect, thereby shows mechanics, calorifics, electricity, magnetic and the optical property that is different from general macroscopical matrix material.
Organic conductive material is because its particular performances having a wide range of applications such as aspects such as chemical sensor, battery, optical material, electronic cables, electromagnetic shielding, microwave are stealthy, receives the concern of scientific circles and industry member.In numerous conductive polymerss, polyaniline (PANI) makes it become the conductive polymers that application prospect is arranged most owing to the mechanism of doping effect with diversified structure, uniqueness, excellent chemical property, good chemical stability and electricity are led adjustability.Its specific conductivity of the conductive polymers of micrometer/nanometer structure depends on factors such as doping content, doping agent, synthesis condition, pattern, caliber, measurement temperature, ambient pressure consumingly.But conductive polymers exists processability poor, and mechanical strength is not high, shortcomings such as use cost height, thereby be restricted (Chinese invention patent 2004100989231) in actual applications.In sum as can be known, develop a kind of high comprehensive performance, cost is low and environment amenable conductive nano composite material becomes current key issue.
Summary of the invention
The purpose of this invention is to provide a kind of titanium oxide/polyaniline nano fiber hybrid material and preparation method thereof, polyaniline and titanium oxide are carried out compound preparation titanium oxide/polyaniline nano fiber hybrid material can realize organic phase and inorganic compound on nanoscale, improve thermostability and mechanical property, reduce the cost of conducing composite material
Technical scheme of the present invention is, a kind of titanium oxide/polyaniline nano fiber hybrid material, this material is to be wound with the Nano composite granules that polyaniline nano fiber with one-dimentional structure is composited by the TiOx nano rod surface with one dimension Nano structure, and wherein the content of TiOx nano rod is 20-70wt%.
Titanium oxide/polyaniline nano fiber hybrid material preparation method comprises following several steps:
(1) select for use titanium oxide to make inorganic raw material, aniline is made organic raw material, is doping agent with hydrochloric acid, and ammonium persulphate is an initiator, and aniline monomer is 4:1 with the ratio of ammonium persulphate in the reaction process, and polyvinyl pyrrolidone is a tensio-active agent;
(2) at first the 0.5g titanium dioxide powder is added in the 10-15M potassium hydroxide solution of 30ml, stir half an hour under the room temperature, all change in the band teflon-lined water heating kettle, air-tight state heating down, Heating temperature is 150-200 ℃, reacted 36-72 hour, product, changes filter cake in the vacuum drying oven over to till filtrate pH value is less than 7 with 0.1M hydrochloric acid soln and deionized water repetitive scrubbing and filtration, at 70-85 ℃ of following vacuum-drying 3-6 hour, obtain the TiOx nano rod;
(3) TiOx nano of 0.1-0.5g rod is added in the 1M aqueous hydrochloric acid of 55-65ml and stir, then add 18-20.8mmol aniline monomer and 0.45-0.55g polyvinyl pyrrolidone, continue stirring under the room temperature and whole system was uniformly dispersed in 24-36 hour;
(4) the 1M hydrochloric acid soln with 4.5-5.2mmol ammonium persulphate adding 55-65ml stirs, then under quick stirring condition, with the rapid impouring aniline solution of ammonium persulfate solution, polymerization after half an hour is filtered product, with the deionized water repetitive scrubbing to filtrate colourless till, wash unreacted monomer, initiator, tensio-active agent off;
(5) again filter cake is changed in the vacuum drying oven,, can obtain titanium oxide/polyaniline nano fiber hybrid material after then particle being ground at 70-85 ℃ of following vacuum-drying 3-6 hour.When Heating temperature was 180 ℃ under the air-tight state, effect was best.
Titanium oxide/polyaniline nano fiber hybrid material adopts template-mediated polymerization and hydrothermal method to combine and makes.Can realize organic phase and inorganic compound on nanoscale, all the nano-hybrid material of being made up of unidimensional TiOx nano rod and unidimensional polyaniline nano fiber has given such matrix material new premium properties.Not only give full play to different specialities organic and inorganic materials, combined the characteristic of nano material again, realized mutual supplement with each other's advantages.
The invention has the beneficial effects as follows that the thermostability of titanium oxide/polyaniline nano fiber hybrid material and mechanical property height have reduced the cost of conducing composite material, raw material is easy to get, and is cheap, and product is nontoxic, preparation technology is simple, and component and performance are easy to control.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples.
The transmission electron microscope photo of Fig. 1 TiOx nano rod.
The transmission electron microscope photo of Fig. 2 polyaniline nano fiber.
The transmission electron microscope photo of Fig. 3 titanium oxide/polyaniline nano fiber hybrid material.
The transmission electron microscope photo of Fig. 4 titanium oxide/polyaniline nano fiber hybrid material.
The transmission electron microscope photo of Fig. 5 titanium oxide/polyaniline nano fiber hybrid material.
The transmission electron microscope photo of Fig. 6 titanium oxide/polyaniline nano fiber hybrid material.
Fig. 7 TiOx nano rod, polyaniline nano fiber, the UV-vis curve of titanium oxide/polyaniline nano fiber hybrid material,
Among the figure, a, TiOx nano rod, b, polyaniline nano fiber, c, titanium oxide/polyaniline nano fiber hybrid material.
Embodiment
At first the 0.5g titanium dioxide powder is added in the 10M potassium hydroxide solution of 30ml, stir half an hour under the room temperature, all change in the band teflon-lined water heating kettle, air-tight state is heating down, is maintained at 180 ℃ and reacts 48 hours down, product 0.1M hydrochloric acid soln and deionized water repetitive scrubbing and filtration, till filtrate pH value is less than 7, filter cake is changed in the vacuum drying oven,, obtain the TiOx nano rod 80 ℃ of following vacuum-dryings 4 hours.The transmission electron microscope photo of TiOx nano rod as shown in Figure 1, its diameter is 50-200nm, length is the hundreds of nanometer to several microns.The UV-Vis spectrum of TiOx nano rod has strong absorption at ultraviolet band as shown in Figure 7.
Embodiment two (polyaniline nano fiber)
Stir in the 1M aqueous hydrochloric acid with 20mmol aniline monomer and 0.50g polyvinyl pyrrolidone (PVP) adding 60ml, stirring was uniformly dispersed whole system in 24 hours under the room temperature; The 1M hydrochloric acid soln that the 5.0mmol ammonium persulphate is added 60ml stirs, then under quick stirring condition, with the rapid impouring aniline solution of ammonium persulfate solution, polymerization after half an hour is filtered product, with the deionized water repetitive scrubbing to filtrate colourless till, wash unreacted monomer, initiator, tensio-active agent etc. off; Again filter cake is changed in the vacuum drying oven,, can obtain the polyaniline nano fiber particle after then particle being ground 80 ℃ of following vacuum-dryings 4 hours.
Polyaniline nano fiber particulate lens photo as shown in Figure 2, this nanofiber diameter is about 20-40nm, length is about hundreds of nm to several microns. and the UV-Vis spectrum of polyaniline nano fiber has two strong absorption peaks as shown in Figure 7 near 400nm and 700nm wave band.
Embodiment three (titanium oxide/polyaniline nano fiber hybrid material)
At first the 0.5g titanium dioxide powder is added in the 10M potassium hydroxide solution of 30ml, stir half an hour under the room temperature, all change in the band teflon-lined water heating kettle, air-tight state is heating down, is maintained at 180 ℃ and reacts 48 hours down, product 0.1M hydrochloric acid soln and deionized water repetitive scrubbing and filtration, till filtrate pH value is less than 7, filter cake is changed in the vacuum drying oven,, obtain the TiOx nano rod 80 ℃ of following vacuum-dryings 4 hours; Again the TiOx nano of 0.2g rod is added in the 1M aqueous hydrochloric acid of 60ml and stir, then add the 20mmol aniline monomer, continue under the room temperature to stir and whole system was uniformly dispersed in 24 hours; The 1M hydrochloric acid soln that the 5mmol ammonium persulphate is added 60ml stirs, then under quick stirring condition, with the rapid impouring aniline solution of ammonium persulfate solution, polymerization after half an hour is filtered product, with the deionized water repetitive scrubbing to filtrate colourless till, wash unreacted monomer, initiator, tensio-active agent etc. off; Again filter cake is changed in the vacuum drying oven,, can obtain titanium oxide/polyaniline nano fiber hybrid material after then particle being ground 80 ℃ of following vacuum-dryings 4 hours.Adopting the TiOx nano rod is hard template, and the titanium oxide that induced polymerization obtains/its transmission electron microscope photo of polyaniline nano fiber hybrid material is shown in accompanying drawing 3,4.Inflexible TiOx nano rod surface is wound with polyaniline nano fiber as can be seen, has formed the nano-hybrid material of one-dimentional structure.
Embodiment four (titanium oxide/polyaniline nano fiber hybrid material):
At first the 0.5g titanium dioxide powder is added in the 10M potassium hydroxide solution of 30ml, stir half an hour under the room temperature, all change in the band teflon-lined water heating kettle, air-tight state is heating down, is maintained at 180 ℃ and reacts 48 hours down, product 0.1M hydrochloric acid soln and deionized water repetitive scrubbing and filtration, till filtrate pH value is less than 7, filter cake is changed in the vacuum drying oven,, obtain the TiOx nano rod 80 ℃ of following vacuum-dryings 4 hours; Again the TiOx nano of 0.2g rod is added in the 1M aqueous hydrochloric acid of 60ml and stir, then add 20mmol aniline monomer and 0.50g polyvinyl pyrrolidone (PVP), continue under the room temperature to stir and whole system was uniformly dispersed in 24 hours; The 1M hydrochloric acid soln that the 5mmol ammonium persulphate is added 60ml stirs, then under quick stirring condition, with the rapid impouring aniline solution of ammonium persulfate solution, polymerization after half an hour is filtered product, with the deionized water repetitive scrubbing to filtrate colourless till, wash unreacted monomer, initiator, tensio-active agent etc. off; Again filter cake is changed in the vacuum drying oven,, can obtain titanium oxide/polyaniline nano fiber hybrid material after then particle being ground 80 ℃ of following vacuum-dryings 4 hours.Adopting the TiOx nano rod is hard template, and the micella that utilizes tensio-active agent formation simultaneously is as soft template, and the titanium oxide that the dual mould plate induced polymerization obtains/its transmission electron microscope photo of polyaniline nano fiber hybrid material is shown in accompanying drawing 5,6.Inflexible TiOx nano rod surface is wound with polyaniline nano fiber as can be seen, and compares with the embodiment three that does not adopt tensio-active agent, and TiOx nano rod surface parcel has formed the one-dimentional structure nano-hybrid material of core-shell-type fully.The UV-Vis spectrum of titanium oxide/polyaniline nano fiber hybrid material as shown in Figure 7, except near 400nm and 700nm wave band, having two strong absorption peaks, strong absorption has also appearred in the 200-400nm ultraviolet band, shows that this nano-hybrid material has better optical property.
Claims (3)
1, titanium oxide/polyaniline nano fiber hybrid material, it is characterized in that, this material is by being that the TiOx nano rod surface with one dimension Nano structure is wound with the Nano composite granules that polyaniline nano fiber is composited, and wherein the content of TiOx nano rod is 20-70wt%.
2, prepare the method for the described titanium oxide of claim 1/polyaniline nano fiber hybrid material, it is characterized in that the preparation method comprises following several steps:
(1) select for use titanium oxide to make inorganic raw material, aniline is made organic raw material, is doping agent with hydrochloric acid, and ammonium persulphate is an initiator, and aniline monomer is 4:1 with the ratio of ammonium persulphate in the reaction process, and polyvinyl pyrrolidone is a tensio-active agent;
(2) at first the 0.5g titanium dioxide powder is added in the 10-15M potassium hydroxide solution of 30ml, stir half an hour under the room temperature, all change in the band teflon-lined water heating kettle, air-tight state heating down, Heating temperature is 150-200 ℃, reacted 36-72 hour, product, changes filter cake in the vacuum drying oven over to till filtrate pH value is less than 7 with 0.1M hydrochloric acid soln and deionized water repetitive scrubbing and filtration, at 70-85 ℃ of following vacuum-drying 3-6 hour, obtain the TiOx nano rod;
(3) TiOx nano of 0.1-0.5g rod is added in the 1M aqueous hydrochloric acid of 55-65ml and stir, then add 18-20.8mmol aniline monomer and 0.45-0.55g polyvinyl pyrrolidone, continue stirring under the room temperature and whole system was uniformly dispersed in 24-36 hour;
(4) the 1M hydrochloric acid soln with 4.5-5.2mmol ammonium persulphate adding 55-65ml stirs, then under quick stirring condition, with the rapid impouring aniline solution of ammonium persulfate solution, polymerization after half an hour is filtered product, with the deionized water repetitive scrubbing to filtrate colourless till, wash unreacted monomer, initiator, tensio-active agent off;
(5) again filter cake is changed in the vacuum drying oven,, can obtain titanium oxide/polyaniline nano fiber hybrid material after then particle being ground at 70-85 ℃ of following vacuum-drying 3-6 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710011078 CN100523088C (en) | 2007-04-21 | 2007-04-21 | Hybridization material of Nano fiber of titanium oxide / polyaniline, and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710011078 CN100523088C (en) | 2007-04-21 | 2007-04-21 | Hybridization material of Nano fiber of titanium oxide / polyaniline, and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101050304A CN101050304A (en) | 2007-10-10 |
| CN100523088C true CN100523088C (en) | 2009-08-05 |
Family
ID=38781915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710011078 Expired - Fee Related CN100523088C (en) | 2007-04-21 | 2007-04-21 | Hybridization material of Nano fiber of titanium oxide / polyaniline, and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100523088C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105665013A (en) * | 2015-12-28 | 2016-06-15 | 江南大学 | Three-dimensional bionic composite material based on refection elimination and double-layer P/N heterojunction and application thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735610B (en) * | 2009-12-17 | 2011-11-30 | 华东理工大学 | Hybrid of dedoping-state polyaniline/metallic oxide |
| CN102758264B (en) * | 2011-04-28 | 2016-07-06 | 中国科学院化学研究所 | The preparation method of polymer nanofiber and functionalization/hybrid material thereof and application |
| CN105837053A (en) * | 2015-01-13 | 2016-08-10 | 广东工业大学 | Titanium dioxide/polyaniline nano-composite structure and preparation method thereof |
| CN104695035B (en) * | 2015-03-30 | 2017-05-24 | 中国科学院化学研究所 | Preparation method and application of super-hydrophobic nanofibers of coral structure |
| CN110120307A (en) * | 2019-04-03 | 2019-08-13 | 江汉大学 | A kind of preparation method of composite material, composite material and supercapacitor |
| CN111607960A (en) * | 2020-06-12 | 2020-09-01 | 张家港英华材料科技有限公司 | Preparation method of polyaniline nanofiber-titanium dioxide composite |
-
2007
- 2007-04-21 CN CN 200710011078 patent/CN100523088C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 聚苯胺及二氧化钛纳米管基复合材料的电化学电容行为. 王永刚.新疆大学2004届硕士研究生毕业论文. 2004 |
| 聚苯胺及二氧化钛纳米管基复合材料的电化学电容行为. 王永刚.新疆大学2004届硕士研究生毕业论文. 2004 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105665013A (en) * | 2015-12-28 | 2016-06-15 | 江南大学 | Three-dimensional bionic composite material based on refection elimination and double-layer P/N heterojunction and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101050304A (en) | 2007-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100523088C (en) | Hybridization material of Nano fiber of titanium oxide / polyaniline, and preparation method | |
| Ponnamma et al. | Synthesis, optimization and applications of ZnO/polymer nanocomposites | |
| Deivanayaki et al. | Synthesis and characterization of TiO2-doped Polyaniline nanocomposites by chemical oxidation method | |
| CN101407575B (en) | High dispersibility nano-scale poly (3,4-ehtylene dioxythiophene), preparation and use thereof | |
| CN101191016A (en) | Polyaniline/palygorskite nano composite material and preparation method thereof | |
| CN100480302C (en) | Controllable synthesis method for polyaniline nano structure and use thereof | |
| Mini et al. | Nanostructured multifunctional core/shell ternary composite of polyaniline-chitosan-cobalt oxide: Preparation, electrical and optical properties | |
| Ballav et al. | A conducting composite of polyN-vinylcarbazole and polythiophene | |
| Karim et al. | Conducting polyaniline‐titanium dioxide nanocomposites prepared by inverted emulsion polymerization | |
| Ham et al. | PEDOT‐PSS/singlewall carbon nanotubes composites | |
| CN100567395C (en) | A kind of preparation method of azotized chromium-polyaniline nano-composite material | |
| PH26917A (en) | Electrically conductive pigmentary composites | |
| CN100402583C (en) | Method for synthesizing polyaniline nano particles | |
| Gunasekara et al. | Pyrrole coating with in situ polymerization for piezoresistive sensor development-a review | |
| CN101690880B (en) | Method for preparing nano-structure aniline-co-pyrrole copolymer microsphere | |
| CN101003683A (en) | Nano composite material of Nano fiber polyaniline / kaolin | |
| CN1513858A (en) | Preparation method of multihydroxy sesqui siloxane | |
| CN100365059C (en) | Polymer/inorganic nano particle/graphite nano micro-flake three-phase composite material and preparation method thereof | |
| Sudha et al. | Structure–Directing Effect of Renewable Resource Based Amphiphilic Dopants on the Formation of Conducting Polyaniline‐Clay Nanocomposite | |
| Wang et al. | Large flakes of Al–Ti3C2Tx MXene constructing highly ordered layered MXene/ANF films with integrated multifunctionalities | |
| KR20040073183A (en) | Water-soluble conductive polymer composite, preparing method thereof, and antistatic coating composition containing the same | |
| Ballav et al. | High yield polymerisation of aniline and pyrrole in presence of montmorillonite clay and formation of nanocomposites thereof | |
| KR100475413B1 (en) | Soluble polyaniline in organic solvents, process for synthesizing it and its applications | |
| CN102766250B (en) | Polythiophene microballs and preparation method thereof | |
| Tidke et al. | Magnetic susceptibility and frequency dependence ac conductivity of PPY/PANI/V2O5 nanosheets |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090805 Termination date: 20120421 |