Method for preparing Keggin polycation chloride crystal

Abstract

The invention provides a novel method for preparing Keggin-GaAl12 chloride single crystal and polycrystalline powder, and belongs to the technical field of inorganic high polymer synthesis. The inorganic polymer cluster MeAl12 ([MeO4Al12(OH)24(H2O)12]7+, Me=Al and Ga) with thirteen metal cores is a typical Keggin type polycation, and occupies an important position in modern material chemistry. However, Keggin- MeAl12 (Me = Al and Ga) chloride crystals are not obtained. In the method, a spontaneous hydrolysis product polyaluminum chloride PAC solid is dissolved in a methanol solvent, a galliumchloride solid is dissolved in the solution, and slow crystallization is performed at room temperature to precipitate the Keggin-GaAl12 chloride crystal. The obtained single crystal particles are confirmed to have a Keggin type structure by X-ray single crystal diffraction analysis.

Description

Technical field

[0001] The invention relates to the technical field of inorganic high molecular polymer synthesis, in particular to a novel preparation of Keggin-GaAl 12 Chloride single crystal and polycrystalline powder method. Background technique

[0002] Inorganic polymer cluster compound MeAl with thirteen metal cores 12 ([MeO 4 Al 12 (OH) 24 (H 2 O) 12 ] 7+ , Me=Al, Ga) is a typical Keggin polycation, which occupies an important position in modern material chemistry. Keggin-MeAl 12 (Me=Al, Ga) polymeric chlorides are widely used in all aspects of production and life: sewage treatment chemicals, surfactants, additives for nanomaterials, pillaring agents for montmorillonite materials, coal dyes for fuels , And used as the main ingredient of deodorant and antiperspirant, etc.

[0003] Keggin-Al 13 And Keggin-GaAl 12 The polymer chloride is an important form of the hydrolysis reaction of main group III elements. Its formation mechanism and preparation process have been extensive...

Examples

Embodiment 1

[0030] (1) PAC solid-phase synthesis reaction: at 80℃, slowly melt 3.7g aluminum powder into 87ml C=5mol / lAlCl 3 In the solution, make the degree of alkalinity 0.8. After all the aluminum powder has reacted, filter the solution and evaporate at room temperature. The obtained solid is washed with isopropanol to obtain the PAC solid, which is dried in an oven for use.

[0031] (2) Keggin-GaAl 12 Chloride synthesis reaction: Dissolve 4.5g of the above PAC solid in 25ml methanol, sonicate in an ultrasonic instrument for about 10 minutes, after all the solids are dissolved, the solid GaCl 3 Dissolve in the solution, make n(Al) / n(Ga)=1.6, evaporate and crystallize at room temperature. Get pure Keggin-GaAl in 15 days 12 Chloride crystals.

Embodiment 2

[0033] (1) PAC solid-phase synthesis reaction: 2.6g of pure Al(OH) 3 Slowly dissolve in 12ml C=5.1mol / l HCl solution. After all is dissolved, add 50ml water to make the alkalinity 1.2. At 80°C, after all the solids have reacted, the solution is filtered and evaporated at room temperature. The obtained solid is washed with isopropanol to obtain PAC solid, which is dried in an oven for use.

[0034] (2) Keggin-GaAl 12 Chloride synthesis reaction: Dissolve 4.5g PAC solid in 25ml methanol, sonicate in an ultrasonic instrument for about 10 minutes, after the solids are all dissolved, remove the solid GaCl 3 Dissolve in the solution, make n(Al) / n(Ga)=6.4, evaporate and crystallize at room temperature. Get pure Keggin-GaAl in 15 days 12 Chloride crystals.

Embodiment 3

[0036] (1) PAC solid-phase synthesis reaction: at 80℃, slowly add 19.3g aluminum powder to 103ml C=5.3mol / lAlCl 3 In the solution, make the degree of alkalinity 1.3. After all the aluminum powder has reacted, filter the solution and evaporate at room temperature. The obtained solid is washed with isopropanol to obtain PAC solid, which is dried in an oven for use.

[0037] (2) Keggin-GaAl 12 Chloride synthesis reaction: Dissolve 4.5g PAC solids in 25ml methanol, sonicate them in an ultrasonic instrument for about 10 minutes, after all the solids are dissolved, add solid GaCl 3 Dissolve in the solution, make n(Al) / n(Ga)=26, evaporate and crystallize at room temperature. Get pure Keggin-GaAl in 15 days 12 Chloride crystals.

[0038] In the above cases, single crystal particles with a size of about 3mm and polycrystalline powders can be obtained. The analysis results are shown in the attachment figure 1 , 2, 3.

Technical field

[0001] The invention relates to the technical field of inorganic high molecular polymer synthesis, in particular to a novel preparation of Keggin-GaAl 12 Chloride single crystal and polycrystalline powder method. Background technique

[0002] Inorganic polymer cluster compound MeAl with thirteen metal cores 12 ([MeO 4 Al 12 (OH) 24 (H 2 O) 12 ] 7+ , Me=Al, Ga) is a typical Keggin polycation, which occupies an important position in modern material chemistry. Keggin-MeAl 12 (Me=Al, Ga) polymeric chlorides are widely used in all aspects of production and life: sewage treatment chemicals, surfactants, additives for nanomaterials, pillaring agents for montmorillonite materials, coal dyes for fuels , And used as the main ingredient of deodorant and antiperspirant, etc.

[0003] Keggin-Al 13 And Keggin-GaAl 12 The polymer chloride is an important form of the hydrolysis reaction of main group III elements. Its formation mechanism and preparation process have been extensive...

Examples

Embodiment 1

[0030] (1) PAC solid-phase synthesis reaction: at 80℃, slowly melt 3.7g aluminum powder into 87ml C=5mol / lAlCl 3 In the solution, make the degree of alkalinity 0.8. After all the aluminum powder has reacted, filter the solution and evaporate at room temperature. The obtained solid is washed with isopropanol to obtain the PAC solid, which is dried in an oven for use.

[0031] (2) Keggin-GaAl 12 Chloride synthesis reaction: Dissolve 4.5g of the above PAC solid in 25ml methanol, sonicate in an ultrasonic instrument for about 10 minutes, after all the solids are dissolved, the solid GaCl 3 Dissolve in the solution, make n(Al) / n(Ga)=1.6, evaporate and crystallize at room temperature. Get pure Keggin-GaAl in 15 days 12 Chloride crystals.

Embodiment 2

[0033] (1) PAC solid-phase synthesis reaction: 2.6g of pure Al(OH) 3 Slowly dissolve in 12ml C=5.1mol / l HCl solution. After all is dissolved, add 50ml water to make the alkalinity 1.2. At 80°C, after all the solids have reacted, the solution is filtered and evaporated at room temperature. The obtained solid is washed with isopropanol to obtain PAC solid, which is dried in an oven for use.

[0034] (2) Keggin-GaAl 12 Chloride synthesis reaction: Dissolve 4.5g PAC solid in 25ml methanol, sonicate in an ultrasonic instrument for about 10 minutes, after the solids are all dissolved, remove the solid GaCl 3 Dissolve in the solution, make n(Al) / n(Ga)=6.4, evaporate and crystallize at room temperature. Get pure Keggin-GaAl in 15 days 12 Chloride crystals.

Embodiment 3

[0036] (1) PAC solid-phase synthesis reaction: at 80℃, slowly add 19.3g aluminum powder to 103ml C=5.3mol / lAlCl 3 In the solution, make the degree of alkalinity 1.3. After all the aluminum powder has reacted, filter the solution and evaporate at room temperature. The obtained solid is washed with isopropanol to obtain PAC solid, which is dried in an oven for use.

[0037] (2) Keggin-GaAl 12 Chloride synthesis reaction: Dissolve 4.5g PAC solids in 25ml methanol, sonicate them in an ultrasonic instrument for about 10 minutes, after all the solids are dissolved, add solid GaCl 3 Dissolve in the solution, make n(Al) / n(Ga)=26, evaporate and crystallize at room temperature. Get pure Keggin-GaAl in 15 days 12 Chloride crystals.

[0038] In the above cases, single crystal particles with a size of about 3mm and polycrystalline powders can be obtained. The analysis results are shown in the attachment figure 1 , 2, 3.

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