CN102407160A - Preparation method of core-shell structure CeO2@SiO2 load metalloporphyrin catalyst prepared by double wrapping method - Google Patents
Preparation method of core-shell structure CeO2@SiO2 load metalloporphyrin catalyst prepared by double wrapping method Download PDFInfo
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- CN102407160A CN102407160A CN2011103125217A CN201110312521A CN102407160A CN 102407160 A CN102407160 A CN 102407160A CN 2011103125217 A CN2011103125217 A CN 2011103125217A CN 201110312521 A CN201110312521 A CN 201110312521A CN 102407160 A CN102407160 A CN 102407160A
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Abstract
The invention relates to a preparation method of core-shell structure CeO2@SiO2 load metalloporphyrin catalyst prepared by double wrapping method, and provides a system for forming the core-shell structure CeO2@SiO2 load metalloporphyrin multi-phase catalyst by double wrapping method. The preparation method comprises the following steps of: stirring and dispersing nanometer cerium oxide particles with surfaces modified by sodium citrate, and adding tetraethyl orthosilicate (TEOS) dropwise to obtain once wrapped core-shell structure CeO2@SiO2; stirring and dispersing the once wrapped core-shell structure CeO2@SiO2 and hexadecyl ammonium bromide; adding mixed solution of the TEOS and 3-aminopropyl triethoxy silicane (APTES) to obtain doubly wrapped core-shell structure CeO2@SiO2; and linking cobalt monocarboxyl porphyrin (CoTMCPP) to a doubly wrapped core-shell structure CeO2@SiO2 carrier by amidation reaction so as to obtain the core-shell structure CeO2@SiO2 load metalloporphyrin catalyst prepared by double wrapping method. The catalyst provided by the invention has higher catalytic activity and stability for selective catalytic oxidation reaction of molecular oxygen on diphenylmethane in the absence of solvent, and the preparation method is simple and product quality is easily controlled, so that the catalyst is suitable for use in the fields such as selective oxidation reaction of hydrocarbon alkyl and synthesis of medicine intermediate and the like.
Description
Technical field
The invention belongs to catalyst field, be specifically related to the nucleocapsid structure CeO of double wrapped method preparation
2SiO
2Carried metal porphyrin catalyst preparation method.
Background technology
Benzophenone is a kind of fine chemical product commonly used, is widely used as the ultra-violet absorber of medicine intermediate, spices fixastive, macromolecular material, the sensitising agent of film coating etc.In the industry, the synthetic route of benzophenone mainly contains Fu-Ke acylated method, carbonylation method, nitric acid oxidation method etc.The acylated method requires in the course of reaction definitely anhydrous, be with 2-3 acid of stoichiometric halo Brown's or lewis acid doubly, and equipment corrosion is serious, and catalyst can't reclaim; Carbonylation method not only will be used poisonous raw material (phosgene), also needs the reaction down of high temperature, high pressure; The nitric acid oxidation method time is long, and equipment corrosion is serious, also has serious problems such as " three industrial wastes ".
In recent years, on the market increasing demand of benzophenone is increased, existing benzophenone industry since high pollution, high energy consumption and expensive can't meet the demands.Scientists begins to be devoted to the research of benzophenone new technique for synthesizing, like benzoate thermal decomposition method and heterogeneous catalysis diphenyl-methane oxidizing process.Heterogeneous catalysis diphenyl-methane oxidizing process has obtained bigger progress because abundant raw material, technology are simple, the selectivity advantages of higher enjoys favor.As catalyst, as oxidant, acetic acid is solvent with TBHP like the MCM-41 molecular sieve modified with Mn, and the diphenyl-methane conversion ratio can reach 95%; Use MnO
4 -Exchanged water talcum structural material (Mg-Al, NiAl, Mn-MgAl and Ru-Co-Al) is as catalyst; Under solvent-free normal pressure with oxygen as oxidant; High selectivity catalytic oxidation diphenyl-methane generates benzophenone, but above-mentioned two kinds of methods all exist active ion to come off easily, cause catalysqt deactivation; Be difficult to problems such as recycle and reuse, limited such Application of Catalyst.The macromolecule loading catalysis of metalloporphyrin agent of developed recently; Its carrier provides special microenvironment; On catalytic performance, have synergy, demonstrate the catalyzing cooperation effect of macromolecule carrier, make the catalysis of metalloporphyrin agent of load show more excellent catalytic performance.
In sum, nano-oxide and catalysis of metalloporphyrin agent respectively have its advantage, and therefore, in the present invention, the characteristics of combining nano oxide, organosilicon and metalloporphyrin form " metalloporphyrin-CeO
2-organosilicon microballoon " ternary catalyst system and catalyzing altogether, make the CeO of the nucleocapsid structure of double wrapped
2SiO
2The carried metal porphyrin catalyst.At present, the domestic and international CeO that does not also have about the nucleocapsid structure of double wrapped
2SiO
2Carried metal porphyrin catalyst preparation method's open source literature and patent application.
Summary of the invention
The present invention be directed to a kind of CeO of nucleocapsid structure of double wrapped
2SiO
2Carried metal porphyrin catalyst and the application in the diphenyl-methane oxidation reaction thereof.This method adopts following technical scheme specifically to realize: the surface after the nano-cerium oxide particle dispersed with stirring that natrium citricum is modified, is dropwise added silicon tetraethyl acid esters (TEOS), make the nucleocapsid structure CeO of single parcel
2SiO
2, the nucleocapsid structure CeO that then single is wrapped up
2SiO
2With cetyl amine bromide, dispersed with stirring, add TEOS and 3-aminopropyl triethoxysilane (APTES) mixed liquor again, make double wrapped nucleocapsid structure CeO
2SiO
2, through amidation process, mono carboxylic metallic cobalt porphyrin (CoTMCPP) is linked to double wrapped nucleocapsid structure CeO at last
2SiO
2On the carrier, promptly make the nucleocapsid structure CeO of double wrapped method preparation
2SiO
2The carried metal porphyrin catalyst is called for short S
1-IM-Co.
The present invention is to provide the nucleocapsid structure CeO of double wrapped method preparation
2SiO
2Carried metal porphyrin catalyst preparation method, the mono carboxylic metalloporphyrin arrives CeO through the amido link grafting
2SiO
2On the nucleocapsid structure silicon ball, avoid metalloporphyrin in course of reaction, to run off and dimerization, thereby improved the stability of catalysis of metalloporphyrin agent; Simultaneously, CeO
2SiO
2Nucleocapsid structure silicon ball provides the microenvironment that is beneficial to reaction, has improved activity of such catalysts and selectivity; In addition, the nano Ce O that has storage oxygen function
2Be wrapped feasible " metalloporphyrin-CeO
2-organosilicon microballoon " ternary system forms common catalytic effect, further promoted activity of such catalysts, selectivity and stability.
Above-mentioned CeO
2SiO
2Preparation method's concrete steps of nucleocapsid structure silicon ball carried metal porphyrin catalyst are following:
(1) in the 500ml there-necked flask, add the nano-cerium oxide that the 0.3g surface is modified through natrium citricum, the 40ml deionized water, 160ml ethanol, 5ml ammoniacal liquor under 700r/min mechanical agitation condition, disperses 30min; Add 0.5ml TEOS, continue to stir 6h, suction filtration, washing, drying makes the nucleocapsid structure CeO that single wraps up
2SiO
2Take by weighing the nucleocapsid structure CeO of 0.20g single parcel
2SiO
2, 0.6g cetyl amine bromide joins in 160ml deionized water and the 120ml absolute ethyl alcohol mixed solution; Stir, add 2ml ammoniacal liquor subsequently, after disperseing 30mim under the 700r/min stirring condition; Add 1ml TEOS and 0.2ml APTES mixed liquor again, behind the continuation stirring reaction 6h, through suction filtration; After washing and the drying, promptly get the nucleocapsid structure CeO of double wrapped method preparation
2SiO
2
(2) take by weighing 0.050g CoTMCPP, the nucleocapsid structure CeO of 3.50g double wrapped method preparation
2SiO
2, joining in the 250ml there-necked flask that 100ml DMF solution is housed, back flow reaction 12h boils off 70ml DMF; Add the 70ml deionized water after cooling, filter, spend deionised water to colourless; Again with washed with dichloromethane to colourless, directly go to after draining in the cable type extractor according, with carrene as extract; Be extracted into colourlessly, drying promptly makes the nucleocapsid structure CeO of double wrapped method preparation
2SiO
2The carried metal porphyrin catalyst.
The CeO that the present invention is prepared
2SiO
2Nucleocapsid structure silicon ball carried metal porphyrin catalyst is a substrate with the diphenyl-methane, and oxygen is oxygen source, under solvent-free condition, adopts following method to detect its catalytic performance: with CeO
2SiO
2Nucleocapsid structure silicon ball carried metal porphyrin catalyst reacts in the there-necked flask of being furnished with serpentine condenser, thermometer and air conduit.Reaction condition is: add 30mL diphenyl-methane and proper catalyst; Place flask oil bath pan to be heated to steady temperature; The flow of oxygen is through spinner flowmeter control; The exit of conduit in reactant liquor is the sponge gas distributor, carries out sample analysis at regular intervals, and oxidation product carries out quantitative analysis with gas-chromatography.Reactant liquor is left standstill, use washing with alcohol, filter, after the cable type extractor according extracting, promptly obtain reclaiming catalyst.After washing with alcohol, with the repeat performance of further investigation catalyst.CeO
2SiO
2Nucleocapsid structure silicon ball carried metal porphyrin catalyst stability characterizes shown in accompanying drawing 3.
The invention has the advantages that: (1) CeO
2SiO
2In the nucleocapsid structure silicon ball carried metal porphyrin catalyst, the mono carboxylic metalloporphyrin, has been avoided loss and the dimerization of metalloporphyrin in course of reaction, thereby has been improved the stability of catalysis of metalloporphyrin agent to organosilicon nanometer microsphere through the covalent bond grafting; (2) organosilicon microballoon micropore surface has hydrophilic and hydrophobic alternate character, can provide the microenvironment that is beneficial to reaction, has improved activity of such catalysts and selectivity; (3) nano Ce O
2Has storage oxygen function, feasible " metalloporphyrin-CeO
2-organosilicon microballoon " ternary system forms common catalytic effect, further promoted activity of such catalysts, selectivity and stability.
Description of drawings:
Fig. 1 is CeO
2And the XRD figure of S1-IM-Co spectrum
A is CeO among Fig. 2
2SiO
2The SEM of nuclear-shell silicon ball; B is S
1The SEM of-IM-Co; C is CeO
2SiO
2The TEM of nuclear-shell silicon ball; D is S
1The TEM of-IM-Co
Fig. 3 is the catalyst and the catalyst solid uv absorption of reusing after 6 times of new system, and the characteristic peak of porphyrin appears at 428nm and 541nm place respectively
The specific embodiment
Below in conjunction with embodiment the present invention is further specified:
Embodiment 1
Synthesizing of mono carboxylic porphyrin.In the 500ml there-necked flask, add the 200ml propionic acid, 1.51g benzaldehyde and 2.08g 4-carboxyl benzaldehyde are heated to backflow, with constant pressure funnel 1.36g pyrroles slowly splashed into, the control flow velocity, 20min adds.Under refluxad, continue reaction 30min and finish, after the question response liquid cooling but, put into refrigerator and spend the night, suction filtration, silicagel column separates, promptly synthetic mono carboxylic porphyrin.
Synthesizing of mono carboxylic cobalt porphyrin.In the 250ml there-necked flask, add 100ml DMF, 0.5g mono carboxylic porphyrin is heated to backflow, adds 2.54g CoCl in the 1h in batches
26H
2O.After adding, some plate monitoring reaction process after raw material point disappears, stops reaction.After the question response liquid cooling but, add the distilled water of 2-3 times of volume, hold over night, suction filtration is used the hot water cyclic washing, promptly gets mono carboxylic cobalt porphyrin.
Embodiment 2
Double wrapped nucleocapsid structure CeO
2SiO
2Synthesizing of silicon ball.Take by weighing 5.996g Ce (NO
3)
36H
2O is configured to 250ml solution with deionized water.Under the 500r/min mechanical agitation, NaOH solution slowly is added dropwise to Ce (NO
3)
3In the solution, the pH value is adjusted to 13, continues to stir 30min, suction filtration is dispersed in filter cake in the deionized water, with ultrasonic dispersion washing 2 times, filter cake is being dispersed in the absolute ethyl alcohol supersound washing 2 times.The gained sample is at 70 ℃ of vacuum drying 1h.Dried ceria oxide powder is transferred in the sodium citrate solution of 200ml 0.3mol/L, under the 500r/min mechanical agitation, is heated to 90 ℃ with water-bath and handles 3h, suction filtration promptly gets the nano-cerium oxide particle of finishing after the drying.In the 500ml there-necked flask, add the nano-cerium oxide that the 0.3g surface is modified through natrium citricum, the 40ml deionized water, 160ml ethanol, 5ml ammoniacal liquor under 700r/min mechanical agitation condition, disperses 30min; Add 0.5ml TEOS, continue to stir 6h, suction filtration, washing, drying makes the nucleocapsid structure CeO that single wraps up
2SiO
2Take by weighing the nucleocapsid structure CeO of 0.20g single parcel
2SiO
2, 0.6g cetyl amine bromide joins in 160ml deionized water and the 120ml absolute ethyl alcohol mixed solution; Stir, add 2ml ammoniacal liquor subsequently, after disperseing 30mim under the 700r/min stirring condition; Add 1ml TEOS and 0.2mlAPTES mixed liquor again, behind the continuation stirring reaction 6h, through suction filtration; After washing and the drying, promptly get the nucleocapsid structure CeO of double wrapped method preparation
2SiO
2
Embodiment 3
Take by weighing 0.050g CoTMCPP, the nucleocapsid structure CeO of 3.50g double wrapped method preparation
2SiO
2, joining in the 250ml there-necked flask that 100ml DMF solution is housed, back flow reaction 12h boils off 70ml DMF; Add the 70ml deionized water after cooling, filter, spend deionised water to colourless; Again with washed with dichloromethane to colourless, directly go to after draining in the cable type extractor according, with carrene as extract; Be extracted into colourlessly, drying promptly makes the nucleocapsid structure CeO of double wrapped method preparation
2SiO
2The carried metal porphyrin catalyst.
Embodiment 4
In the there-necked flask of the 100ml that is furnished with serpentine condenser, thermometer and air conduit, add 30ml diphenyl-methane and proper catalyst; Place flask oil bath pan to be heated to steady temperature; The flow of oxygen is through spinner flowmeter control; The exit of conduit in reactant liquor is the sponge gas distributor, carries out sample analysis at regular intervals, and oxidation product carries out quantitative analysis with gas-chromatography.Can know diphenyl-methane oxidation reaction selective data under the condition of different temperatures by table 1.Along with temperature rises, reaction rate increases, and the diphenyl-methane conversion ratio raises.Be respectively 90 ℃ in reaction temperature, 110 ℃, 130 ℃ and 150 ℃, behind the reaction 24h, the diphenyl-methane conversion ratio is respectively 15%, 40%, and 66% and 82%.Can know by the selective data shown in the table 1, under this paper experiment condition, the diphenyl-methane catalytic oxidation, the generation benzophenone of ability high selectivity is under 150 ℃ of conditions, and the benzophenone selectivity descends to some extent, is more excellent condition so select 130 ℃.
Embodiment 5
Reactant liquor is left standstill, use washing with alcohol, filter, after the cable type extractor according extracting, promptly obtain reclaiming catalyst.After washing with alcohol, with the progressive repeat performance of investigating catalyst.CeO
2SiO
2Nucleocapsid structure silicon ball carried metal porphyrin catalyst stability characterizes shown in accompanying drawing 3.
Table 1: diphenyl-methane oxidation reaction selective data under the condition of different temperatures
Claims (2)
1. the nucleocapsid structure CeO of double wrapped method preparation
2SiO
2Carried metal porphyrin catalyst preparation method is characterized in that the surface after the nano-cerium oxide particle dispersed with stirring that natrium citricum is modified, dropwise adding silicon tetraethyl acid esters (TEOS), makes the nucleocapsid structure CeO of single parcel
2SiO
2, the nucleocapsid structure CeO that then single is wrapped up
2SiO
2With cetyl amine bromide, dispersed with stirring, add TEOS and 3-aminopropyl triethoxysilane (APTES) mixed liquor again, make double wrapped nucleocapsid structure CeO
2SiO
2, through amidation process, mono carboxylic metallic cobalt porphyrin (CoTMCPP) is linked to double wrapped nucleocapsid structure CeO at last
2SiO
2On the carrier, promptly make the nucleocapsid structure CeO of double wrapped method preparation
2SiO
2The carried metal porphyrin catalyst.
2. the nucleocapsid structure CeO of double wrapped method preparation according to claim 1
2SiO
2Carried metal porphyrin catalyst preparation method is characterized in that concrete steps are following:
(1) in the 500ml there-necked flask, add the nano-cerium oxide that the 0.3g surface is modified through natrium citricum, the 40ml deionized water, 160ml ethanol, 5ml ammoniacal liquor under 700r/min mechanical agitation condition, disperses 30min; Add 0.5ml TEOS, continue to stir 6h, suction filtration, washing, drying makes the nucleocapsid structure CeO that single wraps up
2SiO
2Take by weighing the nucleocapsid structure CeO of 0.20g single parcel
2SiO
2, 0.6g cetyl amine bromide joins in 160ml deionized water and the 120ml absolute ethyl alcohol mixed solution; Stir, add 2ml ammoniacal liquor subsequently, after disperseing 30mim under the 700r/min stirring condition; Add 1ml TEOS and 0.2mlAPTES mixed liquor again, behind the continuation stirring reaction 6h, through suction filtration; After washing and the drying, promptly get the nucleocapsid structure CeO of double wrapped method preparation
2SiO
2
(2) take by weighing 0.050g CoTMCPP, the nucleocapsid structure CeO of 3.50g double wrapped method preparation
2SiO
2, joining in the 250ml there-necked flask that 100ml DMF solution is housed, back flow reaction 12 hours boils off 70ml DMF; Add the 70ml deionized water after cooling, filter, spend deionised water to colourless; Again with washed with dichloromethane to colourless, directly go to after draining in the cable type extractor according, with carrene as extract; Be extracted into colourlessly, drying promptly makes the nucleocapsid structure CeO of double wrapped method preparation
2SiO
2The carried metal porphyrin catalyst.
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Cited By (5)
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|---|---|---|---|---|
| CN103566935A (en) * | 2013-01-08 | 2014-02-12 | 湖南大学 | Preparation method of monatomic dispersion catalyst with high catalytic performance |
| CN103657726A (en) * | 2013-12-23 | 2014-03-26 | 湖南大学 | Preparation method and application of silica-microsphere-immobilized nanometer metal compound catalyst |
| CN104069858A (en) * | 2013-03-27 | 2014-10-01 | 中国石油化工股份有限公司 | Bifunctional catalyst for synthesis of dimethyl carbonate and preparation and application method thereof |
| CN104910901A (en) * | 2015-05-26 | 2015-09-16 | 哈尔滨工业大学 | Method used for preparing ZnO/SiO2 nano composite material |
| CN112778107A (en) * | 2019-11-06 | 2021-05-11 | 复旦大学 | Method for synthesizing acetophenone or benzoic acid compound by oxidizing toluene compound |
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| CN101775280A (en) * | 2010-01-22 | 2010-07-14 | 上海师范大学 | Water-soluble nuclear-shell magneto-optic dual-function nanoparticle and preparation method thereof |
| CN101898156A (en) * | 2010-07-27 | 2010-12-01 | 湖南大学 | Preparation method for CeO2 doped organosilicon nanometer microsphere metal cobalt loaded (ii) porphyrin catalyst |
-
2011
- 2011-10-14 CN CN2011103125217A patent/CN102407160A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775280A (en) * | 2010-01-22 | 2010-07-14 | 上海师范大学 | Water-soluble nuclear-shell magneto-optic dual-function nanoparticle and preparation method thereof |
| CN101898156A (en) * | 2010-07-27 | 2010-12-01 | 湖南大学 | Preparation method for CeO2 doped organosilicon nanometer microsphere metal cobalt loaded (ii) porphyrin catalyst |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103566935A (en) * | 2013-01-08 | 2014-02-12 | 湖南大学 | Preparation method of monatomic dispersion catalyst with high catalytic performance |
| CN104069858A (en) * | 2013-03-27 | 2014-10-01 | 中国石油化工股份有限公司 | Bifunctional catalyst for synthesis of dimethyl carbonate and preparation and application method thereof |
| CN104069858B (en) * | 2013-03-27 | 2016-04-13 | 中国石油化工股份有限公司 | A kind of bifunctional catalyst of Synthesis of dimethyl carbonate and methods for making and using same thereof |
| CN103657726A (en) * | 2013-12-23 | 2014-03-26 | 湖南大学 | Preparation method and application of silica-microsphere-immobilized nanometer metal compound catalyst |
| CN104910901A (en) * | 2015-05-26 | 2015-09-16 | 哈尔滨工业大学 | Method used for preparing ZnO/SiO2 nano composite material |
| CN112778107A (en) * | 2019-11-06 | 2021-05-11 | 复旦大学 | Method for synthesizing acetophenone or benzoic acid compound by oxidizing toluene compound |
| CN112778107B (en) * | 2019-11-06 | 2022-06-10 | 复旦大学 | Method for synthesizing acetophenone or benzoic acid compound by oxidizing toluene compound |
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Application publication date: 20120411 |