CN107983410A - A kind of preparation method of the compound hole catalyst of graphene/MOFs crystal - Google Patents
A kind of preparation method of the compound hole catalyst of graphene/MOFs crystal Download PDFInfo
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- CN107983410A CN107983410A CN201711155086.5A CN201711155086A CN107983410A CN 107983410 A CN107983410 A CN 107983410A CN 201711155086 A CN201711155086 A CN 201711155086A CN 107983410 A CN107983410 A CN 107983410A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
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Abstract
The present invention provides a kind of preparation method of the compound hole catalyst of graphene/MOFs crystal, and specific preparation method is：Redox graphene is scattered in solvent, obtains graphene dispersing solution, lewis acid metallocene catalyst and 2 dibenzenesulfonyl pyridine template materials are added into graphene dispersing solution, is uniformly mixed, obtains substrate solution；The DMF solution of methylimidazole methylene-benzene ligand will be added in substrate solution, after microwave treatment, potassium tert-butoxide is added and adjusts pH to alkalescent, heating stirring reaction, is cooled to room temperature, obtains crystal crude product；By crystal crude product crushing grinding, adding organic solvent separates out the lewis acid metallocene catalyst of dissolving, separates, dry, obtains the compound hole catalyst of graphene/MOFs crystal.Catalyst prepared by the present invention makes graphene uniform be scattered in MOFs using lewis acid metallocene catalyst, and removes lewis acid metallocene catalyst with organic solvent, obtains compound hole type catalyst.
Description
Technical field
The invention belongs to medicinal chemistry art, and in particular to a kind of system of the compound hole catalyst of graphene/MOFs crystal
Preparation Method.
Background technology
In organic synthesis, people it is expected that cheap, environmental-friendly, high catalytic activity urge can be found always
Agent carries out organic synthesis to replace common toxic or expensive transition-metal catalyst.Louis
Acid refers to a kind of material that can receive electronics pair, is a kind of material with unoccupied orbital from its structure.Due to lewis acid
With good catalytic activity, the reaction time is short, and dosage is appropriate, causes the possibility of side reaction and equipment corrosion smaller, can be with
The advantages that cost-effective, therefore, lewis acid, are increasingly subject to people's as catalyst or the organic synthesis of promotion
Pay attention to, therefore be widely used in the production fields such as food, daily necessities and medicine.Lewis acid directly can act on being formed with substrate
Target product, can also be complexed with substrate make substrate activated, and the reaction with other reagents forms target product, and lewis acid can
Realize dissociation.
A kind of preparation method of graphitization multi-stage porous carbon ball disclosed in Chinese patent CN 105174243B, by polystyrene
Microballoon under the catalysis of anhydrous ferric trichloride lewis acid catalyst, occurs Friedel-Crafts alkylation, is suspended with halogenated hydrocarbons
Liquid, adds toluene, acetone, ethanol or tetrahydrofuran organic solvent, separates out the lewis acid catalyst of dissolving, separation,
The expanded polystyrene microballoon of lewis acid catalyst load is dried to obtain, the porous polyphenyl second that lewis acid catalyst is loaded
Alkene microballoon is carbonized under inertia or protective atmosphere, then acid leach solution, separation, dry, obtains graphitization multi-stage porous carbon ball,
Graphitization multi-stage porous carbon ball prepared by this method can be used for super capacitor, cell negative electrode material and dye cell catalyst carrier etc.
Field.It is a kind of disclosed in Chinese patent CN 105400157B to improve graphene dispersed method in a polymer matrix, will be poly-
Alkene, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polymethyl methacrylate, polyvinyl chloride, poly- carbon
Acid esters, polyformaldehyde either polyvinylidene chloride polymers material, graphene and alchlor, ferric trichloride, boron trifluoride or
Trifluoromethanesulfonic acid lewis acid catalyst three mixes, and the following melt blending of heat decomposition temperature obtains on polymeric material fusing point
To polymer/graphene/lewis acid catalyst composite material, at by the lewis acid catalyst extracting in composite material
Reason, obtains polymer/graphene composite material masterbatch, finally straight polymer by polymer/graphene composite material masterbatch and again
Polymer/graphene composite material is obtained inferior to the following melt blending of heat decomposition temperature on fusing point.The preparation method utilizes road
Lewis acid catalyst improves graphene dispersiveness in a polymer matrix, reduces because caused by aggregate exists the defects of, this
Graphene surface functionalization is not required in kind method, simple and environmentally-friendly.From the above-mentioned prior art, lewis acid catalyst is in graphite
There is prominent action effect in the preparation process of alkene composite material, therefore be also remarkably improved point of graphene and coordination polymer
Property is dissipated, improves its catalytic performance.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation side of the compound hole catalyst of graphene/MOFs crystal
Method, the present invention make graphene uniform be scattered in MOFs using lewis acid metallocene catalyst, and remove road with organic solvent
Lewis acid metallocene catalyst, obtains compound hole type catalyst.The catalyst is fully combined graphene with MOFs, and is had
Good hole, improves the catalytic activity of catalyst, improves the compound hole catalyst of graphene/MOFs crystal in medicine
Application field in intermediate preparation.
In order to solve the above technical problems, the technical scheme is that：
A kind of preparation method of the compound hole catalyst of graphene/MOFs crystal, comprises the following steps：
(1) redox graphene is scattered in solvent, obtains graphene dispersing solution, added into graphene dispersing solution
Lewis acid metallocene catalyst and 2- dibenzenesulfonyl pyridine template materials, are uniformly mixed, obtain substrate solution；
(2) DMF solution of methylimidazole-methylene-benzene ligand will be added in substrate solution, after microwave treatment, adds uncle
Butanol potassium adjusts pH to alkalescent, and heating stirring reaction, is cooled to room temperature, obtains crystal crude product；
(3) by crystal crude product crushing grinding, adding organic solvent separates out the lewis acid metallocene catalyst of dissolving, point
From, it is dry, obtain the compound hole catalyst of graphene/MOFs crystal.
As the preferred of above-mentioned technical proposal, in the step (1), mould material, graphene and Louis in substrate solution
The mass ratio of this sour metallocene catalyst is 100:8-16:0.5-2.
As the preferred of above-mentioned technical proposal, in the step (1), lewis acid metallocene catalyst is by transition metal
Element or thulium and cyclopentadiene or cyclopentadiene derivant composition.
As the preferred of above-mentioned technical proposal, in the step (1), transition metal member in lewis acid metallocene catalyst
Element is titanium, zirconium or antimony.
As the preferred of above-mentioned technical proposal, in the step (2), the condition of microwave treatment is 50-100W, time 5-
15min。
As the preferred of above-mentioned technical proposal, in the step (2), 2- dibenzenesulfonyls pyridine and diformazan in substrate solution
The mass ratio of base imidazoles-methylene-benzene is 6.5-8:5-6.
As the preferred of above-mentioned technical proposal, in the step (2), the temperature of heating stirring reaction is 170-180 DEG C, when
Between be 24-36h.
As the preferred of above-mentioned technical proposal, in the step (2), weakly alkaline pH value is 8.5-10.
As the preferred of above-mentioned technical proposal, in the step (3), organic solvent is ethanol.
As the preferred of above-mentioned technical proposal, in the step (3), the compound hole catalyst of graphene/MOFs crystal
Particle diameter is micron order.
Compared with prior art, the invention has the advantages that：
The compound hole catalyst of graphene prepared by the present invention/MOFs crystal mainly includes graphene and MOFs coordination polymerizations
Thing, in order to improve both graphene and MOFs coordination polymers dispersion performance, stone is added to by lewis acid metallocene catalyst
In the preparation process of black alkene and MOFs coordination polymer, by graphene, lewis acid metallocene catalyst and 2- dibenzenesulfonyls
The substrate solution that pyridine template material is mixed with, then with methylimidazole-methylene-benzene ligand reaction, graphene can be made equal
It is even to be scattered in MOFs, lewis acid metallocene catalyst then is removed with organic solvent ethanol, obtains compound hole type catalysis
Agent.The catalyst is fully combined graphene with MOFs, and has good hole, improves the catalytic activity of catalyst,
Improve application field of the compound hole catalyst of graphene/MOFs crystal in medicine intermediate preparation.
Embodiment
Below in conjunction with specific embodiment, the present invention will be described in detail, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1：
(1) it is 100 according to the mass ratio of mould material, graphene and lewis acid metallocene catalyst:8:0.5, by also
Former graphene oxide is scattered in solvent, obtains graphene dispersing solution, and titaniferous and cyclopentadiene are added into graphene dispersing solution
The lewis acid metallocene catalyst and 2- dibenzenesulfonyl pyridine template materials of composition, are uniformly mixed, obtain substrate solution.
(2) it is 6.5 according to 2- dibenzenesulfonyls pyridine in substrate solution and the mass ratio of methylimidazole-methylene-benzene:
5, the DMF solution of methylimidazole-methylene-benzene ligand will be added in substrate solution, under 50W power after microwave treatment 5min,
Add potassium tert-butoxide and adjust pH to 8.5, heating stirring reacts 24h at 170 DEG C, is cooled to room temperature, obtains crystal crude product.
(3) by crystal crude product crushing grinding, adding organic solvent ethanol analyses the lewis acid metallocene catalyst of dissolving
Go out, separate, it is dry, obtain the compound hole catalyst of micron order graphene/MOFs crystal.
Embodiment 2：
(1) it is 100 according to the mass ratio of mould material, graphene and lewis acid metallocene catalyst:16:2, it will reduce
Graphene oxide is scattered in solvent, obtains graphene dispersing solution, is added into graphene dispersing solution and is spread out containing zirconium with cyclopentadiene
The lewis acid metallocene catalyst and 2- dibenzenesulfonyl pyridine template materials of biotic component, are uniformly mixed, it is molten to obtain substrate
Liquid.
(2) it is 8 according to 2- dibenzenesulfonyls pyridine in substrate solution and the mass ratio of methylimidazole-methylene-benzene:6,
The DMF solution of methylimidazole-methylene-benzene ligand will be added in substrate solution, under 100W power after microwave treatment 15min,
Add potassium tert-butoxide and adjust pH to 10, heating stirring reacts 36h at 180 DEG C, is cooled to room temperature, obtains crystal crude product.
(3) by crystal crude product crushing grinding, adding organic solvent ethanol analyses the lewis acid metallocene catalyst of dissolving
Go out, separate, it is dry, obtain the compound hole catalyst of micron order graphene/MOFs crystal.
Embodiment 3：
(1) it is 100 according to the mass ratio of mould material, graphene and lewis acid metallocene catalyst:10:1.5, by also
Former graphene oxide is scattered in solvent, obtains graphene dispersing solution, is added into graphene dispersing solution and is contained antimony and cyclopentadiene
The lewis acid metallocene catalyst and 2- dibenzenesulfonyl pyridine template materials of composition, are uniformly mixed, obtain substrate solution.
(2) it is 7 according to 2- dibenzenesulfonyls pyridine in substrate solution and the mass ratio of methylimidazole-methylene-benzene:5,
The DMF solution of methylimidazole-methylene-benzene ligand will be added in substrate solution, under 60W power after microwave treatment 10min,
Add potassium tert-butoxide and adjust pH to 9, heating stirring reacts 26h at 175 DEG C, is cooled to room temperature, obtains crystal crude product.
(3) by crystal crude product crushing grinding, adding organic solvent ethanol analyses the lewis acid metallocene catalyst of dissolving
Go out, separate, it is dry, obtain the compound hole catalyst of micron order graphene/MOFs crystal.
Embodiment 4：
(1) it is 100 according to the mass ratio of mould material, graphene and lewis acid metallocene catalyst:12:1, it will reduce
Graphene oxide is scattered in solvent, obtains graphene dispersing solution, and titaniferous and cyclopentadiene group are added into graphene dispersing solution
Into lewis acid metallocene catalyst and 2- dibenzenesulfonyl pyridine template materials, be uniformly mixed, obtain substrate solution.
(2) it is 7.5 according to 2- dibenzenesulfonyls pyridine in substrate solution and the mass ratio of methylimidazole-methylene-benzene:
5.5, the DMF solution of methylimidazole-methylene-benzene ligand, the microwave treatment 10min under 80W power will be added in substrate solution
Afterwards, add potassium tert-butoxide and adjust pH to 9.5, heating stirring reacts 30h at 175 DEG C, is cooled to room temperature, obtains crystal crude product.
(3) by crystal crude product crushing grinding, adding organic solvent ethanol analyses the lewis acid metallocene catalyst of dissolving
Go out, separate, it is dry, obtain the compound hole catalyst of micron order graphene/MOFs crystal.
Embodiment 5：
(1) it is 100 according to the mass ratio of mould material, graphene and lewis acid metallocene catalyst:12:0.9, by also
Former graphene oxide is scattered in solvent, obtains graphene dispersing solution, and titaniferous and cyclopentadiene are added into graphene dispersing solution
The lewis acid metallocene catalyst and 2- dibenzenesulfonyl pyridine template materials of composition, are uniformly mixed, obtain substrate solution.
(2) it is 7 according to 2- dibenzenesulfonyls pyridine in substrate solution and the mass ratio of methylimidazole-methylene-benzene:6,
The DMF solution of methylimidazole-methylene-benzene ligand will be added in substrate solution, under 65W power after microwave treatment 12min,
Add potassium tert-butoxide and adjust pH to 9.5, heating stirring reacts 36h at 170 DEG C, is cooled to room temperature, obtains crystal crude product.
(3) by crystal crude product crushing grinding, adding organic solvent ethanol analyses the lewis acid metallocene catalyst of dissolving
Go out, separate, it is dry, obtain the compound hole catalyst of micron order graphene/MOFs crystal.
Embodiment 6：
(1) it is 100 according to the mass ratio of mould material, graphene and lewis acid metallocene catalyst:14:1, it will reduce
Graphene oxide is scattered in solvent, obtains graphene dispersing solution, is added into graphene dispersing solution containing zirconium and cyclopentadiene group
Into lewis acid metallocene catalyst and 2- dibenzenesulfonyl pyridine template materials, be uniformly mixed, obtain substrate solution.
(2) it is 7.5 according to 2- dibenzenesulfonyls pyridine in substrate solution and the mass ratio of methylimidazole-methylene-benzene:
5.5, the DMF solution of methylimidazole-methylene-benzene ligand, the microwave treatment 12min under 85W power will be added in substrate solution
Afterwards, add potassium tert-butoxide and adjust pH to 9, heating stirring reacts 24h at 180 DEG C, is cooled to room temperature, obtains crystal crude product.
(3) by crystal crude product crushing grinding, adding organic solvent ethanol analyses the lewis acid metallocene catalyst of dissolving
Go out, separate, it is dry, obtain the compound hole catalyst of micron order graphene/MOFs crystal.
After testing, particle diameter, porosity, the yield of the compound hole catalyst of graphene/MOFs crystal prepared by embodiment 1-6
Result it is as follows：
As seen from the above table, the particle diameter of the compound hole catalyst of graphene/MOFs crystal prepared by the present invention is micron order, is deposited
It is high in hole, the yield of the preparation method of catalyst.
The hydrogenation for medicine intermediate of the compound hole catalyst of graphene prepared by embodiment 1-6/MOFs crystal
In catalytic reaction, excellent catalytic effect, and it is good to reuse effect.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. the preparation method of the compound hole catalyst of a kind of graphene/MOFs crystal, it is characterised in that comprise the following steps：
(1) redox graphene is scattered in solvent, obtains graphene dispersing solution, Louis is added into graphene dispersing solution
This sour metallocene catalyst and 2- dibenzenesulfonyl pyridine template materials, are uniformly mixed, obtain substrate solution；
(2) DMF solution of methylimidazole-methylene-benzene ligand will be added in substrate solution, after microwave treatment, adds the tert-butyl alcohol
Potassium adjusts pH to alkalescent, and heating stirring reaction, is cooled to room temperature, obtains crystal crude product；
(3) by crystal crude product crushing grinding, adding organic solvent separates out the lewis acid metallocene catalyst of dissolving, separates,
It is dry, obtain the compound hole catalyst of graphene/MOFs crystal.
2. a kind of preparation method of the compound hole catalyst of graphene/MOFs crystal according to claim 1, its feature exist
In：In the step (1), the mass ratio of mould material, graphene and lewis acid metallocene catalyst is in substrate solution
100:8-16:0.5-2。
3. a kind of preparation method of the compound hole catalyst of graphene/MOFs crystal according to claim 1, its feature exist
In：In the step (1), lewis acid metallocene catalyst is by transition metal or thulium and ring penta 2
Alkene or cyclopentadiene derivant composition.
4. a kind of preparation method of the compound hole catalyst of graphene/MOFs crystal according to claim 1, its feature exist
In：In the step (1), transition metal is titanium, zirconium or antimony in lewis acid metallocene catalyst.
5. a kind of preparation method of the compound hole catalyst of graphene/MOFs crystal according to claim 1, its feature exist
In：In the step (2), the condition of microwave treatment is 50-100W, time 5-15min.
6. a kind of preparation method of the compound hole catalyst of graphene/MOFs crystal according to claim 1, its feature exist
In：In the step (2), 2- dibenzenesulfonyls pyridine and the mass ratio of methylimidazole-methylene-benzene are in substrate solution
6.5-8:5-6。
7. a kind of preparation method of the compound hole catalyst of graphene/MOFs crystal according to claim 1, its feature exist
In：In the step (2), the temperature of heating stirring reaction is 170-180 DEG C, time 24-36h.
8. a kind of preparation method of the compound hole catalyst of graphene/MOFs crystal according to claim 1, its feature exist
In：In the step (2), weakly alkaline pH value is 8.5-10.
9. a kind of preparation method of the compound hole catalyst of graphene/MOFs crystal according to claim 1, its feature exist
In：In the step (3), organic solvent is ethanol.
10. a kind of preparation method of the compound hole catalyst of graphene/MOFs crystal according to claim 1, its feature
It is：In the step (3), the particle diameter of the compound hole catalyst of graphene/MOFs crystal is micron order.
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| CN114471467A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Truncated polyhedral MOFs @ rGO material and preparation method and application thereof |
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