CN101837290B

CN101837290B - Titanium dioxide gold granular composite mesoporous film material, preparation method and application

Info

Publication number: CN101837290B
Application number: CN200910047889.8A
Authority: CN
Inventors: 赵晋津; 陈航榕; 施剑林
Original assignee: Shanghai Institute of Ceramics of CAS
Current assignee: Shanghai Institute of Ceramics of CAS
Priority date: 2009-03-20
Filing date: 2009-03-20
Publication date: 2014-04-02
Anticipated expiration: 2029-03-20
Also published as: CN101837290A

Abstract

The invention relates to a titanium dioxide gold granular composite mesoporous film material which is characterized in that a titanium dioxide material has a mesoporous structure; the pore size is between 2 and 10 nm; and the mass percent of gold is between 0.0001% and 10%. An organic template method is adopted for preparing the film material. The prepared titanium dioxide gold granular composite mesoporous film material has efficient catalytic property, can be used for a catalyst, and is especially used for an efficient catalyst for treating environmental pollution.

Description

Titanium dioxide gold granular composite mesoporous film material and preparation method and purposes

Technical field

The present invention relates to a kind of titanium dioxide gold granular composite mesoporous film material and preparation method and purposes, belong to inorganic material catalysis field.

Background technology

Along with the acceleration day by day of current social progress, industrial wastewater, vehicle exhaust and house refuse are more serious to the harm of environment, and serious threat the mankind's health, administer or control disposal of pollutants, have become the common problem of paying close attention in the whole world.

1998, at G.D.Stucky etc. ⁽¹⁾reported first adopts three block polymerization P 123 (poloxalkol) of nonionic to synthesize specific surface under acid condition, since the high six side's phase SBA-15 mesoporous materials of the degree of order, people are synthetic and at molecular sieve to mesoporous material, catalysis, absorption, electrode material, the application aspect such as magnetic material are carried out increasingly extensive research.The mesoporous material of assembling due to soft template has adjustable aperture, high-specific surface area, and good stability, synthesizes simply and receives much concern.The mesoporous film material of soft template assembling not only can improve the inside and outside transfer rate of guest molecule, and enlarge active surface is beneficial to raising catalytic performance simultaneously, chemical property and magnetic performance.Therefore, the mesoporous film material of this soft template assembling is used as catalyst, semi-conducting material, and sensor, electrode material and magnetic material have more wide application prospect.

From patent application in recent years, the application of optically catalytic TiO 2 is in the majority with coating, as US Patent No. 6653356 (2003.11.25 is open), Japan Patent JP2003275601 (2003.9.30 is open), European patent EP 1316532 (2003.6.4 is open) etc. are the patent report of up-to-date optically catalytic TiO 2 coating.But due to low quantum effect and broad stopband (3.0～3.2ev) of titanic oxide material itself, its photocatalysis performance is lower.The mesoporous TiO 2 powder material (J.Am.Chem.Soc.2007,129,4538) that occurs subsequently noble metal Au doping, adopting three block polymerization P123 of nonionic is directed agents, with TiCl ₄for presoma, AuCl ₃for Jin Yuan, by surfactant self assembly and with after-baking, prepare mesoporous TiO 2 gold doping powder body material.Powder body material catalytic performance prepared by this method is still not ideal enough, poor practicability.Yet there are no afterwards the research report of relevant high efficiency photocatalysis performance both at home and abroad.

Summary of the invention

The object of the present invention is to provide a kind of titanium dioxide gold granular composite mesoporous film material and preparation method and purposes, there is no at present this type of associated materials report.

The titanium dioxide gold granular composite mesoporous film material with efficient catalytic performance the present invention relates to has following composition and architectural feature:

Titanic oxide material has meso-hole structure, pore size 2～10nm, and pore-size distribution is narrow, is vertically poroid, and the loading of gold can regulate as required between 0.0001～10% (mass percent).

The preparation method of titanium dioxide gold granular composite mesoporous film material of the present invention comprises the following steps:

According to following molar percentage, organic formwork KLE is dissolved in to ethanol and tetrahydrofuran solution ultrasonic 5 minutes～2 hours completely.

0.2～10nm gold grain 0.0001%～10%

Titanium tetrachloride 0.01%～10%

KLE nonionic template 30%～99%

Oxolane 0.01%～5%

Ethanol 0.1%～10%

Deionized water 0.01%～5%

Nanogold particle is scattered in ethanolic solution, then adds in (1) solution, stir 10～50 minutes.

According to above-mentioned molar percentage, titanium tetrachloride is dripped in above-mentioned solution, stir 1～4 hour.

By dip coated method, at the silica-based or FTO film of preparing on glass, 1～15 millimeter of membrane speed is per second, damp condition 5～30%.

Dry, calcined crystalline 3～18 hours, calcining heat is controlled at 300～700 ℃.

The present invention has efficient catalytic performance, can be used for catalyst, is used in particular for the effective catalyst that processing environment pollutes.

Accompanying drawing explanation

The technological process of the mesoporous film material that the titanium dioxide gold granular of Fig. 1 efficient catalytic performance provided by the invention is compound

Fig. 2 titanium dioxide titanium composite mesoporous film material provided by the invention is at the stereoscan photograph of different Jin Yuan: (a) mesoporous titanium dioxide film, does not mix gold; (b) mesoporous TiO 2 4% gold medal laminated film, gold grain is Jin Yuan; (c) mesoporous TiO 2 4% gold medal laminated film, chlorauride is Jin Yuan.Illustrate that this material is mesoporous film material, gold grain is scattered in mesopore film.

Fig. 3 titanium dioxide titanium provided by the invention composite mesoporous film material one dimension little angle XRD scattering (Fig. 3 B), titanium deoxid film 0.1% (red line); @4% (blue line); The above Jin Yuan of@10% (black line) is gold grain; @4% (green line); These two kinds of Jin Yuan of@10% (gray line) are chlorauride; The little angle of two dimension XRD scattering (illustration 3A, Fig. 3 C) with titanium dioxide@0.1% gold grain film.XRD scattering curve explanation in the little angle of one dimension is along with the increase of gold grain amount, and mesoporous order disappears, and destroyedly falls; In the mesoporous film material that is 4% at gold content, its mesopore orbit still maintains sequence.Two dimension little angle XRD scattering explanation is at thin film planar direction (x y plane) and thickness direction (x z-plane) pattern of retaining hole still, and hole does not have destroyed.

The XRD collection of illustrative plates of the compound mesoporous film material of Fig. 4 titanium dioxide gold granular provided by the invention under different Jin Yuan and gold content, illustrates that in thin-film material, titanium dioxide crystallization is Detitanium-ore-type.

The catalytic degradation effect of the compound mesoporous film material of the titanium dioxide@gold grain of the golden source category of Fig. 5 difference provided by the invention and content to rhodamine B (red line) and methylene blue (blue line).In figure, solid line represents that gold grain is Jin Yuan, and dotted line represents that chlorauride is Jin Yuan.This explanation titanium dioxide 4% gold grain mesopore film is best to organic catalytic performance, is much better than to take the mesoporous film material catalytic performance that chlorauride is Jin Yuan.

The specific embodiment

Below by embodiment and comparative example, further illustrate the present invention.In the following Examples and Comparative Examples, with the catalytic performance of organic matter degradation time representation material, this numerical value is lower, and illustrative material catalytic is better;

Table 1

Embodiment 1:

Under normal pressure, according to each component of appointment in following table 1, organic formwork KLE is dissolved in the mixture of ethanol and oxolane respectively, ultrasonic 20 minutes, until organic formwork dissolves completely, add the nanogold particle being suspended in ethanol, be slowly added dropwise to titanium tetrachloride, stir 10 minutes, resulting solution, after the stirring of 4 hours, is made the precursor aqueous solution of film.Adopt dip coated method, in silicon base, prepare film, in the air ambient of 80 ℃, be dried 2 hours, thereby make solvent evaporation obtain uniform film.After this film is placed in to the air ambient roasting 12 hours of 300 ℃, latter 5 ℃ are per secondly warmed up to 500 ℃, then with 10 ℃, are per secondly warmed up to 610 ℃, are incubated 1 minute, subsequently cooling.Obtaining thickness is the compound film of mesoporous TiO 2@gold grain of 100～200 nanometers, and the molar content of gold grain is 4%.Then, the catalytic of testing film has been listed test result in table 1.

Embodiment 2

By each constituent content of appointment in following table 1, repeat the method for embodiment 1, but the addition of nm of gold reduces, the molar content of controlling gold grain is 0.1% in table 1, to have listed test result.

Embodiment 3

By each constituent content of appointment in following table 1, repeat the method for embodiment 1, but do not add nanogold particle, in table 1, listed test result.

Comparative example 1

By each constituent content of appointment in following table 1, repeat the method for embodiment 1, but the Jin Yuan of film is three hydration chlorauride AuCl ₃3H ₂o, the molar content of gold is 4% in table 1, to have listed test result.

Comparative example 2

By each constituent content of appointment in following table 1, repeat the method for embodiment 1, but the Jin Yuan of film is three hydration chlorauride AuCl ₃3H ₂o, and reduce golden addition, controls golden molar content and is 10% and in table 1, listed test result.

Claims

1. the preparation method of titanium dioxide gold granular composite mesoporous film material, it is characterized in that, under normal pressure, respectively according to mass percent titanium tetrachloride 0.5, nanogold particle 0.006, ethanol 3.8, deionized water 0.43, oxolane 0.764 and organic formwork KLE94.5, organic formwork KLE is dissolved in the mixture of ethanol and oxolane, ultrasonic 20 minutes, until organic formwork dissolves completely, add the nanogold particle being suspended in ethanol, slowly be added dropwise to titanium tetrachloride, stir 10 minutes, resulting solution is after the stirring of 4 hours, make the precursor aqueous solution of film, adopt dip coated method, in silicon base, prepare film, in the air ambient of 80 ℃, be dried 2 hours, thereby make solvent evaporation obtain uniform film, after this film is placed in to the air ambient roasting 12 hours of 300 ℃, latter 5 ℃ are per secondly warmed up to 500 ℃, then with 10 ℃, be per secondly warmed up to 610 ℃, be incubated 1 minute, cooling subsequently, obtain the film that thickness is 100～200 nanometers, the molar content of gold grain is 4%.