CN103657726B - 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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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 a kind of catalysis of silicon dioxide microsphere immobilized nano metal compound
Agent and preparation method and application.
Background technology
Because metalloporphyrin has good catalytic effect for the activation of c h bond, therefore in the past few decades, Gu
The research carrying catalysis of metalloporphyrin agent is in the ascendant.But, in homogeneous catalysis system, metalloporphyrin cannot be carried out reclaiming, and
After being easy to autohemagglutination or degraded although being supported on metalloporphyrin on the carrier have larger specific area, metalloporphyrin can be stoped
The problems such as dimerization, but, carried metal porphyrin catalyst still suffers from the problems such as unstable and inactivation is very fast.
In order to solve catalysis of metalloporphyrin agent deactivation prob, by dividing middle roasting supported metalloporphyrin to obtain height in nitrogen
Scattered multivalent state metal compound as catalyst.Early in eighties of last century 90 years, ferriporphyrin was just loaded to stone by Widelov et al.
On black carbon, then carry out high-temperature roasting in an inert atmosphere, gained catalyst is as the positive electrode of fuel cell, anti-in redox
Higher catalysis activity and stability is shown in answering.Lee et al. passes through polypyrrole modified graphite carbon recently, is subsequently adding metal
Cobalt ions, forms metallo-organic complex, and products obtained therefrom, through high-temperature roasting under an inert atmosphere, obtains fuel battery anode catalysis
Agent, and, they think after roasting, form two kinds of new nitrogen, i.e. pyrroles and graphite mould nitrogen-atoms, to anode catalyst
Activity has the effect of greatly facilitating.
Content of the invention
The technical problem to be solved is to overcome the drawbacks described above of prior art presence, provide a kind of titanium dioxide
Silicon microballoon immobilized nano metal compound catalyst and preparation method thereof and its application.
The technical solution adopted for the present invention to solve the technical problems is,
The preparation method of the silica-microsphere-inanometerd nanometerd metal compound catalyst of the present invention, comprises the following steps：
（1）The synthesis of mono carboxylic porphyrin, mass ratio is 1:The benzaldehyde of 3-4 and 4- carboxyl benzaldehyde are dispersed in propionic acid
In, propionic acid is 1 with the mass ratio of benzaldehyde：30-60, is heated to flowing back, the pyrroles with benzaldehyde equivalent is slowly dropped into, control
Flow velocity processed, 20-30min adds, and under reflux conditions, continues reaction 30-60min（Preferably 40min）Terminate, question response liquid cools down
Afterwards, put into fridge overnight, suction filtration, silica gel post separation, that is, synthesize mono carboxylic porphyrin；
（2）Mono carboxylic metalloporphyrin synthesizes, by step（1）Gained mono carboxylic porphyrin is dispersed in dimethylformamide, single
Carboxyl porphyrin is 1 with the mass ratio of dimethylformamide:150-200, is heated to flowing back, is dividedly in some parts and mono carboxylic porphyrin in 1h
Mass ratio is 1:2-5（Preferably 1：2.5-3）MnCl2·4H2O and FeCl2·4H2O, after adding, point plate monitoring reaction process,
After raw material point disappears, stop reaction, after the cooling of question response liquid, add the distilled water of 2-3 times of volume of dimethylformamide, standing
Overnight, suction filtration, uses hot water cyclic washing, obtains mono carboxylic manganoporphyrin and mono carboxylic ferriporphyrin；
（3）The synthesis of amino modified silicon dioxide microsphere:Weigh silica ultrasonic disperse in toluene, silica with
Toluene mass ratio is 1:10-30（Preferably 1：15）, magnetic agitation, it is warming up to backflow, be slowly added dropwise triethoxysilane solution
(APTES) and toluene solution analysis is pure, the addition volume ratio of triethoxysilane solution and toluene is 1：1-2（Preferably 1：1.2-
1.5）, react 12-24h, washing, in 80 DEG C of dried in vacuum overnight, obtain amino modified silicon dioxide microsphere（SiO2-NH2）；
（4）The synthesis of amino modified silicon dioxide microsphere carried metal porphyrin：Weighing mass ratio is 1:10-15（Preferably 1：
10）Step（2）Gained mono carboxylic metalloporphyrin（MTPCPP）And step（3）The amino modified silicon dioxide microsphere of synthesis divides
It is dispersed in dichloromethane solution, the mass ratio of silicon dioxide microsphere and dichloromethane is 1：10-50（Preferably 1:15-20）, backflow
Reflux 12-24h, cooling, washing, it is vacuum dried 12h at 80 DEG C, obtain amino modified silicon dioxide microsphere carried metal porphyrin
(SiO2-NH2-MPCPP)；
(5) synthesis of the amino modified silicon dioxide microsphere carried metal porphyrin of carbonization：Weigh step（2）The amino of gained
Improved silica micro-ball load metalloporphyrin is loaded in reaction tube, is warming up to 300-800 DEG C（Preferably 400-600 DEG C）, calcining
1-2h（Preferably 1-1.5h, more preferably 1h）, whole process is passed through N2Protection, is then naturally cooling to room temperature, obtains the amino modified of carbonization
Silicon dioxide microsphere carried metal porphyrin (SiO2-NH2-MTPCPP/AC).
The silica-microsphere-inanometerd nanometerd metal compound catalyst of the present invention, can be used for being catalyzed oxidation reaction of ethylbenzene.
The silica-microsphere-inanometerd nanometerd metal compound catalyst catalytic performance of present invention preparation is good, and stability is relatively
Height, can reclaim, and reuse；Organosilicon microballoon micropore surface has hydrophilic and hydrophobic alternate property, is provided that and is conducive to
The microenvironment of reaction, improves the activity and selectivity of catalyst.
Brief description
Fig. 1 is catalyst SiO2-NH2- FeTPCPP/AC reuses effect to ethylbenzene selectivity catalytic oxidation；
Reaction condition：Catalyst quality 30mg, ethylbenzene 10mL, O2Pressure 0.8atm, 120 DEG C of reaction temperature, the reaction time
5h；
Fig. 2 is catalyst SiO2-NH2- MnTPCPP/AC reuses effect to ethylbenzene selectivity catalytic oxidation；
Reaction condition：Catalyst quality 30mg, ethylbenzene 10mL, O2Pressure 0.8atm, 120 DEG C of reaction temperature, the reaction time
5h.
Specific embodiment
With reference to embodiment, the present invention will be further described：
Embodiment 1
The present embodiment prepares the amino modified silicon dioxide microsphere load manganoporphyrin of carbonization（SiO2-NH2-MnTPCPP/AC）
Amino modified silicon dioxide microsphere load ferriporphyrin with carbonization（SiO2-NH2-FeTPCPP/A）, its preparation method is as follows：
（1）The synthesis of mono carboxylic porphyrin, in 500mL there-necked flask, add 250mL propionic acid, 5.565g benzaldehyde and
2.625g4- carboxyl benzaldehyde, is heated to flowing back, is slowly dropped into 4.69g pyrroles with constant pressure funnel, coutroi velocity,
20min adds, and under reflux conditions, continues reaction 30min and terminates, after the cooling of question response liquid, put into fridge overnight, suction filtration,
Silica gel post separation, that is, synthesize mono carboxylic porphyrin；
（2）Mono carboxylic manganoporphyrin and the synthesis of mono carboxylic ferriporphyrin, in 250mL there-necked flask, add 100mL dimethyl
Formamide, 1.0g step（1）Gained mono carboxylic porphyrin, is heated to flowing back, is dividedly in some parts the corresponding MnCl of 2g in 1h2·4H2O and
FeCl2·4H2O, after adding, point plate monitoring reaction process, after raw material point disappears, stop reaction, after the cooling of question response liquid, plus
Enter the distilled water of 2 times of volumes, stand overnight, suction filtration, use hot water cyclic washing, obtain mono carboxylic manganoporphyrin and mono carboxylic ferriporphyrin；
（3）The synthesis of amino modified silica silicon ball, weighs 1g silica silicon and is dispersed in 30mL toluene, ultrasonic point
Scattered 10min, magnetic agitation, it is warming up to 60 DEG C, is slowly added dropwise 12mL APTES solution and 15mL toluene solution, react 24h, respectively
Washed with 30mL toluene and 30mL methyl alcohol respectively washes twice, in 80 DEG C of dried in vacuum overnight, obtain SiO2-NH2；
（4）The synthesis of amino modified silicon dioxide microsphere carried metal porphyrin, weighs 0.010g step（1）Single carboxylic of gained
Base manganoporphyrin and mono carboxylic ferriporphyrin, 0.1g step（2）The amino modified silicon dioxide microsphere of gained, is all added to equipped with 20mL
CH2Cl2In the 50mL single-necked flask of solution, back flow reaction 24h, cooling, then use 30mL CH2Cl2Each washing two with 30mL ethanol
Secondary, it is vacuum dried 12h at 80 DEG C, the amino modified silicon dioxide microsphere of gained loads manganoporphyrin（SiO2-NH2-MnTPCPP）And ammonia
Base improved silica micro-ball load ferriporphyrin（SiO2-NH2-FeTPCPP）；
（5）The synthesis of the amino modified silicon dioxide microsphere carried metal porphyrin of carbonization：Weigh 0.01g step respectively（4）
The amino modified silicon dioxide microsphere of gained loads manganoporphyrin（SiO2-NH2-MnTPCPP）Micro- with the amino modified silica of carbonization
Ball loads ferriporphyrin（SiO2-NH2-FeTPCPP）, it is loaded in reaction tube, is warming up to 500 DEG C, calcine 1h, whole process is passed through N2Protection,
Then it is naturally cooling to room temperature, products obtained therefrom is referred to as the amino modified silicon dioxide microsphere load manganoporphyrin of carbonization（SiO2-
NH2-MnTPCPP/AC）Amino modified silicon dioxide microsphere load ferriporphyrin with carbonization（SiO2-NH2-FeTPCPP/A）.
The silica-microsphere-inanometerd nanometerd metal compound catalyst that the present embodiment is obtained is used for being catalyzed ethylbenzene oxidation anti-
Should, autoclave is separately added into 30mgSiO2-NH2/ AC, 30mg SiO2-NH2- FeTPCPP/AC, 30mg
MnTPCPP/AC and 30mg SiO2-NH2- MnTPCPP/AC and 10mL ethylbenzene, are heated to 120 DEG C, and the pressure of oxygen is 0.8atm,
Reaction 5h, oxidation product carries out quantitative analysis with gas-chromatography.
Table 1：The contrast to selective oxidation ethylbenzene reacting catalytic performance for the different catalysts
Note：Reaction evaluating condition：Catalyst quality：30mg, ethylbenzene：10ml, O2Pressure：0.8atm, reaction temperature：120
DEG C, the reaction time：5h.
Under different catalysts catalytic condition, oxidation reaction of ethylbenzene selective data understands as shown in Table 1, tests bar herein
Under part, select SiO2-NH2- MTPCPP/AC is catalyzed oxidation reaction of ethylbenzene, the generation benzyl carbinol of energy high selectivity and acetophenone.
SiO2-NH2- MTPCPP/AC catalyst repeat performance is investigated, and reactant liquor is stood, is washed with ethanol, filters,
After drying, that is, it is recycled catalyst, standby, repeat performance to investigate catalyst further；
Silica-microsphere-inanometerd nanometerd metal compound catalyst study on the stability result is as shown in figure 1 and 2.
Embodiment 2
The present embodiment comprises the following steps：
（1）The synthesis of mono carboxylic porphyrin, mass ratio is 1:3 benzaldehyde and 4- carboxyl benzaldehyde are dispersed in propionic acid
In, propionic acid is 1 with the mass ratio of benzaldehyde：30, it is heated to flowing back, the pyrroles with benzaldehyde equivalent is slowly dropped into, control
Flow velocity, 20min adds, and under reflux conditions, continues reaction 30min and terminates, after the cooling of question response liquid, put into fridge overnight,
Suction filtration, silica gel post separation, that is, synthesize mono carboxylic porphyrin；
（2）Mono carboxylic metalloporphyrin synthesizes, by step（1）Gained mono carboxylic porphyrin is dispersed in dimethylformamide, single
Carboxyl porphyrin is 1 with the mass ratio of dimethylformamide:150, it is heated to flowing back, be dividedly in some parts in 1h and mono carboxylic porphyrin quality
Than for 1:2 MnCl2·4H2O and FeCl2·4H2O, after adding, point plate monitoring reaction process, after raw material point disappears, stop
Reaction, after the cooling of question response liquid, adds the distilled water of 2 times of volumes of dimethylformamide, stands overnight, suction filtration, with hot water repeatedly
Washing, obtains mono carboxylic manganoporphyrin and mono carboxylic ferriporphyrin；
（3）The synthesis of amino modified silicon dioxide microsphere:Weigh silica ultrasonic disperse in toluene, silica with
Toluene mass ratio is 1:10, magnetic agitation, it is warming up to backflow, be slowly added dropwise triethoxysilane solution (APTES) and toluene is molten
Liquid analysis is pure, and the addition volume ratio of triethoxysilane solution and toluene is 1：1, react 12h, washing, be vacuum dried at 80 DEG C
Overnight, obtain amino modified silicon dioxide microsphere（SiO2-NH2）；
（4）The synthesis of amino modified silicon dioxide microsphere carried metal porphyrin：Weighing mass ratio is 1:10 step（2）Institute
Obtain mono carboxylic metalloporphyrin（MTPCPP）And step（3）It is molten that the amino modified silicon dioxide microsphere of synthesis is dispersed in dichloromethane
In liquid, the mass ratio of silicon dioxide microsphere and dichloromethane is 1：10, reflux 12h, cooling, washing, do in 80 DEG C of vacuum
Dry 12h, obtains amino modified silicon dioxide microsphere carried metal porphyrin (SiO2-NH2-MPCPP)；
(5) synthesis of the amino modified silicon dioxide microsphere carried metal porphyrin of carbonization：Weigh step（2）The amino of gained
Improved silica micro-ball load metalloporphyrin is loaded in reaction tube, is warming up to 300 DEG C, calcines 1h, and whole process is passed through N2Protection, so
After be naturally cooling to room temperature, obtain the amino modified silicon dioxide microsphere carried metal porphyrin (SiO of carbonization2-NH2-MTPCPP/AC).
For being catalyzed oxidation reaction of ethylbenzene.
Embodiment 3
The present embodiment comprises the following steps：
（1）The synthesis of mono carboxylic porphyrin, mass ratio is 1:4 benzaldehyde and 4- carboxyl benzaldehyde are dispersed in propionic acid
In, propionic acid is 1 with the mass ratio of benzaldehyde：60, it is heated to flowing back, the pyrroles with benzaldehyde equivalent is slowly dropped into, control
Flow velocity, 30min adds, and under reflux conditions, continues reaction 60min and terminates, after the cooling of question response liquid, put into fridge overnight,
Suction filtration, silica gel post separation, that is, synthesize mono carboxylic porphyrin；
（2）Mono carboxylic metalloporphyrin synthesizes, by step（1）Gained mono carboxylic porphyrin is dispersed in dimethylformamide, single
Carboxyl porphyrin is 1 with the mass ratio of dimethylformamide:200, it is heated to flowing back, be dividedly in some parts in 1h and mono carboxylic porphyrin quality
Than for 1:5 MnCl2·4H2O and FeCl2·4H2O, after adding, point plate monitoring reaction process, after raw material point disappears, stop
Reaction, after the cooling of question response liquid, adds the distilled water of 2-3 times of volume of dimethylformamide, stands overnight, suction filtration, anti-with hot water
After backwashing is washed, and obtains mono carboxylic manganoporphyrin and mono carboxylic ferriporphyrin；
（3）The synthesis of amino modified silicon dioxide microsphere:Weigh silica ultrasonic disperse in toluene, silica with
Toluene mass ratio is 1:30, magnetic agitation, it is warming up to backflow, be slowly added dropwise triethoxysilane solution (APTES) and toluene is molten
Liquid analysis is pure, and the addition volume ratio of triethoxysilane solution and toluene is 1：2, react 24h, washing, be vacuum dried at 80 DEG C
Overnight, obtain amino modified silicon dioxide microsphere（SiO2-NH2）；
（4）The synthesis of amino modified silicon dioxide microsphere carried metal porphyrin：Weighing mass ratio is 1:15（Step（2）
Gained mono carboxylic metalloporphyrin（MTPCPP）And step（3）The amino modified silicon dioxide microsphere of synthesis is dispersed in dichloromethane
In solution, the mass ratio of silicon dioxide microsphere and dichloromethane is 1：50, reflux 24h, cooling, washing, in 80 DEG C of vacuum
12h is dried, obtains amino modified silicon dioxide microsphere carried metal porphyrin (SiO2-NH2-MPCPP)；
(5) synthesis of the amino modified silicon dioxide microsphere carried metal porphyrin of carbonization：Weigh step（2）The amino of gained
Improved silica micro-ball load metalloporphyrin is loaded in reaction tube, is warming up to 800 DEG C, calcines 2h, and whole process is passed through N2Protection, so
After be naturally cooling to room temperature, obtain the amino modified silicon dioxide microsphere carried metal porphyrin (SiO of carbonization2-NH2-MTPCPP/AC).
For being catalyzed oxidation reaction of ethylbenzene.
Embodiment 4
The present embodiment comprises the following steps：
（1）The synthesis of mono carboxylic porphyrin, mass ratio is 1:3.5 benzaldehyde and 4- carboxyl benzaldehyde are dispersed in propionic acid
In, propionic acid is 1 with the mass ratio of benzaldehyde：50, it is heated to flowing back, the pyrroles with benzaldehyde equivalent is slowly dropped into, control
Flow velocity, 30min adds, and under reflux conditions, continues reaction 40min and terminates, after the cooling of question response liquid, put into fridge overnight,
Suction filtration, silica gel post separation, that is, synthesize mono carboxylic porphyrin；
（2）Mono carboxylic metalloporphyrin synthesizes, by step（1）Gained mono carboxylic porphyrin is dispersed in dimethylformamide, single
Carboxyl porphyrin is 1 with the mass ratio of dimethylformamide:200, it is heated to flowing back, be dividedly in some parts in 1h and mono carboxylic porphyrin quality
Than for 1:2.5 MnCl2·4H2O and FeCl2·4H2O, after adding, point plate monitoring reaction process, after raw material point disappears, stops
Only react, after the cooling of question response liquid, add the distilled water of 3 times of volumes of dimethylformamide, stand overnight, suction filtration, anti-with hot water
After backwashing is washed, and obtains mono carboxylic manganoporphyrin and mono carboxylic ferriporphyrin；
（3）The synthesis of amino modified silicon dioxide microsphere:Weigh silica ultrasonic disperse in toluene, silica with
Toluene mass ratio is 1:15, magnetic agitation, it is warming up to backflow, be slowly added dropwise triethoxysilane solution (APTES) and toluene is molten
Liquid analysis is pure, and the addition volume ratio of triethoxysilane solution and toluene is 1：1.2, react 24h, washing, do in 80 DEG C of vacuum
Dry overnight, obtain amino modified silicon dioxide microsphere（SiO2-NH2）；
（4）The synthesis of amino modified silicon dioxide microsphere carried metal porphyrin：Weighing mass ratio is 1:10 step（2）Institute
Obtain mono carboxylic metalloporphyrin（MTPCPP）And step（3）It is molten that the amino modified silicon dioxide microsphere of synthesis is dispersed in dichloromethane
In liquid, the mass ratio of silicon dioxide microsphere and dichloromethane is 1：20, reflux 24h, cooling, washing, do in 80 DEG C of vacuum
Dry 12h, obtains amino modified silicon dioxide microsphere carried metal porphyrin (SiO2-NH2-MPCPP)；
(5) synthesis of the amino modified silicon dioxide microsphere carried metal porphyrin of carbonization：Weigh step（2）The amino of gained
Improved silica micro-ball load metalloporphyrin is loaded in reaction tube, is warming up to 600 DEG C, calcines 1.5h, and whole process is passed through N2Protection,
Then it is naturally cooling to room temperature, obtain the amino modified silicon dioxide microsphere carried metal porphyrin (SiO of carbonization2-NH2-MTPCPP/
AC). can be used for being catalyzed oxidation reaction of ethylbenzene.
Claims (6)
1. it is used for the preparation method of the silica-microsphere-inanometerd nanometerd metal compound catalyst in oxidation reaction of ethylbenzene, it is special
Levy and be, comprise the following steps：
(1) synthesis of mono carboxylic porphyrin, mass ratio is 1:The benzaldehyde of 3-4 and 4- carboxyl benzaldehyde are dispersed in propionic acid,
Propionic acid is 1 with the mass ratio of benzaldehyde：30-60, is heated to flowing back, the pyrroles with benzaldehyde equivalent is slowly dropped into, control
Flow velocity, 20-30min adds, and under reflux conditions, continues reaction 30-60min and terminates, after the cooling of question response liquid, put in refrigerator
Overnight, suction filtration, silica gel post separation, that is, synthesize mono carboxylic porphyrin；
(2) synthesis of mono carboxylic metalloporphyrin, step (1) gained mono carboxylic porphyrin is dispersed in dimethylformamide, mono carboxylic
Porphyrin is 1 with the mass ratio of dimethylformamide:150-200, is heated to flowing back, is dividedly in some parts and mono carboxylic porphyrin quality in 1h
Than for 1:The MnCl of 2-52·4H2O and FeCl2·4H2O, after adding, point plate monitoring reaction process, after raw material point disappears, stops
Only react, after the cooling of question response liquid, add the distilled water of 2-3 times of volume of dimethylformamide, stand overnight, suction filtration, use hot water
Cyclic washing, obtains mono carboxylic manganoporphyrin and mono carboxylic ferriporphyrin；
(3) synthesis of amino modified silicon dioxide microsphere:Weigh silica ultrasonic disperse in toluene, silica and toluene
Mass ratio is 1:10-30, magnetic agitation, it is warming up to backflow, be slowly added dropwise triethoxysilane solution and toluene solution analysis is pure,
The addition volume ratio of triethoxysilane solution and toluene is 1：1-2, reacts 12-24h, washs, in 80 DEG C of dried in vacuum overnight,
Obtain amino modified silicon dioxide microsphere；
(4) synthesis of amino modified silicon dioxide microsphere carried metal porphyrin：Weighing mass ratio is 1:Step (2) institute of 10-15
The amino modified silicon dioxide microsphere that synthesizes of mono carboxylic metalloporphyrin and step (3) is dispersed in dichloromethane solution, two
The mass ratio of silicon oxide microsphere and dichloromethane is 1：10-50, reflux 12-24h, cooling, washing, it is vacuum dried at 80 DEG C
12h, obtains amino modified silicon dioxide microsphere carried metal porphyrin；
(5) synthesis of the amino modified silicon dioxide microsphere carried metal porphyrin of carbonization：Weigh the amino modified of step (2) gained
Silicon dioxide microsphere carried metal porphyrin is loaded in reaction tube, is warming up to 300-800 DEG C, calcines 1-2h, and whole process is passed through N2Protection,
Then it is naturally cooling to room temperature, obtain the amino modified silicon dioxide microsphere carried metal porphyrin of carbonization.
2. according to claim 1 urge for the immobilized nano metal compound of the silicon dioxide microsphere in oxidation reaction of ethylbenzene
The preparation method of agent is it is characterised in that in described step (1), the time continuing to react under counterflow condition is 40min.
3. according to claim 1 urge for the immobilized nano metal compound of the silicon dioxide microsphere in oxidation reaction of ethylbenzene
The preparation method of agent it is characterised in that in described step (2), MnCl2·4H2O and FeCl2·4H2O and mono carboxylic porphyrin matter
Amount ratio is 1：2.5-3.
4. according to claim 1 urge for the immobilized nano metal compound of the silicon dioxide microsphere in oxidation reaction of ethylbenzene
The preparation method of agent is it is characterised in that in described step (3), silica and toluene mass ratio are 1：15, triethoxysilicane
The addition volume ratio of alkane solution and toluene is 1：1.2-1.5, reacts 12-24h, washing, in 80 DEG C of dried in vacuum overnight, obtains amino
Improved silica microballoon.
5. according to claim 1 urge for the immobilized nano metal compound of the silicon dioxide microsphere in oxidation reaction of ethylbenzene
The preparation method of agent it is characterised in that in described step (4), mono carboxylic metalloporphyrin (MTPCPP) and amino modified two
The mass ratio of silicon oxide microsphere is 1：10, the mass ratio of silicon dioxide microsphere and dichloromethane is 1:15-20.
6. according to claim 1 urge for the immobilized nano metal compound of the silicon dioxide microsphere in oxidation reaction of ethylbenzene
The preparation method of agent is it is characterised in that in described step (5), amino modified silicon dioxide microsphere carried metal porphyrin is loaded on
In reaction tube, it is warming up to 400-600 DEG C, calcine 1-1.5h.
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| CN108176413B (en) * | 2017-12-22 | 2020-09-04 | 西北大学 | Quaternary ammonium salt type Mn (III) porphyrin-SiO2Preparation and use of catalysts |
| CN111841637B (en) * | 2020-06-23 | 2021-04-16 | 泰州九润环保科技有限公司 | Metalloporphyrin-mesoporous organic silicon oxide photocatalytic material and preparation method thereof |
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| CN115137842B (en) * | 2022-05-25 | 2023-09-29 | 华南农业大学 | Silica microsphere capable of adsorbing nano vesicles for treating ulcerative colitis and preparation method and application thereof |
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