CN101550044B - Application of polyoxometalate/silicon dioxide catalyst in controllable oxidization of sulfide - Google Patents
Application of polyoxometalate/silicon dioxide catalyst in controllable oxidization of sulfide Download PDFInfo
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- CN101550044B CN101550044B CN2009100669626A CN200910066962A CN101550044B CN 101550044 B CN101550044 B CN 101550044B CN 2009100669626 A CN2009100669626 A CN 2009100669626A CN 200910066962 A CN200910066962 A CN 200910066962A CN 101550044 B CN101550044 B CN 101550044B
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Abstract
The present invention relates to the application of polyoxometalate/silicon dioxide hybrid catalyst modified by surfactant in controllable oxidization of sulfide. The surfactant-modified polyoxometalate and siloxane agent generate alcohol exchange reaction. The siloxane agent is hydrolyzed and condensed to a network through a method of sol-gel for forming the polyoxometalate/silicon dioxide hybridcatalyst. The hybrid catalyst has an advantage of simultaneously settling the mass transfer reaction between the polyoxometalate catalyst center and organosulfur compound and the recovery problem of catalyst. The prepared hybrid catalyst can effectively and controllably realize the high-selective oxidization of sulfur-containing compound, and simultaneously ensures that the usage factor of hydrogen peroxide which is taken as oxidant obtains 80%. The hybrid catalyst has higher catalytic efficiency to various sulfur-containing compounds and has broad application prospect in the fields of fine synthesis of chemical, preparing pharmaceutical molecule, deep desulfurizing of fuel oil, etc.
Description
Technical field
The invention belongs to catalysis technical field, be specifically related to the application of surfactant modified multi-metal oxygen cluster/SiO 2 hybrid catalyzer aspect the controllable oxidization of organosulfur compound.
Background technology
Gasoline and diesel oil are two kinds of important dynamic fuel oils, in various countries' fuel structure, all occupy higher share.Along with industrialized fast development, the demand of gasoline and diesel oil and consumption are just growing, and the waste gas that discharge their burning backs also is on the rise to the pollution of environment.In fuel oil combustion produced pollution thing, organosulfur compound is especially serious to the pollution of environment.Organosulfur compound can generate oxysulfide SO after burning
x, SO most importantly wherein
2SO
2Being atmospheric environment major pollution source, is the immediate cause that forms acid rain.Remove SO
xOutward, the fuel combustion that contains organosulfur compound also can produce vitriol, thereby has increased the discharging of burning particles pollutent.In addition, the resultant after the sulphides burn can make the poisoning of catalyst in the vehicle exhaust convertor, has influenced the performance of convertor, makes other obnoxious flavour CO in the vehicle exhaust, NO
xDeng quantity discharged increase.Therefore, the oil fuel ultra-deep desulfurization has become one of most important environmental research problem of being badly in need of solution in the world wide.
The exist form of sulphur in oil has types such as elementary sulfur, hydrogen sulfide, mercaptan, thioether, disulphide, thiophene, is main with thiophene-based wherein, accounts for more than 85% of sulfur-bearing total amount.And in thiophene-type sulfide, the content of thionaphthene and dibenzothiophene reaches more than 70%, is the main existence form of sulfide in the oil fuel.At present, comparatively sophisticated desulfurization of fuel oil technology is a hydrogenating desulfurization technology, and it is a kind of in the presence of hydrogen, the organic sulfide in the diesel oil is converted into hydrogen sulfide and the method for removing through catalyst action.The method of hydrogenating desulfurization has the characteristics of desulfurization degree height, productive rate height, technical maturity, is that the sulfur method of main employing is gone up in industry at present.But since content is the highest in oil fuel thiophene-type sulfide especially thionaphthene and dibenzothiophene etc. have aromaticity; Chemical property is stable; Even under high temperature, high pressure, also be difficult to, therefore rely on the very difficult ultra-deep desulfurization of realizing oil fuel of method of hydrogenating desulfurization by hydrogenation and removing.In addition, the hydrogenating desulfurization technology must realize under high-temperature and high-pressure conditions that operating process is dangerous, cost of equipment is high, and therefore in recent years, mild condition, the oxidation desulfurizing method that equipment cost is lower receive more multiple looking.The method of oxidation sweetening is in the presence of catalyzer, through the oxygenant effect organosulfur compound to be oxidized to corresponding sulfoxide or sulfone compound, the method that through follow-up extraction process sulfoxide or the relatively large compound of sulfone class isopolarity is removed from oil fuel again.Because the oxidising process mild condition of organosulfur compound, reaction are thoroughly, therefore can realize the ultra-deep desulfurization of oil fuel by this method easily.In sum, select suitable reaction system, exploitation high-level efficiency, the organosulfur compound catalyst for oxidation reaction that is prone to reclaim just become the key issue of this research field.
In addition, the selective oxidation of organosulfur compound also is one of key issue that fine chemicals is synthetic and the drug manufacture field is paid close attention to.By the sulfone compound that the organosulfur compound oxidation obtains, be midbody or high-temperature solvent important in the Minute Organic Synthesis like METHYL SULFONYL METHANE., mould sulfone class, tetramethylene sulfone etc.And sulfoxide compound, especially chiral sulfoxide compounds such as omeprazole, lansoprazole etc. are the effective constituent in well-known medicine or the agricultural chemicals.Therefore realize organosulfur compound controllably selective oxidation be that corresponding sulfone or sulfoxide compound are very necessary.
USP 6,160,193 disclose and a kind of organosulfur compound have been oxidized to the method for corresponding sulfone, can be applied in the oxidation sweetening field of distillate.Yet the oxygenant that this patent is used is that strong oxidizer such as peroxyboric acid, persulfuric acid and temperature of reaction are higher, causes that a large amount of secondary reactions produce in the reaction process, and environmental pollution is very serious.
USP 6,916,938 to disclose a kind of oxide compound with tungsten and molybdenum be catalyzer, is oxygenant with the hydrogen peroxide, the oxidation organosulfur compound prepares the method for sulfone and sulfoxide compound.This method is for various thioether classes, and substituted thiophene class organosulfur compound generally is suitable for, and is a kind of general method for preparing sulfone and sulfoxide compound.Yet, cause its catalytic efficiency (not high, and this method is also not ideal enough to the selectivity of sulfoxide compound because the oxide compound and the consistency between organic substrates and the solvent of tungsten and molybdenum are poor.
Chinese patent 200710176267.6 discloses a kind of under the katalysis of the amphipathic catalyzer of surfactant modified multi-metal oxygen cluster; Organosulfur compound is corresponding sulfone in the use hydrogen peroxide oxidation diesel oil, and then removes the method that sulfide acquisition sulphur content is lower than the ultra-low-sulphur diesel of 10ppm through method of extraction.This catalyzer has extremely strong catalytic activity and selectivity to organosulfur compound, and technological process economy, environmental protection.But this reaction system still exists catalyst recovery difficulty and the lower deficiency of hydrogen peroxide utilization ratio.
Can find out that through above instance the hydrogen peroxide that development in recent years is got up/multi-metal oxygen cluster system can realize the oxidising process of sulfur-containing organic compound efficiently.In this system; Multi-metal oxygen cluster efficiently catalyzing hydrogen peroxide to the oxidising process of sulfur-bearing substrate; Play the effect of catalyzer; And hydrogen peroxide only generates water as oxygenant after reaction, and entire reaction course does not have the generation of other by product, is the organosulfur compound method for oxidation of a kind of green, environmental protection.But also there is certain problem in this reaction system, and multi-metal oxygen cluster is difficult to be dissolved in the organic systems such as gasoline, diesel oil as inorganics, and the effect of mass transmitting between the organosulfur compound is poor, has a strong impact on its catalytic effect.Present terms of settlement mainly is in reaction system, to add tensio-active agent as phase transfer reagent; Improve the consistency between multi-metal oxygen cluster catalyst and the organic substrates, yet consequent new problem is exactly the recycling of how from reaction system, to remove catalyzer and catalyzer.There is very big limitation in the existing reaction system that is used for the organosulfur compound catalyzed oxidation aspect activity of such catalysts and recycling; Therefore, can to solve mass transfer and the novel multi-metal oxygen cluster catalyst of recycling problem simultaneously all be ten minutes necessity for the theoretical investigation of the organic synthesis of sulfone or sulfoxide compound and oil fuel deep oxidation desulfurization and practical application in exploitation.
Summary of the invention
A kind of new purposes that the purpose of this invention is to provide surfactant modified multi-metal oxygen cluster/SiO 2 hybrid catalyzer, promptly this hybrid catalyst is the application aspect corresponding sulfone or the sulfoxide compound at the organosulfur compound controllable oxidization.
Above-mentioned catalyzer can solve multi-metal oxygen cluster simultaneously as consistency between catalyzer and the organic phase and recycling problem.This invention relates to chemistry and fields such as chemical industry, oil, environment, and resulting hybrid catalyst can be used for the organic synthesis of sulfone and sulfoxide compound, and the preparation of drug molecule and gasoline are in the deep oxidation desulfurization technology of oil fuel such as diesel oil.
Carrying out through tensio-active agent that static coats is to modify multi-metal oxygen cluster and with the effective means of its surface-treated; The present invention is exactly that the cats product coating multi-metal oxygen cluster that utilizes hydrophobic end to have hydroxyl obtains the surfactant modified multi-metal oxygen cluster organic/inorganic composite that outside surface has hydroxyl; Combine pure permutoid reaction and so-gel process again, prepare novel surfactant modified multi-metal oxygen cluster/SiO 2 hybrid catalyzer.Its inventive point is that surfactant modified multi-metal oxygen cluster mixture can type of being counted as reverse micelle system.Hydrophilic multi-metal oxygen cluster is positioned at the center, and peripheral alkyl chain is that multi-metal oxygen cluster provides a hydrophobic microenvironment, helps catching organic substrates, has solved consistency and mass transfer problem between multi-metal oxygen cluster and the organic substrates.In addition, because the mixture periphery has oh group, make it by covalently bound in silica matrix, to have played immobilized effect.The hybrid catalyst that obtains belongs to a kind of different-phase catalyst essentially, is convenient to the recycling of post catalyst reaction.The catalyzer that recovery obtains need not regeneration, can directly reuse, and utilize the catalytic efficiency (of catalyzer in the process to keep well again.In oxidation reaction process, as oxygenant, making does not have other by product to generate beyond dewatering in the entire reaction course, is the process of an environmental protection with hydrogen peroxide for we.In system, the utilization ratio of hydrogen peroxide can reach 80%.
The present invention realizes through following technical scheme: the cats product that utilizes hydrophobic end to have hydroxyl coats multi-metal oxygen cluster type of obtaining reverse micelle type supramolecular complex through static, combines sol-gel process that this mixture is obtained hybrid catalyst with common silicone agent mixing copolymerization again; At last, under the katalysis of this hybrid catalyst, as oxygenant organosulfur compound is oxidized to corresponding sulfone or sulfoxide compound with hydrogen peroxide.
The present invention includes following steps:
(1) hydroxyl cats product static coats the multi-metal oxygen cluster anions and makes mixture
The hydrophobic end that the present invention relates to has the cats product of hydroxyl, and its substruction is made up of cationic hydrophilic head groups such as quaternary ammonium salt or pyridinium salt and the terminal hydrophobic alkyl chain that has hydroxyl.Through the functional group and the alkyl chain length of design and adjusting surfactant molecule hydrophobic part, the surfactant modified multi-metal oxygen cluster/SiO 2 hybrid catalyzer that can obtain having different hydrophobic microenvironments and polarity size as required.
Wherein the synthetic of hydrophobic side hydroxyl quaternary ammonium salt cationic surfactant is through corresponding haloalkane [X (CH
2)
mCH
3], halo alkanol [X (CH
2)
mOH] and tertiary alcohol amine [(CH
3)
2N (CH
2)
mOH], tertiary amine [(CH
3)
2N (CH
2)
mCH
3] (X=Cl, Br here, quaterisation m=2-18) or halo alkanol and secondary amine { N [(CH
2)
nCH
3]
2(n=0-2) carry out two-step reaction quaternized realization.
The synthetic of the pyridine salt type cats product of hydrophobic side hydroxyl is through halo alkanol [X (CH
2)
mOH] realize with the quaterisation of pyridine.Can realize the synthetic of various tensio-active agents with different alkyl chain length and different quantities oh group by above method, thereby reach the purpose of peripheral hydrophobic part size of control mixture and hydrophobicity.
General molecular formula: (CH
3)
3N
+(CH
2)
nOH, (CH
3)
2N
+[(CH
2)
nOH]
2, (CH
3)
2N
+[(CH
2)
mCH
3] [(CH
2)
nOH], (C
6NH
5)
+[(CH
2)
nOH] tensio-active agent of (1≤n≤18,1≤m≤18 here) all be fit to the present invention (concrete compound method can reference Adv.Mater.2007,19,1983-1987; Adv.Mater.2005,17,2688-2692; Chem.Commun.2005,3785-3787).
The compound method of multi-metal oxygen cluster is simple, and a lot of bibliographical informations have been arranged, and the part multi-metal oxygen cluster is commercially produced, and therefore will directly use as raw material in the present invention.The multi-metal oxygen cluster of selecting for use among the present invention has: H
3PW
12O
40, H
4SiW
12O
40, H
3PMo
12O
40, Na
9[EuW
10O
36], K
12[EuP
5W
30O
110].Wherein, H
3PW
12O
40, H
4SiW
12O
40And H
3PMo
12O
40Buy from the Beijing Chemical Plant; K
12[EuP
5W
30O
110] with reference to Inorg.Chem.1993,32,1573 is synthetic; Na
9[EuW
10O
36] with reference to Bull.Chem.Soc.Jpn.1993,66,444 is synthetic.Other common multi-metal oxygen cluster is like H
4SiMo
12O
40, H
3AsW
12O
40, K
6P
2W
18O
62, K
6P
2Mo
18O
62, K
6As
2W
18O
62, Na
9FeMo
6O
24, Na
3{ PO
4[WO (O
2)
2]
4, Na
12[ZnWZn
2(H
2O)
2(ZnW
9O
34)
2] also all be fit to the present invention.Because surfactant molecule and multi-metal oxygen cluster compound motivating force are electrostatic forces; Therefore the method for this surfactant modified multi-metal oxygen cluster all is blanket for all multi-metal oxygen clusters, in practical application, can select the multi-metal oxygen cluster of other type to coat as required.On method for coating, because the dissolubility difference of surfactant can adopt " homogeneous phase coats in the aqueous solution " and " coating of organic and inorganic two-phase " dual mode.Be suitable for adopting the method that homogeneous phase coats in the aqueous solution for tensio-active agent soluble in water,, be fit to the method that adopts organic and inorganic two to coat mutually for the tensio-active agent that is soluble in organic solvent.
The homogeneous phase coating is that multi-metal oxygen cluster to be coated is soluble in water in the aqueous solution, and keeping concentration is 5～15 mg/ml; In addition that the cats product of hydrophobic side hydroxyl is soluble in water, keeping concentration is 5～10 mg/ml; Control the two consumption, making the ratio of total charge number of total charge number and the multi-metal oxygen cluster of tensio-active agent is 0.80: 1～1: 1, and wherein the total charge number equals the individual molecule charge number and multiply by molar weight.Under whipped state; The multi-metal oxygen cluster aqueous solution is added drop-wise in the water phase surfactant mixture, continues to stir after 0.2～10 hour, generate mixture and separate out with precipitation forms; Collect and to precipitate; Be drying to obtain the multi-metal oxygen cluster electrostatic complexes that the hydroxyl cats product is modified, because the existence of peripheral oh group, the gained mixture can be dissolved in the ethanol well.
It is that multi-metal oxygen cluster to be coated is soluble in water that organic and inorganic two coats mutually, and keeping concentration is 5～15 mg/ml; Cats product with the hydrophobic side hydroxyl is dissolved in the organic solvent (like methylene dichloride, ethylene dichloride, chloroform, benzene, toluene and ether) again, and keeping concentration is 5～10 mg/ml; Control the two consumption, making the ratio of total charge number of total charge number and the multi-metal oxygen cluster of tensio-active agent is 0.80: 1～1: 1, and wherein the total charge number equals the individual molecule charge number and multiply by molar weight; Under whipped state; The organic solution (not dissolving each other with water) of tensio-active agent is added drop-wise in the multi-metal oxygen cluster aqueous solution; Continue to stir after 0.2～10 hour and with separating funnel organic phase is told, organic phase adds anhydrous sodium sulfate drying by/100 milliliters of 0.2～0.5 grams and handles again with washing 2～5 times; Filter at last and solvent evaporated; Obtain the multi-metal oxygen cluster electrostatic complexes that the hydroxyl cats product is modified, because the existence of peripheral oh group, the gained mixture can be dissolved in the ethanol well.
(2) mixture and silicone agent make hybrid catalyst by sol-gel process
Pure permutoid reaction can take place with silicone agent in the mixture that is obtained by above method, and silicone agent connects into network through method hydrolysis, the condensation of sol-gel, forms surfactant modified multi-metal oxygen cluster/SiO 2 hybrid catalyzer.Being fit to silicone agent of the present invention has tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane and four butoxy silanes, and these silicone agents can be commercially produced, and will directly use as raw material in the present invention.
The surfactant modified multi-metal oxygen cluster mixture that the outside surface that obtains in the step (1) is had hydroxyl is dissolved in ethanol, propyl alcohol, Virahol or the butanols; Concentration is 5～10 mg/ml; Adding and silicone agent mol ratio are 1: 1～1: 20 water, add silicone agent again, and making the doping mass percent of mixture in the reaction system (it is outer to desolventize alcohols and water) is 1～50 (wt) %; Be that mixture/(mixture+silicone agent) is 1～50 (wt) %; Stirring at room 1～3 hour is abundant to guarantee hydrolysis, with this colloidal sol sealing aged at room temperature 10～15 days, uncoveredly again is placed in the air Air drying 5～10 days; Obtain block gel solid, at last with this solid vacuum-drying after 24～36 hours porphyrize promptly obtain surfactant modified multi-metal oxygen cluster/SiO 2 hybrid catalyzer.
(3) catalytic oxidation of sulfocompound
Multi-metal oxygen cluster can be oxidized to highly active peroxide multi-metal oxygen cluster compound in the presence of oxidants hydrogen peroxide; And surfactant modified multi-metal oxygen cluster mixture has a hydrophobic shell; Hydrophobic organosulfur compound can attracted near the active peroxide multi-metal oxygen cluster compound through hydrophobic interaction; And be oxidized into bigger sulfone of polarity or sulfoxide compound; Thereby the hydrophobic microenvironment that is constituted by the tensio-active agent alkyl chain discharges, and multi-metal oxygen cluster returns to original state and accomplished the catalytic chain process one time simultaneously.Oxidized fully when substrate, after reaction stopped, catalyzer can obtain reclaiming with filtering method, and the catalyzer that recovery obtains has represented and the identical catalytic effect of new preparation catalyzer.
With organosulfur compound; Like thionaphthene, dibenzothiophene, 4; 6-dimethyl--dibenzothiophene, diphenyl sulfide, hexichol ethyl thioether, diphenyl-methyl thioether, thioanisole, ethyl phenyl sulfide, diethyl thioether; Dimethyl sulphide is dissolved in acetonitrile, acetone, chloroform, normal hexane or the dodecyl, keeps concentration 1～10 mg/ml, and adding and organosulfur compound mol ratio are 1: 200～1: 1000 hybrid catalyst; Add hydrogen peroxide again, the mol ratio that makes hydrogen peroxide and organosulfur compound is 1: 1～3: 1.40 ℃～80 ℃ following stirring reactions 0.5～2.0 hour, make to react completely.Reaction with the filtering of solid hybrid catalyst, promptly obtains the solution of oxidation products sulfone or sulfoxide after finishing.The catalyzer that recovery obtains can directly reuse, and the catalytic efficiency (of catalyzer does not obviously descend for five times through recycle.
Compare with known technology, the present invention has following characteristics and advantage:
(1) surfactant molecule is in hydrophobic nanometer microenvironment of the peripheral formation of multi-metal oxygen cluster; Can be adsorbed with organic sulfur compound effectively; Solved the problem of consistency between multi-metal oxygen cluster and the organic phase; Improved activity of such catalysts, enabled the oxidizing reaction of efficient catalytic sulfocompound, the dibenzothiophene that particularly is difficult to remove for conventional hydrodesulfurizationprocess process can be realized slap-up oxidation.
(2) owing to adopted the mode of heterocatalysis, catalyzer can obtain through the method for simple filtering reclaiming.The catalyzer that recovery obtains need not regeneration and just can directly utilize again, and the catalytic activity of catalyzer does not obviously descend through recycle.
(3) in oxidation reaction process, utilize hydrogen peroxide as oxygenant, do not have any by product beyond dewatering in the entire reaction course and generate, be the process of an environmental protection.
(4) through control to reaction conditions; This catalyzer can be realized the high-selectivity oxidation to organic sulfide; Thereby be used for preparing sulfoxide class or sulfone compound, be expected to, the deep oxidation desulfurization field performance using value of medication preparation and oil fuel in Minute Organic Synthesis.
Description of drawings
Fig. 1: multi-metal oxygen cluster/SiO 2 hybrid Preparation of Catalyst and catalytic process synoptic diagram;
The NMR spectrum of Fig. 2: surfactant D OHDA (a) and ir spectra (b);
The H that Fig. 3: surfactant D OHDA modifies
3PW
12O
40Mixture and H
3PW
12O
40/ DOHDA/SiO
2The ir spectra of hybrid catalyst;
The K that Fig. 4: surfactant D OHDA modifies
12[EuP
5W
30O
110] mixture and K
12[EuP
5W
30O
110]/DOHDA/SiO
2The ir spectra of hybrid catalyst;
Fig. 5: H
3PW
12O
40/ DOHDA/SiO
2The N of hybrid catalyst
2Adsorption curve (a) and graph of pore diameter distribution (b and illustration);
Fig. 6: the NMR spectrum of substrate dibenzothiophene (DBT) under different microenvironments;
Fig. 7: the performance liquid chromatography of hybrid catalyst catalyzed oxidation dibenzothiophene reaction process;
Fig. 8: material is the NMR spectrum (a) and the ir spectra (b) of dibenzothiophene (DBT) and dibenzothiophene sulfone (DBTS) before and after the catalytic oxidation.
Fig. 1 has described hydroxyl cats product static and has coated multi-metal oxygen cluster; Form organic-inorganic composite body, this mixture further with the oxidation reaction process of silicone agent prepared in reaction multi-metal oxygen cluster/SiO 2 hybrid catalyzer and hybrid catalyst catalysis sulfocompound.Wherein, hydroxyl cats product intermediate cam shape is the positively charged ion head partly, has positive charge, and oval part is an oh group.Multi-metal oxygen cluster has negative charge owing to surperficial counter ion in water dissociate.Through electrostatic interaction, obtain having the surfactant modified multi-metal oxygen cluster mixture of hydrophobic shell.Obtain tensio-active agent through sol gel reaction again and coat multi-metal oxygen cluster/SiO 2 hybrid catalyzer, wherein rectangular boxes is represented silica matrix.At last, hybrid catalyst can be used for the reaction of catalyzing hydrogen peroxide oxidation organosulfur compound.
Fig. 2 is NMR spectrum figure (a) and the infrared spectrogram (b) of surfactant D OHDA, through (the 3365cm that points out that points out (seeing among the figure) and ir spectra peak to nuclear magnetic signal
-1, O-H antisymmetric stretching vibration, 2921,2849cm
-1, CH
2Unsymmetrically and symmetrical stretching vibration, 1468cm
-1, CH
2Scissoring vibration, 1055cm
-1, the C-O stretching vibration.), confirm to successfully synthesize title product: N, two (the 11-hydroxyl undecyl) brometo de amonios of N-dimethyl-.
Fig. 3 (rolling off the production line) is embodiment 1-1 synthetic H
3PW
12O
40The infrared spectrogram of/DOHDA mixture through to the pointing out of ir spectra, is found multi-metal oxygen cluster H
3PW
12O
40Eigen vibration peak (1080cm
-1, P-O stretching vibration, 981cm
-1, W-O
dAntisymmetric stretching vibration, 896cm
-1, W-Oc-W antisymmetric stretching vibration, 807cm
-1, W-O
c-W antisymmetric stretching vibration.) and the eigen vibration peak of surfactant D OHDA (2921,2851cm
-1, CH
2Unsymmetrically and symmetrical stretching vibration, 1468cm
-1, CH
2Scissoring vibration.) exist simultaneously, confirm to coat successfully.
Fig. 3 (reaching the standard grade) is embodiment 2-1 synthetic H
3PW
12O
40/ DOHDA/SiO
2The infrared spectrogram of hybrid catalyst can be found eigen vibration peak all embodiments to some extent in the ir spectra of the hybrid catalyst of final gained of tensio-active agent and multi-metal oxygen cluster in the mixture, (DOHDA:2924,2853cm through contrast
-1, CH
2Unsymmetrically and symmetrical stretching vibration, H
3PW
12O
40: 807cm
-1, the W-Oc-W antisymmetric stretching vibration.) and at 1068cm
-1And 1158cm
-1Two new vibration peak appear, respectively the stretching vibration of corresponding C-O-Si and Si-O-Si.These show all that mixture successfully is incorporated in the silicon dioxide hybrid materials and through covalent linkage and are connected on the silicon dioxide skeleton that we have obtained the hybrid catalyst of design in advance.
Fig. 4 (rolling off the production line) is embodiment 1-3 synthetic K
12[EuP
5W
30O
110The infrared spectrogram of]/DOHDA mixture through to the pointing out of ir spectra, is found multi-metal oxygen cluster K
12[EuP
5W
30O
110] eigen vibration peak (1157cm
-1, P-O
dAntisymmetric stretching vibration, 918cm
-1, W-Oc-W antisymmetric stretching vibration, 794cm
-1, W-O
c-W antisymmetric stretching vibration.) and the eigen vibration peak of surfactant D OHDA (2921,2850cm
-1, CH
2Unsymmetrically and symmetrical stretching vibration, 1467cm
-1, CH
2Scissoring vibration, 1064cm
-1, the C-O stretching vibration.) exist simultaneously, confirm to coat successfully.
Fig. 4 (reaching the standard grade) is embodiment 2-1 synthetic K
12[EuP
5W
30O
110]/DOHDA/SiO
2The infrared spectrogram of hybrid catalyst can be found eigen vibration peak all embodiments to some extent in the ir spectra of the hybrid catalyst of final gained of tensio-active agent and multi-metal oxygen cluster in the mixture, (DOHDA:2921,2850cm through contrast
-1, CH
2Unsymmetrically and symmetrical stretching vibration, H
3PW
12O
40: 794cm
-1, the W-Oc-W antisymmetric stretching vibration.) and at 1082cm
-1And 1165cm
-1Two new vibration peak appear, respectively the stretching vibration of corresponding C-O-Si and Si-O-Si.These show all that mixture successfully is incorporated in the silicon dioxide hybrid materials and through covalent linkage and are connected on the silicon dioxide skeleton that we have obtained the hybrid catalyst of design in advance.
Fig. 5 is H
3PW
12O
40/ DOHDA/SiO
2The N of hybrid catalyst
2Adsorption curve (a) and graph of pore diameter distribution (b and illustration).Analysis and calculating through to figure a can be confirmed H
3PW
12O
40/ DOHDA/SiO
2The specific surface area of hybrid catalyst is 365.9m
2/ g, total pore volume are 1.05cm
3/ g.Can find out H from figure b
3PW
12O
40/ DOHDA/SiO
2Hybrid catalyst has represented the pore size distribution range of a non-constant width.The existence of this micropore/meso-hole structure makes organic substrates and product can free in and out catalyzer inside, contacts with the multi-metal oxygen cluster catalytic center and reacts.
Fig. 6 be substrate dibenzothiophene (descending) and dibenzothiophene respectively with pure SiO
2(in) and H
3PW
12O
40/ DOHDA/SiO
2Hybrid catalyst (on) the blended NMR spectrum.Can find out from this figure: as substrate dibenzothiophene and SiO
2After the mixing, nuclear magnetic signal reduces but chemical displacement value is constant.This shows SiO
2Can adsorb dibenzothiophene, but its chemical environment is basic identical with in solution the time.As substrate dibenzothiophene and H
3PW
12O
40/ DOHDA/SiO
2After hybrid catalyst mixed, nuclear magnetic signal further descended and chemical displacement value increases.This shows H
3PW
12O
40/ DOHDA/SiO
2Hybrid catalyst can more effectively adsorb dibenzothiophene, and dibenzothiophene is not to be adsorbed on SiO in hybrid catalyst
2The matrix part, but more be prone to be adsorbed on H
3PW
12O
40The hydrophobic part that/DOHDA mixture is constituted.The explanation of above experimental data we can adsorb hydrophobic substrate dibenzothiophene by the hybrid catalyst with similar reverse micelle structure of design effectively, solved the mass transfer problem between hydrophilic multi-metal oxygen cluster in the catalytic process and the hydrophobic substrate.
Fig. 7 follows the tracks of H with the method for performance liquid chromatography
3PW
12O
40/ DOHDA/SiO
2The color atlas that the oxidizing reaction process of hybrid catalyst catalyzed oxidation dibenzothiophene obtains.As can be seen from the figure, (0min) only has a kind of chromatographic signal of material when reacting initial, i.e. the chromatographic signal of substrate dibenzothiophene.(chromatographic signal of 5～30min) dibenzothiophene weakens gradually, a chromatographic peak appearance and the enhancing gradually that new chromatographic peak is a product dibenzothiophene sulfone along with the carrying out that reacts.Reaction is when proceeding to 40min, and the chromatographic peak of dibenzothiophene disappears, and the chromatogram peak value of product dibenzothiophene sulfone reaches maximum, shows that reaction accomplished, and dibenzothiophene has been converted into corresponding sulfone fully.
Fig. 8 is the NMR spectrum figure (a) and the infrared spectrogram (b) of material before and after the catalytic oxidation.Through confirming that to the pointing out of chemical displacement value (seeing among the figure) among the figure a substrate dibenzothiophene is converted into the dibenzothiophene sulfone fully through catalytic oxidation process.Ir spectra has proved this point equally.In the infrared spectrogram of substrate dibenzothiophene, 3062 and 3021cm
-1It is the stretching vibration peak of CH on the phenyl ring; 1584 and 1430cm
-1It is phenyl ring skeletal vibration characteristic peak; 735cm
-1It is the flexural vibration peak of CH on the phenyl ring.And in the infrared spectrogram of product except the eigen vibration peak of dibenzothiophene occurs, also 1288 and 1166cm
-1Two new peaks occur, corresponded respectively to unsymmetrically and the symmetrical stretching vibration of S=O.The appearance of the characteristic peak of these two sulfone compounds has proved that also product is the dibenzothiophene sulfone.
Table 1 is H
3PW
12O
40/ DOHDA mixture and K
12[EuP
5W
30O
110The results of elemental analyses of]/DOHDA mixture can be confirmed the substruction of two kinds of mixtures through the comparative analysis of experimental value and theoretical value.For H
3PW
12O
40/ DOHDA mixture, on average each multi-metal oxygen cluster H
3PW
12O
40On coating 3 DOHDA molecules, and for K
12[EuP
5W
30O
110]/DOHDA mixture, on average each multi-metal oxygen cluster K
12[EuP
5W
30O
110] on coating 11 DOHDA molecules.
Table 1:H
3PW
12O
40/ DOHDA and K
12[EuP
5W
30O
110The results of elemental analyses of]/DOHDA mixture
Table 2 is H
3PW
12O
40/ DOHDA/SiO
2The catalytic kinetics of hybrid catalyst catalyzing hydrogen peroxide oxidation dibenzothiophene reaction in the opposed polarity solvent and the conclusive table of efficient.Wherein, the oxidizing reaction that is defined as organosulfur compound proceeded to for 99% needed time the reaction times; The first order reaction rate constant of reaction rate constant for calculating through the performance liquid chromatography monitoring reaction; Turn over number is defined as the organosulfur compound mole number that every mol catalyst in the unit time can catalyzed oxidation; Transformation efficiency is defined as the conversion mole number of substrate organosulfur compound and the per-cent of initial mole number ratio; The hydrogen peroxide utilization ratio is defined as the hydrogen peroxide mole number of participating in reaction and the per-cent that drops into hydrogen peroxide mole number ratio.From then on can find out in the table: no matter our synthetic hybrid catalyst is that the oxidizing reaction of dibenzothiophene is carried out fully.Be reflected in 45-200 minute and accomplish.
Table 2:H
3PW
12O
40/ DOHDA/SiO
2Hybrid catalyst is catalyzing hydrogen peroxide oxidation dibenzothiophene response data conclusive table in different solvents
| Solvent | Density (g/cm -3) | Polarity (relatively) | Reaction times (min) | Reaction rate constant (min -1) | Turn over number (min -1) | Transformation efficiency | The hydrogen peroxide utilization ratio |
| Acetonitrile | 0.78 | 6.2 | 42 | 0.111 | 9.52 | 100％ | 80％ |
| Acetone | 0.79 | 5.4 | 58 | 0.078 | 6.90 | 100％ | 80％ |
| Chloroform | 1.50 | 4.4 | 153 | 0.030 | 2.61 | 100％ | 80％ |
| Normal hexane | 0.66 | 0.06 | 43 | 0.107 | 9.30 | 100％ | 80％ |
| Dodecyl | 0.75 | 0 | 38 | 0.118 | 10.53 | 100％ | 80％ |
Table 3 is H
3PW
12O
40/ DOHDA/SiO
2The catalytic kinetics of hybrid catalyst different organosulfur compounds of catalyzing hydrogen peroxide oxidation in acetonitrile solvent and the conclusive table of efficient.Wherein, turn over number is defined as the organosulfur compound mole number that every mol catalyst in the unit time can catalyzed oxidation; Transformation efficiency is defined as the conversion mole number of substrate organosulfur compound and the per-cent of initial mole number ratio; The selectivity definition is the per-cent of principal product mole number with whole product mole number ratios.From then on can find out in the table: we have good catalytic efficiency (and selectivity for the reaction that various organic sulfides are oxidized to corresponding sulfone or sulfoxide by the synthetic hybrid catalyst.
Table 3:H
3PW
12O
40/ DOHDA/SiO
2The catalytic kinetics of hybrid catalyst different sulfur-bearing substrates of catalyzing hydrogen peroxide oxidation in acetonitrile solvent and the conclusive table of efficient
The reaction times turn over number
Organosulfur compound principal product transformation efficiency selectivity
(min) (min
-1)
Dibenzothiophene 42 dibenzothiophene sulfones 9.52 100% 100%
Diphenyl sulfide 22 diphenyl sulfide sulfones 18.18 100% 100%
Thioanisole 24 thioanisole sulfones 16.67 100% 100%
Dimethyl sulphide 17 dimethyl sulphide sulfones 23.52 100% 100%
Dibenzothiophene 120 dibenzothiophene sulfoxides 7.25 87% 66%
Diphenyl sulfide 90 diphenyl sulfide sulfoxides 11.11 100% 100%
Thioanisole 70 thioanisole sulfoxides 14.29 100% 100%
Dimethyl sulphide 70 dimethyl sulphide sulfoxides 14.29 100% 100%
Embodiment
Following specific embodiment is that the present invention is done further elaboration, does not limit the invention and do not represent according to this.
1, reverse micelle type hydroxyl surface promoting agent is modified constructing of multi-metal oxygen cluster mixture
Embodiment 1-1:
N, two (11-hydroxyl undecyl) brometo de amonios of N-dimethyl-(being called for short DOHDA) coat H
3PW
12O
40
0.2 gram DOHDA is dissolved in 30 ml waters 0.41 gram H
3PW
12O
40Be dissolved in 20 ml waters DOHDA and H
3PW
12O
40Mol ratio be 3: 1 (charge ratio is 3: 3).Under whipped state, with H
3PW
12O
40The aqueous solution is added drop-wise in the DOHDA aqueous solution.Continue to stir after 1 hour, the deposition that generates is leached with molten hourglass bucket, obtain white solid, room temperature vacuum-drying, productive rate 50%.
Embodiment 1-2:
N, two (11-hydroxyl undecyl) brometo de amonios of N-dimethyl-(being called for short DOHDA) coat H
4SiW
12O
40
0.2 gram DOHDA is dissolved in 30 ml waters 0.31 gram H
4SiW
12O
40Be dissolved in 20 ml waters DOHDA and H
4SiW
12O
40Mol ratio be 4: 1 (charge ratio is 4: 4).Under whipped state, with H
4SiW
12O
40The aqueous solution is added drop-wise in the DOHDA aqueous solution.Continue to stir after 1 hour, the deposition that generates is leached with molten hourglass bucket, obtain white solid, room temperature vacuum-drying, productive rate 50%.
Embodiment 1-3:
N, two (11-hydroxyl undecyl) brometo de amonios of N-dimethyl-(being called for short DOHDA) coat K
12[EuP
5W
30O
110]
0.2 gram DOHDA is dissolved in 30 ml waters 0.29 gram K
12[EuP
5W
30O
110] be dissolved in 20 ml waters DOHDA and K
12[EuP
5W
30O
110] mol ratio be 12: 1 (charge ratio is 12: 12).Under whipped state, with K
12[EuP
5W
30O
110] aqueous solution is added drop-wise in the DOHDA aqueous solution.Continue to stir after 1 hour, the deposition that generates is leached with molten hourglass bucket, obtain white solid, room temperature vacuum-drying, productive rate 50%.
Embodiment 1-4:
N, two (11-hydroxyl undecyl) brometo de amonios of N-dimethyl-(being called for short DOHDA) coat Na
9EuW
10O
36
0.2 gram DOHDA is dissolved in 30 ml waters 0.16 gram Na
9EuW
10O
36Be dissolved in 20 ml waters DOHDA and Na
9EuW
10O
36Mol ratio be 9: 1 (charge ratio is 9: 9).Under whipped state, with Na
9EuW
10O
36The aqueous solution is added drop-wise in the DOHDA aqueous solution.Continue to stir after 1 hour, the deposition that generates is leached with molten hourglass bucket, obtain white solid, room temperature vacuum-drying, productive rate 50%.
Embodiment 1-5:
N, two (11-hydroxyl undecyl) brometo de amonios of N-dimethyl-(being called for short DOHDA) coat H
3PMo
12O
40
0.2 gram DOHDA is dissolved in 30 ml waters 0.26 gram H
3PMo
12O
40Be dissolved in 20 ml waters DOHDA and H
3PMo
12O
40Mol ratio be 3: 1 (charge ratio is 3: 3).Under whipped state, with H
3PMo
12O
40The aqueous solution is added drop-wise in the DOHDA aqueous solution.Continue to stir after 1 hour, the deposition that generates is leached with molten hourglass bucket, obtain white solid, room temperature vacuum-drying, productive rate 50%.
Embodiment 1-6:
Bromination 11-pyridone salt coats H
3PW
12O
40
0.2 gram bromination 11-pyridone salt is dissolved in 30 ml waters 0.56 gram H
3PW
12O
40Be dissolved in 20 ml waters bromination 11-pyridone salt and H
3PW
12O
40Mol ratio be 3: 1 (charge ratio is 3: 3).Under whipped state, with H
3PW
12O
40The aqueous solution is added drop-wise in the bromination 11-pyridone salt brine solution.Continue to stir after 1 hour, the deposition that generates is leached with molten hourglass bucket, obtain white solid, room temperature vacuum-drying, productive rate 50%.
Embodiment 1-7:
N, N-dimethyl stearyl (11-hydroxyl) undecyl brometo de amonio coats H
3PW
12O
40
With 0.2 gram N, N-dimethyl stearyl (11-hydroxyl) undecyl brometo de amonio is dissolved in 30 milliliters of chloroforms, 0.35 gram H
3PW
12O
40Be dissolved in 30 ml waters N, N-dimethyl stearyl (11-hydroxyl) undecyl brometo de amonio and H
3PW
12O
40Mol ratio be 3: 1 (charge ratio is 3: 3).Under whipped state, with N, N-dimethyl stearyl (11-hydroxyl) undecyl brometo de amonio chloroformic solution is added drop-wise to H
3PW
12O
40In the aqueous solution.Continue to stir after 1 hour, static layering is told lower floor's organic phase with separating funnel.Organic phase water washed twice adds anhydrous sodium sulfate drying, (the SODIUM SULPHATE ANHYDROUS 99PCT consumption is about/100 milliliters of 0.2 grams).After 1 hour, leach sodium sulfate, filtrating gets the white compound solid after rotary evaporation is removed chloroform, obtain white solid, room temperature vacuum-drying, productive rate 50%.
2, mixture and silicone agent reaction, the preparation of hybrid catalyst
Embodiment 2-1:
H
3PW
12O
40/ DOHDA mixture and tetraethoxysilane sol gel reaction
The mixture that 0.1 gram embodiment 1-1 is made is dissolved in 20 milliliters of ethanol, adds 0.3 ml water, stirring, ultrasonic mixing; Add 0.9 gram tetraethoxysilane; Stirring at room 3 hours with solvent rotary evaporation to 2 milliliter, is sealed this colloidal sol aging 15 days; Uncovered drier 10 days, can obtain mixture quality percentage composition and be 10% hybrid catalyst.
Use the same method, change the mixture quality, can obtain mixture quality percentage composition and be 1～50% tensio-active agent and coat multi-metal oxygen cluster/SiO 2 hybrid catalyzer.
Embodiment 2-2:
H
4SiW
12O
40/ DOHDA mixture and tetraethoxysilane sol gel reaction
The mixture that 0.1 gram embodiment 1-2 is made is dissolved in 20 milliliters of ethanol, adds 0.3 ml water, stirring, ultrasonic mixing; Add 0.9 gram tetraethoxysilane; Stirring at room three hours with solvent rotary evaporation to 2 milliliter, is sealed this colloidal sol aging 15 days; Uncovered drier 10 days, can obtain mixture quality percentage composition and be 10% hybrid catalyst.
Use the same method, change the mixture quality, can obtain mixture quality percentage composition and be 1～50% tensio-active agent and coat multi-metal oxygen cluster/SiO 2 hybrid catalyzer.
Embodiment 2-3:
K
12[EuP
5W
30O
110]/DOHDA mixture and tetraethoxysilane sol gel reaction
The mixture that 0.1 gram embodiment 1-3 is made is dissolved in 20 milliliters of ethanol, adds 0.3 ml water, stirring, ultrasonic mixing; Add 0.9 gram tetraethoxysilane; Stirring at room three hours with solvent rotary evaporation to 2 milliliter, is sealed this colloidal sol aging 15 days; Uncovered drier 10 days, can obtain mixture quality percentage composition and be 10% hybrid catalyst.
Use the same method, change the mixture quality, can obtain mixture quality percentage composition and be 1～50% tensio-active agent and coat multi-metal oxygen cluster/SiO 2 hybrid catalyzer.
Embodiment 2-4:
Na
9EuW
10O
36/ DOHDA mixture and tetraethoxysilane sol gel reaction
The mixture that 0.1 gram embodiment 1-4 is made is dissolved in 20 milliliters of ethanol, adds 0.3 ml water, stirring, ultrasonic mixing; Add 0.9 gram tetraethoxysilane; Stirring at room three hours with solvent rotary evaporation to 2 milliliter, is sealed this colloidal sol aging 15 days; Uncovered drier 10 days, can obtain mixture quality percentage composition and be 10% hybrid catalyst.
Use the same method, change the mixture quality, can obtain mixture quality percentage composition and be 1～50% tensio-active agent and coat multi-metal oxygen cluster/SiO 2 hybrid catalyzer.
Embodiment 2-5:
H
3PW
12O
40/ bromination 11-pyridone salt composite and tetraethoxysilane sol gel reaction
The mixture that 0.1 gram embodiment 1-6 is made is dissolved in 20 milliliters of ethanol, adds 0.3 ml water, stirring, ultrasonic mixing; Add 0.9 gram tetraethoxysilane; Stirring at room three hours with solvent rotary evaporation to 2 milliliter, is sealed this colloidal sol aging 15 days; Uncovered drier 10 days, can obtain mixture quality percentage composition and be 10% hybrid catalyst.
Use the same method, change the mixture quality, can obtain mixture quality percentage composition and be 1～50% tensio-active agent and coat multi-metal oxygen cluster/SiO 2 hybrid catalyzer.
3, the process of hybrid catalyst catalyzed oxidation sulfocompound
Embodiment 3-1:
H
3PW
12O
40/ DOHDA/SiO
2Hybrid catalyst catalyzed oxidation dibenzothiophene is the dibenzothiophene sulfone
0.1 gram substrate dibenzothiophene is dissolved in 100 milliliters of acetonitriles; Add hybrid catalyst 0.055 gram that embodiment 2-1 makes; Add massfraction again and be 30% aqueous hydrogen peroxide solution 0.154 gram; Make multi-metal oxygen cluster, dibenzothiophene with the mole ratio of hydrogen peroxide is: 1: 400: 1000.Stirred this mixing solutions 45 minutes down at 40 ℃, after the cooling, detect, have the dibenzothiophene more than 99% to be converted into corresponding sulfone through NMR spectrum and chromatogram.
Acetone, chloroform, hexane or dodecyl also can be used as reaction solvent and use, and are respectively 58,153,43 and 38 minutes in the identical following reaction times of reaction conditions.
Embodiment 3-2:
H
4SiW
12O
40/ DOHDA/SiO
2Hybrid catalyst catalyzed oxidation dibenzothiophene is the dibenzothiophene sulfone
0.1 gram substrate dibenzothiophene is dissolved in 100 milliliters of acetonitriles; Add hybrid catalyst 0.060 gram that embodiment 2-2 makes; Add massfraction again and be 30% aqueous hydrogen peroxide solution 0.154 gram; Make multi-metal oxygen cluster, dibenzothiophene with the mole ratio of hydrogen peroxide is: 1: 400: 1000.Stirred this mixing solutions 50 minutes down at 40 ℃, after the cooling, detect, have the dibenzothiophene more than 99% to be converted into corresponding sulfone through NMR spectrum and chromatogram.
Embodiment 3-3:
K
12[EuP
5W
30O
110]/DOHDA/SiO
2Hybrid catalyst catalyzed oxidation dibenzothiophene is the dibenzothiophene sulfone
0.1 gram substrate dibenzothiophene is dissolved in 100 milliliters of acetonitriles; Add hybrid catalyst 0.161 gram that embodiment 2-3 makes; Add massfraction again and be 30% aqueous hydrogen peroxide solution 0.154 gram; Make multi-metal oxygen cluster, dibenzothiophene with the mole ratio of hydrogen peroxide is: 1: 400: 1000.Stirred this mixing solutions 50 minutes down at 40 ℃, after the cooling, detect, have the dibenzothiophene more than 99% to be converted into corresponding sulfone through NMR spectrum and chromatogram.
Embodiment 3-4:
H
3PW
12O
40/ DOHDA/SiO
2Hybrid catalyst catalyzed oxidation diphenyl sulfide is the diphenyl sulfide sulfone
0.1 gram substrate diphenyl sulfide is dissolved in 100 milliliters of acetonitriles; Add hybrid catalyst 0.054 gram that embodiment 2-1 makes; Add massfraction again and be 30% aqueous hydrogen peroxide solution 0.152 gram; Make multi-metal oxygen cluster, diphenyl sulfide with the mole ratio of hydrogen peroxide is: 1: 400: 1000.Stirred this mixing solutions 22 minutes down at 40 ℃, after the cooling, detect, have the diphenyl sulfide more than 99% to be converted into corresponding diphenyl sulfide sulfone through NMR spectrum and chromatogram.
Embodiment 3-5:
H
3PW
12O
40/ DOHDA/SiO
2Hybrid catalyst catalyzed oxidation thioanisole is the thioanisole sulfone
0.1 gram substrate thioanisole is dissolved in 100 milliliters of acetonitriles; Add hybrid catalyst 0.082 gram that embodiment 2-1 makes; Add massfraction again and be 30% aqueous hydrogen peroxide solution 0.228 gram; Make multi-metal oxygen cluster, thioanisole with the mole ratio of hydrogen peroxide is: 1: 400: 1000.Stirred this mixing solutions 24 minutes down at 40 ℃, after the cooling, detect, have the thioanisole more than 99% to be converted into corresponding thioanisole sulfone through NMR spectrum and chromatogram.
Embodiment 3-6:
H
3PW
12O
40/ DOHDA/SiO
2Hybrid catalyst catalyzed oxidation dimethyl sulphide is the dimethyl sulphide sulfone
0.1 gram substrate dimethyl sulphide is dissolved in 100 milliliters of acetonitriles; Add hybrid catalyst 0.16 gram that embodiment 2-1 makes; Add massfraction again and be 30% aqueous hydrogen peroxide solution 0.456 gram; Make multi-metal oxygen cluster, dimethyl sulphide with the mole ratio of hydrogen peroxide is: 1: 400: 1000.Stirred this mixing solutions 17 minutes down at 40 ℃, after the cooling, detect, have the dimethyl sulphide more than 99% to be converted into corresponding dimethyl sulphide sulfone through NMR spectrum and chromatogram.
Embodiment 3-7:
H
3PW
12O
40/ DOHDA/SiO
2Hybrid catalyst catalyzed oxidation dibenzothiophene is the dibenzothiophene sulfoxide
0.1 gram substrate dibenzothiophene is dissolved in 100 milliliters of acetonitriles; Add hybrid catalyst 0.022 gram that embodiment 2-1 makes; Add massfraction again and be 30% aqueous hydrogen peroxide solution 0.154 gram; Make multi-metal oxygen cluster, dibenzothiophene with the mole ratio of hydrogen peroxide is: 1: 1000: 1000.Down stirred these mixing solutionss 120 minutes at 40 ℃, after the cooling, detect, have 66% dibenzothiophene to be converted into corresponding dibenzothiophene sulfoxide through NMR spectrum.
Embodiment 3-8:
H
3PW
12O
40/ DOHDA/SiO
2Hybrid catalyst catalyzed oxidation diphenyl sulfide is the diphenyl sulfide sulfoxide
0.1 gram substrate diphenyl sulfide is dissolved in 100 milliliters of acetonitriles; Add hybrid catalyst 0.022 gram that embodiment 2-1 makes; Add massfraction again and be 30% aqueous hydrogen peroxide solution 0.152 gram; Make multi-metal oxygen cluster, diphenyl sulfide with the mole ratio of hydrogen peroxide is: 1: 1000: 1000.Stirred this mixing solutions 90 minutes down at 40 ℃, after the cooling, detect, have the diphenyl sulfide more than 99% to be converted into corresponding diphenyl sulfide sulfoxide through NMR spectrum and chromatogram.
Embodiment 3-9:
H
3PW
12O
40/ DOHDA/SiO
2Hybrid catalyst catalyzed oxidation thioanisole is the thioanisole sulfoxide
0.1 gram substrate thioanisole is dissolved in 100 milliliters of acetonitriles; Add hybrid catalyst 0.033 gram that embodiment 2-1 makes; Add massfraction again and be 30% aqueous hydrogen peroxide solution 0.228 gram; Make multi-metal oxygen cluster, thioanisole with the mole ratio of hydrogen peroxide is: 1: 1000: 1000.Stirred this mixing solutions 70 minutes down at 40 ℃, after the cooling, detect, have the thioanisole more than 99% to be converted into corresponding thioanisole sulfoxide through NMR spectrum and chromatogram.
Embodiment 3-10:
H
3PW
12O
40/ DOHDA/SiO
2Hybrid catalyst catalyzed oxidation dimethyl sulphide is the dimethyl sulphide sulfoxide
0.1 gram substrate dimethyl sulphide is dissolved in 100 milliliters of acetonitriles; Add hybrid catalyst 0.064 gram that embodiment 2-1 makes; Add massfraction again and be 30% aqueous hydrogen peroxide solution 0.456 gram; Make multi-metal oxygen cluster, dimethyl sulphide with the mole ratio of hydrogen peroxide is: 1: 1000: 1000.Stirred this mixing solutions 70 minutes down at 40 ℃, after the cooling, detect, have the dimethyl sulphide more than 99% to be converted into corresponding dimethyl sulphide sulfoxide through NMR spectrum and chromatogram.
Claims (4)
1. the application of surfactant modified multi-metal oxygen cluster/SiO 2 hybrid catalyzer aspect the organosulfur compound controllable oxidization is characterized in that:
1) be that the method that adopts homogeneous phase coats in the aqueous solution method or organic and inorganic two to coat mutually prepares the multi-metal oxygen cluster mixture of hydroxyl cats product modification; This multi-metal oxygen cluster mixture is dissolved in ethanol, propyl alcohol, Virahol or the butanols, concentration is 5～10 mg/ml again, and adding and silicone agent mol ratio are 1: 1～1: 20 water; Add silicone agent again; In mixture and silicone agent, the mass content of mixture is 1～50%, and stirring at room 1～3 hour is abundant to guarantee hydrolysis; This colloidal sol is sealed aged at room temperature 10～15 days; Uncoveredly again be placed in the air Air drying 5～10 days, obtain block gel solid, at last with this solid vacuum-drying after 24～36 hours porphyrize promptly obtain surfactant modified multi-metal oxygen cluster/SiO 2 hybrid catalyzer;
2) be that organosulfur compound is dissolved in acetonitrile, acetone, chloroform, normal hexane or the dodecyl; Keep concentration 1～10 mg/ml; Adding and organosulfur compound mol ratio are surfactant modified multi-metal oxygen cluster/SiO 2 hybrid catalyzer of 1: 200～1: 1000; Add hydrogen peroxide again, the mol ratio that makes hydrogen peroxide and organosulfur compound is 1: 1～3: 1; 40 ℃～80 ℃ following stirring reactions 0.5～2.0 hour, make to react completely that reaction with the filtering of solid hybrid catalyst, promptly obtains the solution of oxidation products sulfone or sulfoxide after finishing, thereby accomplish catalytic oxidation organosulfur compound;
3) wherein organosulfur compound is thionaphthene, dibenzothiophene, 4,6-dimethyl--dibenzothiophene, diphenyl sulfide, hexichol ethyl thioether, diphenyl-methyl thioether, thioanisole, ethyl phenyl sulfide, diethyl thioether or dimethyl sulphide; Multi-metal oxygen cluster is H
3PW
12O
40, H
4SiW
12O
40, H
3PMo
12O
40, Na
9[EuW
10O
36] or K
12[EuP
5W
30O
110]; Tensio-active agent is (CH
3)
3N
+(CH
2)
nOH, (CH
3)
2N
+[(CH
2)
nOH]
2, (CH
3)
2N
+[(CH
2)
mCH
3] [(CH
2)
nOH] or (C
6NH
5)
+[(CH
2)
nOH], 1≤n≤18,1≤m≤18.
2. the surfactant modified application of multi-metal oxygen cluster/SiO 2 hybrid catalyzer aspect the organosulfur compound controllable oxidization as claimed in claim 1, it is characterized in that: silicone agent is tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane or four butoxy silanes.
3. the surfactant modified application of multi-metal oxygen cluster/SiO 2 hybrid catalyzer aspect the organosulfur compound controllable oxidization as claimed in claim 1; It is characterized in that: the homogeneous phase coating is that multi-metal oxygen cluster to be coated is soluble in water in the aqueous solution, and keeping concentration is 5～15 mg/ml; In addition that the cats product of hydrophobic side hydroxyl is soluble in water, keeping concentration is 5～10 mg/ml; Control the two consumption, making the ratio of total charge number of total charge number and the multi-metal oxygen cluster of tensio-active agent is 0.80: 1～1: 1; Under whipped state; The multi-metal oxygen cluster aqueous solution is added drop-wise in the aqueous solution of tensio-active agent, continues to stir after 0.2～10 hour, generate mixture and separate out with precipitation forms; Collect and to precipitate, be drying to obtain the multi-metal oxygen cluster mixture that the hydroxyl cats product is modified.
4. the surfactant modified application of multi-metal oxygen cluster/SiO 2 hybrid catalyzer aspect the organosulfur compound controllable oxidization as claimed in claim 1; It is characterized in that: it is that multi-metal oxygen cluster to be coated is soluble in water that organic and inorganic two coats mutually, and keeping concentration is 5～15 mg/ml; Cats product with the hydrophobic side hydroxyl is dissolved in the organic solvent again, and keeping concentration is 5～10 mg/ml; Control the two consumption, making the ratio of total charge number of total charge number and the multi-metal oxygen cluster of tensio-active agent is 0.80: 1～1: 1; Under whipped state; The organic solution of tensio-active agent is added drop-wise in the multi-metal oxygen cluster aqueous solution; Continue to stir after 0.2～10 hour and with separating funnel organic phase is told, organic phase adds anhydrous sodium sulfate drying by/100 milliliters of 0.2～0.5 grams and handles again with washing 2～5 times; Filter at last and solvent evaporated, obtain the multi-metal oxygen cluster mixture that the hydroxyl cats product is modified.
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| CN102351758A (en) * | 2011-08-25 | 2012-02-15 | 吴江市北厍盛源纺织品助剂厂 | New preparation method of 4,4-dichlorodiphenyl sulfone |
| CN103012366B (en) * | 2011-09-28 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of method of thiophene-type sulfide oxidation |
| CN102515999B (en) * | 2011-11-30 | 2013-10-23 | 浙江大学 | Method for selectively oxidizing sulfide |
| CN103910658B (en) * | 2013-12-23 | 2016-08-17 | 宁夏大学 | A kind of sulfide oxidation becomes the method for sulfone |
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| CN104475162B (en) * | 2014-12-15 | 2016-06-08 | 湖南科技大学 | A kind of sandwich phosphotungstate-Si/AlO2Nanocatalyst and methods for making and using same thereof |
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| CN105949018B (en) * | 2016-06-23 | 2018-09-11 | 南阳师范学院 | The selective catalytic oxidation reaction system of sulfur-containing compound in a kind of water phase |
| CN107866281A (en) * | 2016-09-28 | 2018-04-03 | 中国科学院宁波材料技术与工程研究所 | Hydroxy functionalized heteropolyacid catalyst, its preparation method and application |
| CN111065715A (en) * | 2017-07-21 | 2020-04-24 | 圣地亚哥德孔波斯特拉大学 | Process for oxidizing organosulfur compounds |
| CN108558716B (en) * | 2018-04-12 | 2020-05-26 | 南阳师范学院 | Method for preparing sulfone compound by oxidizing thioether under static condition |
| CN113248533B (en) * | 2021-04-01 | 2022-04-26 | 江苏大学 | Preparation method of porous ionic liquid extractant and extraction desulfurization application thereof |
| CN114522732B (en) * | 2022-01-07 | 2024-03-08 | 中南大学 | Preparation and application of chiral titanium oxide cluster capable of serving as chiral construction unit |
| CN115957716B (en) * | 2022-12-16 | 2024-09-24 | 浙江工业大学 | Ag2O/SiO2@Imprint composite aerogel adsorbent and preparation method and application thereof |
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| CN1915870A (en) * | 2006-08-30 | 2007-02-21 | 吉林大学 | Method for preparing transparent hybridization material of polymetal oxygen cluster/ silicon dioxide |
| CN101173179A (en) * | 2007-10-24 | 2008-05-07 | 中国科学院大连化学物理研究所 | Catalyst for diesel oil oxidation distillation ultra-deepness desulfurization and desulfurization method |
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