CN101607213A - Palladium coordination polymer molecule aggregate catalysis material and its production and use - Google Patents
Palladium coordination polymer molecule aggregate catalysis material and its production and use Download PDFInfo
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- CN101607213A CN101607213A CNA2009100548335A CN200910054833A CN101607213A CN 101607213 A CN101607213 A CN 101607213A CN A2009100548335 A CNA2009100548335 A CN A2009100548335A CN 200910054833 A CN200910054833 A CN 200910054833A CN 101607213 A CN101607213 A CN 101607213A
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Abstract
The present invention relates to a kind of palladium coordination polymer molecule aggregate catalysis material and its production and use, described catalysis material is fixed on the Coordination Polymers molecule aggregate catalysis material that the solid substrate surface forms by self assembly, the precursor of catalysis material comprises the palladium coordination ion, and contain pyridine multidentate ligand or macromolecule ligand, wherein, described palladium coordination ion is selected from tetrachloro and closes the palladium acid group, two chloro-2,2 '-bipyridyl closes palladium, the dichloro ethylenediamine closes a kind of in the palladium, describedly contain the pyridine multidentate ligand or macromolecule ligand is selected from 4,4 '-bipyridyl, 2,4, the 6-TPTZ, metal or hollow four pyridine radicals porphyrins, anti-form-1,2-bipyridyl ethene, the di-thiopyridines, a kind of in the polyvinyl pyridine.Utilize the preparation of LB membrane preparation technology or layer assembly method, be used for the organic hydrogenation reaction of organic matter selectivity ethylene linkage.Have high catalytic efficiency, easily realize separating of catalyst and reactant and product, simple operation, cost is low.
Description
Technical field
The invention belongs to molecular material and chemical catalysis technical field, be specially and utilize the group of molecules packing technique that a kind of palladium coordination polymer molecule aggregate catalysis material and its production and use is provided.
Background technology
Different with traditional top-down method, the group of molecules packing technique from bottom to top that last century end grows up is structure and the characteristic according to individual molecule, use intermolecular effect, the molecular material that design and preparation have specific function, and utilize these molecular material assembling molecular device and molecule machines, realize the miniaturization and the multifunction of product.The technology of molecule assembling mainly contains: Langmuir-Blodgett (LB) film, self-assembled film and layer assembly film; The intermolecular force that they relied on is generally Van der Waals force, electrostatic interaction, hydrogen bond and coordination etc.The molecular material that forms by these package techniques not only shows the function of the molecule self of ingredient material, but also because the interaction between the molecular material interior molecules of formation produces new function.
Palladium catalyst is a kind of metallic catalyst commonly used, is widely used in the synthetic and field of petrochemical industry of organic compound.In order to improve the efficient of palladium catalyst, in the past few decades between, people have finished a large amount of work at the chemical modification of palladium metal, the aspects such as preparation of composite catalyst, have proposed the method for effective raising catalyst efficient.In general, palladium catalyst mainly is divided into homogeneous catalyst and different-phase catalyst two big classes, and homogeneous catalyst has mainly been represented orgnometallic catalyst, its catalytic efficiency height, but reclaim difficulty; Different-phase catalyst is mainly represented traditional palladium-carbon catalyst, and in general its catalytic efficiency is lower than homogeneous catalyst, and is reusable to a certain extent, is not very high though reuse efficient.
For the recuperability in conjunction with the efficient and different-phase catalyst of homogeneous catalyst, the research of composite catalyst becomes the forward position.Very effective method be with palladium catalyst deposition or grafting in the hole of porous carriers such as molecular sieve or aluminium oxide.The catalytic efficiency of the palladium catalyst of institute's load and the specific area of carrier, the particle size of catalyst etc. have confidential relation.In general, the specific area of carrier is big more, and the catalyst particle of load is more little, and the catalytic efficiency of composite catalyst is high more.
Disperse because the catalyst particle of composite catalyst can't reach unimolecule, therefore efficient still has the space of lifting in theory.In order to obtain higher catalytic efficiency, and solve catalyst and the problem that reactant/product is difficult to separate, the present invention proposes a kind of new technical scheme.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of palladium coordination polymer molecule aggregate catalysis material, has the ability of the organic hydrogenation reaction of efficient catalytic, and the hydrogen source of the reduction of palladium ion and catalytic hydrogenation is hydrogen, simple operation, and cost is lower.
Another technical problem to be solved by this invention is to provide the preparation method of above-mentioned palladium coordination polymer molecule aggregate catalysis material.
A technical problem more to be solved by this invention is to provide the purposes of above-mentioned palladium coordination polymer molecule aggregate catalysis material.
The present invention solves the problems of the technologies described above the technical scheme of being taked: a kind of palladium coordination polymer molecule aggregate catalysis material, being fixed on the solid substrate surface by self assembly with covalent bond forms, the preceding body material of described catalysis material comprises the palladium coordination ion, and contain the pyridine multidentate ligand or contain pyridine high molecular polymer part, wherein, described palladium coordination ion is selected from (a) tetrachloro and closes the palladium acid group, (b) two chloro-2,2 '-bipyridyl closes palladium, (c) the dichloro ethylenediamine closes a kind of in the palladium, the described pyridine multidentate ligand that contains is selected from (A) 4,4 '-bipyridyl, (B) 2,4, the 6-TPTZ, (C) metal four pyridine radicals porphyrins (MTPyP), hollow four pyridine radicals porphyrins (TPyP), (D) anti-form-1,2-bipyridyl ethene, perhaps a kind of in (E) di-thiopyridines, it is described that to contain pyridine high molecular polymer part be (F) polyvinyl pyridine (PVP), wherein, the concentration of described palladium ligand ion is 0.001～0.1M, and the concentration that contains pyridine multidentate ligand or high molecular polymer part is 0.1～0.5mM.
Concrete, the concentration of palladium ligand ion can be 0.001, O.002, and 0.005,0.008,0.01,0.02,0.05,0.08 or 0.1M;
The concentration that contains pyridine multidentate ligand or high molecular polymer part can be 0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45 or 0.5mM.
The structural formula of palladium coordination ion is:
(a) (b) (c)
The structural formula that contains pyridine multidentate ligand or macromolecule ligand is:
(A) (B) (C)
(D) (E) (F)
The present invention combines palladium ion in this molecule aggregate material with the mode of coordinate bond and multidentate ligand or macromolecule ligand, and is dispersed in the three-dimensional structure that Coordination Polymers forms.Then form the Pd (0) with catalytic capability when palladium ion is reduced, the palladium of these zeroth orders is dispersed in the molecule aggregate material, thereby has the ability of the organic hydrogenation reaction of catalysis efficiently.
On the basis of such scheme, described solid substrate is glass, quartz or mica substrate.
The present invention is by the distribution of palladium and the orientation of part in selection multidentate ligand or the sub-aggregate material of palladium complex ion controllable sub, thereby the three-D space structure of regulatory molecule aggregate material and specific area thereof are divided two kinds at the preparation method of above-mentioned palladium coordination polymer molecule aggregate catalysis material.
A kind of preparation method utilizes the Langmuir-Blodgett method to prepare palladium coordination polymer molecule aggregate catalysis material at liquid-vapor interface, form the palladium coordination polymer monomolecular film earlier at liquid-vapor interface, by the LB membrane preparation technology palladium coordination polymer monomolecular film is deposited to the solid substrate surface again and form the three-dimensional molecular aggregate material, reaction is at room temperature carried out, and needs to use the Langmuir groove.
Concrete, utilize the Langmuir-Blodgett membrane preparation technology, in the Langmuir groove, add 0.001～0.1M and contain the solution (aqueous solution) of palladium coordination ion, the organic solution that 0.1～0.5mM is contained pyridine multidentate ligand or high molecular polymer part spreads over solution (the being commonly referred to parfacies) surface that contains the palladium coordination ion, the organic solution that can adopt micro syringe will contain pyridine multidentate ligand or macromolecule ligand drips at liquid-vapor interface, with solvent evaporates, contain that pyridine multidentate ligand or macromolecule ligand and palladium ligand ion react completely and form one deck palladium coordination polymer monomolecular film at the interface, to reacting completely to need 20 minutes, at 10～30mN/m
2Surface pressing under, carry film with the Langmuir-Blodgett membrane preparation technology, at the multilayer film of solid substrate surface deposition palladium coordination polymer molecule aggregate, the general number of plies is 2 to 8 layers.Make palladium coordination polymer molecule aggregate catalysis material.
On the basis of above-mentioned Langmuir-Blodgett membrane preparation method, the solvent of palladium coordination ion is water or hot water, and the solvent that contains pyridine multidentate ligand or macromolecule ligand is chloroform or methyl alcohol.
Another kind of preparation method utilizes coordination between the pyridine radicals of palladium complex ion and multidentate ligand or high molecular polymer part at the surface of solids, directly assemble the three-dimensional molecular aggregation catalysis material of palladium coordination polymer at the surface of solids by the technology of molecule layer assembly, reaction is at room temperature carried out, and does not need special consersion unit:
Concrete, adopt the layer assembly method, comprise the steps:
The preparation of A, solid substrate: will be through pre-treatment, comprise the solid substrate soaking with sodium hydroxide that washing lotion, distilled water and ethanol clean, be generally 4% soaking with sodium hydroxide 24 hours, obtain hydroxylated solid hydrophilic substrate, 120 ℃ the oven dry 2 hours after, soak with halogeno-benzene methylchlorosilane solution again, be generally 2% chlorobenzene methylchlorosilane solution and soaked 5～10 hours, obtain the solid substrate of self assembly silanization;
The formation of B, macromolecule layer: solid substrate is placed in the organic solution of polyvinyl pyridine, adds hot reflux, form polyvinyl pyridine macromolecule layer, the high molecular polymer that flush away is residual on the solid substrate surface;
The preparation of C, catalysis material: the solid substrate of B step is immersed in 0.001～0.1M palladium ligand ion (K
2PdCl
4, Pd (bpy)
2Cl
2, Pd (en)
2Cl
2Deng) solution in, carry out complexation reaction, form the palladium ion layer on macromolecule layer surface, wash residual palladium ligand ion; Be immersed in the solution that 0.1～0.5mM contains pyridine multidentate ligand or macromolecule ligand, reaction forms organic ligand layer, alternately repeats above-mentioned steps, makes the multilayer film of palladium coordination polymer molecule aggregate again, and the general number of plies is 2 to 8 layers.
In the B of above-mentioned layer assembly method step, described organic solvent is acetonitrile or methyl alcohol, and the concentration of polyvinyl pyridine is 1.5～2.5mM, and described heating reflux temperature is 64～80 ℃, and the time is 8～24 hours.
Concrete, the concentration of polyvinyl pyridine can be 1.5,1.6,1.8,2,2.2,2.4 or 2.5mM; Temperature can be 64,70 or 80 ℃; Time can be 8,10,12,16,20 or 24 hours.
Described multilayer is further explained, for example:
Pd-MTPyP is 2 layers;
Pd-MTPyP-Pd-MTPyP is 4 layers;
Pd-PVP-Pd-PVP-Pd-PVP-Pd-PVP is 8 layers.
The invention provides the purposes of described palladium coordination polymer molecule aggregate catalysis material, as the out-phase molecular catalyst, with hydrogen is hydrogen source, be used for connecting the conjugated alkenes or the α of aromatic ring in catalysis, the organic hydrogenation reaction of the organic selectivity ethylene linkage of beta-unsaturated ketone, wherein, described conjugated alkenes is a kind of in styrene, halogenated styrenes, methoxy styrene, the naphthalene ethene, α, beta-unsaturated ketone are a kind of in butenone, the methyl acrylate.
The process of this hydrogenation catalyst is divided following two kinds of situations:
(1) solid substrate that the surface is fixed with 2 to 8 layers of palladium coordination polymer molecule aggregate catalysis material is used in the saturated solvent of hydrogen, makes the palladium ion reduction, adds the organic matter for the treatment of catalytic hydrogenation, carries out catalytic hydrogenation reaction.
(2) solid substrate that the surface is fixed with 2 to 8 layers of palladium coordination polymer molecule aggregate catalysis material is soaked in to contain and treats in the organic solution of catalytic hydrogenation, feeds hydrogen, carries out catalytic hydrogenation reaction.
If wish to detect the composition or the output of hydrogenation process intermediate product, then only need solid substrate is taken out from reaction system, this catalytic reaction can stop; Continue reaction if desired, then solid substrate is immersed in the reaction system again, catalytic hydrogenation reaction can be proceeded, and is easy to realize separating of catalyst and reactant and product.
The palladium coordination polymer molecule aggregate catalysis material preparation process that the present invention is based on the preparation of group of molecules packing technique is simple; The Metal Palladium of catalyst core reaches the unimolecule degree of scatter, is arranged in the middle of the polymer array of rule the catalytic efficiency height; Convenient separation between catalyst and reactant and the product can reuse; Can also stop or restarting catalytic reaction at any time, be highly suitable for the tracking of catalytic reaction process and the analysis of reaction intermediate.The type catalyst has had the recuperability of the efficient and different-phase catalyst of homogeneous catalyst concurrently in general.
The present invention is fixed in the surface of solid substrate with the form of molecule aggregate by covalent bond with palladium coordination polymer, has following beneficial effect:
(1), thereby has high catalytic reaction efficient owing to be that palladium ion/atom is dispersed in the three dimensions material that Coordination Polymers forms;
(2), thereby can realize separating of catalyst and reactant and product easily because palladium coordination polymer molecule aggregate material is the surface that is fixed on solid substrate;
(3) owing to the palladium molecule aggregate catalysis material that is fixed in the solid substrate surface can arbitrarily insert or take out, thereby can control the process of catalytic reaction at any time from reaction system, reach the purpose of control catalytic reaction products according to response situation;
(4) hydrogen source of the reduction of palladium ion and catalytic hydrogenation is hydrogen, and reaction environment is the room temperature normal pressure, and it is very convenient to operate, and cost is lower.In a word, the technology of preparing of this method is simple, equipment, production environment is required low, and can realize simply the component of molecular material and the regulation and control of space structure.
Description of drawings
Fig. 1 is the structural formula of palladium coordination polymer molecule aggregate.
Fig. 2 is for the polyvinyl pyridine being the structural formula of the Pd-PVP Coordination Polymers molecule aggregate of part formation.
Fig. 3 is for hollow porphyrin being the structural formula of the Pd-TPyP Coordination Polymers molecule aggregate of part formation.
The specific embodiment
One, utilize the Langmuir-Blodgett method to prepare palladium coordination polymer molecule aggregate catalysis material at liquid-vapor interface.
Embodiment 1
Utilize the Langmuir-Blodgett membrane preparation technology, add 0.002M two chloro-2 in the Langmuir groove of cleaning, 2 '-bipyridyl closes palladium (Pd (en)
2Cl
2) the aqueous solution, chloroformic solution with 0.5mM metal four pyridine radicals porphyrins (MTPyP) drips about 100 microlitres with micro syringe at liquid-vapor interface then, 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 the LB membrane preparation technology to carry film, at the multilayer film of the palladium coordination polymer molecule aggregate catalysis material Pd-MTPyP of the quartz substrate surface deposition containing metal porphyrin of cleaning.
Embodiment 2
Utilize the Langmuir-Blodgett membrane preparation technology, in the Langmuir groove of cleaning, add the tetrachloro-palladium potassium chlorate (K that contains 0.002M
2PdCl
4) aqueous solution, chloroformic solution with 0.5mM polyvinylpyridine (PVP) drips about 100 microlitres with micro syringe at liquid-vapor interface then, 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 clean glass substrate surface deposition palladium coordination polymer molecule aggregate catalysis material Pd-PVP.
Two, the technology of utilizing the molecule layer assembly is directly at the three-dimensional molecular aggregation catalysis material of surface of solids assembling palladium coordination polymer.
The preparation method comprises the steps:
The preparation of A, solid substrate: with the solid substrate soaking with sodium hydroxide, obtain hydroxylated solid hydrophilic substrate, soak with the halogeno-benzene methylchlorosilane again, obtain the solid substrate of self assembly silanization;
The formation of B, macromolecule layer: solid substrate is placed in the organic solution of polyvinyl pyridine, adds hot reflux, form polyvinyl pyridine macromolecule layer, the macromolecule that flush away is residual on the solid substrate surface;
The preparation of C, catalysis material: solid substrate is immersed in the solution of 0.001～0.1M palladium ligand ion, carries out complexation reaction, form the palladium coordination polymer monomolecular film, wash residual palladium ligand ion on the macromolecule layer surface; Be immersed in the solution that 0.1～0.5mM contains pyridine multidentate ligand or macromolecule ligand, reaction forms organic ligand layer, alternately repeats above-mentioned steps, makes the multilayer film of palladium coordination polymer molecule aggregate again, and the number of plies is 2 to 8 layers.
The structural formula of palladium coordination polymer molecule aggregate is for as shown in Figure 1.
Embodiment 3
The preparation of A, solid substrate: the mica substrate cleaned and with 4% soaking with sodium hydroxide 24 hours, obtain hydroxylated solid hydrophilic substrate, chloroform or methanol solution with 2% chlorobenzene methylchlorosilane soaks again, and reaction forms the solid substrate that contains the self assembly silanization that active chlorine modifies for benzyl chlorosilane monofilm;
The formation of B, macromolecule layer: the mica substrate is placed in the organic solution of polyvinyl pyridine of 2mM, heating reflux reaction 10 hours forms layer of polyethylene pyridine high molecular layer at the surface of solids, with residual macromolecule on the washed with methanol mica substrate;
The preparation of C, catalysis material: the mica substrate is immersed in 0.002mM tetrachloro-palladium potassium chlorate (K
2PdCl
4) in the aqueous solution, the pyridine radicals on palladium coordination ion and the macromolecule carries out complexation reaction, forms the palladium ion layer at the polyvinyl pyridine macromolecule laminar surface, residual K on the water rinse substrate
2PdCl
4Be immersed in again in the organic solution of 0.5mM polyvinyl pyridine, reaction forms the polyvinyl pyridine macromolecule layer, alternately repeat coordination step between above-mentioned metal ion, macromolecule layer (organic coordination layer), make the multilayer film of the palladium coordination polymer molecule aggregate Pd-PVP that directly grafts in the mica substrate surface.
The structural formula that with the polyvinyl pyridine is the Pd-PVP Coordination Polymers molecule aggregate that forms of part is shown in Figure 2.
Embodiment 4
The preparation of A, solid substrate: with embodiment 3;
The formation of B, macromolecule layer: with embodiment 3;
The preparation of C, catalysis material: the mica substrate is immersed in 0.002mM tetrachloro-palladium potassium chlorate (K
2PdCl
4) in the aqueous solution, the pyridine radicals on palladium coordination ion and the macromolecule carries out complexation reaction, forms the palladium ion layer at the polyvinyl pyridine macromolecule laminar surface, residual K on the water rinse substrate
2PdCl
4Be immersed in again in the organic solution of the hollow four pyridine radicals porphyrins (TPyP) of 0.5mM, reaction forms organic coordination sphere, alternately repeat coordination step between above-mentioned metal ion, hollow porphyrin layer (organic coordination layer), make the multilayer film of the palladium coordination polymer molecule aggregate Pd-TPyP that directly grafts in the mica substrate surface.
The method is because the rigid structure of hollow porphyrin, easily form palladium and porphyrin and arrange very orderly array, therefore under the situation of the known chip area and the number of plies, can accurately measure Metal Palladium in on-chip amount, thereby be convenient to further study catalytic reaction kinetics.
With hollow porphyrin is that the structural formula of the Pd-TPyP Coordination Polymers molecule aggregate that forms of part is shown in Figure 3.
Application examples
The quartz substrate that the surface is fixed with 8 layers of (Pd-PVP-Pd-PVP-Pd-PVP-Pd-PVP) palladium coordination polymer molecule aggregate catalysis material is soaked in the saturated 4ml tetrahydrofuran solvent of usefulness hydrogen, make the palladium ion reduction, add 0.1ml then and treat the organic matter (as unsaturated compoundses such as styrene, halogenated styrenes, butenone, methyl acrylates) of catalytic hydrogenation, and at the airtight balloon that is full of hydrogen of inserting beyond the Great Wall as hydrogen source, catalytic hydrogenation reaction promptly begins.In the time of need stopping the catalytic hydrogenation 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.In the course of reaction or reaction end back is taken out the 0.1ml reaction solution and is dissolved in CDCl
3By
1H nuclear magnetic resonance or take out the inversion quantity of 1 microlitre reaction solution by interior target gas chromatography determination benzene alkene etc. also can be determined hydrogenated products with application of gas chromatorgraphy/mass.
Claims (9)
1, a kind of palladium coordination polymer molecule aggregate catalysis material, it is characterized in that: described catalysis material is fixed on the Coordination Polymers molecule aggregate catalysis material that the solid substrate surface forms by self assembly, the preceding body material of described catalysis material comprises the palladium coordination ion, and contain the pyridine multidentate ligand or contain pyridine high molecular polymer part, wherein, described palladium coordination ion is selected from tetrachloro and closes the palladium acid group, two chloro-2,2 '-bipyridyl closes palladium, the dichloro ethylenediamine closes a kind of in the palladium, the described pyridine multidentate ligand that contains is selected from 4,4 '-bipyridyl, 2,4, the 6-TPTZ, metal or hollow four pyridine radicals porphyrins, anti-form-1,2-bipyridyl ethene, perhaps a kind of in the di-thiopyridines, the described pyridine high molecular polymer part that contains is a polyvinyl pyridine, wherein, the concentration of described palladium ligand ion is 0.001～0.1M, and the concentration that contains pyridine multidentate ligand or high molecular polymer part is 0.1～0.5mM.
2, palladium coordination polymer molecule aggregate catalysis material according to claim 1 is characterized in that: described solid substrate is glass, quartz or mica substrate.
3, preparation method at claim 1 or 2 described palladium coordination polymer molecule aggregate catalysis materials, it is characterized in that: utilize the Langmuir-Blodgett membrane preparation technology, in the Langmuir groove, add 0.001～0.1M and contain the solution of palladium coordination ion, the organic solution that 0.1～0.5mM is contained pyridine multidentate ligand or high molecular polymer part spreads over the solution surface that contains the palladium coordination ion, with solvent evaporates, contain that pyridine multidentate ligand or macromolecule ligand and palladium ligand ion react completely and form one deck palladium coordination polymer monomolecular film at the interface, under the surface pressure of 10～30mN/m, carry film with the Langmuir-Blodgett membrane preparation technology, at the multilayer film of solid substrate surface deposition palladium coordination polymer molecule aggregate, make palladium coordination polymer molecule aggregate catalysis material.
4, the preparation method of palladium coordination polymer molecule aggregate catalysis material according to claim 3, it is characterized in that: the solvent of palladium coordination ion is water or hot water, the solvent that contains pyridine multidentate ligand or high molecular polymer part is chloroform or methyl alcohol.
5, at the preparation method of claim 1 or 2 described palladium coordination polymer molecule aggregate catalysis materials, it is characterized in that: adopt the layer assembly method, comprise the steps:
The preparation of A, solid substrate: with the solid substrate soaking with sodium hydroxide, obtain hydroxylated solid hydrophilic substrate, soak with the halogeno-benzene methylchlorosilane again, obtain the solid substrate of self assembly silanization;
The formation of B, macromolecule layer: solid substrate is placed in the organic solution of polyvinyl pyridine, adds hot reflux, form polyvinyl pyridine macromolecule layer, the high molecular polymer that flush away is residual on the solid substrate surface;
The preparation of C, catalysis material: the solid substrate of B step is immersed in the solution of 0.001～0.1M palladium ligand ion, carries out complexation reaction, form the palladium ion layer, wash residual palladium ligand ion on the macromolecule layer surface; Be immersed in the solution that 0.1～0.5mM contains pyridine multidentate ligand or macromolecule ligand, reaction forms organic ligand layer, alternately repeats above-mentioned steps, makes the multilayer film of palladium coordination polymer molecule aggregate again.
6, the preparation method of palladium coordination polymer molecule aggregate catalysis material according to claim 5, it is characterized in that: in the B step, described organic solvent is acetonitrile or methyl alcohol, the concentration of polyvinyl pyridine is 1.5～2.5mM, described heating reflux temperature is 64～80 ℃, and the time is 8～24 hours.
7, at the purposes of claim 1 or 2 described palladium coordination polymer molecule aggregate catalysis materials, it is characterized in that: as the out-phase molecular catalyst, with hydrogen is hydrogen source, be used for connecting the conjugated alkenes or the α of aromatic ring in catalysis, the organic hydrogenation reaction of the organic selectivity ethylene linkage of beta-unsaturated ketone, wherein, described conjugated alkenes is a kind of in styrene, halogenated styrenes, methoxy styrene, the naphthalene ethene, α, beta-unsaturated ketone are a kind of in butenone, the methyl acrylate.
8, the purposes of described palladium coordination polymer molecule aggregate catalysis material according to claim 7, it is characterized in that: described catalytic hydrogenation reaction is that the solid substrate that the surface is fixed with 2 to 8 layers of palladium coordination polymer molecule aggregate catalysis material is put into the saturated solvent of hydrogen, make the palladium ion reduction, add the organic matter for the treatment of catalytic hydrogenation, carry out catalytic hydrogenation reaction.
9, the purposes of palladium coordination polymer molecule aggregate catalysis material according to claim 7, it is characterized in that: described catalytic hydrogenation reaction is the solid substrate that the surface is fixed with 2 to 8 layers of palladium coordination polymer molecule aggregate catalysis material to be soaked in to contain treat in the organic solution of catalytic hydrogenation, feed hydrogen, carry out catalytic hydrogenation reaction.
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