CN1186774A

CN1186774A - Large mass TiO2 mesohole solid and preparing method

Info

Publication number: CN1186774A
Application number: CN98111118A
Authority: CN
Inventors: 冯素平; 孟国文; 张立德
Original assignee: INST OF SOLID PHYSICS CHINESE
Current assignee: INST OF SOLID PHYSICS CHINESE
Priority date: 1998-01-14
Filing date: 1998-01-14
Publication date: 1998-07-08
Anticipated expiration: 2018-01-14
Also published as: CN1057982C

Abstract

Through sol-gel process using butyl carbonate and distilled water as material and alcohol as solvent, titanium dioxide solution is prepred, which is then gelatinized, dried and heat treated to obtain the said porous solid TiO2 material. The said porous solid material has porosity over 40%, specific surface area over 70 sq m each gram, aperture in 8-10 nm and lumpiness over 150 cu mm. The said material is used not only as catalyst carrier but also as support for nanomenter grain of semiconductor or metal and for preparing special compound porous material.

Description

Large mass TiO 2 mesohole solid and preparation method

The present invention relates to mesoporous TiO 2 block and preparation.

Titanium dioxide is important inorganic functional material, and it not only has good air-sensitive, wet quick characteristic and higher dielectric properties, also be widely used aspect catalysis, and the range of application of the titanium dioxide powder of nano-scale is wider.In recent years, medium porosity assembling system is owing to have particular performances and important potential using value, and causes people's extensive attention and interest.Present research concentrates on porous silicon, porous silica and porous alumina system mostly, yet to the rare report of the research of mesoporous titanium dioxide assembly system, tracing it to its cause mainly is that the titanium dioxide solid is difficult for obtaining.

Purpose of the present invention just provides a kind of preparation large mass TiO 2 mesohole solid and preparation method thereof.

The inventive method is: use colloidal sol---gel method is a raw material with butyl (tetra) titanate and distilled water, and alcohol is prepared TiO 2 sol for solvent, and gelling again, drying, last thermal treatment make large mass TiO 2 mesohole solid.

Be described in detail the present invention below:

Step 1. with butyl (tetra) titanate and distilled water is raw material, and alcohol is solvent, and Glacial acetic acid is a catalyzer, prepares TiO 2 sol, is encapsulated in the container;

Step 2. will be encapsulated in TiO 2 sol 40～60 ℃ of gelations in baking oven in the container, more aging dry 2～3 weeks under 50～70 ℃ of temperature; Again respectively through 70～80 ℃ 1～2 day; 90～100 ℃ 2～4 days; 120～130 ℃ of 4～6 days dry xerogel pieces that obtain that slowly heat up make the xerogel piece descend with oven temperature at last and slowly cool to room temperature;

Step 3. in 450～600 ℃ of annealing 4～8 hours, temperature rise rate made large mass TiO 2 mesohole solid less than 6 ℃/min to the xerogel piece that step 2 is made in atmosphere furnace.

Used alcohol is propyl carbinol, dehydrated alcohol in the inventive method step 1; The mol ratio of butyl (tetra) titanate and Glacial acetic acid is 1: 1.5～8; The mol ratio of butyl (tetra) titanate and water is 1: 2～8; Butyl (tetra) titanate is 1: 8～14 with the mol ratio of alcohol.

With the porosity of the large mass TiO 2 mesohole solid of the inventive method preparation more than 40%, specific surface＞70m ²g ^-1Pore size distribution is narrow, mainly at 8～10nm; Block volume can reach more than 150 cubic millimeters.

Mesoporous titanium dioxide solid with the inventive method preparation not only can be used as various support of the catalyst, also can be used as the nano particle of upholder assembled semiconductor or metal, in order to prepare multiple novel mesic hole compound with property.In a word, the inventive method and the product of preparing are current material preparation FRONTIER IN SCIENCE, also are the bases of preparation nano structure device of future generation.

Embodiment:

In a beaker, add 34 milliliters of analytical pure butyl (tetra) titanates, add 40 milliliters of dehydrated alcohols again, stir, add 9 milliliters of Glacial acetic acid while stirring;

In another beaker, add 6 ml distilled waters, add 35 milliliters of dehydrated alcohols again, make it dilution, stir;

The mixing solutions of dehydrated alcohol in second beaker and distilled water is slowly splashed in first beaker, obtain yellow clear sol, be encapsulated in the container, be placed on 1 week in 60 ℃ of baking ovens, make it that colloidal sol---gel conversion take place, aging; And then respectively through 70 ℃ 1 day; 80 ℃ 2 days; 100 ℃ 2 days; 120 ℃ obtained the xerogel piece after the slow intensification drying in 4 days; Turn-off the baking oven power supply, just xerogel slowly cools to room temperature; The xerogel piece is put into atmosphere furnace heat-treats; 120 ℃ are incubated 1 hour; In 2 hours, be warming up to 450 ℃, be incubated 4.5 hours; Power cutoff is cooled to room temperature.The mesoporous titanium dioxide solid porosity of preparing is 48%, and specific surface is 80m ²g ^-1Pore size distribution is at 8～10nm; Block volume is more than 160 cubic millimeters.

Claims

1. the preparation method of a large mass TiO 2 mesohole solid is characterized in that, uses colloidal sol---gel method, with butyl (tetra) titanate and distilled water is raw material, and alcohol is solvent, prepares TiO 2 sol, gelling again, drying, last thermal treatment makes large mass TiO 2 mesohole solid.

2. the method for claim 1 is characterized in that:

3. method as claimed in claim 2 is characterized in that, used alcohol is positive ethanol, dehydrated alcohol in the described step 1; The mol ratio of butyl (tetra) titanate and Glacial acetic acid is 1: 1.5～8; The mol ratio of butyl (tetra) titanate and water is 1: 2～8; Butyl (tetra) titanate is 1: 8～14 with the mol ratio of alcohol.

4. the method for claim 1 is characterized in that, adds 34 milliliters of analytical pure butyl (tetra) titanates in a beaker, adds 40 milliliters of dehydrated alcohols again, stirs, and adds 9 milliliters of Glacial acetic acid while stirring; In another beaker, add 6 ml distilled waters, add 35 milliliters of dehydrated alcohols again, make it dilution, stir; The mixing solutions of dehydrated alcohol in second beaker and distilled water is slowly splashed in first beaker, obtain yellow clear sol, be encapsulated in the container, be placed on 1 week in 60 ℃ of baking ovens, make it that colloidal sol---gel conversion take place, aging; And then respectively through 70 ℃ 1 day; 80 ℃ 2 days; 100 ℃ 2 days; 120 ℃ obtained the xerogel piece after the slow intensification drying in 4 days; Turn-off the baking oven power supply, just xerogel slowly cools to room temperature; The xerogel piece is put into atmosphere furnace heat-treats: 120 ℃ are incubated 1 hour; In 2 hours, be warming up to 450 ℃, be incubated 4.5 hours; Power cutoff is cooled to room temperature.

5. the large mass TiO 2 mesohole solid of method preparation according to claim 1 is characterized in that, mesoporous titanium dioxide solid porosity is more than 40%, specific surface＞70m ²g ^-1Pore size distribution is mainly at 8～10nm; Block volume can reach more than 160 cubic millimeters.