CN101298054A - Coordination polymer molecular aggregate catalyst material containing metalloporphyrin and preparation thereof - Google Patents
Coordination polymer molecular aggregate catalyst material containing metalloporphyrin and preparation thereof Download PDFInfo
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- CN101298054A CN101298054A CNA200810039206XA CN200810039206A CN101298054A CN 101298054 A CN101298054 A CN 101298054A CN A200810039206X A CNA200810039206X A CN A200810039206XA CN 200810039206 A CN200810039206 A CN 200810039206A CN 101298054 A CN101298054 A CN 101298054A
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Abstract
The invention pertains to the technical filed of molecular materials and chemical catalyzing, in particular to a molecular assembly material for a coordination polymer containing metalloporphyrin and a preparation method thereof. The assembly material is a multi-layer film formed on a solid base on an immiscible gas-liquid or solid-liquid interface by self-assembly technology; the formation and the structure of the assembly material can be adjusted and controlled by changing the reaction precursors (metal ions or the metalloporphyrin) of two phases. The material is fixed on the surface of the solid base in a film state, has the features of molecular material and nano material, thus having relatively high thermal and chemical stability and structural controllability as well as being able to serve as a heterogeneous catalyst with relatively high catalyzing efficiency used for the catalytic oxidation of organics. Meanwhile, the separation of the catalyst and products is extremely simple and a 'plug and play' mode of being able to stop or restart at any time during the process of a catalytic reaction can be realized, thus being extremely applicable to tracing and regulating a catalytic reaction process.
Description
Technical field
The invention belongs to molecular material and chemical catalysis technical field, be specifically related to a kind of Coordination Polymers molecule aggregate catalysis material and preparation method thereof.
Technical background
It is guiding that the research that group of molecules packing technique from bottom to top prepares molecular material is turned to the function by the sign of the physicochemical properties such as design, assembling, structure and photoelectromagnetic of molecular material, according to the structure of individual molecule and characteristic, intermolecular effect, the compound molecule aggregate material that design and preparation have specific function, and assembling molecular device and molecule machine, realize miniaturization, microminiaturization and the high-density multifunctionization of product, and the aspects such as matter and energy transmittance process of simulation organism.The technology of molecule assembling mainly contains: Langmuir-Blodgett (LB) film, self-assembled film and layer assembly film; The intermolecular active force that they relied on is generally Van der Waals force, electrostatic interaction, hydrogen bond and coordination etc.Not only show the function of the molecule self of forming aggregation, the function of molecular level (nanoscale) material by the formed molecule aggregate material of these package techniques, the new function that the interior intermolecular special role of also possible aggregation owing to formation produces.
Porphyrins by four pyrroles constitute, rubber-like hither plane conjugated system.This structure extensively is formed in the bodies of aminal and plant, and is important living matter, as ferroheme, cobalamin, hemoglobin, cromoci, and the key structure unit at light compositing center.Porphyrin ring is the π-electron system of a delocalization, armaticity, and this makes porphyrin have power supply and nucleophobic dual performance concurrently, can absorb luminous energy effectively and carry out opto-electronic conversion.The hydrogen atom at the aromatic ring center of porphyrin can be replaced by multiple metal ion, not only enriched the physicochemical characteristics of derivatives of porphyrin aspect optics and electricity, more make derivatives of porphyrin have specific photosensitive, oxygen carrier, catalysis and power conversion performance, become the important part of nature.Since the strong functions of metalloporphyrin, research manually synthetic and the simulation metalloporphyrin is the important topic that people are concerned about just always in recognizing organism.Can be used as light absorption units (light-harvesting unit) as metal porphyrin derivative and array structure thereof is widely used in the solar energy conversion and simulates in the research of relevant theory and molecular material and molecular device.Oxygen transmission, oxygen activation and the electronics transmission etc. undertaken by the porphyrin central metallic ions.Metalloporphyrin also can be used as catalyst and is applied to the oxidation scission of many organic oxidations, dna molecular, organic synthetic and cyclisation etc.
Because the synthetic of metal porphyrins all has higher requirement to production equipment, reaction condition usually, the process of preparation is the separation difficulty of more complicated, particularly product also, and productive rate is low; Shortcomings such as problem, catalyst and the reactant/product that may run into solvent in catalytic process again is difficult to separate propose new technology and solve above-mentioned difficulties, satisfy scientific research and industrial needs so press for.
Summary of the invention
It is simple to the objective of the invention is to propose a kind of course of reaction, convenient product separation, molecule aggregate catalysis material of the containing metal porphyrin Coordination Polymers that catalytic efficiency is higher and preparation method thereof.
The molecule aggregate material of the containing metal porphyrin Coordination Polymers that the present invention proposes is to be fixed in the multilayer film that forms on the solid substrate by pre-reaction material by the group of molecules packing technique,
The containing metal porphyrin Coordination Polymers molecule aggregate preparation methods that the present invention proposes is divided two kinds.A kind of is at liquid-vapor interface, deposits containing metal porphyrin Coordination Polymers molecule aggregate material by the LB membrane preparation technology at the surface of solids.Another kind is a molecule aggregate material of at first directly assembling containing metal porphyrin Coordination Polymers by the molecule self assembly then by the technology of molecule layer assembly at the surface of solids.
Predecessor among the present invention comprises the metalloporphyrin or derivatives thereof as main body, and as the metal ion or the metal coordination ion of linking group.Wherein, the chemical structural formula of metalloporphyrin or derivatives thereof is respectively metal four pyridine radicals porphyrins (M-TPyP), metal tetraphenylporphyrin (M-TPP), metal N-methyl four pyridine radicals porphyrins (M-TMPyP) or metal tetrasulfonic acid base porphyrin (M-TSPP) as shown in Figure 1.The central metallic ions of porphyrin is Fe
3+, Co
2+Or Mn
3+In addition, also comprise the derivative (compound) that a class forms by above-mentioned metalloporphyrin and polyvinyl pyridine (metalloporphyrin/PVP).In addition, in the metalloporphyrin or derivatives thereof, also can add multidentate ligand.The chemical structural formula of these multidentate ligands is respectively 4 as shown in Figure 2,4 '-bipyridyl, 2,4,6-TPTZ or polyvinyl pyridine.These metalloporphyrins, metalloporphyrin-polypyridine compound and multidentate ligand normally are dissolved in the organic solvents such as chloroform or methyl alcohol (minority is dissolved in the water).
Metal ion and metal coordination ion as linking group among the present invention can be CdCl
2, AgNO
3, HgCl
2, K
2PdCl
4, K
2PtCl
4, or K
2PtCl
6They all are dissolved in the water.The preparation method of molecular material all at room temperature carries out among the present invention, except that the LB technology need be used the Langmuir groove, does not need special consersion unit.
By selecting the metalloporphyrin complex (M-TPyP, M-TPP, M-TMPyP or M-TSPP) of different structure, the multidentate ligand of common coordination (4,4 '-bipyridyl, 2,4,6-TPTZ and polyvinyl pyridine), or as the metal ion or the complex ion (CdCl of linking group
2, AgNO
3, HgCl
2, K
2PdCl
4, K
2PtCl
4, K
2PtCl
6) distribution and the orientation of the sub-aggregate material mesoporphyrin of controllable sub ring, the size and the specific area in molecule aggregate material three-dimensional space structure and the molecule aggregate material Zhong Na hole that formed by Coordination Polymers can reach the purpose that improves catalytic efficiency.The structure of these molecule aggregate material mesoporphyrin, the size in hole received are decided by the distribution of metal ion outer-shell electron cloud and the orientation and the size of part (metalloporphyrin and multidentate ligand).
Two kinds of preparation methods of the Coordination Polymers molecule aggregate catalysis material of the containing metal porphyrin that the present invention proposes are described below respectively:
(1) utilize the Langmuir-Blodgett method to prepare containing metal porphyrin Coordination Polymers molecule aggregate multi-layer film material by the interface complexation reaction at liquid-vapor interface
The solution that is dissolved in metal (as Fe, Co or Mn) the porphyrin or derivatives thereof of the 0.1-0.5mM in the organic solvent is spread over the aqueous solution (the being commonly referred to parfacies) surface of containing 0.001-0.1M metal ion or metal coordination ion.Along with the volatilization of organic solvent, the metal ion reaction in metalloporphyrin or derivatives thereof and the parfacies forms one deck Coordination Polymers monomolecular film at the interface; This monomolecular film under the surface pressure of 10-30mN/m, is utilized the surface deposition of LB membrane preparation device at solid substrate, obtain the multi-layer film material of containing metal porphyrin Coordination Polymers molecule aggregate.
In this method, also can add multidentate ligand in the solution of metalloporphyrin or derivatives thereof, the concentration of multidentate ligand is 1-5mM.
(2) prepare containing metal porphyrin Coordination Polymers molecule aggregate multi-layer film material at the surface of solids by the coordination between the pyridine radicals on metal ion and the metalloporphyrin group
Solid (as porphyrin, quartz and mica) the substrate volume ratio that to clean through washing lotion, distilled water and ethanol is that the sodium hydroxide solution of 3-5% soaked 15-30 hour, obtains hydroxylated solid hydrophilic substrate; After the oven dry, be immersed in weight content again and be the solid substrate that forms silanization in the solution of silane of halogeno-benzene methyl of 2-10% by self assembly.The organic solution heating reflux reaction that the solid substrate and the weight content of this silanization is 5-10% polyvinylpyridine 10-20 hour, form layer of polyethylene yl pyridines molecular layer on the solid substrate surface, it is immersed in forms the metal ion layer in the aqueous solution that contains 0.01-3mM metal coordination ion or metal coordination ion then.After cleaning, with the reaction of the metal that contains 0.1-0.5mM (as Fe, Co or Mn) porphyrin or derivatives thereof (as M-TPyP or metalloporphyrin/PVP compound) organic solvent solution, form layer of metal porphyrin layer again.The above-mentioned steps that so hockets can be prepared into the Coordination Polymers molecule aggregate multilayer film (referring to accompanying drawing 3,4) of containing metal porphyrin, and till satisfying needed thickness.
In this method, also can add multidentate ligand in the solution of metalloporphyrin or derivatives thereof, the concentration of multidentate ligand is 1-5mM.
Containing metal porphyrin Coordination Polymers molecule aggregate material by the present invention's preparation can be used as different-phase catalyst and is used for the catalytic oxidation organic matter, and specific practice is as follows:
The solid substrate that the surface is fixed with 3-7 layer containing metal porphyrin Coordination Polymers molecule aggregate material film is soaked in the solution that contains the organic matter (as unsaturated compoundses such as cyclohexene, cyclo-octene, cyclohexanone, styrene or aromatic etc.) for the treatment of catalytic oxidation, after adding oxidant (as iodosobenzene, hydrogen peroxide or clorox etc.), catalytic oxidation begins.If wish to detect the composition or the output of oxidizing process intermediate product, then only need solid substrate is taken out from reaction system, this catalytic reaction can stop; And realize separating between catalyst and the product.Continue reaction if desired, then solid substrate is immersed in the reaction system again, catalytic oxidation can be proceeded, thereby is implemented in " plug and play " formula catalytic reaction process that stops at any time in the reaction process and restart.
Material of the present invention also can be used for the catalytic process of analog cytochrome p450.
The present invention is based on the group of molecules packing technique of molecular engineering, metalloporphyrin is fixed in the surface of solid substrate by artificial design with the form of complex molecule aggregation, have following advantage: (1) is owing to being molecular material thereby can improving catalytic reaction efficient, (2) because being the surface that is fixed on solid substrate, Coordination Polymers molecule aggregate material can realize separating of catalysis material and reactant and product easily, (3) owing to the molecule aggregate catalysis material that is fixed in the solid substrate surface can arbitrarily insert or take out from reaction system, thereby can control the process of catalytic reaction at any time according to response situation, reach the purpose of control catalytic reaction products.The technology of preparing of this method is simple, equipment, production environment is required low, and can realize component and structure Design and regulation and control to metalloporphyrin in the molecule aggregate simply.
Description of drawings
Fig. 1. metalloporphyrin and derivative molecular structural formula thereof.Wherein (a) is M-TPyP type metalloporphyrin, (b) is M-TMPyP type metalloporphyrin, (c) is M-TPP type metalloporphyrin, (d) is M-TSPP type metalloporphyrin, (e) is the derivative that metalloporphyrin and polyvinyl pyridine form.
Fig. 2. the chemical structural formula of the multidentate ligand that uses among the present invention.Wherein (a) is 4, and 4 '-bipyridyl is 2,4 (b), and the 6-TPTZ (c) is polyvinyl pyridine.
Fig. 3. transition metal ions-(Fe, Co, Mn) the metalloporphyrin molecule aggregate membrane structure schematic diagram that makes with the present invention.
Fig. 4. transition metal ions-(Fe, Co, Mn) metalloporphyrin-polyvinyl pyridine molecule aggregate membrane structure schematic diagram that makes with the present invention.
The specific embodiment
The invention is further illustrated by the following examples.
Embodiment 1:
In the Langmuir groove of cleaning, add the CdCl that contains 0.05 mol
2The aqueous solution, then with syringe liquid-vapor interface drip about 100 microlitres, 0.3 mM/liter the chloroformic solution of metal M n porphyrin.Treat that chloroform solvent volatilizees fully and the interface complexation reaction finish after (needing usually more than 20 minutes), compressive surfaces to surface pressure rises to about 20mN/m.Keep this surface pressure, utilize LB to carry the multilayer film of membrane technology at the molecule aggregate material C d-MnTPyP of the quartz substrate surface deposition containing metal porphyrin of cleaning.
Embodiment 2:
In the Langmuir groove of cleaning, add contain 0.1 mM/liter K
2PdCl
4The aqueous solution, then with syringe liquid-vapor interface drip about 100 microlitres, 0.3 mM/liter the chloroformic solution of metal M n porphyrin/PVP compound.Treat that chloroform solvent volatilizees fully and the interface complexation reaction finish after (needing usually more than 20 minutes), compressive surfaces to surface pressure rises to about 20mN/m.Keep this surface pressure, utilize LB to carry the multilayer film of membrane technology at the molecule aggregate material Pd MnTPyP/PVP of the quartz substrate surface deposition containing metal porphyrin of cleaning.
Embodiment 3:
Clean and utilize solid (glass, quartz after the 4% NaOH hydrophilic treated, mica or conduction porphyrin) substrate at first forms with 2% bromobenzene methyl-monosilane chloroform or methanol solution reaction and contains the solid substrate that active bromobenzene monosilane monofilm is modified, be reflected at the surface of solids with 5% polyvinyl pyridine then and form the monofilm that one deck is covered by polyvinyl pyridine.Once more, by with the CdCl of 0.1 mol
2Or 0.3 mM/liter K
2PdCl
4Carry out complexation reaction, on the polyvinyl pyridine surface in conjunction with one deck transition metal ions layer, and with contain 2 mMs/liter the metal Fe porphyrin effect of four pyridine radicals form the metalloporphyrin molecular layer.At last, repeat the coordination of above-mentioned metal ion, four pyridine radicals metalloporphyrins, form the Cd-FeTPyP or the Pd-FeTPyP molecule aggregate material that directly graft in the solid substrate surface.
Embodiment 4:
At first utilize the coordination between metal (Fe, Co or Mn) porphyrin and the polyvinylpyridine to form metal (Fe, Co or Mn) porphyrin-polyvinylpyridine Coordination Polymers.With four pyridine radicals metalloporphyrins in this metalloporphyrin-polyvinylpyridine Coordination Polymers replacement example 2, form transition metal ions-metal (Fe, Co or Mn) porphyrin-polyvinyl pyridine molecule aggregate material then by the interlayer coordination.
Embodiment 5:
In 5 milliliters of carrene, add the organic matter (as cyclo-octene) that 10 microlitres are treated oxidation, 10 microlitre dichloro-benzenes are as interior mark (also can interiorly marking during application of gas chromatorgraphy/mass), with hydrogen peroxide or iodosobenzene (PhIO) as oxidant, being fixed with five layers of metal (Fe, Co or Mn) quartz substrate of porphyrin molecule aggregate material inserts in the above-mentioned reaction system, and catalytic oxidation begins.In the time of need stopping the catalytic oxidation detection reaction and carry out process, this solid substrate taken out from reaction system get final product, thereby realize separating between catalyst and the product, and be implemented in the catalytic reaction process of " plug and play " formula that stops at any time in the reaction process or restart.1 microlitre reaction solution injection gas chromatography view is taken out in the course of reaction or reaction end back, measures the inversion quantity of cyclo-octene.
Claims (6)
1, a kind of Coordination Polymers molecule aggregate material of containing metal porphyrin is characterized in that it being the multilayer film that is formed on solid substrate by numerator self-assembly technique by pre-reaction material; Wherein, described presoma comprises as the metalloporphyrin of main body and derivative thereof, and as the metal ion or the metal coordination ion of linking group; Metalloporphyrin is for containing the central metal ion porphyrin of Fe, Co or Mn, and the derivative of metalloporphyrin is metalloporphyrin-polyvinyl pyridine compound that these metalloporphyrins and polyvinyl pyridine form; Described is CdCl with the metal ion
2, AgNO
3Or HgCl
2, metal coordination ion is K
2PdCl
4, K
2PtCl
4Or K
2PtCl
6
2, the Coordination Polymers molecule aggregate material of containing metal porphyrin according to claim 1, it is characterized in that in the described presoma metalloporphyrin or derivatives thereof also adding that multidentate ligand, this multidentate ligand are arranged is 4,4 '-bipyridyl, 2,4,6-TPTZ or polyvinyl pyridine.
3, the Coordination Polymers molecule aggregate material of containing metal porphyrin according to claim 2 is characterized in that described metalloporphyrin is for being metal four pyridine radicals porphyrins, metal tetraphenylporphyrin, metal N-methyl four pyridine radicals porphyrins or metal tetrasulfonic acid base porphyrin.
4, according to the Coordination Polymers molecule aggregate preparation methods of the described containing metal porphyrin of one of claim 1-3, it is characterized in that adopting a kind of of following two kinds of methods:
(1) utilize the Langmuir-Blodgett method to prepare containing metal porphyrin Coordination Polymers molecule aggregate multi-layer film material by the interface complexation reaction at liquid-vapor interface
The solution that is dissolved in the metalloporphyrin or derivatives thereof of the 0.1-0.5mM in the organic solvent is spread over the aqueous solution surface of containing 0.001-0.1M metal ion or metal coordination ion, volatilization along with organic solvent, metal ion reaction in the metalloporphyrin or derivatives thereof and the aqueous solution forms one deck Coordination Polymers monomolecular film at the interface; This monomolecular film under the surface pressure of 10-30mN/m, is utilized the surface deposition of LB membrane preparation device at solid substrate, obtain the multi-layer film material of containing metal porphyrin Coordination Polymers molecule aggregate;
(2) prepare containing metal porphyrin Coordination Polymers molecule aggregate multi-layer film material at the surface of solids by the coordination between the pyridine radicals on metal ion and the metalloporphyrin group
The solid substrate volume ratio that to clean through washing lotion, distilled water and ethanol is that the sodium hydroxide solution of 3-5% soaked 15-30 hour, obtains hydroxylated solid hydrophilic substrate; After the oven dry, be immersed in weight content again and be the solid substrate that forms silanization in the solution of silane of halogeno-benzene methyl of 2-10% by self assembly; The organic solution heating reflux reaction that the solid substrate and the weight content of this silanization is 5-10% polyvinylpyridine 10-20 hour, form layer of polyethylene yl pyridines molecular layer on the solid substrate surface, it is immersed in forms the metal ion layer in the aqueous solution that contains 0.01-3mM metal coordination ion or metal coordination ion then; After cleaning, the organic solvent solution with the metalloporphyrin or derivatives thereof that contains 0.1-0.5mM reacts again, forms layer of metal porphyrin layer; The above-mentioned steps that so hockets promptly is prepared into the Coordination Polymers molecule aggregate multilayer film of containing metal porphyrin, and till satisfying needed thickness.
5, preparation method according to claim 4 is characterized in that also adding in the solution of described metalloporphyrin or derivatives thereof that multidentate ligand, the concentration of multidentate ligand are arranged is 1-5mM, this multidentate ligand is 4,4 '-bipyridyl, 2,4,6-TPTZ or polyvinyl pyridine.
6, containing metal porphyrin Coordination Polymers molecule aggregate material as claimed in claim 1 is as the application of different-phase catalyst in the catalytic oxidation organic matter.
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