CN104475156A - Method for synthesizing immobilized polyoxometallate material by one step - Google Patents
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Abstract
The invention provides a method for synthesizing an immobilized polyoxometallate material by one step. The method comprises the following steps: dissolving a template agent into a hydrochloric acid solution; adding tetraethoxysilane as well as chlorinated N-(3-triethoxysilicyl), N(3)-(3-trimethoxyoxysilicyl)-4,5-dihydroimidazole and polyoxometallate to stir; ageing, collecting solids, washing and drying to obtain solids; filtering and refluxing the obtained solids in alcohol, and drying to obtain the material. According to the method for synthesizing the immobilized polyoxometallate material by one step disclosed by the invention, the active center of the bridge-bond embedded type organic-inorganic hybrid mesoporous material is uniformly distributed and the duct is not blocked, so that the catalytic active center with uniform microchemistry environment is constructed in a facilitated manner, and the reaction selectivity can be improved. The immobilized polyoxometallate material can be used for performing liquid phase air selective oxidation on alcohols to obtain aldehydes, is very high in conversion rate and selectivity, easy to separate, and capable of being recycled.
Description
Technical field
The present invention relates to a kind of method of one-step synthesis solid-carrying type polyoxometallic acid salt material.
Background technology
Polyoxometallate is the class multi-metal oxygen cluster compound being connected by oxygen by early transition metal ion and formed.Since 20 century 70 Japan adopt the hydration of polyoxometallate catalyzing propone to realize industrialization, polyoxometallate catalyst has difunctional green catalyst that is acid and oxidisability as a kind of, have the features such as unique " false liquid phase " property, low temperature high activity and Heat stability is good concurrently, get the attention in organic synthesis and petrochemical industry.
But polyoxometallate solubility in polar solvent is higher, and not easily reclaims; In non-polar solven, specific area is low, and catalytic performance is restricted.In order to address these problems, be an effective approach by polyoxometallate solid-carrying type.By its specific area can be increased immobilized for polyoxometallate on the carriers such as zeolite, porous charcoal, metal oxide, organic material, clay, metal organic frame, siliceous material, realize heterogeneousization.In various carrier, there is order mesoporous silica and be considered to efficient carrier.The advantages such as it has high specific area, variable pore passage structure and surface nature, the chemical inertness that pore-size distribution is narrow and relative.Use it as the specific area that carrier effectively can increase catalyst, make catalyst heterogeneousization, advantageously in the separation of catalyst and the extraction of product.
Nearest Chinese patent (CN103846099A) provides a kind of support type polyoxometallate and preparation method thereof, comprise: PEO-PPOX-PEO triblock copolymer is dissolved in the HCl aqueous solution, add ethyl orthosilicate and gamma-aminopropyl-triethoxy-silane mixes, obtain the first mixed solution; Add H
5pV
2mo
10o
40, after reaction, collect solid; Described solid is carried out back flow reaction in ethanol, filters, after drying, obtain support type polyoxometallate.
In this patent, add organosilicon source, polyoxometallate is better combined in mesoporous material.And according to organic component distributing position in the material, organic-inorganic hybrid mesoporous material can be divided into surface conjunction shaped material and the large class of bridged bond Intercalation material two substantially.Gamma-aminopropyl-triethoxy-silane is while combine with the silica in mesoporous material, and another side and polyoxometallate combine, and this combination is defined as surface conjunction shaped material.And relative to surface conjunction shaped material, in the organic-inorganic hybrid mesoporous material of bridged bond embedded type, the both sides, organosilicon source added are all be combined with mesoporous material, and mid portion and polyoxometallate combine, thus infer that bridged bond Intercalation material is more evenly distributed and can not blocks duct; What is more important, the existence of organic component in this type of material is very favourable to the catalytic active center building mi-crochemistry environment homogeneous, greatly can improve selective (B. Hatton, the K. Landskron in reaction, W. Whitnall, D. Perovic, G. A. Ozin. " Past, present; and future of periodic mesoporous organosilicas-The PMOs ". Acc. Chem. Res., 2005,38,305).
Up to the present, in the report with polyoxometallate liquid phase oxidation alcohols, in the majority with hydrogen peroxide, and choice for use air Middle molecule oxygen makes oxidant, and selective, conversion ratio, repeats in practicality, and the report all had superiority is little.Chinese patent (CN101486621A) with 1 ~ 8% 2,2,6,6-tetramethyl piperidine-oxygen radical (TEMPO) or derivatives thereof, the halide-containing of 4 ~ 20% and the nitrite of 4 ~ 10% or nitrites are catalyst, be oxidant with the oxygen of 0.1 ~ 0.8 MPa or air, 0 ~ 80
oreact 1 ~ 36 hour under C condition, highly selective a series of alcohol can be oxidized to aldehydes or ketones.In this method, condition is harsher.
Summary of the invention
The present invention passes through at mesopore silicon oxide surface design anchor point, polyoxometallate is made to be combined on the inwall of duct with the dispersion of the form of chemical bond, not only effectively can increase the specific area of catalyst, reduce coming off of reacted rear avtive spot, and construct the homogeneous catalytic active center of mi-crochemistry environment, improve with air alcohols selectivity when being oxidant and be oxidized to the selective of aldehydes.
The present invention at ambient pressure, can make oxidant with air Middle molecule oxygen, liquid phase oxidation alcohols, and have high selective and conversion ratio, and can reuse repeatedly, the activity of catalyst is influenced hardly.
Concrete preparation process of the present invention is as follows:
(1) PEO-PPOX-PEO triblock copolymer is dissolved in hydrochloric acid solution;
(2) in (1), add ethyl orthosilicate, and chlorination N-(3-triethoxysilicane alkyl), N (3)-(the two hydrogen imidazoles of 3-trimethoxy TMOS base-4,5-and polyoxometallate fully stir;
(3) burin-in process is carried out to (2), collect solid, washing, dry;
(4) solid in (3) is carried out back flow reaction in ethanol, filter, after drying, obtain solid-carrying type polyoxometallic acid salt material.
Preferably, in step (1):
Will 55
oc PEO-PPOX-PEO triblock copolymer is dissolved in HCl solution.
Preferably, the concentration of described HCl solution is 1.6 mol/L.
In step (2), after adding ethyl orthosilicate, hydrolysis time is 1 ~ 10 hour.
Preferably, in step (2), after adding ethyl orthosilicate, hydrolysis time is 3 ~ 5 hours.
In step (2), add chlorination N-(3-triethoxysilicane alkyl), N (3)-(after the two hydrogen imidazoles of 3-trimethoxy TMOS base-4,5-, then the time interval adding polyoxometallate be 1 ~ 60 minute.
Preferably, in step (2), after adding, then the time interval adding polyoxometallate be 1 ~ 30 minute.
In step (2), mixing time is 18 ~ 24 hours.
Preferably, in step (2), mixing time is 20 hours.
Preferably, in step (2), adding every molar ratio is:
Ethyl orthosilicate: chlorination N-(3-triethoxysilicane alkyl), N (3)-(two hydrogen imidazoles of 3-trimethoxy TMOS base-4,5-: polyoxometallate=40: 3: 1.5.
Preferably, in step (2), reaction temperature is 35
oc.
The polyoxometallate that this patent is suitable for has Keggin-type to contain the molybdovanaphosphoric acid (H of a vanadium
4pMo
11vO
40), Keggin-type is containing the molybdovanaphosphoric acid (H of two vanadium
5pMo
10v
2o
40), Keggin-type is containing the molybdovanaphosphoric acid (H of three vanadium
6pMo
9v
3o
40), Keggin-type phosphomolybdic acid (H
3pMo
12o
40), Dawson type phosphomolybdic acid (H
6p
2mo
18o
62), Dawson type is containing the molybdovanaphosphoric acid (H of a vanadium
7p
2mo
17vO
62), Dawson type is containing the molybdovanaphosphoric acid (H of two vanadium
8p
2mo
16v
2o
62), Dawson type is containing the molybdovanaphosphoric acid (H of three vanadium
9p
2mo
15v
3o
62).
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail:
Embodiment 1
55
ounder C, the PEO-PPOX-PEO triblock copolymer of 4.0 g is dissolved in the hydrochloric acid solution of 150 ml 1.6 mol/L, after PEO-PPOX-PEO triblock copolymer dissolves completely, temperature is adjusted to 35
oc.Dropwise add the ethyl orthosilicate of 8.4 g, be hydrolyzed 3 hours.Add the chlorination N-(3-triethoxysilicane alkyl) of 1.4 g again, N (3)-(the two hydrogen imidazoles of 3-trimethoxy TMOS base-4,5-, stirred after 1 minute, added the molybdovanaphosphoric acid (H of Keggin-type containing a vanadium of 5.7 g
4pMo
11vO
40), continue stirring 20 hours.Gained mixture is placed in polytetrafluoroethylene (PTFE) reactor, 80
oc ageing 48 hours.After filtration, washing, till without Cl-(silver nitrate detection) for product.80
oafter C vacuum drying, with absolute ethyl alcohol soxhlet extraction 48 hours removing templates, vacuum drying, (total BET specific surface area is 299 m namely to obtain solid-carrying type polyoxometallic acid salt material
2/ g, average pore size is 8 nm).
When detecting this example catalysis characteristics:
In the three-neck flask of 50 ml, add 0.15 g and obtain material, add 1 ml phenmethylol subsequently, 10 ml dimethyl sulfoxide (DMSO)s, are placed in 150
oin the oil bath of C, stirring and refluxing 6 hours.After having reacted cooling, add 40 ml water, then use the absolute ether extractive reaction thing of 15 ml and product (extracting 3 times, each 5 ml).After having reacted, with washed with diethylether catalyst three times (each 5 ml), ether layer separatory is removed, steam and dewater and methyl-sulfoxide, the catalyst 80 obtained
ofor use next time after C vacuum drying.Obtaining conversion ratio is 96%, the selective >99% of benzaldehyde, reuses six conversion ratios and selectively not to reduce.
Embodiment 2
55
ounder C, the PEO-PPOX-PEO triblock copolymer of 4.0 g is dissolved in the hydrochloric acid solution of 150 ml 1.6 mol/L, after PEO-PPOX-PEO triblock copolymer dissolves completely, temperature is adjusted to 35
oc.Dropwise add the ethyl orthosilicate of 8.4 g, be hydrolyzed 4 hours.Add the chlorination N-(3-triethoxysilicane alkyl) of 1.4 g again, N (3)-(the two hydrogen imidazoles of 3-trimethoxy TMOS base-4,5-, stirred after 5 minutes, added the molybdovanaphosphoric acid (H of Keggin-type containing two vanadium of 5.6 g
5pMo
10v
2o
40), continue stirring 20 hours.Gained mixture is placed in polytetrafluoroethylene (PTFE) reactor, 80
oc ageing 48 hours.After filtration, washing, till without Cl-(silver nitrate detection) for product.80
oafter C vacuum drying, with absolute ethyl alcohol soxhlet extraction 48 hours removing templates, vacuum drying, (total BET specific surface area is 310 m namely to obtain solid-carrying type polyoxometallic acid salt material
2/ g, average pore size is 7 nm).
When detecting this example catalysis characteristics:
In the three-neck flask of 50 ml, add 0.15 g and obtain material, add 1 ml phenmethylol subsequently, 10 ml dimethyl sulfoxide (DMSO)s, are placed in 150
oin the oil bath of C, stirring and refluxing 6 hours.After having reacted cooling, add 40 ml water, then use the absolute ether extractive reaction thing of 15 ml and product (extracting 3 times, each 5 ml).Obtaining conversion ratio is 97%, benzyl alcohol selective >99%.
Embodiment 3
55
ounder C, the PEO-PPOX-PEO triblock copolymer of 4.0 g is dissolved in the hydrochloric acid solution of 150 ml 1.6 mol/L, after PEO-PPOX-PEO triblock copolymer dissolves completely, temperature is adjusted to 35
oc.Dropwise add the ethyl orthosilicate of 8.4 g, be hydrolyzed 5 hours.Add the chlorination N-(3-triethoxysilicane alkyl) of 1.4 g again, N (3)-(the two hydrogen imidazoles of 3-trimethoxy TMOS base-4,5-, stirred after 10 minutes, added the molybdovanaphosphoric acid (H of Keggin-type containing three vanadium of 5.4 g
6pMo
9v
3o
40), continue stirring 20 hours.Gained mixture is placed in polytetrafluoroethylene (PTFE) reactor, 80
oc ageing 48 hours.After filtration, washing, till without Cl-(silver nitrate detection) for product.80
oafter C vacuum drying, with absolute ethyl alcohol soxhlet extraction 48 hours removing templates, vacuum drying, (total BET specific surface area is 330 m namely to obtain solid-carrying type polyoxometallic acid salt material
2/ g, average pore size is 7 nm).
When detecting this example catalysis characteristics:
In the three-neck flask of 50 ml, add 0.15 g and obtain material, add 1 ml phenmethylol subsequently, 10 ml dimethyl sulfoxide (DMSO)s, are placed in 150
oin the oil bath of C, stirring and refluxing 6 hours.After having reacted cooling, add 40 ml water, then use the absolute ether extractive reaction thing of 15 ml and product (extracting 3 times, each 5 ml).Obtaining conversion ratio is 94%, the selective >99% of benzaldehyde.
Embodiment 4
55
ounder C, the PEO-PPOX-PEO triblock copolymer of 4.0 g is dissolved in the hydrochloric acid solution of 150 ml 1.6 mol/L, after PEO-PPOX-PEO triblock copolymer dissolves completely, temperature is adjusted to 35
oc.Dropwise add the ethyl orthosilicate of 8.4 g, be hydrolyzed 3 hours.Add the chlorination N-(3-triethoxysilicane alkyl) of 1.4 g again, N (3)-(the two hydrogen imidazoles of 3-trimethoxy TMOS base-4,5-, stirs after 20 minutes, adds the Keggin-type phosphomolybdic acid (H of 5.8 g
3pMo
12o
40), continue stirring 20 hours.Gained mixture is placed in polytetrafluoroethylene (PTFE) reactor, and 80
oc ageing 48 hours.After filtration, washing, till without Cl-(silver nitrate detection) for product.80
oafter C vacuum drying, with absolute ethyl alcohol soxhlet extraction 48 hours removing templates, vacuum drying, (total BET specific surface area is 276 m namely to obtain solid-carrying type polyoxometallic acid salt material
2/ g, average pore size is 8 nm).
When detecting this example catalysis characteristics:
In the three-neck flask of 50 ml, add 0.15 g and obtain material, add 1 ml phenmethylol subsequently, 10 ml dimethyl sulfoxide (DMSO)s, are placed in 150
oin the oil bath of C, stirring and refluxing 6 hours.After having reacted cooling, add 40 ml water, then use the absolute ether extractive reaction thing of 15 ml and product (extracting 3 times, each 5 ml).Obtaining conversion ratio is 93%, benzyl alcohol selective >99%.
Embodiment 5
55
ounder C, the PEO-PPOX-PEO triblock copolymer of 4.0 g is dissolved in the hydrochloric acid solution of 150 ml 1.6 mol/L, after PEO-PPOX-PEO triblock copolymer dissolves completely, temperature is adjusted to 35
oc.Dropwise add the ethyl orthosilicate of 8.4 g, be hydrolyzed 5 hours.Add the chlorination N-(3-triethoxysilicane alkyl) of 1.4 g again, N (3)-(the two hydrogen imidazoles of 3-trimethoxy TMOS base-4,5-, stirs after 10 minutes, adds the Dawson type phosphomolybdic acid (H of 8.9 g
6p
2mo
18o
62), continue stirring 20 hours.Then polytetrafluoroethylene (PTFE) reactor is placed in, 80
oc ageing 48 hours.After filtration, washing, till without Cl-(silver nitrate detection) for product.80
oafter C vacuum drying, with absolute ethyl alcohol soxhlet extraction 48 hours removing templates, vacuum drying, (total BET specific surface area is 281m namely to obtain solid-carrying type polyoxometallic acid salt material
2/ g, average pore size is 7 nm).
When detecting this example catalysis characteristics:
In the three-neck flask of 50 ml, add 0.15 g and obtain material, add 1 ml phenmethylol subsequently, 10 ml dimethyl sulfoxide (DMSO)s, are placed in 150
oin the oil bath of C, stirring and refluxing 6 hours.After having reacted cooling, add 40 ml water, then use the absolute ether extractive reaction thing of 15 ml and product (extracting 3 times, each 5 ml).Obtaining conversion ratio is 92%, the selective >99% of benzaldehyde.
Embodiment 6
55
ounder C, the PEO-PPOX-PEO triblock copolymer of 4.0 g is dissolved in the hydrochloric acid solution of 150 ml 1.6 mol/L, after PEO-PPOX-PEO triblock copolymer dissolves completely, temperature is adjusted to 35
oc.Dropwise add the ethyl orthosilicate of 8.4 g, be hydrolyzed 4 hours.Add the chlorination N-(3-triethoxysilicane alkyl) of 1.4 g again, N (3)-(the two hydrogen imidazoles of 3-trimethoxy TMOS base-4,5-, stirred after 10 minutes, added the molybdovanaphosphoric acid (H of Dawson type containing a vanadium of 8.8 g
7p
2mo
17vO
62), continue stirring 20 hours.Gained mixture is placed in polytetrafluoroethylene (PTFE) reactor, 80
oc ageing 48 hours.After filtration, washing, till without Cl-(silver nitrate detection) for product.80
oafter C vacuum drying, with absolute ethyl alcohol soxhlet extraction 48 hours removing templates, vacuum drying, (total BET specific surface area is 267 m namely to obtain solid-carrying type polyoxometallic acid salt material
2/ g, average pore size is 7 nm).
When detecting this example catalysis characteristics:
In the three-neck flask of 50 ml, add 0.15 g and obtain material, add 1 ml phenmethylol subsequently, 10 ml dimethyl sulfoxide (DMSO)s, are placed in 150
oin the oil bath of C, stirring and refluxing 6 hours.After having reacted cooling, add 40 ml water, then use the absolute ether extractive reaction thing of 15 ml and product (extracting 3 times, each 5 ml).Obtaining conversion ratio is 95%, the selective >99% of benzaldehyde.
Embodiment 7
55
ounder C, the PEO-PPOX-PEO triblock copolymer of 4.0 g is dissolved in the hydrochloric acid solution of 150 ml 1.6 mol/L, after PEO-PPOX-PEO triblock copolymer dissolves completely, temperature is adjusted to 35
oc.Dropwise add the ethyl orthosilicate of 8.4 g, be hydrolyzed 5 hours.Add the chlorination N-(3-triethoxysilicane alkyl) of 1.4 g again, N (3)-(the two hydrogen imidazoles of 3-trimethoxy TMOS base-4,5-, stirred after 10 minutes, added the molybdovanaphosphoric acid (H of Dawson type containing two vanadium of 8.6 g
8p
2mo
16v
2o
62), continue stirring 20 hours.Gained mixture is placed in polytetrafluoroethylene (PTFE) reactor, 80
oc ageing 48 hours.After filtration, washing, till without Cl-(silver nitrate detection) for product.80
oafter C vacuum drying, with absolute ethyl alcohol soxhlet extraction 48 hours removing templates, vacuum drying, (total BET specific surface area is 285 m namely to obtain solid-carrying type polyoxometallic acid salt material
2/ g, average pore size is 7 nm).
When detecting this example catalysis characteristics:
In the three-neck flask of 50 ml, add 0.15 g and obtain material, add 1 ml phenmethylol subsequently, 10 ml dimethyl sulfoxide (DMSO)s, are placed in 150
oin the oil bath of C, stirring and refluxing 6 hours.After having reacted cooling, add 40 ml water, then use the absolute ether extractive reaction thing of 15 ml and product (extracting 3 times, each 5 ml).Obtaining conversion ratio is 92%, the selective >99% of benzaldehyde.
Embodiment 8
55
ounder C, the PEO-PPOX-PEO triblock copolymer of 4.0 g is dissolved in the hydrochloric acid solution of 150 ml 1.6 mol/L, after PEO-PPOX-PEO triblock copolymer dissolves completely, temperature is adjusted to 35
oc.Dropwise add the ethyl orthosilicate of 8.4 g, be hydrolyzed 5 hours.Add the chlorination N-(3-triethoxysilicane alkyl) of 1.4 g again, N (3)-(the two hydrogen imidazoles of 3-trimethoxy TMOS base-4,5-, stirred after 1 minute, added the molybdovanaphosphoric acid (H of Dawson type containing three vanadium of 8.5 g
9p
2mo
15v
3o
62), continue stirring 20 hours.Gained mixture is placed in polytetrafluoroethylene (PTFE) reactor, 80
oc ageing 48 hours.After filtration, washing, till without Cl-(silver nitrate detection) for product.80
oafter C vacuum drying, with absolute ethyl alcohol soxhlet extraction 48 hours removing templates, vacuum drying, (total BET specific surface area is 299 m namely to obtain solid-carrying type polyoxometallic acid salt material
2/ g, average pore size is 8 nm).
When detecting this example catalysis characteristics:
In the three-neck flask of 50 ml, add 0.15 g and obtain material, add 1 ml phenmethylol subsequently, 10 ml dimethyl sulfoxide (DMSO)s, are placed in 150
oin the oil bath of C, stirring and refluxing 6 hours.After having reacted cooling, add 40 ml water, then use the absolute ether extractive reaction thing of 15 ml and product (extracting 3 times, each 5 ml).Obtaining conversion ratio is 93%, the selective >99% of benzaldehyde.
Claims (8)
1. concrete preparation process of the present invention is as follows:
(1) PEO-PPOX-PEO triblock copolymer is dissolved in hydrochloric acid solution;
(2) in (1), add ethyl orthosilicate, and chlorination N-(3-triethoxysilicane alkyl), N (3)-(the two hydrogen imidazoles of 3-trimethoxy TMOS base-4,5-and polyoxometallate fully stir;
(3) burin-in process is carried out to (2), collect solid, washing, dry;
(4) solid in (3) is carried out back flow reaction in ethanol, filter, after drying, obtain solid-carrying type polyoxometallic acid salt material.
2. according to claim 1, it is characterized in that, in step (1):
55
ounder C, PEO-PPOX-PEO triblock copolymer is dissolved in HCl solution.
3. according to claim 1, it is characterized in that, in step (1):
The concentration of described HCl solution is 1.6 mol/L.
4. according to claim 1, it is characterized in that, in step (2):
Add chlorination N-(3-triethoxysilicane alkyl), N (3)-(after the two hydrogen imidazoles of 3-trimethoxy TMOS base-4,5-, then the time interval adding polyoxometallate be 1 ~ 60 minute.
5. according to claim 1, it is characterized in that, in step (2):
Mixing time is 18 ~ 24 hours.
6. according to claim 1, it is characterized in that, in step (2):
Adding every molar ratio is:
Ethyl orthosilicate: chlorination N-(3-triethoxysilicane alkyl), N (3)-(two hydrogen imidazoles of 3-trimethoxy TMOS base-4,5-: polyoxometallate=40: 3: 1.5.
7. according to claim 1, it is characterized in that, in step (2):
Reaction temperature is 35
oc.
8. according to claim 1, it is characterized in that, the polyoxometallate that this patent is suitable for has Keggin-type to contain the molybdovanaphosphoric acid (H of a vanadium
4pMo
11vO
40), Keggin-type is containing the molybdovanaphosphoric acid (H of two vanadium
5pMo
10v
2o
40), Keggin-type is containing the molybdovanaphosphoric acid (H of three vanadium
6pMo
9v
3o
40), Keggin-type phosphomolybdic acid (H
3pMo
12o
40), Dawson type phosphomolybdic acid (H
6p
2mo
18o
62), Dawson type is containing the molybdovanaphosphoric acid (H of a vanadium
7p
2mo
17vO
62), Dawson type is containing the molybdovanaphosphoric acid (H of two vanadium
8p
2mo
16v
2o
62), Dawson type is containing the molybdovanaphosphoric acid (H of three vanadium
9p
2mo
15v
3o
62).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108465486A (en) * | 2018-03-19 | 2018-08-31 | 山西大学 | A kind of preparation method and applications of temperature sensitive interfacial catalysis agent |
| CN109174183A (en) * | 2018-08-28 | 2019-01-11 | 东北师范大学 | The method for preparing oxalic acid with POMs/HAP catalysis of solid catalyst glycerol |
| CN111514933A (en) * | 2020-05-29 | 2020-08-11 | 辽宁师范大学 | Preparation method and application of functional polyacid-based solid acid catalyst |
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| WO2008128638A1 (en) * | 2007-04-19 | 2008-10-30 | Exxonmobil Chemical Patents Inc. | Process for oxidizing alkylaromatic compounds |
| CN103041847A (en) * | 2012-12-25 | 2013-04-17 | 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 |
| CN103846099A (en) * | 2014-02-20 | 2014-06-11 | 宁波高新区夏远科技有限公司 | Supported polyoxometallate and preparation method thereof |
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2014
- 2014-12-10 CN CN201410749902.5A patent/CN104475156A/en active Pending
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| WO2008128638A1 (en) * | 2007-04-19 | 2008-10-30 | Exxonmobil Chemical Patents Inc. | Process for oxidizing alkylaromatic compounds |
| CN103041847A (en) * | 2012-12-25 | 2013-04-17 | 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 |
| CN103846099A (en) * | 2014-02-20 | 2014-06-11 | 宁波高新区夏远科技有限公司 | Supported polyoxometallate and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| HAIHONG ZHAO ET AL.: "Polyoxometalate-based ionic complexes immobilized in mesoporous silicas prepared via a one-pot procedure: Efficient and reusable catalysts for H2O2-mediated alcohol oxidations in aqueous media", 《MICROPOROUS AND MESOPOROUS MATERIALS》, vol. 172, 26 January 2013 (2013-01-26), pages 67 - 76 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108465486A (en) * | 2018-03-19 | 2018-08-31 | 山西大学 | A kind of preparation method and applications of temperature sensitive interfacial catalysis agent |
| CN108465486B (en) * | 2018-03-19 | 2021-02-02 | 山西大学 | Preparation method and application of temperature-sensitive interface catalyst |
| CN109174183A (en) * | 2018-08-28 | 2019-01-11 | 东北师范大学 | The method for preparing oxalic acid with POMs/HAP catalysis of solid catalyst glycerol |
| CN111514933A (en) * | 2020-05-29 | 2020-08-11 | 辽宁师范大学 | Preparation method and application of functional polyacid-based solid acid catalyst |
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