CN104841468A - Carbon-based nonmetal solid alkali nanometer catalyst, and preparation method and application thereof - Google Patents
Carbon-based nonmetal solid alkali nanometer catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a carbon-based nonmetal solid alkali nanometer catalyst, and a preparation method and an application thereof, and belongs to the fields of chemical catalysts, and preparation methods and applications thereof. The catalyst includes a nanometer carbon skeleton and a carbon-based nonmetal solid alkali surface layer. The shape of the catalyst is determined by the shape of selected nanometer carbon; and the number of the surface alkali layer is adjustable, and the lowest number can be one. The preparation method of the catalyst is characterized in that a monolayer coated ionic liquid/nanometer carbon host-guest composite nanometer material is obtained through adjusting the thickness of a nitrogen-containing ionic liquid used as a precursor on the surface of nanometer carbon. A carbon-based solid alkali material with different alkalinities and alkali amounts can be obtained by adjusting the type of the ionic liquid and the carbonization temperature. The type of nonmetal solid alkalis is widened; the obtained solid alkali layer is completely exposed, and has the structure advantage of the nanometer carbon material; and the solid alkali layer can fully contact with a reaction substrate in the catalysis process as a catalyst in order to efficiently use all active sites.
Description
Technical field
The present invention relates to a kind of carbon back non-metal solid base catalyst and its preparation method and application, belong to chemical catalyst and Synthesis and applications field thereof.
Background technology
From early 1990s, people start the environmental protection advantage recognizing catalyzed by solid base, and catalyzed by solid base material and catalytic reaction obtain very fast development.But compared with a large amount of solid acid catalysis research work, still some proves definitely inferior in the research of catalyzed by solid base.Especially the exploitation of non-metal kind solid base, is subject to people's attention not yet.
Compared to soluble liquid base catalyst (as sodium hydroxide solution), without the need to using higher than stoichiometric alkali during its reaction, stoichiometric slaine (as sodium chloride) after reaction, can not be produced.Replace liquid base can make the separation of product, catalysts and solvents and reclaim more simple with solid base, also can reduce discarded object, and solid base is noncorrosive simultaneously.Solid base catalyst does not need to select specific solvent to dissolve it specially in the reaction, thus avoids the limitation that generation selected by solvent, adds the chance of exploitation new reaction system.
In addition, by the finding to document, the current research for catalyzed by solid base mainly concentrates on containing metal solid base association area, and the domestic research to non-metal type solid base is considerably less especially.Relative to containing metal solid base, non-metal solid alkali evenly, more stable, controllable performance is good, be not easy run off, more green economy.
Nano-carbon material is directly one of direction, forward position of current material science and catalytic field as the non-metal carbon catalysis of catalyst.Relative to conventional metals catalyst, nano-carbon material catalyst has that high-efficiency environment friendly, skeleton structure are stable, low energy consumption, the advantage such as corrosion-resistant, the performance being better than conventional metals catalyst is shown in multiple fields such as the hydrocarbon conversion, fine chemistry industry, fuel cell, solar energy conversion, there is huge development potentiality, one of direction, forward position becoming nonmetal catalyzed field gradually.Nano-sized carbon is nonmetal catalyzed is directly use nano-carbon material self as catalyst, not load or add any metal, and activated centre is defect sturcture or the functional group on surface.Relative to metallic catalyst, nano-carbon material possesses as catalyst that with low cost, heavy metal free pollutes, advantages of environment protection, shows the advantages such as selective height, mild condition, long-time stability are good in many catalytic process.
Summary of the invention
The object of this invention is to provide a kind of novel nano carbon-base non-metal solid base catalyst, the structural advantage of nano-carbon material can be comprised, the solid base layer being exposed to surface completely can be provided again, make it well to contact with reaction media in course of reaction; By regulating and controlling the kind of ionic liquid, the original position realizing different hetero atom and different types of structure alkali layer is introduced, to adapt to various different base catalyzed reactions.
The present invention is achieved through the following technical solutions:
A kind of carbon back non-metal solid alkali nanocatalyst, this catalyst comprises nano-sized carbon skeleton and is coated on the carbon back non-metal solid alkali layer outside nano-sized carbon skeleton, and described carbon back non-metal solid alkali layer thickness is 0.3-1.5nm.The shape that this catalyst shape has for nano-sized carbon skeleton.
Described nano-sized carbon skeleton is the nano-carbon materials such as SWCN, multi-walled carbon nano-tubes, carbon nano-fiber, Nano diamond, graphite or Graphene.
The preparation method of described carbon back non-metal solid alkali nanocatalyst comprises the following steps:
(1) dispersion of nano-carbon material in ionic liquid: mixed with the part by weight of ionic liquid according to 1:10 by nano-carbon material, gained mixture carries out ultrasonic disperse 30-120 minute, obtains even turbid solution;
(2) prepare ionic liquid/nano-sized carbon skeleton colloid: after step (1) gained turbid solution is carried out centrifugation, topple over recovery supernatant fluid, gained lower black colloid is ionic liquid/nano-sized carbon skeleton colloid;
(3) host and guest's build composite nano materials of ionic liquid/nano-sized carbon is prepared: step (2) gained colloid is placed in alumina crucible and carries out hyperthermic treatment at tube furnace, Elevated Temperature Conditions is lower 5 DEG C/min of vacuum condition, rise to 220-500 DEG C and stop 5-300 minute, obtain host and guest's build composite nano materials of the solid-state ionic liquid/nano-carbon material of desired thickness;
(4) carbon back non-metal solid alkali nanocatalyst is prepared: host and guest's build composite nano materials of step (3) gained ionic liquid/nano-sized carbon is carried out condensation process (temperature and time of condensation process is determined by the kind of composite nano materials and actual needs), obtain carbon back non-metal solid alkali nanocatalyst.
First carry out purification process to nano-carbon material before above-mentioned steps (1), step is as follows:
A carbon nanomaterial adds in the hydrochloric acid solution of 1 ~ 5mol/L by (), at normal temperatures magnetic agitation 1 ~ 3h, to remove kish catalyst, then suction filtration, be washed to neutrality, the grinding of last vacuum drying is stand-by;
B (), by the carbon nanomaterial after step (a) process, is placed in tube furnace, is warming up to more than 1300 DEG C under argon gas atmosphere, to remove disordered carbon and the oxygen functional group on nano-carbon material surface.
The salt that described in step (1), ionic liquid is made up of organic cation and organic or inorganic anion, wherein: described cation is selected from one or more in two methylimidazole, acetonitrile-base methylimidazole, amino, two amino, piperidines, pyridines, guanidine class and alcamines cation; Described anion is one or more in borate, phosphate radical, dicyanamide anion (dca), triflate anion and trifluoroacetic acid anion.
The carbon back non-metal solid alkali nanocatalyst of gained is applied to liquid phase reactor or gas-phase reaction, as: this catalyst is used for Knoevenal condensation reaction, and the solvent that course of reaction is selected is toluene or methyl alcohol etc.; By this catalyst for Baeyer-Villiger oxidation reaction, the solvent that course of reaction is selected is dichloroethanes or carbon tetrachloride etc.; This catalyst is used for ester hydrolysis reaction, and the solvent that course of reaction is selected is water etc.
The catalytic reaction thing of described catalyst is respectively: the reactant of Knoevenal condensation reaction is aldehyde and cyan-acetic ester or malononitrile; Baeyer-Villiger oxidation reaction reactant is ketone and oxygen; The reactant of ester hydrolysis reaction is ester and water.
The reaction condition of described catalytic reaction is: Knoevenal condensation reaction is carried out in the three-necked bottle that condenser pipe is housed, get the aldehydes of 20 mMs and cyan-acetic ester or malononitrile respectively as reactant, 10 milliliters of solvents, reaction temperature is 30-80 DEG C, and the consumption of catalyst is 10-50 milligram; The reaction of Baeyer-Villiger oxidation reaction is carried out in the two-neck bottle that serpentine condenser is housed, ketone 4 mMs, initator benzaldehyde 4 mMs, solvent is 10 milliliters, oxygen flow is 10-25 ml/min, and reaction temperature is 25 DEG C-50 DEG C, and the consumption of catalyst is 10-50 milligram; Ester hydrolysis reaction gets the mixture of 50 ml waters and ester in heavy wall air-tight pressure-bottle, catalyst amount 10-50 milligram, and reaction temperature is 80-150 DEG C.
Compared with prior art, the present invention has following remarkable advantage:
1, the present invention is as a kind of non-metallic catalyst, possesses that with low cost, heavy metal free pollutes, advantages of environment protection, shows the advantages such as selective height, mild condition, long-time stability are good in many catalytic process.
2, the present invention is as a kind of solid base catalyst, and catalytic process is non-stoichiometry and heterogeneous catalysis process, produces refuse less, to reactor without any corrosivity in course of reaction.
3, the present invention is without the need to solvent dispersion in catalytic process, only need stir and fully can contact with reactant, selects no requirement (NR) to reaction dissolvent.Inertia carbon skeleton can all stable existence in liquid phase reaction, and embodies and very excellent recycle performance.
4, catalyst of the present invention comprises nano-sized carbon skeleton and carbon back non-metal solid alkali top layer.The shape of catalyst is determined by the shape of the nano-sized carbon chosen; Surface alkali number of layers (thickness) controllable, minimumly reaches individual layer.In its preparation process with nitrogen containing plasma liquid for presoma, by regulating and controlling its thickness on nano-sized carbon surface, obtain host and guest's build composite nano materials of the coated ionic liquid/nano-sized carbon of individual layer.By regulating the kind of ionic liquid, the conditions such as carburizing temperature obtain the carbon-based solid base material of different alkalescence and alkali number.The present invention has widened the kind of non-metal solid alkali; The solid base alkali layer obtained exposes completely, and includes the structural advantage of nano-carbon material; Fully can contact with reaction substrate in catalytic process as catalyst, the avtive spot that efficiency utilization is all.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of Different Alkali layer thickness catalyst prepared by embodiment 1; In figure: (a) is CNT, (b) is ionic liquid/carbon mano-tube composite, and (c) is the process of-400 DEG C, carbon-based solid alkali, and (d) is the process of-500 DEG C, carbon-based solid alkali.
Fig. 2 is the nitrogen species classification of its XPS swarming result of catalyst embodiment prepared by embodiment 3; In figure: (a) is presoma, (b) is NCNT460, and (c) is NCNT700.
Detailed description of the invention
Be described in further detail the present invention below in conjunction with embodiment, what be necessary to herein means out is that following examples are only used to further illustrate the present invention, and can not be interpreted as limiting the scope of the invention.
Embodiment 1
(1) purification process of CNT: CNT adds in the hydrochloric acid solution of 1 ~ 5mol/L by (a), at normal temperatures magnetic agitation 1 ~ 3h, to remove kish catalyst, then suction filtration, be washed to neutrality, the grinding of last vacuum drying is stand-by.B (), by removing the CNT of metal in (a) step, is placed in tube furnace, under argon gas atmosphere temperature programming at least 1300 DEG C to remove disordered carbon and the oxygen functional group on nano-sized carbon surface.
(2) dispersion of CNT in ionic liquid: step (1) gained CNT is mixed with the part by weight of 1:10 with ionic liquid 1-octyl group-3-methyl imidazolium tetrafluoroborate, mixing gained mixture is placed in ultrasonic wave dispersion instrument and carries out ultrasonic disperse, the ultrasonic kind according to ionic liquid and nano-sized carbon skeleton is chosen as 50 minutes, obtains the turbid solution be evenly distributed.
(3) ionic liquid/CNT skeleton colloid is obtained: move in centrifuge tube by step (2) gained turbid solution, under the rotating speed of 9500 revs/min centrifugal 15 minutes.Topple over and reclaim supernatant ionic liquid, lower black colloid is ionic liquid/CNT skeleton colloid.
(4) host and guest's build composite nano materials of ionic liquid/CNT is obtained: step (3) gained colloid is placed in alumina crucible in the hyperthermic treatment of tube furnace Program.Under vacuum condition, be warming up to 350 DEG C with 5 DEG C/min and stop 5-300 minute, obtain the host and guest's build composite nano materials (time of staying is different, and thickness is different) containing the solid-state ionic liquid/CNT of different-thickness.
(5) carbon back non-metal solid alkali nanocatalyst is obtained: host and guest's build composite nano materials of step (4) gained ionic liquid/CNT is carried out carbonization treatment, obtains carbon back non-metal solid base catalyst.This catalyst comprises CNT and surface coated one deck carbon back non-metal solid alkali layer thereof, and the solid base surface of the carbon conjugation of F, B, N Heteroatom doping that what the present embodiment obtained is, Fig. 1 provides the transmission electron microscope photo of Different Alkali layer thickness.Fig. 1 result illustrates, gained solid base catalyst of the present invention, top layer solid base is controlled is made as individual layer, exposes completely to make catalytic active site.
(6) gained non-metal solid base catalyst is applied to Baeyer-Villiger oxidation reaction.Reactant cyclohexanone and initator 4 mMs of equal proportions are mixed and is dissolved in 10 milliliters of carbon tetrachloride solvents, catalyst amount is 10mg, reactor is two-neck bottle, one neck is equipped with serpentine condenser, another bottleneck is equipped with wireway, pass into oxidant oxygen with the intake velocity of 10 ml/min, the reaction time is chosen as 4 hours.
(7) in the present embodiment, the conversion ratio of catalytic reaction reactant cyclohexanone is 84.5%, and product caprolactone is selective is 100%, and productive rate is 84.5%.
Embodiment 2
(1) purification process of CNT: CNT adds in the hydrochloric acid solution of 1 ~ 5mol/L by (a), at normal temperatures magnetic agitation 1 ~ 3h, to remove kish catalyst, then suction filtration, be washed to neutrality, the grinding of last vacuum drying is stand-by.B () will remove the CNT of metal in (a) step, be placed in tube furnace, under nitrogen atmosphere, temperature programming is at least 2700 DEG C to remove disordered carbon and the oxygen functional group on nano-sized carbon surface, obtains being tending towards the impact that perfect graphite surface produces ionic liquid thoroughly to remove catalyst surface defect.
(2) dispersion of CNT in ionic liquid: by step (1) gained CNT with the ratio of quality proportion 1:10 and ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphate, 1-octyl group-3-methylimidazole hexafluorophosphate mixes respectively, mixing gained mixture is placed in ultrasonic wave dispersion instrument and carries out ultrasonic disperse, ultrasonic time is chosen as 60 minutes, obtains the turbid solution be evenly distributed.
(3) ionic liquid/CNT skeleton colloid is obtained: move in centrifuge tube by step (2) gained turbid solution, under the rotating speed of 9500 revs/min centrifugal 15 minutes.Topple over and reclaim supernatant ionic liquid, lower black colloid is ionic liquid/CNT skeleton colloid.
(4) host and guest's build composite nano materials of ionic liquid/CNT is obtained: step (3) gained colloid is placed in alumina crucible in the hyperthermic treatment of tube furnace Program.Under vacuum condition, be warming up to 350 DEG C with 5 DEG C/min and stop 5-300 minute, obtain the host and guest's build composite nano materials containing the solid-state ionic liquid/CNT of different-thickness.
(5) carbon back non-metal solid alkali nanocatalyst is obtained: under host and guest's build composite Nano of step (4) gained ionic liquid/CNT is placed in argon gas condition, 330 DEG C are warming up to 5 DEG C/min, 350 DEG C, 370 DEG C, 390 DEG C, 410 DEG C, stop 60 minutes, obtain the solid base layer/CNT host and guest build composite nano-catalyst containing N, P, O containing different ionic liquid dissociation degree.
(6) gained non-metal solid base catalyst is applied to the decomposition reaction of ethyl acetate ester.
(7), in the present embodiment, catalytic reaction reactant ethyl acetate can reach more than 75% by conversion ratio in 50 hours.
Embodiment 3
(1) purification process of Nano diamond: Nano diamond adds in the hydrochloric acid solution of 1 ~ 5mol/L by (a), at normal temperatures magnetic agitation 1 ~ 3h, to remove kish catalyst, then suction filtration, be washed to neutrality, the grinding of last vacuum drying is stand-by.B (), by removing the Nano diamond of metal in (a) step, is placed in tube furnace, under air atmosphere temperature programming at least 430 DEG C to remove disordered carbon and the SP on Nano diamond surface
2the carbon of structure.
(2) dispersion of Nano diamond in ionic liquid: step (1) gained Nano diamond is mixed with ionic liquid 1-ethyl-3-methylimidazole dicyan amine salt with the ratio of quality proportion 1:10, mixing gained mixture is placed in ultrasonic wave dispersion instrument and carries out ultrasonic disperse, ultrasonic time is 30 minutes, obtains the turbid solution be evenly distributed.
(3) ionic liquid/Nano diamond skeleton colloid is obtained: move in centrifuge tube by step (2) gained turbid solution, under the rotating speed of 8000 revs/min centrifugal 10 minutes.Topple over and reclaim supernatant ionic liquid, lower black colloid is ionic liquid/Nano diamond skeleton colloid.
(4) host and guest's build composite nano materials of ionic liquid/Nano diamond is obtained: step (3) gained colloid is placed in alumina crucible in the hyperthermic treatment of tube furnace Program.Under vacuum condition, be warming up to 220 DEG C with 5 DEG C/min and stop 60 minutes, obtain the host and guest's build composite nano materials containing the solid-state ionic liquid/Nano diamond of different-thickness.
(5) carbon back non-metal solid alkali nanocatalyst is obtained: host and guest's build composite nano materials of step (4) gained ionic liquid/Nano diamond is carried out 1 hour carbonization treatment, carburizing temperature is chosen for 460 DEG C and 700 DEG C, carbonization obtain containing hetero atom N be stronger basic nitrogen species.What Fig. 2 provided is the nitrogen species classification that XPS swarming result embodies, and Fig. 2 result can be found out, solid base catalyst surface institute nitrogen containing species, is the lewis base position that alkalescence is stronger.
(6) by the catalyst application that obtains in Knoevenal condensation reaction.The reaction condition of Knoevenal condensation reaction is: carry out in the three-necked bottle that condenser pipe is housed, and get the benzaldehyde of 20 mMs and malononitrile respectively as reactant, 10 milliliters of solvents, reaction temperature is 30 to 80 DEG C, and the consumption of catalyst is 10 milligrams-50 milligrams;
(7) in the present embodiment, the conversion ratio of catalytic reaction reactant benzaldehyde can reach 100%, and the selective of product also can reach 100%.
Embodiment 4
(1) purification process of few layer graphene: (a) is by Graphene (few layer?) add in the hydrochloric acid solution of 1 ~ 5mol/L, magnetic agitation 1 ~ 3h at normal temperatures, to remove kish catalyst, then suction filtration, be washed to neutrality, the grinding of last vacuum drying is stand-by.B (), by removing the Graphene of metal in (a) step, is placed in tube furnace, under argon gas atmosphere temperature programming at least 1300 DEG C to remove disordered carbon and the oxygen functional group on nano-sized carbon surface.
(2) dispersion of Graphene in ionic liquid: by step (1) gained Graphene with the ratio of quality proportion 1:20 and variety classes ionic liquid 1-octyl group-3-methyl imidazolium tetrafluoroborate, hexafluorophosphate, dicyan amine salt, triflate class, trifluoroacetic acid class etc.The kind of ionic liquid is chosen as one.Mixing gained mixture is placed in ultrasonic wave dispersion instrument and carries out ultrasonic disperse, and ultrasonic time is chosen as 30-60 minute according to the viscosity degree of ionic liquid, until obtain the turbid solution be evenly distributed.
(3) ionic liquid/Graphene skeleton colloid is obtained: move in centrifuge tube by step (2) gained turbid solution, under the rotating speed of 8000 to 10000 revs/min centrifugal 15 minutes.Topple over and reclaim supernatant ionic liquid, lower black colloid is ionic liquid/Graphene skeleton colloid.
(4) host and guest's build composite nano materials of ionic liquid/Graphene is obtained: step (3) gained colloid is placed in respectively alumina crucible in the hyperthermic treatment of tube furnace Program.Under vacuum condition, be warming up to uniform temperature with 5 DEG C/min, stop 5-300 minute, obtain the host and guest's build composite nano materials containing the solid-state ionic liquid/Graphene of different-thickness.
(5) carbon back non-metal solid alkali nanocatalyst is obtained: host and guest's build composite nano materials of step (4) gained ionic liquid/Graphene is carried out carbonization treatment, the carbonization treatment temperature different according to the different choice of ionic liquid kind, can obtain the graphene interlayers structure of one or several doping in F, B, N, S, P, O hetero atom respectively.Wherein, Graphene is intermediate layer, and gained solid base layer is in the both sides of graphene layer.
Claims (10)
1. a carbon back non-metal solid alkali nanocatalyst, is characterized in that: this catalyst comprises nano-sized carbon skeleton and is coated on the carbon back non-metal solid alkali layer outside nano-sized carbon skeleton, and described carbon back non-metal solid alkali layer thickness is 0.3-1.5nm.
2. carbon back non-metal solid alkali nanocatalyst according to claim 1, is characterized in that: the shape that this catalyst shape has for nano-sized carbon skeleton.
3. carbon back non-metal solid alkali nanocatalyst according to claim 1, is characterized in that: described nano-sized carbon skeleton is the nano-carbon materials such as SWCN, multi-walled carbon nano-tubes, carbon nano-fiber, Nano diamond, graphite or Graphene.
4. the preparation method of carbon back non-metal solid alkali nanocatalyst according to claim 1, is characterized in that: the method comprises the following steps:
(1) dispersion of nano-carbon material in ionic liquid: mixed with the part by weight of ionic liquid according to 1:10 by nano-carbon material, gained mixture carries out ultrasonic disperse 30-120 minute, obtains even turbid solution;
(2) prepare ionic liquid/nano-sized carbon skeleton colloid: after step (1) gained turbid solution is carried out centrifugation, topple over recovery supernatant fluid, gained lower black colloid is ionic liquid/nano-sized carbon skeleton colloid;
(3) host and guest's build composite nano materials of ionic liquid/nano-sized carbon is prepared: step (2) gained colloid is placed in alumina crucible and carries out hyperthermic treatment at tube furnace, Elevated Temperature Conditions is lower 5 DEG C/min of vacuum condition, rise to 220-500 DEG C and stop 5-300 minute, obtain the host and guest's build composite nano materials containing the solid-state ionic liquid/nano-carbon material of different-thickness;
(4) prepare carbon back non-metal solid alkali nanocatalyst: host and guest's build composite nano materials of step (3) gained ionic liquid/nano-sized carbon is carried out condensation process, obtain carbon back non-metal solid alkali nanocatalyst.
5. the preparation method of carbon back non-metal solid alkali nanocatalyst according to claim 4, is characterized in that: first carry out purification process to nano-carbon material before step (1), step is as follows:
A carbon nanomaterial adds in the hydrochloric acid solution of 1 ~ 5mol/L by (), at normal temperatures magnetic agitation 1 ~ 3h, to remove kish catalyst, then suction filtration, be washed to neutrality, the grinding of last vacuum drying is stand-by;
B (), by the carbon nanomaterial after step (a) process, is placed in tube furnace, is warming up to more than 1300 DEG C under argon gas atmosphere, to remove disordered carbon and the oxygen functional group on nano-carbon material surface.
6. the preparation method of carbon back non-metal solid alkali nanocatalyst according to claim 4, it is characterized in that: the salt that described in step (1), ionic liquid is made up of organic cation and organic or inorganic anion, wherein: described cation is selected from one or more in two methylimidazole, acetonitrile-base methylimidazole, amino, two amino, piperidines, pyridines, guanidine class and alcamines cation; Described anion is one or more in borate, phosphate radical, dicyanamide anion (dca), triflate anion and trifluoroacetic acid anion.
7. the application of carbon back non-metal solid alkali nanocatalyst according to claim 1, is characterized in that: this catalyst is used for liquid phase reactor or gas-phase reaction.
8. the application of carbon back non-metal solid alkali nanocatalyst according to claim 7, is characterized in that: this catalyst is used for Knoevenal condensation reaction, and the solvent that course of reaction is selected is toluene or methyl alcohol etc.; By this catalyst for Baeyer-Villiger oxidation reaction, the solvent that course of reaction is selected is dichloroethanes or carbon tetrachloride etc.; This catalyst is used for ester hydrolysis reaction, and the solvent that course of reaction is selected is water etc.
9. the application of carbon back non-metal solid alkali nanocatalyst according to claim 8, is characterized in that: the catalytic reaction thing of described catalyst is: the reactant of Knoevenal condensation reaction is aldehyde and cyan-acetic ester or malononitrile; Baeyer-Villiger oxidation reaction reactant is ketone and oxygen; The reactant of ester hydrolysis reaction is ester and water.
10. the application of carbon back non-metal solid alkali nanocatalyst according to claim 9, it is characterized in that: the reaction condition of described catalyst is: Knoevenal condensation reaction is carried out in the three-necked bottle that condenser pipe is housed, get the aldehydes of 20 mMs and cyan-acetic ester or malononitrile respectively as reactant, 10 milliliters of solvents, reaction temperature is 30-80 DEG C, and the consumption of catalyst is 10-50 milligram; The reaction of Baeyer-Villiger oxidation reaction is carried out in the two-neck bottle that serpentine condenser is housed, ketone 4 mMs, initator benzaldehyde 4 mMs, solvent is 10 milliliters, oxygen flow is 10-25 ml/min, and reaction temperature is 25 DEG C-50 DEG C, and the consumption of catalyst is 10-50 milligram; Ester hydrolysis reaction gets the mixture of 50 ml waters and ester in heavy wall air-tight pressure-bottle, catalyst amount 10-50 milligram, and reaction temperature is 80-150 DEG C.
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| CN105720255A (en) * | 2016-03-04 | 2016-06-29 | 深圳市翔丰华科技有限公司 | Preparation method of nitrogen and phosphorus co-doped carbon-coated graphite anode material |
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