CN103055938A - An acid-base bifunctional graphene-based nano heterogeneous catalyst and a preparation method thereof - Google Patents
An acid-base bifunctional graphene-based nano heterogeneous catalyst and a preparation method thereof Download PDFInfo
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- CN103055938A CN103055938A CN2012105800521A CN201210580052A CN103055938A CN 103055938 A CN103055938 A CN 103055938A CN 2012105800521 A CN2012105800521 A CN 2012105800521A CN 201210580052 A CN201210580052 A CN 201210580052A CN 103055938 A CN103055938 A CN 103055938A
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Abstract
The invention belongs to the field of catalyst preparation, and in particular relates to an acid-base bifunctional graphene-based nano heterogeneous catalyst and a preparation method thereof. In the catalyst, graphene oxide is used as a carrier and the surface of the graphene oxide is modified with amino groups; the catalyst has a two-dimensional planar structure of a thickness of 1.0-5.0nm. The preparation method of the catalyst comprises: the graphene oxide is dispersed in an organic solvent by using ultrasonic dispersion, and a silane coupling agent is slowly added in and a protective gas is fed into the organic solution; and the mixed reaction system is heated and held, stood, filtered, and dried to obtain the sample. The heterogeneous catalyst has both acid and base active sites on the surface, and the acid and base active sites are independent of each other to achieve individula catalytic effect without neutralizing each other, and have relatively high catalytic activity, thereby improving the reaction efficiency and reducing the production costs. The catalyst has good chemical stability and good thermal stability, and the preparation process is simple, and easy in operation.
Description
Technical field
The invention belongs to the catalyst preparation field, particularly difunctional nanometer heterogeneous catalysis of a kind of graphene-based soda acid and preparation method thereof.
Background technology
In organic synthesis, the synthetic of many complicated molecules often needs multistep to finish, and wherein related to loaded down with trivial details separation and purification process, angle from economy and environmental protection, be very worthless, be necessary to reduce step, avoid substantially the Separation ﹠ Purification of intermediate.Cascade reaction (tandem reactions, domino or cascade reactions), it is not to carry out simply in succession the multistep independent reaction in a reactor, but the reactive intermediate that the first reaction generates then carries out second step, the reaction in the 3rd step.At present, cascade reaction is being applied in the middle of the especially asymmetric syntheses process of most organic synthesis process of success, and in these reactions, cascade reaction has fully shown the superiority than conventional method.
But traditional homogeneous catalyst is applied in the catalyst of a series of problem, especially metal species such as existing catalytic active site coexistence and catalyst recovery use in these cascade reactions, and not only price, cost are high, but also can cause certain pollution.If the employing difunction catalyst namely by the synergy of acid catalysis and base catalysis and bring into play the catalyst of catalysis, just can solve many problems that typical catalyst is brought.In catalytic reaction, these molecules with soda acid double-functional group are played the part of dual role, receive proton as proton acceptor on the one hand, can be used as again on the other hand proton donor and provide proton, so these molecules that play catalytic action are called as difunction catalyst.The concerted catalysis of metal ion type acid base catalysator can make the activation energy of reaction be even lower, thereby accelerates reaction rate, improves productive rate.But how successfully to synthesize and have the difunctional heterogeneous catalysis of soda acid, so that catalyst backbone is not yielding, keep certain distance when the acid on surface, base groups distribution, can avoid the inside neutralization between acid, the alkali, can work in coordination with simultaneously the priming reaction substrate again, be a difficult problem that needs at present solution.
Summary of the invention
The purpose of this invention is to provide the difunctional nanometer heterogeneous catalysis of a kind of graphene-based soda acid (hereinafter to be referred as NH
2-GO), this catalyst has two-dimension plane structure, and surperficial amino group and acid carboxylic group with alkalescence, can be dispersed in reaction system well, and catalytic efficiency significantly improves.
Another object of the present invention provides a kind of method for preparing the difunctional nanometer heterogeneous catalysis of above-mentioned graphene-based soda acid.
Purpose of the present invention can be achieved through the following technical solutions:
The difunctional nanometer heterogeneous catalysis of a kind of graphene-based soda acid is characterized in that: this catalyst is take graphene oxide as carrier, and in the finishing of graphene oxide amino group arranged; This catalyst has the two-dimension plane structure of 1.0-5.0nm thickness.
A kind of method for preparing the difunctional nanometer heterogeneous catalysis of above-mentioned graphene-based soda acid, its step comprises: be dispersed in the organic solvent graphene oxide is ultrasonic, slowly add silane coupler and pass into protective gas in this organic solution; This hybrid reaction system is heated and is incubated, leaves standstill, filters, dries must sample.
Preferably, described organic solvent is dry toluene, nitromethane or nitroethane.
Preferably, described protective gas is nitrogen, argon gas.
The adding proportioning of described organic solvent, graphene oxide, silane coupler is 15-30mL:0.5g:0.1-0.4mL.Preferably, the adding proportioning of described organic solvent, graphene oxide, silane coupler is 20mL:0.5g:0.2-0.25mL.
Described silane coupler is 3-aminopropyl triethoxysilane or 3-aminopropyl trimethoxysilane.
The heating-up temperature of described hybrid reaction system is 105 ℃-115 ℃, and temperature retention time is 24-30 hour.
Behind the described reacting liquid filtering, the filter cake that obtains is washed with absolute ethyl alcohol, acetone and distilled water respectively, under 55 ℃ of-60 ℃ of vacuum conditions, dry.
The present invention is by at the mode of silicon oxygen bond (Si-O) the finishing amino group at graphene oxide, formed the difunctional heterogeneous catalysis of a kind of soda acid, this catalyst can be applicable in the soda acid cascade reaction, and in the reaction of a series of acid promotion base catalysis such as Henry reaction, Michael reaction and Richard-Hsung reaction, all has good catalytic activity, and this heterogeneous catalysis good dispersion degree in solution, catalysis efficiency significantly improves former because:
(1) NH for preparing of the mode by rear grafting
2Namely exist on-the GO alkalescence-NH
2Group also exists acid-COOH group, because the two all has been fixed on the different position of graphene oxide carrier ,-NH
2The group major part is fixed on the surface of graphene oxide, and-the COOH group substantially all is present in the edge of graphene oxide, so the two can play the catalytic action of self and can mutually not neutralize in reaction system.These characteristics had both guaranteed the catalytic activity of the soda acid avtive spot on this catalyst, guaranteed that again it can not neutralize mutually in reaction, this is that homogeneous catalyst institute is inaccessiable, so catalyst of the present invention can increase substantially the catalytic efficiency of soda acid cascade reaction.
(2) catalytic active site can have fully with reaction substrate and contacts on the catalyst of the present invention, has eliminated the impact that the reaction substrate diffusion brings fully, and catalyst of the present invention can extraordinaryly be dispersed in the reaction system, can improve catalytic efficiency.
Graphene oxide used in the present invention is to adopt improvement Hummers method to prepare.
Compared with prior art, beneficial effect of the present invention is: 1, the difunctional nanometer heterogeneous catalysis of described graphene-based soda acid surface has the soda acid avtive spot simultaneously, these avtive spots can be separate realization separately catalytic action and can mutually not neutralize, can be used for the organic synthesis that soda acid cascade reaction and a series of acid promote base catalysis, the difunctional nanometer heterogeneous catalysis of graphene-based soda acid that participates in reaction can repeatedly use through after reclaiming, still have higher catalytic activity, when improving reaction efficiency, also reduced production cost.2, described catalyst has unique monoatomic layer two-dimension plane structure, can eliminate the impact of the reaction substrate diffusion that traditional catalyst brings, and catalyst can well be dispersed in the reaction system simultaneously, and chemical stability and heat endurance are fine.3, simple, the simple operation of the preparation technology of described catalyst, draw materials conveniently, production cost is low.
Description of drawings
Fig. 1 is the XRD figure of the difunctional nanometer heterogeneous catalysis of graphene-based soda acid among the embodiment 1.
Fig. 2 is the SEM figure of graphene oxide among the embodiment 1.
Fig. 3 is the SEM figure of the difunctional nanometer heterogeneous catalysis of graphene-based soda acid among the embodiment 1.
Fig. 4 is the TEM figure of the difunctional nanometer heterogeneous catalysis of graphene-based soda acid among the embodiment 1.
The specific embodiment
Below in conjunction with embodiment, the invention will be further described:
Test used equipment: Rigaku D/Max-RB type X-ray diffractometer, JEOL JEM2011 type high-resolution-ration transmission electric-lens, S4800 type awkward silence at a meeting emission scan electron microscope.
Embodiment 1
(1), the preparation of graphene oxide: take by weighing respectively native graphite and the 1g anhydrous nitric acid sodium of 1g, slowly add 98% the concentrated sulfuric acid of 40ml after mixing with the speed of 1ml/min, in ice-water bath, stirred 2 hours; Keep under the state of ice-water bath that the speed with 0.1g/min slowly adds 5g potassium permanganate in the above-mentioned mixed solution, after the end temperature of reaction system risen to 35 ℃ and keep temperature to stir 2 hours; Above-mentioned temperature of reaction system is risen to 60 ℃, slowly add 5% dilute sulfuric acid of 100ml behind the temperature stabilization with the speed of 1ml/min in the solution, keep temperature to stir 1 hour after finishing; Above-mentioned temperature of reaction system is risen to 95 ℃, and the speed with 10ml/min behind the temperature stabilization slowly adds the hydrogen peroxide of 30ml30% and the distilled water of 1000ml in solution, keep temperature to stir 30 minutes after finishing; After stir finishing aforesaid liquid left standstill and centrifugal, use respectively the solid 5 times that 5% watery hydrochloric acid and distilled water washing centrifugal sedimentation gets off, last 60 ℃ of vacuum dryings namely obtain graphene oxide.
(2), the preparation of the difunctional nanometer heterogeneous catalysis of graphene-based soda acid: the graphene oxide that takes by weighing the above-mentioned preparation of 0.5g, in the ultrasonic dry toluene that is dispersed in 20mL, slowly drip again the 3-aminopropyl triethoxysilane (APTES) of 200ul in the solution, pass into nitrogen and with temperature increase to 110 ℃ to reaction system, keep this heating-up temperature and stirred 24 hours, then above-mentioned mixed liquor is left standstill and filters, and use respectively absolute ethyl alcohol, acetone and distilled water washing leaching cake, under 60 ℃ of vacuum conditions, dry filter cake at last, namely get NH
2-GO.
(1), the preparation of graphene oxide is with embodiment 1
(2), the preparation of the difunctional nanometer heterogeneous catalysis of graphene-based soda acid: the graphene oxide that takes by weighing the above-mentioned preparation of 0.5g, in the ultrasonic nitromethane that is dispersed in 25mL, slowly drip again the 3-aminopropyl trimethoxysilane of 250ul in the solution, pass into nitrogen and with temperature increase to 115 ℃ to reaction system, keep this heating-up temperature and stirred 30 hours, then above-mentioned mixed liquor is left standstill and filters, and use respectively absolute ethyl alcohol, acetone and distilled water washing leaching cake, under 60 ℃ of vacuum conditions, dry filter cake at last, namely get NH
2-GO.The performance characterization of the difunctional nanometer heterogeneous catalysis of graphene-based soda acid (following used NH
2-GO is NH prepared among the embodiment 1
2-GO):
1, NH
2-GO participates in the catalysis efficiency analysis of chemical reaction:
(1), NH
2-GO is applied to the soda acid cascade reaction:
The benzaldehyde dimethyl acetal that in the 25mL round-bottomed flask of reflux condensing tube, adds 1.00mmol, the ethyl cyanoacetate of 2.00mmol, the deionized water of 80uL is adding 0.1gNH
2-GO, reaction is 12 hours under 80 ℃ of conditions, and products therefrom carries out product analysis by HPLC-MS, result such as following table after dividing 3 extractions with the 10mL absolute methanol:
First step reaction is acid catalyzed reaction for benzaldehyde dimethyl acetal hydrolysis; Second step is the Knoevenagel reaction that benzaldehyde and ethyl cyanoacetate occur, and is base catalyzed reactions.
After reaction was finished, with the catalyst isolated by filtration, and with deionized water washing 2-4 time, vacuum drying under 80 ℃ of conditions was again through applying mechanically experiment after 80 ℃ of lower vacuum drying, result of the test demonstration, NH
2Still have preferably catalytic activity after-GO repeats to apply mechanically five times, the efficiency of pcr product of this soda acid cascade reaction of its participation still remains on more than 85%.
(2), NH
2-GO is applied to the Henry reaction:
The formaldehyde that adds 3.00mmol at the bottom of with the 25mL of reflux condensing tube in the flask, the nitromethane of 3.00ml, 0.04g NH
2-GO, 100 ℃ of lower reactions 6 hours, products therefrom carries out product analysis by HPLC-MS, result such as following table after dividing 3 extractions with the 10mL absolute methanol:
| Catalyst | Conversion ratio (%) | Selectively (%) | Yield (%) |
| NH 2-GO | 90 | 99 | 89 |
(3) NH
2The process that-GO is applied to the Michael reaction is as follows:
The trans nitrostyrolene that in the 25mL round-bottomed flask of reflux condensing tube, adds 2.00mmol, the malononitrile of 2.40mmol, the NH of 0.05g
2-GO, 30 ℃ of lower reactions 6 hours, products therefrom carries out product analysis by HPLCMS, result such as following table after dividing 3 extractions with the 10mL absolute methanol:
| Catalyst | Conversion ratio (%) | Selectively (%) | Yield (%) |
| NH 2-GO | 89 | 99 | 88 |
(4), NH
2-GO is applied to the Richard-Hsung reaction:
The cyclohexanedione that in the 25mL round-bottomed flask of reflux condensing tube, adds 2.10mmol, the 3-of 2.00mmol (9-anthracene) methacrylaldehyde, the dimethyl carbonate of 5.00mL, 0.05g NH
2-GO, 35 ℃ of lower reactions 24 hours, products therefrom carries out product analysis by HPLC-MS, result such as following table after dividing 3 extractions with the 10mL absolute methanol:
| Catalyst | Conversion ratio (%) | Selectively (%) | Yield (%) |
| NH 2-GO | 85 | 95 | 81 |
So, the NH that the present invention is prepared
2-GO is applied in the above-mentioned reaction, can improve well catalysis efficiency, and product yield is more than 85%, and product yield selectively more than 95%, illustrates this NH more than 81%
2-GO is a very outstanding catalyst, and the catalysis efficiency of traditional metal ion catalyst is close, but has low price, pollutes the advantage that reduces than traditional metal ionic catalyst.
2, NH
2The structural analysis of-GO:
Fig. 1 is the XRD figure of the difunctional nanometer heterogeneous catalysis of graphene-based soda acid, and as can be seen from Figure, the peak intensity about 11 degree is very low, illustrates that graphene sheet layer is strutted substantially, and interlamellar spacing disappears.Peak about 22 degree is the characteristic peak of graphite.
Fig. 2 is the SEM figure of graphene oxide, can know from figure and find out, monoatomic graphene oxide is stacking forms by a lot of layers for the graphene oxide of unmodified amino group, also has between layers certain interlamellar spacing.
Fig. 3 is the SEM figure of the difunctional nanometer heterogeneous catalysis of graphene-based soda acid, graphene oxide among Fig. 3 is modified by amino group, compare with the graphene oxide of unmodified among Fig. 2, can be clear that, graphene oxide catalyst after the modification is significantly loose by stripping, and interlamellar spacing also disappears substantially.
Fig. 4 is the TEM figure of the difunctional nanometer heterogeneous catalysis of graphene-based soda acid, can find out clearly that from figure graphene oxide is after amido modified, possessed the structure of low layer even individual layer, interlamellar spacing has also disappeared, and this two-dimension plane structure thickness is 1.0-5.0nm.
Claims (9)
1. difunctional nanometer heterogeneous catalysis of graphene-based soda acid is characterized in that: this catalyst is take graphene oxide as carrier, and in the finishing of graphene oxide amino group arranged; This catalyst has the two-dimension plane structure of 1.0-5.0nm thickness.
2. the preparation method of the difunctional nanometer heterogeneous catalysis of graphene-based soda acid claimed in claim 1, its step comprises: be dispersed in the organic solvent graphene oxide is ultrasonic, slowly add silane coupler and pass into protective gas in this organic solution; This hybrid reaction system is heated and is incubated, leaves standstill, filters, dries must sample.
3. the preparation method of the difunctional nanometer heterogeneous catalysis of graphene-based soda acid according to claim 2, it is characterized in that: the adding proportioning of described organic solvent, graphene oxide, silane coupler is 15-30mL:0.5g:0.1-0.4mL.
4. the preparation method of the difunctional nanometer heterogeneous catalysis of graphene-based soda acid according to claim 3, it is characterized in that: the adding proportioning of described organic solvent, graphene oxide, silane coupler is 20mL:0.5g:0.2-0.25mL.
5. according to claim 2, the preparation method of the difunctional nanometer heterogeneous catalysis of 3 or 4 described graphene-based soda acids, it is characterized in that: described silane coupler is 3-aminopropyl triethoxysilane or 3-aminopropyl trimethoxysilane.
6. the preparation method of the difunctional nanometer heterogeneous catalysis of graphene-based soda acid according to claim 2, it is characterized in that: the heating-up temperature of described hybrid reaction system is 105 ℃-115 ℃, and temperature retention time is 24-30 hour.
7. the preparation method of the difunctional nanometer heterogeneous catalysis of graphene-based soda acid according to claim 2, it is characterized in that: behind the described reacting liquid filtering, the filter cake that obtains is washed with absolute ethyl alcohol, acetone and distilled water respectively, under 55 ℃ of-60 ℃ of vacuum conditions, dry.
8. the preparation method of the difunctional nanometer heterogeneous catalysis of graphene-based soda acid according to claim 2, it is characterized in that: described organic solvent is dry toluene, nitromethane or nitroethane.
9. the preparation method of the difunctional nanometer heterogeneous catalysis of graphene-based soda acid according to claim 2, it is characterized in that: described protective gas is nitrogen, argon gas.
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| CN108807993A (en) * | 2018-06-11 | 2018-11-13 | 四会市恒星智能科技有限公司 | Anode material of lithium battery preparation method |
| CN110368986A (en) * | 2019-07-18 | 2019-10-25 | 常州大学 | A kind of preparation method of the Pickering lotion catalyst system for Knoevenagel reaction |
| CN111195528A (en) * | 2020-03-09 | 2020-05-26 | 常州大学 | Preparation method of bifunctional Pickering emulsion catalyst |
| CN113304775A (en) * | 2021-05-08 | 2021-08-27 | 沈阳药科大学 | Surface chemical grafting graphene oxide supported molybdenum catalyst, preparation and application |
| CN113856726A (en) * | 2021-10-28 | 2021-12-31 | 中南大学 | High-efficiency low-cost heterogeneous catalyst suitable for preparation of beta-nitroalcohol |
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| CN104841468A (en) * | 2014-02-19 | 2015-08-19 | 中国科学院金属研究所 | Carbon-based nonmetal solid alkali nanometer catalyst, and preparation method and application thereof |
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| CN110368986A (en) * | 2019-07-18 | 2019-10-25 | 常州大学 | A kind of preparation method of the Pickering lotion catalyst system for Knoevenagel reaction |
| CN111195528A (en) * | 2020-03-09 | 2020-05-26 | 常州大学 | Preparation method of bifunctional Pickering emulsion catalyst |
| CN113304775A (en) * | 2021-05-08 | 2021-08-27 | 沈阳药科大学 | Surface chemical grafting graphene oxide supported molybdenum catalyst, preparation and application |
| CN113304775B (en) * | 2021-05-08 | 2023-05-26 | 沈阳药科大学 | Graphene oxide supported molybdenum catalyst with surface chemically grafted, and preparation and application thereof |
| CN113856726A (en) * | 2021-10-28 | 2021-12-31 | 中南大学 | High-efficiency low-cost heterogeneous catalyst suitable for preparation of beta-nitroalcohol |
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