Polyaniline/titanium dioxide/clay nanometer composite photocatalyst and preparation method thereof

A titanium dioxide and nano-composite technology, applied in the direction of organic compound/hydride/coordination complex catalysts, physical/chemical process catalysts, chemical instruments and methods, etc., can solve the difficulties of catalyst separation and recovery, small particle size of nano-titanium dioxide, Reduce the number of hydroxyl radicals, etc., to save the acid addition step, save acid consumption, and realize the effect of regeneration and recycling

Active Publication Date: 2012-03-28
CHANGZHOU UNIV
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Problems solved by technology

The suspended state is to suspend the nano-titanium dioxide catalyst evenly in the form of powder in the reaction solution. Since there is almost no mass transfer resistance and the catalyst particles have a large specific surface area, the organic pollutants can fully contact or be easily transferred to the surface of the catalyst particles. It has a higher catalytic efficiency, but due to the small particle size of nano-titanium dioxide, it is easy to lose, and the separation and recovery of the catalyst in the later stage are difficult, making it difficult to be widely used in actual wastewater treatment; catalyst fixation is to use appropriate methods to fix the catalyst. On a suitable carrier, the carrier for immobilizing the catalyst generally includes light-transmitting glass (sheet, tube, ring, bead), quartz fiber, quartz particle, activated carbon, stainless steel and alloy, etc., but the immobilization of the catalyst solves the problem of the suspension state. At the same time, new problems have also arisen, such as the limited effective surface area of ​​organic pollutants in contact with the catalyst, and the existence of mass transfer resistance, so the catalytic efficiency is lower than that of the suspended state
The second is the problem of photocatalytic activity. Since the electron-hole pairs generated by light are easily recombined to generate heat, the number of hydroxyl radicals generated in the photocatalytic process is reduced, and the photocatalytic activity is reduced. Therefore, in recent years, the development of new high-efficiency photocatalysts has become increasingly It has attracted more and more people's attention; a lot of research has been done on improving the photocatalytic activity of titanium dioxide in recent years. Chinese patent CN101721990A discloses a preparation method of a double rare earth element La and Y doped TiO Tetrabutyl nitrate, lanthanum nitrate and yttrium nitrate were used as raw materials, first prepared into a gel, then dried at 60°C to obtain a xerogel, and finally calcined at 400~700°C to obtain La and Y co-doped TiO 2 Photocatalyst, this method requires high temperature calcination, which increases the cost and leads to the agglomeration of nanoparticles. Chinese patent CN101362087A discloses a preparation method of noble metal modified titanium dioxide photocatalyst, by depositing Ag, Au, Noble metals such as Pt and Pd promote the separation of photogenerated electron-hole pairs and improve the activity of titanium dioxide photocatalysts, but the expensive metals such as Ag, Au, Pt and Pd used in this method limit their popularization and application

Method used

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  • Polyaniline/titanium dioxide/clay nanometer composite photocatalyst and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0021] Example 1: 200 g of deionized water was added to 20 g of attapulgite, ultrasonically dispersed for 0.5 hour with a JYD650 intelligent ultrasonic cell pulverizer, and a slurry with a mass ratio of water to attapulgite of 10:1 was prepared.

[0022] At 20°C, add the prepared attapulgite slurry to 60 ml with a molar concentration of 2 mol L -1 In the titanium tetrachloride aqueous solution, stir evenly, acidify for 0.5 hours, heat the system to 95° C., and keep it warm for 4 hours to obtain a titanium dioxide / attapulgite nanocomposite slurry.

[0023] Cool the titanium dioxide / attapulgite nanocomposite slurry to 15 °C, add 2 g of aniline, and use a molar concentration of 1 mol L -1 Aqueous sodium hydroxide solution to adjust the pH value of the system to 1, stir and mix evenly, and then add 21.5 milliliters of it dropwise with a dropper to the mixed system with a molar concentration of 1mol L -1 Ammonium persulfate aqueous solution, the dripping time of the ammonium persu...

Embodiment 2

[0026] Example 2: Add 4000 grams of deionized water to 200 grams of attapulgite, and disperse at high speed (7000 rpm) for 3 hours with a ME100 type high-shear mixing emulsifier, and prepare a mass ratio of water to attapulgite of 20 :1 slurry.

[0027] At 60°C, add the prepared attapulgite slurry to 625 ml with a molar concentration of 4mol L -1 In the aqueous solution of titanium tetrachloride, stir evenly, acidify for 2 hours, heat the system to 80° C., and keep it warm for 10 hours to obtain a titanium dioxide / attapulgite nanocomposite slurry.

[0028] Cool the titanium dioxide / attapulgite nanocomposite slurry to 0 °C, add 30 g of aniline, and use a molar concentration of 3 mol L -1 The pH value of the ammonia solution to adjust the system is 4. After stirring and mixing evenly, add 1610.5 milliliters of the solution dropwise with a dropper to the mixing system and the molar concentration is 0.4mol L -1 Ammonium persulfate aqueous solution, the dropwise addition time of ...

Embodiment 3

[0031] Embodiment 3: Add 1000 grams of deionized water to 200 grams of attapulgite, disperse for 1 hour with a small-scale high-pressure homogenizer (Shanghai Donghua High Pressure Homogenizer Factory), and prepare a mass ratio of water to attapulgite of 5 : 1 slurry, at 0°C, the prepared attapulgite slurry was added to 1000 milliliters with a molar concentration of 0.5mol L -1In the aqueous solution of titanium tetrachloride, stir evenly, acidify for 4 hours, heat the system to 120° C., and keep it warm for 1 hour to obtain a titanium dioxide / attapulgite nanocomposite slurry.

[0032] Cool the titanium dioxide / attapulgite nanocomposite slurry to 30 °C, add 4 g of aniline, and use a molar concentration of 2 mol L -1 Potassium hydroxide aqueous solution to adjust the pH value of the system to 3, after stirring and mixing evenly, add 13.45 milliliters of 1.6 mol L dropwise to the mixing system with a dropper -1 Ammonium persulfate aqueous solution, the dropwise addition time of...

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Abstract

The invention relates to a nanometer TiO2 photocatalyst, in particular to a polyaniline/titanium dioxide/clay nanometer composite photocatalyst and a preparation method thereof. Titanium tetrachloride and clay are firstly used as raw materials, an in-situ synthesis method is adopted for preparing nanometer titanium dioxide/clay composite material, hydrochloric acid generated by titanium tetrachloride hydrolysis is used for providing the acid environment required by aniline polymerization, the polyaniline conductive polymer loaded titanium dioxide surface is synthesized, the conductive polyaniline is used for receiving electrons generated by the photon excitation on the titanium dioxide, the electron-electronhole pair compounding is inhibited, and the photocatalytic performance of the composite material is improved.

Description

technical field [0001] The present invention relates to nanometer TiO 2 The photocatalyst specifically refers to a polyaniline / titanium dioxide / clay nanocomposite photocatalyst and a preparation method thereof. Background technique [0002] Photocatalytic oxidation technology is an emerging modern environmental pollution control technology. Its principle is to irradiate semiconductor materials with light whose energy is equal to or greater than the band gap of semiconductor materials, so that the electrons on the valence band (e - ) is excited to transition to the conduction band, generating corresponding holes in the valence band (h + ), photo-induced holes (h + ) has a very strong ability to gain electrons, and the OH adsorbed on its surface - and H 2 O is oxidized to hydroxyl radicals (OH), and the standard oxidation potential of OH is 2.8eV. It is the strongest oxidant except elemental fluorine, and can completely oxidize most organic substances to CO without select...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/38C02F1/32
Inventor 姚超李超吴凤芹孔泳纪俊玲刘文杰王茂华李霞章
Owner CHANGZHOU UNIV
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