CN100450609C - Hybridization materials of polymetallic salts of oxygen and acid / mesoporous molecular sieve, and preparation method - Google Patents
Hybridization materials of polymetallic salts of oxygen and acid / mesoporous molecular sieve, and preparation method Download PDFInfo
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- CN100450609C CN100450609C CNB2006100973641A CN200610097364A CN100450609C CN 100450609 C CN100450609 C CN 100450609C CN B2006100973641 A CNB2006100973641 A CN B2006100973641A CN 200610097364 A CN200610097364 A CN 200610097364A CN 100450609 C CN100450609 C CN 100450609C
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- molecular sieve
- silicotungstate
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Abstract
A multimetallic salt of oxygenic acid-mesoporous molecular sieve hybrid material is composed of mesoporous SiO2 molecular sieve and SiW11O39 [O (SiO) 2]. Its preparing process includes such steps as dissolving P123 in diluted hydrochloric acid, heating, dropping ethyl n-silicate, pre-hydrolyzing, adding K8SiW11O39.12H2O and water, crystallizing, ageing, filtering, water washing, drying in the air, and removing template P123 by alcohol.
Description
Technical field
The invention belongs to technical field of inorganic material, be specifically related to hybrid material of a kind of silicotungstate and mesopore molecular sieve covalent bond and preparation method thereof.
Technical background
Polyoxometallate (also claiming heteropoly compound) is as outstanding catalysis material, has the not available excellent characteristic of traditional catalyst, from the seventies in 20th century Japan since making catalyst with heteropoly acid in the propylene hydration production and successfully realizing industrialization, polyoxometallate is subjected to people's common concern as the catalyst in organic synthesis and the petrochemical industry, particularly in recent years, along with the generally attention of people, adopt eco-friendly polyoxometallate to replace traditional liquid acid catalyst (HF, AlCl to environmental problem
3, H
2SO
4Deng) and some cost an arm and a leg, non-ambient close friend's oxidation-reduction catalysis agent seems and becomes more and more important.In addition, people also find polyoxometallate in the environmental improvement field in recent years, as organic pollution aspect in the photocatalytic degradation water good catalytic action are arranged.
Yet utilize polyoxometallate also to have following limitation as all kinds of catalyst at present: at first, the water-soluble and polar organic solvent of many polyoxometallates is so reclaim difficulty in water and some organic solvents are done the reaction of medium.Secondly, its specific area is little, is unfavorable for giving full play to catalytic activity.If polyoxometallate is loaded on the porous carrier materials, then not only can improve its surface area greatly, improve its utilization rate and catalytic activity, and owing to be the heterogeneous catalysis process, can make technological process simplify, and the recycling of realization catalyst, thereby make polyoxometallate catalyst obtain to use widely.In various carrier materials, mesopore molecular sieve is a kind of desirable porous material that is used for Preparation of Catalyst with high surface area, regular pore structure.
At present using infusion process aspect the load of polyoxometallate both at home and abroad more.People such as the Wu Yue of Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences have reported the research [Wu Yue that goes up carried heteropoly acid at different porous carrier (as silica, titanium oxide, aluminium oxide, active carbon, bentonite, diatomite etc.), Ye Xingkai, poplar Xiang Guang etc., " Journal of Molecular Catalysis ", 1996,10,299-319]; On the mesopore molecular sieve carrier, both at home and abroad the researcher generally also adopt infusion process carry out the load of polyoxometallate [Sun Yu, happy English is red, Li Huiyun is highly grown " chemical journal ", 1999,57,746-753; D.Brunel, A.C.Blanc, A.Galarneau, F.Fajula, Cataysis Today, 2002,73,139-152].The composite that obtains in this way, lack strong chemistry contact between polyoxometallate and carrier, mainly be carried on the carrier by physical action, therefore, though it is more stable in some gas-solid phase reactions, but in the reaction that has polar solvent or water to participate in, polyoxometallate still is easy to solution-off and runs off.
Summary of the invention
The objective of the invention is at the immobilized not firm shortcoming of polyoxometallate in the existing support type polyoxometallate catalysis material, develop a kind of can firmly immobilized polyoxometallate composite on high surface area carrier-mesopore molecular sieve.The characteristics of this material support type composite different from the past are: 1) between polyoxometallate and the mesopore molecular sieve by chemical bond (covalent bond) binding, even like this in polarizable medium, polyoxometallate also is difficult for the solution-off loss.2) the synthetic preparation process of this material was with the support type composite was different in the past: synthetic and the surface bonded of polyoxometallate of mesopore molecular sieve are finished simultaneously, the synthetic hybridization materials of polymetallic salts of oxygen and acid/mesoporous molecular sieve that obtains of a step.At present, this with polyoxometallate by the covalent bond binding to the mesopore molecular sieve surface, and one go on foot the research synthesize hybrid material and still be not reported.
For achieving the above object, the present invention has taked following measure: 1) adopt the vacant unsaturated silicotungstate (SiW in surface
11) as reactant, such polyoxometallate surface exists reaction site, can binding take place with the SiOH species effect on mesopore molecular sieve surface.2) adopt certain hour to carry out the prehydrolysis of TEOS, to guarantee SiW
11Adding can not cross the assembling and the structure of earth effect mesopore molecular sieve structure, thereby obtain order mesoporous structure.3) for avoiding the pyrolytic of polyoxometallate, the present invention adopts solvent (ethanol) extracting (rather than high-temperature roasting) removed template method.
In view of the above, the present invention has prepared a kind of hybridization materials of polymetallic salts of oxygen and acid/mesoporous molecular sieve.The feature of this hybrid material is: silicotungstate is not to be carried on the mesopore molecular sieve surface simply, but and link with covalent bond between the mesopore molecular sieve, thereby polyoxometallate is immobilized securely in the mesoporous material surface.The formation of this hybrid material is: silica mesoporous zeolite and SiW
11O
39[O (SiO)
2]
6-Wherein the quality percentage composition of silicotungstate is (with SiW
11O
39Meter)≤30%.This hybrid material has orderly six sides or class hexagonal hole battle array structure, and the aperture is 6.0～7.5 nanometers, and pore volume is 0.35～0.80cm
3/ g, specific area is 300～600m
2/ g.
The present invention's hybridization materials of polymetallic salts of oxygen and acid/mesoporous molecular sieve is the hybrid material for preparing in order to the below method: dissolving triblock copolymer EO
20PO
70EO
20(P123) (M
Av=5800) in watery hydrochloric acid, be warming up to 40 ℃.Under this temperature, drip ethyl orthosilicate (TEOS), and make its prehydrolysis certain hour (according to used SiW
11What, the prehydrolysis time was controlled at 30 minutes～2 hours), add K then
8SiW
11O
3912H
2O (SiW
11) and a certain amount of water, make the mol ratio (to 1gP123) of each material in the system be: (0.01-x) TEOS: x K
8SiW
11O
3912H
2O: 0.06HCl: 1.96H
2O, wherein x=0.0001～0.001.Continue to stir crystallization, aging in the insulating box; Filter, wash, dry; With ethanol is solvent, with Soxhlet extractor extracting sample removed template method P123, promptly gets the present invention's hybrid material.
The synthetic method of the present invention's hybridization materials of polymetallic salts of oxygen and acid/mesoporous molecular sieve is as follows: the template agent that synthesising mesoporous molecular sieve is used is dissolved in the watery hydrochloric acid, and 40 ℃ add ethyl orthosilicate (TEOS), polyoxometallate and a certain amount of water down.Through crystallization, aging hybrid material, and be that solvent comes removed template method with ethanol.
Specifically, the synthetic of the present invention's hybrid mesoporous material finished as follows:
Dissolving triblock copolymer EO
20PO
70EO
20(P123) (M
Av=5800) in 2mol/L hydrochloric acid, be warming up to 40 ℃.Under this temperature, drip ethyl orthosilicate (TEOS), and make its prehydrolysis certain hour (according to used SiW
11What, the prehydrolysis time was controlled at 30 minutes～2 hours), add K then
8SiW
11O
3912H
2O (SiW
11) and a certain amount of water, make the mol ratio (to 1gP123) of each material in the system be: (0.01-x) TEOS: x K
8SiW
11O
3912H
2O: 0.06HCl: 1.96H
2O, wherein x=0.0001～0.001.Continue to stir crystallization, total crystallization time (containing the prehydrolysis time) is 26 hours, wears out 24 hours in 60～100 ℃ of insulating boxs again.Sample filters after being chilled to room temperature, washing, dries in the air.With ethanol is solvent, with 30～40 hours removed template method P123 of Soxhlet extractor extracting sample, promptly gets the present invention's hybrid material.
Through ICP, XRD, IR, TEM, UV/DRS, N
2The adsorption-desorption Experimental Characterization proves: 1) in the present invention's the hybrid material, the Keggin structure of polyoxometallate keeps complete, vacant silicotungstate (SiW
11) with the SiOH species binding on mesopore molecular sieve surface, formed saturated silicotungstate species SiW
11O
39[O (SiO)
2]
6-2) the present invention's hybrid material has orderly six sides or class hexagonal hole battle array structure, and the aperture is 6.0～7.5 nanometers, and pore volume is 0.35～0.80cm
3/ g, specific area is 300～600m
2/ g.3) by regulating SiW in the preparation process
11Inventory, can regulate the content of silicotungstate in the final gained hybrid material.But with SiW
11The increase of inventory, the content of silicotungstate is (with SiW in the hybrid material
11O
39Meter) gradually saturated, high-load is no more than 30%.
Hybrid material and silicotungstate/mesopore molecular sieve (pure silicon SBA-15) composite (H that uses immersion process for preparing with the present invention
4SiW
12O
40/ SBA-15 and K
4SiW
11O
39[O (SiOH)
2]/SBA-15) carried out in the water solution-off experiment relatively.Under 25 ℃, (solid-to-liquid ratio=0.01g/40mL) certain hour is stirred in suspension, collects the aqueous solution also with the W content in the icp analysis water, and the calculating solution-off of comparing with the W content in former solid material rate the results are shown in Table 1 in the water.As seen the silicotungstate in the present invention's the hybrid material can be fixed on the carrier well, and the solution-off rate is far below the composite of immersion process for preparing.
The solution-off experiment relatively in table 1 water
The present invention has following advantage:
1. link with covalent bond between polyoxometallate and the mesopore molecular sieve in the present invention's the hybrid material, so polyoxometallate can be by firmly immobilized on mesoporous carrier.When this material uses as catalyst, not only can be used for nonpolar reaction system, also can be used in the system of water or polar solvent, the active component difficult drop-off runs off, and catalyst can recycling.
2. to select mesopore molecular sieve be carrier in the present invention, the pore passage structure of its regular homogeneous, high specific area and heat endurance make when this hybrid material uses as catalyst, not only have active component utilization rate height, active big, characteristics that heat endurance is high, and also may have the shape of selecting selectivity some reaction.
3. the present invention has created the preparation method that a synthetic step of the surface bonded and mesopore molecular sieve of polyoxometallate is finished, the reaction condition gentleness, and technological process is simple.
Description of drawings
Fig. 1 is the IR spectrogram (a.SiW of hybrid material
11O
39Content is about 19%; B.SiW
11O
39Content is about 26%).
Fig. 2 is the XRD figure (a.SiW of hybrid material
11O
39Content is about 19%; B.SiW
11O
39Content is about 26%).
Fig. 3 is the TEM figure (a.SiW of hybrid material
11O
39Content is about 19%; B.SiW
11O
39Content is about 26%).
Fig. 4 is typical hybrid material (SiW
11O
39Content is about 26%) N
2Adsorption-desorption thermoisopleth (a) and graph of pore diameter distribution (b).
The specific embodiment
Dissolving 1.0004g P123 is warming up to 40 ℃ in 30mL 2mol/L hydrochloric acid, dropwise add 2.1019g TEOS under the vigorous stirring.Prehydrolysis adds 0.4085g SiW after 0.5 hour
11With 7.5mL water, continue to stir crystallization 25.5 hours, in 80 ℃ of insulating boxs, left standstill again aging 24 hours.Sample filters after being chilled to room temperature, washing, dries in the air.With ethanol is solvent, with 36 hours removed template method P123 of Soxhlet extractor extracting, promptly gets silicotungstate/mesoporous molecular sieve hybrid material.SiW in this material
11O
39Content is about 19%, and the aperture is 7.5 nanometers, and pore volume is 0.71cm
3/ g, specific area is 564m
2/ g.Its IR, XRD and TEM see accompanying drawing 1a, 2a and 3a respectively.
Dissolving 2.0003g P123 is warming up to 40 ℃ in 60mL 2mol/L hydrochloric acid, dropwise add 4.0394g TEOS under the vigorous stirring.Prehydrolysis adds 3.2678g SiW after 2 hours
11With 15mL water, continue to stir crystallization 24 hours, in 80 ℃ of insulating boxs, left standstill again aging 24 hours.Sample filters after being chilled to room temperature, washing, dries in the air.With ethanol is solvent, with 36 hours removed template method P123 of Soxhlet extractor extracting, promptly gets silicotungstate/mesoporous molecular sieve hybrid material.SiW in this material
11O
39Content is about 26%, and the aperture is 6.1 nanometers, and pore volume is 0.52cm
3/ g, specific area is 429m
2/ g.Its IR, XRD and TEM see accompanying drawing 1b, 2b and 3b, N respectively
2Adsorption-desorption thermoisopleth and graph of pore diameter distribution are seen accompanying drawing 4.
Embodiment 3, and is substantially the same manner as Example 1, but following change is arranged:
P123 is 1.0028g, and TEOS is 1.9172g, prehydrolysis 2h, SiW
11Be 3.2758g, water is 7.5ml.
P123 is 1.0000g, and TEOS is 2.1038g, prehydrolysis 0.5h, SiW
11Be 0.3267g, water is 7.5ml.
Embodiment 5, and is substantially the same manner as Example 1, but following change is arranged:
P123 is 1.0010g, and TEOS is 1.9701g, prehydrolysis 2h, SiW
11Be 2.4576g, water is 7.5ml.
Claims (4)
1, a kind of silicotungstate/mesoporous molecular sieve hybrid material is characterized in that, the formation of this material is: silica mesoporous zeolite and silicotungstate link with covalent bond; The anion of described silicotungstate is SiW
11O
39[O (SiO)
2]
6-The quality percentage composition of silicotungstate wherein is with SiW
11O
39Meter is less than 30%; Greater than 19%.
2, silicotungstate/mesoporous molecular sieve hybrid material according to claim 1 is characterized in that, this material has orderly six sides or class hexagonal hole battle array structure, and the aperture is 6.0～7.5 nanometers, and pore volume is 0.35～0.80cm
3/ g, specific area is 300～600m
2/ g.
3, silicotungstate/mesoporous molecular sieve hybrid material according to claim 1 and 2 is characterized in that, this material prepares in order to the below method:
Dissolving triblock copolymer EO
20PO
70EO
20In watery hydrochloric acid, be warming up to 40 ℃; Under this temperature, drip ethyl orthosilicate, and make its prehydrolysis certain hour, add K then
8SiW
11O
3912H
2O and a certain amount of water make in the system each material to EO
20PO
70EO
20Ratio be EO
20PO
70EO
20: TEOS: K
8SiW
11O
3912H
2O: HCl: H
2O=1g: 0.01-x mole: x mole: 0.06 mole: 1.96 moles; X=0.0001～0.001 wherein; Continue to stir in crystallization, the insulating box aging; Filter, wash, dry; With ethanol is solvent, with Soxhlet extractor extracting sample, removed template method EO
20PO
70EO
20, promptly get hybrid material.
4, a kind of preparation method of silicotungstate/mesoporous molecular sieve hybrid material as claimed in claim 1 is characterized in that, concrete steps are:
The template agent EO that synthesising mesoporous molecular sieve is used
20PO
70EO
20Be dissolved in the watery hydrochloric acid, be warming up to 40 ℃; Under this temperature, drip ethyl orthosilicate, and make its prehydrolysis certain hour, add K then
8SiW
11O
3912H
2O and a certain amount of water make in the system each material to EO
20PO
70EO
20Ratio be EO
20PO
70EO
20: TEOS: K
8SiW
11O
3912H
2O: HCl: H
2O=1g: 0.01-x mole: x mole: 0.06 mole: 1.96 moles; X=0.0001～0.001 wherein; Continue to stir in crystallization, the insulating box aging; Filter, wash, dry; With ethanol is solvent, with Soxhlet extractor extracting sample, removed template method EO
20PO
70EO
20, promptly get hybrid material.
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|---|---|---|---|
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| CN100450609C true CN100450609C (en) | 2009-01-14 |
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|---|---|---|---|---|
| CN102218347B (en) * | 2011-04-19 | 2013-04-10 | 东北师范大学 | Polyoxometalates-based organic-inorganic hybrid catalyst with core-shell structure and preparation method thereof |
| CN103041847B (en) * | 2012-12-25 | 2015-06-17 | 辽宁师范大学 | In-situ synthesized catalyst by polyoxometallate and silicon-containing molecular sieve, as well as preparation method and application of same |
| CN112479954B (en) * | 2020-11-27 | 2021-09-03 | 山东益丰生化环保股份有限公司 | Method for reducing water content of polythiol |
| CN115282993B (en) * | 2022-09-28 | 2023-02-03 | 中国华电科工集团有限公司 | Regenerated catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5919725A (en) * | 1993-11-19 | 1999-07-06 | Exxon Research And Engineering Co. | Heteropoly salts or acid salts deposited in the interior of porous supports |
| JP2003261484A (en) * | 2002-03-08 | 2003-09-16 | Sumitomo Chem Co Ltd | Method for producing cyclohexanol and/or cyclohexanone |
| CN1554482A (en) * | 2003-12-26 | 2004-12-15 | 华东师范大学 | In situ crystilization assembling method for heteropolyacid nano particles in mesoporous material |
| CN1724365A (en) * | 2005-06-15 | 2006-01-25 | 浙江大学 | Process for synthesizing mesic porous molecular sieve SBA-15 |
| CN1768937A (en) * | 2004-11-05 | 2006-05-10 | 中国石油化工股份有限公司 | Microcellular structured heteropoly acid/ silicon dioxide catalyst |
-
2006
- 2006-11-01 CN CNB2006100973641A patent/CN100450609C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5919725A (en) * | 1993-11-19 | 1999-07-06 | Exxon Research And Engineering Co. | Heteropoly salts or acid salts deposited in the interior of porous supports |
| JP2003261484A (en) * | 2002-03-08 | 2003-09-16 | Sumitomo Chem Co Ltd | Method for producing cyclohexanol and/or cyclohexanone |
| CN1554482A (en) * | 2003-12-26 | 2004-12-15 | 华东师范大学 | In situ crystilization assembling method for heteropolyacid nano particles in mesoporous material |
| CN1768937A (en) * | 2004-11-05 | 2006-05-10 | 中国石油化工股份有限公司 | Microcellular structured heteropoly acid/ silicon dioxide catalyst |
| CN1724365A (en) * | 2005-06-15 | 2006-01-25 | 浙江大学 | Process for synthesizing mesic porous molecular sieve SBA-15 |
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