CN105948109A - Preparation method of mesoporous barium titanate particles - Google Patents

Abstract

The invention relates to a method for preparing mesoporous barium titanate particles. The invention adopts a two-step hydrothermal method to prepare mesoporous barium titanate particles. First, titanium oxyhydroxide precipitation was used as the precursor, potassium hydroxide was used as the mineralizer, and K _{2 Ti 6 O 13 nanowires were prepared by hydrothermal reaction at 200°C for 12 hours, and then K 2 Ti 6 O 13 nanowires were prepared} by The wire is the titanium source, using barium hydroxide octahydrate as the barium source, adding a suitable concentration of mineralizer NaOH, adjusting the Ba/Ti ratio and reaction time to affect the nucleation and particle self-assembly process, hydrothermal synthesis of cubic phase mesoporous titanic acid barium particles. The invention has the advantages of simple process, easy control, no pollution, low cost and easy large-scale production, and the prepared mesoporous barium titanate particles have high purity, good dispersion performance and large relative area. It has broad application prospects in the fields of catalysis, adsorption, separation, and sensing.

Description

A kind of preparation method of mesoporous barium titanate particle

technical field

The invention relates to a method for preparing mesoporous barium titanate particles, which belongs to the field of electrodeless non-metallic materials.

Background technique

Nano-mesoporous materials have large specific surface area and pore volume, uniform pore arrangement, and adjustable pore diameter. They have very important applications in the fields of photochemistry, catalysis, and separation. The preparation of silicon-based mesoporous materials generally uses a silica matrix, using tetramethylcationylsilane or tetraethoxysilane as a precursor, and synthesizes mesoporous structure materials through physical and chemical methods. Non-silicon-based mesoporous materials are mainly concentrated in metal oxide mesoporous materials, carbon mesoporous materials, carbonate mesoporous materials and titanium-containing mesoporous materials. Among them, in the study of titanium-containing mesoporous materials, there are many reports on mesoporous titanium dioxide, zirconium dioxide, niobium oxide, tantalum oxide, strontium titanate, etc., but few reports on mesoporous barium titanate. Barium titanate (BaTiO ₃ ) is a widely used and very popular ferroelectric material. The Curie temperature of BaTiO ₃ crystal is 120°C. When the temperature is above 120°C, the barium titanate crystal is paraelectric, and the temperature is 120°C. Below ℃, the barium titanate crystal is ferroelectric and has the potential of photocatalysis, and the preparation of mesoporous barium titanate will further enrich the perovskite photocatalyst.

Contents of the invention

The object of the present invention is to provide a method for preparing mesoporous barium titanate particles with simple process and easy process control.

A preparation method of mesoporous barium titanate particles, comprising the following process steps:

1) 5mM tetrabutyl titanate was dissolved in ethylene glycol methyl ether, and 2mL of ammonia water with a mass concentration of 30% was added to prepare a titanium oxyhydroxide precipitate, which was washed with deionized water for 3 to 5 times;

2) Add the precipitated titanium oxyhydroxide prepared in step 1) into potassium hydroxide mineralizer with a concentration of 6M, conduct a hydrothermal reaction at 200°C for 12 hours, wash with deionized water and ethanol for 3 to 4 times, and place in drying at 60°C to obtain K ₂ Ti ₆ O ₁₃ nanowire powder;

3) dissolving barium hydroxide octahydrate in deionized water, stirring and dissolving to form an aqueous solution of barium hydroxide;

4) Add the K ₂ Ti ₆ O ₁₃ nanowire powder prepared in step 2) to the solution in step 3), stir for no less than 20 minutes to obtain a suspension, and adjust the ratio of the amount of Ba to Ti as 1:1～1.5:1;

5) Add the suspension prepared in step 4) into the sodium hydroxide mineralizer, adjust the concentration of the mineralizer sodium hydroxide to 1.0-7.0M, and stir for at least 30 minutes;

6) Place the reactor liner equipped with reaction materials in step 5) in the reactor, adjust its volume to 1/3 to 4/5 of the volume of the reactor with deionized water, then seal it in the reactor and place Keep it warm in a furnace at 100-220°C. After reacting for 0.5-96 hours, place it in the air and cool it down to room temperature naturally. Take out the reaction product, filter it, wash it with deionized water and 1% nitric acid, and then wash it with deionized water. drying to obtain mesoporous barium titanate particles.

The invention realizes the synthesis of mesoporous barium titanate particles by using K ₂ Ti ₆ O ₁₃ nanowire powder as a precursor, using barium hydroxide octahydrate as a barium source, and sodium hydroxide as a mineralizer. The invention has simple process, easy control, no pollution, low cost and easy production.

Description of drawings

Fig. 1 is the XRD pattern and the SEM photo of K ₂ Ti ₆ O ₁₃ prepared by the present invention;

Fig. 2 is the XRD spectrum of the mesoporous barium titanate particle prepared by the present invention;

Fig. 3 is a SEM photo of mesoporous barium titanate particles prepared in the present invention.

detailed description

Below in conjunction with embodiment further illustrate the present invention.

Example 1

1) 5 mM tetrabutyl titanate was dissolved in ethylene glycol methyl ether, and 2 mL of ammonia water with a mass concentration of 30% was added to prepare a titanium oxyhydroxide precipitate, which was washed three times with deionized water;

2) Add the precipitated titanium oxyhydroxide prepared in step 1) to potassium hydroxide mineralizer with a concentration of 6M, conduct a hydrothermal reaction at 200°C for 12h, wash with deionized water and ethanol four times respectively, and heat at 60°C Drying to obtain K ₂ Ti ₆ O ₁₃ nanowire powder, its XRD pattern and SEM photo are shown in Figure 1;

3) dissolving barium hydroxide octahydrate in deionized water, stirring and dissolving to form an aqueous solution of barium hydroxide;

4) Add the K ₂ Ti ₆ O ₁₃ nanowire powder prepared in step 2) to the solution in step 3), stir for no less than 20 minutes to obtain a suspension, and adjust the ratio of the amount of Ba to Ti as 1.25:1;

5) Add the suspension prepared in step 4) to the sodium hydroxide mineralizer, adjust the concentration of the mineralizer sodium hydroxide to 5.0M, and stir for at least 30 minutes;

6) Place the reactor liner equipped with reaction materials in step 5) in the reactor, adjust its volume to 4/5 of the volume of the reactor with deionized water, then seal it in the reactor and place it in a 200°C Keep warm in the furnace, react for 1 hour, cool down to room temperature naturally in the air, take out the reaction product, filter, wash with deionized water and 1% nitric acid respectively, then wash with deionized water, and dry to obtain mesoporous titanic acid barium nanoparticles. Its XRD spectrum is shown in Figure 2, and the SEM photo is shown in Figure 3.

Example 2

1) 5 mM tetrabutyl titanate was dissolved in ethylene glycol methyl ether, and 2 mL of ammonia water with a mass concentration of 30% was added to prepare a titanium oxyhydroxide precipitate, which was washed three times with deionized water;

2) Add the precipitated titanium oxyhydroxide prepared in step 1) to potassium hydroxide mineralizer with a concentration of 6M, conduct a hydrothermal reaction at 200°C for 12h, wash with deionized water and ethanol four times respectively, and heat at 60°C drying to obtain K ₂ Ti ₆ O ₁₃ nanowire powder;

3) dissolving barium hydroxide octahydrate in deionized water, stirring and dissolving to form an aqueous solution of barium hydroxide;

4) Add the K ₂ Ti ₆ O ₁₃ nanowire powder prepared in step 2) to the solution in step 3), stir for no less than 20 minutes to obtain a suspension, and adjust the ratio of the amount of Ba to Ti as 1:1;

5) Add the suspension prepared in step 4) to the sodium hydroxide mineralizer, adjust the concentration of the mineralizer sodium hydroxide to 7.0M, and stir for at least 30 minutes;

6) Place the reactor liner equipped with reaction materials in step 5) in the reactor, adjust its volume to 1/3 of the volume of the reactor with deionized water, then seal it in the reactor and place it in a 160°C Keep warm in the furnace, after 5 hours of reaction, cool down to room temperature naturally in the air, take out the reaction product, filter, wash with deionized water and 1% nitric acid respectively, then wash with deionized water, and dry to obtain mesoporous titanic acid barium nanoparticles.

Claims (2)

1. the preparation method of a porous barium titanate granule, it is characterised in that comprise the following steps that:

1) 5mM butyl titanate is dissolved in spent glycol methyl ether, and adds the mass concentration of 1～2mL and be The ammonia of 30%, prepares titanium oxyhydroxide precipitation, and deionized water cleans 3～5 times；

2) by step 1) the titanium oxyhydroxide prepared precipitation joins the potassium hydroxide mineralising that concentration is 6M In agent, 200 DEG C of hydro-thermal reactions 12h, and use deionized water, ethanol purge 3～4 times respectively, and at 60 DEG C Dry, prepare K₂Ti₆O₁₃Nano wire powder body；

3) barium hydroxide is dissolved in deionized water, stirring and dissolving, form baryta water.

4) by step 2) prepare K₂Ti₆O₁₃Nano wire powder body joins step 3) solution in, stirring No less than 30 minutes, it is thus achieved that suspension, now, the ratio of the amount of the material of regulation Ba with Ti is 1: 1～1.5: 1；

5) by step 4) prepare suspension join in sodium hydroxide mineralizer, regulate mineralizer hydroxide The concentration of sodium is 1.0～7.0M, stirs at least 30 minutes；

6) by step 5) the reactor inner bag that is configured with reaction mass is placed in reactor, adjusts with deionized water Save that its volume is reactor volume 1/3～4/5, then, is enclosed within reactor, is placed in 100～220 DEG C Stove is incubated, after reacting 0.5～96 hour, is placed in air and is naturally cooling to room temperature, take out product, Filter, clean with the nitric acid of deionized water and 1% respectively, then deionized water cleans, and dries, obtains mesoporous titanium Acid titanate particle.

2. according to the preparation method of a kind of porous barium titanate granule described in claims 1, it is characterised in that: Described butyl titanate, barium hydroxide, potassium hydroxide and sodium hydroxide purity are not less than chemical pure.