CN102503834A - Preparation method for porous sulfo-indium salt - Google Patents
Preparation method for porous sulfo-indium salt Download PDFInfo
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- CN102503834A CN102503834A CN2011102937157A CN201110293715A CN102503834A CN 102503834 A CN102503834 A CN 102503834A CN 2011102937157 A CN2011102937157 A CN 2011102937157A CN 201110293715 A CN201110293715 A CN 201110293715A CN 102503834 A CN102503834 A CN 102503834A
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- sulfo
- transition metal
- thioaluminate
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Abstract
The invention discloses a preparation method for porous sulfo-indium salt, which includes the step of mixing sulfur, indium and dimethylformamide via thermal reaction in solvent for 4-8 days at the temperature ranging from 120 DEG C to 180 DEG C so that the porous sulfo-indium salt is prepared. The molecular formula of the porous sulfo-indium salt is (DMA (dimethylamine)) 6In10S18. Simultaneously, the invention further discloses a method for doping transition metal in sulfo-indium salt, which includes the steps of mixing the transition metal, sulfur, indium and dimethylformamide via thermal reaction in solvent for 4-8 days at the temperature ranging from 120 DEG C to 180 DEG C so that the porous sulfo-indium salt doped with the transition metal is prepared, wherein the transition metal is selected from iron or cobalt. Since the preparation methods adopt conventional, inexpensive and available DMF (dimethylformamide) solvent instead of DMA synthesis, cost and environmental pollution are reduced while the porous sulfo-indium salt or the porous sulfo-indium salt doped with the transition metal are obtained conveniently and cheaply.
Description
Technical field
The present invention relates to a kind of preparation method of microporous materials, be specifically related to a kind of preparation method of porous thioaluminate.
Background technology
Because the constructional feature and the special performance of microporous materials demonstrate very strong application prospect in industry, be applied to many aspects such as catalysis, separation, atmosphere storage like aluminosilicate.Since Barrer in 1948 etc. synthesized artificial zeolite's molecular sieve first, people constantly made great efforts to develop new porous material, have obtained many new oxide poromerics.For widening the conventional use of poromerics, with the TO in the oxide compound framework
4Tetrahedron is by TS
4After the replacement, the semiconductor property of oxide porous property and chalcogen combines, and porous chalcongen semiconductor material has obtained attention, becomes very active field.The chalcogen compound that this type has particular structure utilizes organic amine as structure directing reagent or template usually; The employing hydrothermal method is synthetic; The potential application in aspect such as concurrent present catalysis, IX, pl-, ionic conductance, semi-conductor (referring to: N.Zheng, X.Bu and P.Feng, Science 2002; 298,2366-2369; Nature, 2003,426,428-432.).
Is that solvent has synthesized compound (DMA) at Parise in 1998 with the mixing solutions of n n dimetylaniline (DMA) and water
6In
10S
18, its structure for the interspersed pore passage structure that is polymerized by tetrahedral cluster (referring to Christopher L.Cahill, Younghee Ko, John B.Parise.Chem.Mater.1998,10,19-21.).But n n dimetylaniline is low-flash (17.8 ℃) pungency inflammable substance, is prone to cause environmental pollution.
Some organic amine ion in the porous thioaluminate can carry out IX with metals ion.The method that in the past adopts was with in porous crystal dipping and the metal ion solution, through in a few days even tens days slow diffusion and obtain mixing.This method long reaction time, it is inhomogeneous to mix.
Summary of the invention
Goal of the invention of the present invention provides a kind of preparation method of porous thioaluminate; Adopt solvent-thermal method; With common agents N (DMF) is reaction solvent; Utilize its n n dimetylaniline (DMA) that in reaction, self generates for structure directing reagent or template, can make things convenient for to prepare thioaluminate at an easy rate with pore space structure.Further, the present invention also utilizes the method for reaction in to prepare the thioaluminate of containing transition metal.
For reaching the foregoing invention purpose; The technical scheme that the present invention adopts is: a kind of preparation method of porous thioaluminate; Sulphur, indium, N are mixed, under 120～180 ℃, through solvent thermal reaction 4～8 days; Prepare the porous thioaluminate, the molecular formula of said porous thioaluminate is (DMA)
6In
10S
18
In the technique scheme, the mol ratio of sulphur and indium is 3～5: 1.
In the technique scheme, N (DMF) can be used as reaction solvent on the one hand, utilizes its n n dimetylaniline (DMA) that in reaction, self generates to be structure directing reagent or template on the other hand.
In the technique scheme, solvent thermal reaction generally all carries out in airtight reactor drum, and solvent can produce autogenous pressure in airtight reactor drum; In the optimized technical scheme, the volume of N is 1: 2～5 with the volumetrical of reactor drum ratio; Said reactor drum is the stainless steel cauldron of inner liner polytetrafluoroethylene.
In the technique scheme, the molecular formula of said porous thioaluminate is (DMA)
6In
10S
18, this compound is colourless vesicular structure, can be used for ion isolation and catalysis.
Further, the present invention also utilizes the method for reaction in to prepare the thioaluminate of containing transition metal.A kind of preparation method of thioaluminate of containing transition metal: transition metal, sulphur, indium and N are mixed, under 120～180 ℃,, prepare transient metal doped porous thioaluminate through solvent thermal reaction 4～8 days; Said transition metal is selected from: iron or cobalt.
In the technique scheme, the mol ratio of sulphur, indium, transition metal is 3～5: 1: 1.
The principle of technique scheme is mainly: because the DMA volume is easy to and other IX for a short time, transition-metal Fe or/and Co is incorporated in the above-mentioned binary solvent hot system, is made the part Fe of reaction in generation
2+, Co
2+Substitute as balance cation among the hole of protonated DMA entering indium sulfur compound framework, single stage method has been synthesized the indium sulfur compound that is doped with transition-metal cation.
The transient metal doped porous thioaluminate that adopts technique scheme to prepare has the spectral absorption band of broad, and the semiconductor property of indium sulfide and big surface are arranged again, can be used as a kind of catalytic material.
Because the technique scheme utilization, the present invention compared with prior art has advantage:
1. the present invention adopts conventional and cheap and easy to get and safe DMF solvent to replace synthesizing of DMA; Utilize its generated in-situ n n dimetylaniline (DMA) in reaction to be structure directing reagent or template; When conveniently having obtained having the thioaluminate of pore space structure at an easy rate, also reduced cost and reduced pollution environment;
2. the present invention is incorporated into transition-metal Fe and Co in the above-mentioned binary solvent hot system, the Fe that utilizes reaction in to generate
2+, Co
2+Partly substitute as balance cation among the hole of protonated DMA entering indium sulfur compound framework, single stage method has been synthesized the indium sulfur compound that is doped with transition-metal cation.
Description of drawings
Fig. 1 is the product (DMA) that obtains among the embodiment one
6In
10S
18X ray single crystal diffraction structure iron.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further described:
Embodiment one: (58mg, 0.5mmol), (64mg 2mmol) joins among the 10mL DMF sulphur powder, then reactant is mixed the stainless steel cauldron (volume 18mL) that places inner liner polytetrafluoroethylene with the indium silk.Reaction kettle is put in 160 ℃ of baking ovens of people, at the cool to room temperature gradually after 4 days of reaction under the autogenous pressure condition.Product dries under room temperature after filtration and raw spirit washing, obtains colourless rhombus microcrystal, is porous thioaluminate (DMA)
6In
10S
18, calculate productive rate by indium and be about 38%.
Adopt the structure of X ray single crystal diffraction technical Analysis products therefrom, get Fig. 1, wherein, Figure 1A is a tetrahedron InS clustering architecture; Figure 1B and Fig. 1 C bunch banded vesicular structure figure that serves as reasons.
Compound (DMA)
6In
10S
18The crystal structure determination parameter see the following form:
Compound (DMA)
6In
10S
18Part bond distance
And bond angle (°) see the following form:
Embodiment two: with the indium silk (58mg, 0.5mmol), the sulphur powder (64mg, 2mmol) and iron powder (112mg 2mmol) joins among the 10mL DMF, then reactant is mixed the stainless steel cauldron (volume 18mL) place inner liner polytetrafluoroethylene.Reaction kettle is put in 160 ℃ of baking ovens of people, at the cool to room temperature gradually after 4 days of reaction under the autogenous pressure condition.Product dries under room temperature after filtration and raw spirit washing, obtains purple rhombus microcrystal, Fe in the atomic absorption proof dopant material
2+Content be 24.5mg/g.
With the indium silk (58mg, 0.5mmol), the sulphur powder (64mg, 2mmol) and cobalt powder (118mg 2mmol) joins among the 10mL DMF, then reactant is mixed the stainless steel cauldron (volume 18mL) place inner liner polytetrafluoroethylene.Reaction kettle is put in 160 ℃ of baking ovens of people, at the cool to room temperature gradually after 4 days of reaction under the autogenous pressure condition.Product dries under room temperature after filtration and raw spirit washing, obtains yellow rhombus microcrystal, Co in the atomic absorption proof dopant material
2+Content be 13.5mg/g.
Adopt (DMA) of X ray single crystal diffraction technology to above-mentioned doping iron
6In
10S
18Crystalline structure analyze, gained is the result see the following form:
(DMA) of doping iron
6In
10S
18Part bond distance
And bond angle (°) data see the following form:
Dopant ion is evenly distributed in the present embodiment gained material, has the spectral absorption band of broad, and its color changes with the difference of dopant ion, and has the semiconductor property of indium sulfide and the catalytic property of transition metal ion, can be used as catalytic material.
Claims (5)
1. the preparation method of a porous thioaluminate; It is characterized in that: sulphur, indium, N are mixed, under 120～180 ℃, through solvent thermal reaction 4～8 days; Prepare the porous thioaluminate, the molecular formula of said porous thioaluminate is (DMA)
6In
10S
18
2. according to the preparation method of the said porous thioaluminate of claim 1, it is characterized in that the mol ratio of sulphur and indium is 3～5: 1.
3. according to the preparation method of the said porous thioaluminate of claim 1, it is characterized in that solvent thermal reaction carries out in airtight reactor drum, used solvent is a N, and the volume of N is 1: 2～5 with the volumetrical of reactor drum ratio.
4. the method for a containing transition metal in thioaluminate is characterized in that, transition metal, sulphur, indium and N are mixed, and under 120～180 ℃, through solvent thermal reaction 4～8 days, prepares transient metal doped porous thioaluminate; Said transition metal is selected from: iron or cobalt.
According to claim 4 said in thioaluminate the method for containing transition metal, it is characterized in that the mol ratio of sulphur, indium, transition metal is 3～5: 1: 1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101808985A (en) * | 2007-11-28 | 2010-08-18 | 江原大学校产学协力团 | Methods for the synthesis of organic sulfides by using sulfides and organic sulfur-indium complexes |
| CN102134092A (en) * | 2011-02-17 | 2011-07-27 | 四川大学 | Simple preparation method of hollow-spherical and flower-shaped indium oxide with secondary structure and application |
-
2011
- 2011-09-29 CN CN2011102937157A patent/CN102503834B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101808985A (en) * | 2007-11-28 | 2010-08-18 | 江原大学校产学协力团 | Methods for the synthesis of organic sulfides by using sulfides and organic sulfur-indium complexes |
| CN102134092A (en) * | 2011-02-17 | 2011-07-27 | 四川大学 | Simple preparation method of hollow-spherical and flower-shaped indium oxide with secondary structure and application |
Non-Patent Citations (1)
| Title |
|---|
| CHRISTOPHER L. CAHILL ET AL.: "A Novel 3-Dimensional Open Framework Sulfide Based upon the [In10S20]10- Supertetrahedron: DMA-InS-SB1", 《CHEM. MATER.》 * |
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