JPH08245209A - Fullerene carrying laminar porous body - Google Patents

Abstract

PURPOSE: To provide a Fullerene carrying laminar porous body excellent in catalytic performance and easy to handle by introducing a polar group into Fullerene, adding the resultant water-soluble Fullerene to a laminar compd. swollen with water, bringing them into a reaction and carrying out firing. CONSTITUTION: Fullerene (e.g. C60) is allowed to react with a compd. having a polar group such as a hydroxyl, amino or carboxyl group and active hydrogen in the same molecule (e.g. methanolamine) in a solvent and the polar group is introduced into the Fullerene to produce a water-soluble Fullerene deriv. An aq. soln. of the Fullerene deriv. is added to a laminar clay compd. (e.g. Na montmorillonite or acid clay) swollen with water and they are brought into an intercalation reaction. The resultant product is separated by filtration, washed, dried and fired at 350-600 deg.C to obtain the objective laminar porous body carrying Fullerene as a prop compd. This porous body is useful as a material of a hydrogenation reaction catalyst, a separating membrane, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fullerene-supporting layered porous material which can be used as a catalyst, a separating material and the like.

[0002]

[Prior art and its problems]

BACKGROUND OF THE INVENTION Fullerenes have been attracting attention as compounds having catalytic functions such as hydrogenation reaction catalysts and hydrogen activation catalysts.

[0003]

However, fullerene is a fine powder and it is difficult to use it as a catalyst as it is. Therefore, in order to effectively exhibit the catalytic function of fullerenes and to make the fullerenes easier to handle, it has been desired to develop a compound in which fullerenes are supported on a carrier such as a porous substance.

[0004]

The present invention has been made to solve the above problems. That is, the present invention
(1) A fullerene-supporting layered porous body having fullerene as a pillar compound.

In the fullerene-supporting layered porous material of the present invention, a fullerene derivative in which a polar group is introduced into fullerene to make it water-soluble is intercalated with a layered clay compound swollen with water, and then 350 ° C. to 600 ° C. It can be obtained by firing at.

The fullerene used in the present invention is not particularly limited, but has a carbon number of 60, 70, 76, 78, 82, 8
A fullerene of 4 or the like is used, and a fullerene having a carbon number of 60, 70 is preferable from the viewpoint of easy availability. As these fullerenes, metal-encapsulated fullerenes in which atomic metals such as La, Y, and Sc are included in the molecule may be used.

Specific examples of the polar group introduced into these fullerenes include a hydroxyl group, an amino group, a carboxyl group and a mercapto group. In order to introduce these polar groups into fullerenes, a compound having active hydrogen in the same molecule is separately nucleophilically added to fullerenes.

Specific examples of the compound having these polar groups and active hydrogen can be used: methanolamine, ethanolamine, propanolamine, 2-mercaptoethanol, 3-mercaptopropanol, p-hydroxybenzophenone, p-hydroxybenzaldehyde, p −
Examples thereof include hydroxyaniline, and it is also possible to use two or more of them in combination. Hereinafter, these compounds will be referred to as polar group-containing compounds.

The reaction between these polar group-containing compounds and fullerenes is carried out, for example, as follows. When the group having active hydrogen is a primary or secondary amino group, fullerene is dissolved in a solvent such as toluene or benzene to prepare a solution. The concentration of the solution at this time is 0.1 to 3 wt%,
It is preferably 0.5 to 2 wt%. To this solution, the polar group-containing compound as it is, or tetrahydroxyfuran (THF), methyl isobutyl ketone (MIB
The reaction is carried out by adding K), dissolved in a polar solvent having no active hydrogen such as ether, and stirring at 10 to 110 ° C. for 1 to 48 hours. The amount of the polar group-containing compound used in these reactions is 1 to 80 relative to 1 mol of fullerene.
It is a mole, and preferably 3 to 60 moles.

When the polar group is a hydroxyl group or a mercapto group, the reaction is carried out as follows, for example. Metallic sodium or sodium hydride is added to a previously dehydrated solvent such as THF, MIBK and ether. The polar group-containing compound is added dropwise thereto at room temperature or while cooling with ice, and stirred at 0 ° C to 50 ° C for 30 minutes to 5 hours to obtain a sodium salt. This sodium salt is added dropwise to a solution of fullerene dissolved in a solvent such as toluene or benzene which has been dehydrated in advance, at room temperature or while cooling with ice, and after completion of the addition, the mixture is stirred at 10 ° C to 80 ° C for 1 to 48 hours for the purpose. The compound of At this time, the concentration of the fullerene solution is 0.1 to 3 wt%, preferably 0.5 to 2 wt%. Further, the amount of the polar group-containing compound used in the reaction in this case is 1 to 80 mol, preferably 3 to 60 mol, per 1 mol of fullerene.

After the reaction is completed, water is added to the reaction mixture to separate the oil layer and the water layer. After removing the oil layer, if necessary, toluene or benzene is further added to the aqueous layer to extract and remove unreacted fullerenes. This operation is repeated several times if necessary. The aqueous solution of the fullerene derivative (compound in which a polar group is added to fullerene) thus obtained is used as it is or after being concentrated to a predetermined amount of concentration, if necessary, in the step of supporting the fullerene derivative on the layered compound below. can do. Further, in order to remove unreacted compounds (compounds having a polar group and a functional group having active hydrogen) remaining in the above fullerene derivative aqueous solution, the fullerene derivative aqueous solution is directly or, if necessary, concentrated to separate a preparative thin layer. You may process by chromatography, a thin layer chromatography, etc. The compound obtained by adding a polar group to the fullerene obtained as described above is hereinafter referred to as a fullerene derivative.

Next, the method for producing the fullerene-supporting layered porous material of the present invention will be specifically described. First, the layered compound is dispersed in water and swollen. At this time, the amount of the layered compound added is 0.01 to 10% by weight, preferably 0.1 to 3% by weight, based on water.

The layered compound that can be used in the present invention is
There is no particular limitation as long as it is a layered compound that swells when contacted with water, but specific examples that can be used are Na montmorillonite, Ca montmorillonite, acid clay, synthetic smectite, Na teniolite, Li teniolite, Na hectorite, Li hectorite. And synthetic mica.

Then, an aqueous solution of the fullerene derivative obtained above is added. The amount of the derivative added at this time is 0.1 to 5% by weight, preferably 0.1 to 1% by weight, based on the layered compound. Then, the intercalation reaction is carried out by stirring at 10 to 80 ° C, preferably 20 to 60 ° C for 1 to 36 hours. After completion of the reaction, the product is filtered, washed with water, and freeze-dried or heat-dried. Then, add this to a temperature of 350 to 600 ° C for 1 to 24
The fullerene-supporting layered porous body of the present invention can be obtained by firing in air for a period of time. The calcination can be carried out in air, but if necessary, it can also be carried out in an inert gas such as nitrogen, argon or helium.

[0015]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Synthesis Example 1 300 mg of C60 fullerene (manufactured by Hoechst)
200 ml of toluene after placing in a ml-shaped eggplant-shaped flask
Was added and dissolved. There, 5g of ethanolamine 6g
A solution added to 0 ml of THF was added, and the reaction was carried out by stirring at room temperature for 96 hours. After adding 200 ml of water to the obtained reaction product, the oil layer and the water layer were separated, and the water layer was washed several times with toluene to separate unreacted fullerenes. After removing the solvent under reduced pressure, the reaction product and unreacted ethanolamine were separated by preparative thin layer chromatography. Then, water was removed from the resulting aqueous solution under reduced pressure by heating to obtain 282 mg of a fullerene derivative (A-1) which was a brown powder.

[0017] The infrared absorption spectrum of the obtained compound was measured, absorption derived from fullerene C60 to 576cm ^-1 and 527cm ^-1, the 1100cm ^-1 C-O-C
From absorption, absorption derived from C-N to 1320 cm ^-1, absorption derived from C-H in 2810cm ^-1, 3400
absorption derived from cm ^-1 in the N-H, OH to 3410cm ^-1
Absorption derived from was observed. As a result, the compound (A-1) had the following structure.

Synthesis Example 2 Fullerene derivative (A-1) 50 m obtained in Synthesis Example 1
An aqueous solution prepared by dissolving 50 g of water in 50 ml of water is a synthetic smectite (synthetic smectite SWN (manufactured by Corp Chemical)).
1 g was added to a dispersion of 200 ml of water, and 6
The mixture was stirred at 0 ° C. for 24 hours to carry out an intercalation reaction. After washing with water several times using a centrifuge, vacuum drying was performed at 80 ° C. for 24 hours to obtain 870 mg of a layered compound (B-1) containing a fullerene derivative.

The infrared absorption spectrum of the obtained compound (B-1) was measured and found to be C--O-- at 1100 cm ^-1.
Absorption from C and Si-O-Si, 2860 cm
^The absorption derived from C—H was observed at ⁻¹ , the absorption derived from NH at 3460 cm ⁻¹ , and the absorption derived from OH at 3500 cm ⁻¹ . The interlayer distance measured by X-ray diffraction was 1.31 nm.

Synthesis Example 3 50 m of fullerene derivative (A-1) obtained in Synthesis Example 1
1 g of synthetic mica (synthetic mica (manufactured by Coop Chemical Co.)) in 200 ml of water was added to an aqueous solution in which 50 g of water was dissolved, and the mixture was stirred at 60 ° C. for 24 hours,
An intercalation reaction was performed. After washing with water several times using a centrifuge, vacuum drying was carried out at 80 ° C. for 24 hours to carry out layered compound containing a fullerene derivative (B
-2) 980 mg was obtained.

The infrared absorption spectrum of the obtained compound (B-2) was measured and found to be C--O--at 1100 cm ^-1.
Absorption from C and Si-O-Si, 2880 cm
^The absorption derived from C-H was observed at ^-1 , the absorption derived from NH at 3410 cm ^-1 , and the absorption derived from OH at 3500 cm ^-1 . The interlayer distance measured by X-ray diffraction was 1.33 nm.

Example 1 The layered compound (B-1) obtained in Synthesis Example 2 was calcined at 400 ° C. for 3 hours in an electric furnace in which the air was replaced with nitrogen gas, and the fullerene of the present invention was used as a strut compound. A supporting layered porous body (C-1) was obtained. The infrared absorption spectrum of the obtained fullerene-supporting layered porous body (C-1) was measured, and as a result, it was found that the absorption derived from C—H at 2860 cm ⁻¹ and 346
The absorption due to N—H at 0 cm ⁻¹ had disappeared. Moreover, as a result of measuring the interlayer distance by X-ray diffraction, 1.18 nm
And the specific surface area by the BET method was 125 m ² / g.

Example 2 The layered compound (B-2) obtained in Synthesis Example 3 was fired at 400 ° C. for 3 hours in an electric furnace in which the air was replaced with nitrogen gas, and the fullerene of the present invention was used as a strut compound. A supporting layered porous body (C-2) was obtained. As a result of measuring the infrared absorption spectrum of the obtained fullerene-supporting layered porous body (C-2), the absorption derived from C—H at 2880 cm ⁻¹ and 311
The absorption due to N—H at 0 cm ⁻¹ had disappeared. In addition, as a result of measuring the interlayer distance by X-ray diffraction, it is 1.22 nm.
The specific surface area according to the BET method was 98 m ² / g.

[0024]

The fullerene-supporting layered porous material of the present invention makes it easy to handle fine powder fullerenes while maintaining the catalytic function of fullerenes. Materials for hydrogenation reaction catalysts, hydrogen activation catalysts, and separation membranes. Is useful as

Claims (1)

[Claims] 1. A fullerene-supporting layered porous body comprising fullerene as a supporting compound.