CN101050304A - Hybridization material of Nano fiber of titanium oxide / polyaniline, and preparation method - Google Patents

Abstract

The invention relates to a titanium oxide/polyaniline nanofiber hybrid material and a preparation method thereof. The material is a nanocomposite particle composed of titanium oxide nanorods with one-dimensional nanostructure and polyaniline nanofibers, wherein the content of the titanium oxide nanorods is 20-70 wt%. Titanium oxide is selected as the inorganic raw material, aniline is used as the organic raw material, hydrochloric acid is used as the dopant, ammonium persulfate is used as the initiator, and the ratio of aniline monomer to ammonium persulfate is 4:1 during the reaction process, and polyvinyl alcohol pyrrolidone is used as the surface Active agent; prepared by combining template-induced polymerization and hydrothermal method. The beneficial effect of the present invention is that the thermal stability and mechanical properties of the titanium oxide/polyaniline nanofiber hybrid material are high, the cost of the conductive composite material is reduced, the raw material is easy to obtain, the price is low, the product is non-toxic and harmless, and the preparation process is simple , the components and properties are easy to control, and can realize industrial production and wide application.

Description

Titanium oxide/polyaniline nanofiber hybrid material and preparation method thereof

technical field

The invention relates to a nanometer hybrid material and its preparation technology, in particular to a titanium oxide/polyaniline nanofiber hybrid material and its preparation method.

Background technique

Organic/inorganic composite materials not only combine the elasticity, toughness, and processability of organic materials, but also combine the rigidity, dimensional stability, and thermal stability of inorganic materials. The low-dimensional organic/inorganic composite materials further combine the advantages of nanomaterials, and the composite has a strong synergistic effect, thus exhibiting mechanical, thermal, electrical, magnetic and optical properties different from general macroscopic composite materials.

Due to their unique properties, organic conductive materials have broad application prospects in chemical sensors, batteries, optical materials, electronic cables, electromagnetic shielding, microwave stealth, etc., and have attracted the attention of the scientific and industrial circles. Among many conducting polymers, polyaniline (PANI) has become the most promising due to its diverse structure, unique doping mechanism, excellent electrochemical performance, good chemical stability and conductance tunability. conductive polymers. The conductivity of conductive polymers with micro/nano structures strongly depends on factors such as doping concentration, dopant, synthesis conditions, morphology, pipe diameter, measurement temperature, external pressure, etc. However, conductive polymers have poor processability, The disadvantages of low mechanical strength and high cost of use are thus limited in practical application (Chinese invention patent 2004100989231). In summary, it can be seen that the development of a conductive nanocomposite material with excellent comprehensive performance, low cost and environmental friendliness has become a key issue at present.

Contents of the invention

The purpose of the present invention is to provide a titanium oxide/polyaniline nanofiber hybrid material and a preparation method thereof. The titanium oxide/polyaniline nanofiber hybrid material can be prepared by compounding polyaniline and titanium oxide, which can realize the organic phase and the inorganic phase. Composite at the nanoscale, improve thermal stability and mechanical properties, reduce the cost of conductive composites,

The technical solution of the present invention is a titanium oxide/polyaniline nanofiber hybrid material, which is a nanocomposite particle composed of titanium oxide nanorods with a one-dimensional nanostructure and polyaniline nanofibers with a one-dimensional structure , wherein the content of titanium oxide nanorods is 20-70wt%.

The preparation method of titanium oxide/polyaniline nanofiber hybrid material comprises the following steps:

(1) Titanium oxide is selected as the inorganic raw material, aniline is used as the organic raw material, hydrochloric acid is used as the dopant, and ammonium persulfate is used as the initiator. is a surfactant;

(2) First, add 0.5g of titanium oxide powder into 30ml of 10-15M potassium hydroxide solution, stir at room temperature for half an hour, transfer all of it to a hydrothermal kettle with a polytetrafluoroethylene liner, heat in a closed state, and heat The temperature is 150-200°C, and the reaction is 36-72 hours. The product is washed and filtered repeatedly with 0.1M hydrochloric acid solution and deionized water until the pH value of the filtrate is less than 7. vacuum drying at ℃ for 3-6 hours to obtain titanium oxide nanorods;

(3) Add 0.1-0.5g of titanium oxide nanorods into 55-65ml of 1M hydrochloric acid aqueous solution and stir evenly, then add 18-20.8mmol of aniline monomer and 0.45-0.55g of polyvinyl alcohol pyrrolidone, and continue stirring at room temperature for 24- 36 hours to make the whole system uniformly dispersed;

(4) Add 4.5-5.2mmol ammonium persulfate to 55-65ml of 1M hydrochloric acid solution and stir evenly, then pour the ammonium persulfate solution into the aniline solution rapidly under the condition of rapid stirring, filter the product after half an hour of polymerization, and use Wash with deionized water repeatedly until the filtrate is colorless, and wash off unreacted monomers, initiators, and surfactants;

(5) Transfer the filter cake into a vacuum drying oven, dry it under vacuum at 70-85° C. for 3-6 hours, and then grind the particles to obtain the titanium oxide/polyaniline nanofiber hybrid material. The effect is best when the heating temperature is 180°C in a closed state.

Titanium oxide/polyaniline nanofiber hybrid materials were prepared by combining template-induced polymerization and hydrothermal methods. It can realize the composite of organic phase and inorganic phase on the nanometer scale, and the nano-hybrid material composed of one-dimensional titanium oxide nanorods and one-dimensional polyaniline nanofibers endows this type of composite material with new and excellent properties. It not only gives full play to the different strengths of organic and inorganic materials, but also integrates the characteristics of nanomaterials to achieve complementary advantages.

The beneficial effect of the present invention is that the titanium oxide/polyaniline nanofiber hybrid material has high thermal stability and mechanical properties, reduces the cost of the conductive composite material, has easy-to-obtain raw materials, low price, non-toxic and harmless product, and simple preparation process , components and properties are easy to control.

Description of drawings

The present invention will be further described below in conjunction with drawings and embodiments.

Fig. 1 Transmission electron micrograph of titanium oxide nanorods.

Figure 2 Transmission electron micrographs of polyaniline nanofibers.

Fig. 3 Transmission electron micrograph of titanium oxide/polyaniline nanofiber hybrid material.

Fig. 4 Transmission electron micrograph of titanium oxide/polyaniline nanofiber hybrid material.

Fig. 5 Transmission electron micrograph of titanium oxide/polyaniline nanofiber hybrid material.

Fig. 6 Transmission electron micrograph of titanium oxide/polyaniline nanofiber hybrid material.

Figure 7 UV-vis curves of titanium oxide nanorods, polyaniline nanofibers, titanium oxide/polyaniline nanofiber hybrid materials,

In the figure, a, titanium oxide nanorod, b, polyaniline nanofiber, c, titanium oxide/polyaniline nanofiber hybrid material.

Detailed ways

First, add 0.5g of titanium oxide powder into 30ml of 10M potassium hydroxide solution, stir at room temperature for half an hour, transfer the whole into a hydrothermal kettle with a Teflon liner, heat it in a closed state, and keep it at 180°C for reaction For 48 hours, the product was repeatedly washed and filtered with 0.1M hydrochloric acid solution and deionized water until the pH value of the filtrate was less than 7. The filter cake was transferred to a vacuum drying oven and dried in vacuum at 80°C for 4 hours to obtain titanium oxide nanorods . The transmission electron micrograph of titanium oxide nanorods is shown in Figure 1, with a diameter of 50-200 nm and a length of several hundred nanometers to several microns. The UV-Vis spectrum of titanium oxide nanorods is shown in Figure 7, which has strong absorption in the ultraviolet band.

Example 2 (polyaniline nanofibers)

Add 20mmol of aniline monomer and 0.50g of polyvinylpyrrolidone (PVP) into 60ml of 1M hydrochloric acid aqueous solution and stir, and stir at room temperature for 24 hours to disperse the whole system evenly; add 5.0mmol of ammonium persulfate into 60ml of 1M hydrochloric acid solution and stir evenly, Then, under the condition of rapid stirring, the ammonium persulfate solution was quickly poured into the aniline solution, and after half an hour of polymerization, the product was filtered, and washed repeatedly with deionized water until the filtrate was colorless, and unreacted monomers, initiators, Surfactants, etc.; then transfer the filter cake into a vacuum drying oven, dry it in vacuum at 80°C for 4 hours, and then grind the particles to obtain polyaniline nanofiber particles.

The lens photograph of polyaniline nanofiber particle is shown in Figure 2, and this nanofiber diameter is about 20-40nm, and length is about hundreds of nm to several micrometers. The UV-Vis spectrum of polyaniline nanofiber is shown in Figure 7 , there are two strong absorption peaks near the 400nm and 700nm bands.

Example 3 (Titanium Oxide/Polyaniline Nanofiber Hybrid Material)

First, add 0.5g of titanium oxide powder into 30ml of 10M potassium hydroxide solution, stir at room temperature for half an hour, transfer the whole into a hydrothermal kettle with a Teflon liner, heat it in a closed state, and keep it at 180°C for reaction For 48 hours, the product was repeatedly washed and filtered with 0.1M hydrochloric acid solution and deionized water until the pH value of the filtrate was less than 7. The filter cake was transferred to a vacuum drying oven and dried in vacuum at 80°C for 4 hours to obtain titanium oxide nanorods Add 0.2g of titanium oxide nanorods into 60ml of 1M hydrochloric acid aqueous solution and stir evenly, then add 20mmol of aniline monomer, and continue stirring at room temperature for 24 hours to make the whole system uniformly dispersed; add 5mmol of ammonium persulfate into 60ml of 1M hydrochloric acid solution Stir evenly, then pour the ammonium persulfate solution into the aniline solution quickly under the condition of rapid stirring, filter the product after polymerization for half an hour, and wash repeatedly with deionized water until the filtrate is colorless, washing away unreacted monomers, Initiator, surfactant, etc.; then transfer the filter cake into a vacuum drying oven, dry it in vacuum at 80° C. for 4 hours, and then grind the particles to obtain the titanium oxide/polyaniline nanofiber hybrid material. The transmission electron micrographs of the titanium oxide/polyaniline nanofiber hybrid material obtained by inductive polymerization using titanium oxide nanorods as a hard template are shown in Figures 3 and 4. It can be seen that polyaniline nanofibers are wound on the surface of the rigid titanium oxide nanorods, forming a one-dimensional nano-hybrid material.

Example 4 (Titanium Oxide/Polyaniline Nanofiber Hybrid Material):

First, add 0.5g of titanium oxide powder into 30ml of 10M potassium hydroxide solution, stir at room temperature for half an hour, transfer the whole into a hydrothermal kettle with a Teflon liner, heat it in a closed state, and keep it at 180°C for reaction For 48 hours, the product was repeatedly washed and filtered with 0.1M hydrochloric acid solution and deionized water until the pH value of the filtrate was less than 7. The filter cake was transferred to a vacuum drying oven and dried in vacuum at 80°C for 4 hours to obtain titanium oxide nanorods Add the titanium oxide nanorods of 0.2g in the 1M aqueous hydrochloric acid solution of 60ml and stir evenly, then add 20mmol aniline monomer and 0.50g polyvinylpyrrolidone (PVP), and continue to stir at room temperature for 24 hours to make the whole system uniformly dispersed; Add 5mmol of ammonium persulfate to 60ml of 1M hydrochloric acid solution and stir evenly, then pour the ammonium persulfate solution into the aniline solution under rapid stirring conditions, filter the product after half an hour of polymerization, and wash repeatedly with deionized water until the filtrate is colorless Wash away unreacted monomers, initiators, surfactants, etc.; then transfer the filter cake to a vacuum drying oven, and dry it in vacuum at 80°C for 4 hours, and then grind the particles to obtain titanium oxide/polymer Aniline nanofiber hybrid materials. Titanium oxide nanorods are used as hard templates, and micelles formed by surfactants are used as soft templates. The transmission electron microscope photos of titanium oxide/polyaniline nanofiber hybrid materials obtained by dual template-induced polymerization are shown in Figures 5 and 6. . It can be seen that polyaniline nanofibers are entangled on the surface of the rigid titanium oxide nanorods, and compared with Example 3 without surfactant, the surface of the titanium oxide nanorods is completely wrapped, forming a core-shell type one-dimensional structure nano-hybrid material. The UV-Vis spectrum of the titanium oxide/polyaniline nanofiber hybrid material is shown in Figure 7. In addition to two strong absorption peaks near the 400nm and 700nm bands, there is also a strong absorption in the 200-400nm ultraviolet band, showing that the Nano-hybrid materials have better optical properties.

Claims (3)

1, titanium oxide/polyaniline nano fiber hybrid material is characterized in that, the Nano composite granules that this material is excellent by the TiOx nano with one dimension Nano structure and 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.

3,, the method for preparing the described titanium oxide of claim 1/polyaniline nano fiber hybrid material according to claim 2, it is characterized in that Heating temperature is 180 ℃ under the described air-tight state.

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