CN103657726A - Preparation method and application of silica-microsphere-immobilized nanometer metal compound catalyst - Google Patents
Preparation method and application of silica-microsphere-immobilized nanometer metal compound catalyst Download PDFInfo
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- CN103657726A CN103657726A CN201310715000.5A CN201310715000A CN103657726A CN 103657726 A CN103657726 A CN 103657726A CN 201310715000 A CN201310715000 A CN 201310715000A CN 103657726 A CN103657726 A CN 103657726A
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Abstract
The invention relates to a silica-microsphere-immobilized nanometer metal compound catalyst as well as a preparation method and an application thereof. The preparation method comprises the following steps: (1) the synthesis of monocarboxyl porphyrin; (2) the synthesis of monocarboxyl metal porphyrin; (3) the synthesis of amino-modified silica microspheres; (4) the synthesis of amino-modified silica microsphere-loaded metal porphyrin; (5) the synthesis of carbonized amino-modified silica microsphere-loaded metal porphyrin. The invention further provides the application of the nanometer metal compound catalyst in an ethylbenzene oxidation reaction. The silica-microsphere-immobilized nanometer metal compound catalyst has good catalytic performance and high stability and can be recycled and used repeatedly. The microporous surface of the organosilicone microspheres has an alternate hydrophilic and hydrophobic property, a microenvironment beneficial to the reaction can be provided, and the activity and selectivity of the catalyst are improved.
Description
Technical field
The invention belongs to catalyst field, especially relate to immobilized nano metal compound catalyst of a kind of silicon dioxide microsphere and preparation method thereof and application.
Background technology
Because metalloporphyrin has good catalytic effect for the activation of c h bond, therefore in the past few decades, the research of supported metalloporphyrin catalyst is in the ascendant.But, in homogeneous catalysis system, metalloporphyrin cannot reclaim, and be easy to autohemagglutination or degraded, although after metalloporphyrin being loaded on the carrier with larger specific area, the problems such as dimerization that can stop metalloporphyrin, still, still there is the problems such as unstable and inactivation is very fast in carried metal porphyrin catalyst.
In order to solve catalysis of metalloporphyrin agent inactivation problem, by the multivalence state metal compound as catalyst that divides middle roasting supported metalloporphyrin to obtain high dispersive at nitrogen.As far back as eighties of last century 90 years, the people such as Widelov just loaded to ferriporphyrin on graphitic carbon, then carry out high-temperature roasting in inert atmosphere, and gained catalyst, as the positive electrode of fuel cell, shows higher catalytic activity and stability in redox reaction.The people such as Lee are recently by polypyrrole modified graphite carbon, then add metallic cobalt ion, form metallo-organic complex, products obtained therefrom, through high-temperature roasting under inert atmosphere, obtains fuel battery anode catalyst, and, they think after roasting, form two kinds of new nitrogen, i.e. pyrroles and graphite mould nitrogen-atoms, the activity of antianode catalyst has great facilitation.
Summary of the invention
Technical problem to be solved by this invention is, overcomes the above-mentioned defect that prior art exists, and immobilized nano metal compound catalyst of a kind of silicon dioxide microsphere and preparation method thereof and application thereof are provided.
The technical solution adopted for the present invention to solve the technical problems is,
The preparation method of the present invention's the immobilized nano metal compound catalyst of silicon dioxide microsphere, comprises the following steps:
(1) mono carboxylic porphyrin is synthetic, and the benzaldehyde that is 1:3-4 by mass ratio and 4-carboxyl benzaldehyde are dispersed in propionic acid, and the mass ratio of propionic acid and benzaldehyde is 1:30-60, be heated to reflux, will slowly splash into the pyrroles of benzaldehyde equivalent coutroi velocity, 20-30min adds, under reflux conditions, continue the preferred 40min of reaction 30-60min() finish, after question response liquid cooling but, putting into refrigerator spends the night, suction filtration, silicagel column is separated, i.e. synthetic mono carboxylic porphyrin;
(2) mono carboxylic metalloporphyrin is synthetic, step (1) gained mono carboxylic porphyrin is dispersed in dimethyl formamide, the mass ratio of mono carboxylic porphyrin and dimethyl formamide is 1:150-200, be heated to reflux, in 1h, add with mono carboxylic porphyrin mass ratio is the preferred 1:2.5-3 of 1:2-5(in batches) MnCl
24H
2o and FeCl
24H
2o, after adding, some plate monitoring reaction process, after raw material point disappears, stops reaction, after question response liquid cooling but, adds the distilled water of dimethyl formamide 2-3 times volume, standing over night, suction filtration, uses hot water cyclic washing, obtains mono carboxylic manganoporphyrin and mono carboxylic ferriporphyrin;
(3) amino modified silicon dioxide microsphere is synthetic: take that silica is ultrasonic to be dispersed in toluene, silica and toluene mass ratio are the preferred 1:15 of 1:10-30(), magnetic agitation, be warming up to backflow, slowly dripping triethoxysilane solution (APTES) and toluene solution analyzes pure, the volume ratio that adds of triethoxysilane solution and toluene is the preferred 1:1.2-1.5 of 1:1-2(), reaction 12-24h, washing, 80 ℃ of vacuum drying, spend the night, obtain amino modified silicon dioxide microsphere (SiO
2-NH
2);
(4) step (2) gained mono carboxylic metalloporphyrin (MTPCPP) and the synthetic amino modified silicon dioxide microsphere of step (3) synthesizing of amino modified silicon dioxide microsphere carried metal porphyrin: taking mass ratio is the preferred 1:10 of 1:10-15() are dispersed in dichloromethane solution, the mass ratio of silicon dioxide microsphere and carrene is the preferred 1:15-20 of 1:10-50(), reflux 12-24h, cooling, washing, at 80 ℃ of vacuum drying 12h, obtain amino modified silicon dioxide microsphere carried metal porphyrin (SiO
2-NH
2-MPCPP);
(5) the amino modified silicon dioxide microsphere carried metal porphyrin of carbonization is synthetic: the amino modified silicon dioxide microsphere carried metal porphyrin that takes step (2) gained is loaded in reaction tube, be warming up to 300-800 ℃ (preferably 400-600 ℃), the preferred 1-1.5h of calcining 1-2h(, more preferably 1h), whole process passes into N
2protection, is then cooled to room temperature naturally, obtains the amino modified silicon dioxide microsphere carried metal porphyrin (SiO of carbonization
2-NH
2-MTPCPP/AC).
The present invention's the immobilized nano metal compound catalyst of silicon dioxide microsphere, can be used for catalysis oxidation reaction of ethylbenzene.
The immobilized nano metal compound catalyst of silicon dioxide microsphere catalytic performance prepared by the present invention is good, and stability is higher, can reclaim, and reuses; Organosilicon microballoon micropore surface has hydrophilic and hydrophobic alternate character, can provide the microenvironment that is beneficial to reaction, has improved the activity and selectivity of catalyst.
Accompanying drawing explanation
Fig. 1 is catalyst S iO
2-NH
2-FeTPCPP/AC reuses effect to ethylbenzene selectivity catalytic oxidation;
Reaction condition: catalyst quality 30mg, ethylbenzene 10mL, O
2pressure 0.8atm, 120 ℃ of reaction temperatures, reaction time 5h;
Fig. 2 is catalyst S iO
2-NH
2-MnTPCPP/AC reuses effect to ethylbenzene selectivity catalytic oxidation;
Reaction condition: catalyst quality 30mg, ethylbenzene 10mL, O
2pressure 0.8atm, 120 ℃ of reaction temperatures, reaction time 5h.
The specific embodiment
Below in conjunction with embodiment, the present invention will be further described:
The present embodiment is prepared the amino modified silicon dioxide microsphere Supported Manganese porphyrin (SiO of carbonization
2-NH
2-MnTPCPP/AC) and the amino modified silicon dioxide microsphere load iron porphyrin (SiO of carbonization
2-NH
2-FeTPCPP/A), its preparation method is as follows:
(1) mono carboxylic porphyrin is synthetic, in 500mL there-necked flask, adds 250mL propionic acid, 5.565g benzaldehyde and 2.625g4-carboxyl benzaldehyde, be heated to reflux, and with constant pressure funnel, 4.69g pyrroles slowly splashed into, coutroi velocity, 20min adds, under reflux conditions, continuing reaction 30min finishes, after question response liquid cooling but, put into refrigerator and spend the night, suction filtration, silicagel column is separated, i.e. synthetic mono carboxylic porphyrin;
(2) mono carboxylic manganoporphyrin and mono carboxylic ferriporphyrin is synthetic, in 250mL there-necked flask, adds 100mL dimethyl formamide, and 1.0g step (1) gained mono carboxylic porphyrin is heated to reflux, and adds the corresponding MnCl of 2g in 1h in batches
24H
2o and FeCl
24H
2o, after adding, some plate monitoring reaction process, after raw material point disappears, stops reaction, after question response liquid cooling but, adds the distilled water of 2 times of volumes, standing over night, suction filtration, uses hot water cyclic washing, obtains mono carboxylic manganoporphyrin and mono carboxylic ferriporphyrin;
(3) amino modified silica silicon ball is synthetic, taking 1g silica silicon is dispersed in 30mL toluene, ultrasonic dispersion 10min, magnetic agitation, is warming up to 60 ℃, slowly drips 12mL APTES solution and 15mL toluene solution, reaction 24h, use respectively 30mL toluene wash and each washed twice of 30mL methyl alcohol, 80 ℃ of vacuum drying, spend the night, obtain SiO
2-NH
2;
(4) amino modified silicon dioxide microsphere carried metal porphyrin is synthetic, takes mono carboxylic manganoporphyrin and the mono carboxylic ferriporphyrin of 0.010g step (1) gained, and the amino modified silicon dioxide microsphere of 0.1g step (2) gained, all joins 20mL CH is housed
2cl
2in the 50mL single port flask of solution, back flow reaction 24h, cooling, then use 30mL CH
2cl
2with each washed twice of 30mL ethanol, at 80 ℃ of vacuum drying 12h, the amino modified silicon dioxide microsphere Supported Manganese of gained porphyrin (SiO
2-NH
2-MnTPCPP) and amino modified silicon dioxide microsphere load iron porphyrin (SiO
2-NH
2-FeTPCPP);
(5) the amino modified silicon dioxide microsphere carried metal porphyrin of carbonization is synthetic: take respectively the amino modified silicon dioxide microsphere Supported Manganese of 0.01g step (4) gained porphyrin (SiO
2-NH
2-MnTPCPP) and the amino modified silicon dioxide microsphere load iron porphyrin (SiO of carbonization
2-NH
2-FeTPCPP), be loaded in reaction tube, be warming up to 500 ℃, calcining 1h, whole process passes into N
2protection, is then cooled to room temperature naturally, and products obtained therefrom is referred to as the amino modified silicon dioxide microsphere Supported Manganese porphyrin (SiO of carbonization
2-NH
2-MnTPCPP/AC) and the amino modified silicon dioxide microsphere load iron porphyrin (SiO of carbonization
2-NH
2-FeTPCPP/A).
The immobilized nano metal compound catalyst of silicon dioxide microsphere that the present embodiment makes, for catalysis oxidation reaction of ethylbenzene, adds respectively 30mgSiO in autoclave
2-NH
2/ AC, 30mg SiO
2-NH
2-FeTPCPP/AC, 30mg MnTPCPP/AC and 30mg SiO
2-NH
2-MnTPCPP/AC and 10mL ethylbenzene, be heated to 120 ℃, and the pressure of oxygen is 0.8atm, reaction 5h, and oxidation product carries out quantitative analysis by gas-chromatography.
Table 1: the contrast of different catalysts to selective oxidation ethylbenzene reacting catalytic performance
Note: reaction evaluating condition: catalyst quality: 30mg, ethylbenzene: 10ml, O
2pressure: 0.8atm, reaction temperature: 120 ℃, the reaction time: 5h.
Under different catalysts catalytic condition, oxidation reaction of ethylbenzene selective data is known as shown in Table 1, under this paper experiment condition, selects SiO
2-NH
2-MTPCPP/AC catalysis oxidation reaction of ethylbenzene, generation benzyl carbinol and the acetophenone of energy high selectivity.
SiO
2-NH
2-MTPCPP/AC catalyst repeat performance is investigated, and reactant liquor is standing, with ethanol washing, filters, and after being dried, is recycled catalyst, standby, further to investigate the repeat performance of catalyst;
The immobilized nano metal compound catalyst of silicon dioxide microsphere study on the stability result is as shown in attached Fig. 1 and 2.
The present embodiment comprises the following steps:
(1) mono carboxylic porphyrin is synthetic, and the benzaldehyde that is 1:3 by mass ratio and 4-carboxyl benzaldehyde are dispersed in propionic acid, and the mass ratio of propionic acid and benzaldehyde is 1:30, be heated to reflux, will slowly splash into the pyrroles of benzaldehyde equivalent coutroi velocity, 20min adds, under reflux conditions, continue reaction 30min and finish, after question response liquid cooling but, putting into refrigerator spends the night, suction filtration, silicagel column is separated, i.e. synthetic mono carboxylic porphyrin;
(2) mono carboxylic metalloporphyrin is synthetic, step (1) gained mono carboxylic porphyrin is dispersed in dimethyl formamide, the mass ratio of mono carboxylic porphyrin and dimethyl formamide is 1:150, is heated to reflux, the MnCl that to add with mono carboxylic porphyrin mass ratio in 1h be 1:2 in batches
24H
2o and FeCl
24H
2o, after adding, some plate monitoring reaction process, after raw material point disappears, stops reaction, after question response liquid cooling but, adds the distilled water of 2 times of volumes of dimethyl formamide, standing over night, suction filtration, uses hot water cyclic washing, obtains mono carboxylic manganoporphyrin and mono carboxylic ferriporphyrin;
(3) amino modified silicon dioxide microsphere is synthetic: take that silica is ultrasonic to be dispersed in toluene, silica and toluene mass ratio are 1:10, magnetic agitation, be warming up to backflow, slowly drip triethoxysilane solution (APTES) and toluene solution and analyze purely, the volume ratio that adds of triethoxysilane solution and toluene is 1:1, reaction 12h, washing, spends the night 80 ℃ of vacuum drying, obtains amino modified silicon dioxide microsphere (SiO
2-NH
2);
(4) amino modified silicon dioxide microsphere carried metal porphyrin is synthetic: take the synthetic amino modified silicon dioxide microsphere of the step that mass ratio is 1:10 (2) gained mono carboxylic metalloporphyrins (MTPCPP) and step (3) and be dispersed in dichloromethane solution, the mass ratio of silicon dioxide microsphere and carrene is 1:10, reflux 12h, cooling, washing, at 80 ℃ of vacuum drying 12h, obtain amino modified silicon dioxide microsphere carried metal porphyrin (SiO
2-NH
2-MPCPP);
(5) the amino modified silicon dioxide microsphere carried metal porphyrin of carbonization is synthetic: the amino modified silicon dioxide microsphere carried metal porphyrin that takes step (2) gained is loaded in reaction tube, is warming up to 300 ℃, calcining 1h, and whole process passes into N
2protection, is then cooled to room temperature naturally, obtains the amino modified silicon dioxide microsphere carried metal porphyrin (SiO of carbonization
2-NH
2-MTPCPP/AC).
For catalysis oxidation reaction of ethylbenzene.
The present embodiment comprises the following steps:
(1) mono carboxylic porphyrin is synthetic, and the benzaldehyde that is 1:4 by mass ratio and 4-carboxyl benzaldehyde are dispersed in propionic acid, and the mass ratio of propionic acid and benzaldehyde is 1:60, be heated to reflux, will slowly splash into the pyrroles of benzaldehyde equivalent coutroi velocity, 30min adds, under reflux conditions, continue reaction 60min and finish, after question response liquid cooling but, putting into refrigerator spends the night, suction filtration, silicagel column is separated, i.e. synthetic mono carboxylic porphyrin;
(2) mono carboxylic metalloporphyrin is synthetic, step (1) gained mono carboxylic porphyrin is dispersed in dimethyl formamide, the mass ratio of mono carboxylic porphyrin and dimethyl formamide is 1:200, is heated to reflux, the MnCl that to add with mono carboxylic porphyrin mass ratio in 1h be 1:5 in batches
24H
2o and FeCl
24H
2o, after adding, some plate monitoring reaction process, after raw material point disappears, stops reaction, after question response liquid cooling but, adds the distilled water of dimethyl formamide 2-3 times volume, standing over night, suction filtration, uses hot water cyclic washing, obtains mono carboxylic manganoporphyrin and mono carboxylic ferriporphyrin;
(3) amino modified silicon dioxide microsphere is synthetic: take that silica is ultrasonic to be dispersed in toluene, silica and toluene mass ratio are 1:30, magnetic agitation, be warming up to backflow, slowly drip triethoxysilane solution (APTES) and toluene solution and analyze purely, the volume ratio that adds of triethoxysilane solution and toluene is 1:2, reaction 24h, washing, spends the night 80 ℃ of vacuum drying, obtains amino modified silicon dioxide microsphere (SiO
2-NH
2);
(4) amino modified silicon dioxide microsphere carried metal porphyrin is synthetic: take the synthetic amino modified silicon dioxide microsphere of the step that mass ratio is 1:15((2) gained mono carboxylic metalloporphyrins (MTPCPP) and step (3) and be dispersed in dichloromethane solution, the mass ratio of silicon dioxide microsphere and carrene is 1:50, reflux 24h, cooling, washing, at 80 ℃ of vacuum drying 12h, obtain amino modified silicon dioxide microsphere carried metal porphyrin (SiO
2-NH
2-MPCPP);
(5) the amino modified silicon dioxide microsphere carried metal porphyrin of carbonization is synthetic: the amino modified silicon dioxide microsphere carried metal porphyrin that takes step (2) gained is loaded in reaction tube, is warming up to 800 ℃, calcining 2h, and whole process passes into N
2protection, is then cooled to room temperature naturally, obtains the amino modified silicon dioxide microsphere carried metal porphyrin (SiO of carbonization
2-NH
2-MTPCPP/AC).
For catalysis oxidation reaction of ethylbenzene.
Embodiment 4
The present embodiment comprises the following steps:
(1) mono carboxylic porphyrin is synthetic, and the benzaldehyde that is 1:3.5 by mass ratio and 4-carboxyl benzaldehyde are dispersed in propionic acid, and the mass ratio of propionic acid and benzaldehyde is 1:50, be heated to reflux, will slowly splash into the pyrroles of benzaldehyde equivalent coutroi velocity, 30min adds, under reflux conditions, continue reaction 40min and finish, after question response liquid cooling but, putting into refrigerator spends the night, suction filtration, silicagel column is separated, i.e. synthetic mono carboxylic porphyrin;
(2) mono carboxylic metalloporphyrin is synthetic, step (1) gained mono carboxylic porphyrin is dispersed in dimethyl formamide, the mass ratio of mono carboxylic porphyrin and dimethyl formamide is 1:200, is heated to reflux, the MnCl that to add with mono carboxylic porphyrin mass ratio in 1h be 1:2.5 in batches
24H
2o and FeCl
24H
2o, after adding, some plate monitoring reaction process, after raw material point disappears, stops reaction, after question response liquid cooling but, adds the distilled water of 3 times of volumes of dimethyl formamide, standing over night, suction filtration, uses hot water cyclic washing, obtains mono carboxylic manganoporphyrin and mono carboxylic ferriporphyrin;
(3) amino modified silicon dioxide microsphere is synthetic: take that silica is ultrasonic to be dispersed in toluene, silica and toluene mass ratio are 1:15, magnetic agitation, is warming up to backflow, slowly drips triethoxysilane solution (APTES) and toluene solution and analyzes pure, the volume ratio that adds of triethoxysilane solution and toluene is 1:1.2,, reaction 24h, washing, 80 ℃ of vacuum drying, spend the night, obtain amino modified silicon dioxide microsphere (SiO
2-NH
2);
(4) amino modified silicon dioxide microsphere carried metal porphyrin is synthetic: take the synthetic amino modified silicon dioxide microsphere of the step that mass ratio is 1:10 (2) gained mono carboxylic metalloporphyrins (MTPCPP) and step (3) and be dispersed in dichloromethane solution, the mass ratio of silicon dioxide microsphere and carrene is 1:20, reflux 24h, cooling, washing, at 80 ℃ of vacuum drying 12h, obtain amino modified silicon dioxide microsphere carried metal porphyrin (SiO
2-NH
2-MPCPP);
(5) the amino modified silicon dioxide microsphere carried metal porphyrin of carbonization is synthetic: the amino modified silicon dioxide microsphere carried metal porphyrin that takes step (2) gained is loaded in reaction tube, is warming up to 600 ℃, calcining 1.5h, and whole process passes into N
2protection, is then cooled to room temperature naturally, obtains the amino modified silicon dioxide microsphere carried metal porphyrin (SiO of carbonization
2-NH
2-MTPCPP/AC). can be used for catalysis oxidation reaction of ethylbenzene.
Claims (7)
1. the preparation method of the immobilized nano metal compound catalyst of silicon dioxide microsphere, is characterized in that, comprises the following steps:
(1) mono carboxylic porphyrin is synthetic, and the benzaldehyde that is 1:3-4 by mass ratio and 4-carboxyl benzaldehyde are dispersed in propionic acid, and the mass ratio of propionic acid and benzaldehyde is 1:30-60, be heated to reflux, will slowly splash into the pyrroles of benzaldehyde equivalent coutroi velocity, 20-30min adds, under reflux conditions, continue reaction 30-60min and finish, after question response liquid cooling but, putting into refrigerator spends the night, suction filtration, silicagel column is separated, i.e. synthetic mono carboxylic porphyrin;
(2) mono carboxylic metalloporphyrin is synthetic, step (1) gained mono carboxylic porphyrin is dispersed in dimethyl formamide, the mass ratio of mono carboxylic porphyrin and dimethyl formamide is 1:150-200, is heated to reflux, the MnCl that to add with mono carboxylic porphyrin mass ratio in 1h be 1:2-5 in batches
24H
2o and FeCl
24H
2o, after adding, some plate monitoring reaction process, after raw material point disappears, stops reaction, after question response liquid cooling but, adds the distilled water of dimethyl formamide 2-3 times volume, standing over night, suction filtration, uses hot water cyclic washing, obtains mono carboxylic manganoporphyrin and mono carboxylic ferriporphyrin;
(3) amino modified silicon dioxide microsphere is synthetic: take that silica is ultrasonic to be dispersed in toluene, silica and toluene mass ratio are 1:10-30, magnetic agitation, be warming up to backflow, slowly drip triethoxysilane solution and toluene solution and analyze purely, the volume ratio that adds of triethoxysilane solution and toluene is 1:1-2, reaction 12-24h, washing, spends the night 80 ℃ of vacuum drying, obtains amino modified silicon dioxide microsphere;
(4) amino modified silicon dioxide microsphere carried metal porphyrin is synthetic: take the synthetic amino modified silicon dioxide microsphere of the step that mass ratio is 1:10-15 (2) gained mono carboxylic metalloporphyrin and step (3) and be dispersed in dichloromethane solution, the mass ratio of silicon dioxide microsphere and carrene is 1:10-50, reflux 12-24h, cooling, washing, at 80 ℃ of vacuum drying 12h, obtain amino modified silicon dioxide microsphere carried metal porphyrin;
(5) the amino modified silicon dioxide microsphere carried metal porphyrin of carbonization is synthetic: the amino modified silicon dioxide microsphere carried metal porphyrin that takes step (2) gained is loaded in reaction tube, is warming up to 300-800 ℃, calcining 1-2h, and whole process passes into N
2protection, is then cooled to room temperature naturally, obtains the amino modified silicon dioxide microsphere carried metal porphyrin of carbonization.
2. the preparation method of the immobilized nano metal compound catalyst of silicon dioxide microsphere according to claim 1, is characterized in that, in described step (1), the time of continuing reaction under counterflow condition is 40min.
3. the preparation method of the immobilized nano metal compound catalyst of silicon dioxide microsphere according to claim 1, is characterized in that, in described step (2), and MnCl
24H
2o and FeCl
24H
2o and mono carboxylic porphyrin mass ratio are 1:2.5-3.
4. the preparation method of the immobilized nano metal compound catalyst of silicon dioxide microsphere according to claim 1, it is characterized in that, in described step (3), silica and toluene mass ratio are 1:15, the volume ratio that adds of triethoxysilane solution and toluene is 1:1.2-1.5, reaction 12-24h, washing, 80 ℃ of vacuum drying, spend the night, obtain amino modified silicon dioxide microsphere.
5. the preparation method of the immobilized nano metal compound catalyst of silicon dioxide microsphere according to claim 1, it is characterized in that, in described step (4), the mass ratio of mono carboxylic metalloporphyrin (MTPCPP) and amino modified silicon dioxide microsphere is 1:10, and the mass ratio of silicon dioxide microsphere and carrene is 1:15-20.
6. the preparation method of the immobilized nano metal compound catalyst of silicon dioxide microsphere according to claim 1, it is characterized in that, in described step (5), amino modified silicon dioxide microsphere carried metal porphyrin is loaded in reaction tube, be warming up to 400-600 ℃, calcining 1-1.5h.
7. the immobilized nano metal compound catalyst of silicon dioxide microsphere as described in the claim 1-7 any one application in oxidation reaction of ethylbenzene.
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