CN105921179B - A kind of supported palladium multi-layer compound film and preparation method thereof - Google Patents
A kind of supported palladium multi-layer compound film and preparation method thereof Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 57
- 150000001875 compounds Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000758 substrate Substances 0.000 claims abstract description 30
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 25
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 229920000620 organic polymer Polymers 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 9
- 238000005859 coupling reaction Methods 0.000 claims abstract description 9
- 150000002940 palladium Chemical class 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 11
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010445 mica Substances 0.000 claims description 7
- 229910052618 mica group Inorganic materials 0.000 claims description 7
- 238000011010 flushing procedure Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims 3
- 238000000576 coating method Methods 0.000 claims 3
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 claims 3
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract description 3
- 239000007921 spray Substances 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000001338 self-assembly Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000002897 polymer film coating Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000003949 imides Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical class IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- OSCBARYHPZZEIS-UHFFFAOYSA-N phenoxyboronic acid Chemical class OB(O)OC1=CC=CC=C1 OSCBARYHPZZEIS-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- -1 temperature Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- YMTQRYMSWUKLIN-UHFFFAOYSA-N C1=CC=NC=C1.C1=CC=C2CC3=CC=CC=C3C2=C1 Chemical compound C1=CC=NC=C1.C1=CC=C2CC3=CC=CC=C3C2=C1 YMTQRYMSWUKLIN-UHFFFAOYSA-N 0.000 description 1
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical class C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 1
- CLWRFNUKIFTVHQ-UHFFFAOYSA-N [N].C1=CC=NC=C1 Chemical group [N].C1=CC=NC=C1 CLWRFNUKIFTVHQ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- JVXZJEUVAOVXIX-UHFFFAOYSA-N propan-2-one;pyridine Chemical compound CC(C)=O.C1=CC=NC=C1 JVXZJEUVAOVXIX-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
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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
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4266—Sonogashira-type, i.e. RY + HC-CR' triple bonds, in which R=aryl, alkenyl, alkyl and R'=H, alkyl or aryl
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a kind of supported palladium multi-layer compound film and preparation method thereof, after substrate surface sprays one layer of organic polymer film, substrate is repeatedly soaked in the palladium salt aqueous solution and Fluorenone pyridine solution, multi-layer compound film is formed by way of self assembly；The preparation process of the film substrate is simple and film performance is stable, can efficient catalytic carbon carbon coupling reaction, can reuse, so as to reduce the consumption of catalyst, reduce environmental pollution, had broad application prospects in catalytic field.
Description
Technical field
The invention belongs to film catalyst field, and in particular to a kind of supported palladium MULTILAYER COMPOSITE for catalyzed coupling reaction
Film substrate and preparation method thereof.
Background technology
The biphenol compound built by carbon carbon coupling reaction is widely present in daily life, such as agriculturalization
Product, pharmaceutical chemistry, natural products, commercial dyes, liquid crystal material and functional material etc., therefore, carbon carbon coupling reaction is that have
One of most important means in machine synthetic reaction, the also always research in the field such as catalytic chemistry, organic chemistry and materials chemistry
Focus.The cross-coupling reaction of transition metal or its complex catalysis is one of structure most important means of biphenyl structural, simultaneously
Some reactions for being difficult to realize by common synthesizing mean, using transition metal or its complex compound as catalyst then can compared with
Completed under temperate condition.Metal Pd or its complex compound are to be employed to be also the most extensively one of maximally efficient catalyst, one
Aspect is excellent because palladium catalyst has that high catalytic efficiency, selectivity are good, wide to the compatibility of substrate, functional group tolerance is good etc.
Point；On the other hand, be because we can by changing the series reaction condition such as part, solvent, temperature, alkali and additive,
So as to realize the conversion do not planted between valence state of palladium.
In recent years, homogeneous palladium catalysts and it is heterogeneous palladium catalyzed be obtained for very big development, homogeneous palladium catalysts due to
Reaction condition is gentle in the reaction, excellent catalytic effect, the advantages that selectivity is high, generation accessory substance is less are used widely, but
It is due to that it is difficult to be separated from product, the shortcomings such as the service life of catalyst is low limit its application, such as Zhao Xiuhua et al. public affairs
A kind of spiro fluorene pyridine palladium nano-particles opened and preparation method thereof (CN103951611A), high catalytic efficiency, but it is not easily recycled profit
With.Heterogeneous catalysis is easy to separate from product, and can be recycled for multiple times, but catalytic efficiency does not have homogeneous palladium to urge
Agent is good, and required reaction temperature is high, therefore, limits application industrially.With reference to existing homogeneous palladium catalysts and non-
The advantage and disadvantage of homogeneous palladium catalysts, present invention design have synthesized a kind of supported palladium multi-layer compound film substrate.This catalyst is
The advantages of possessing homogeneous palladium catalysts, while solve catalyst Recycling, homogeneous between heterogeneous catalysis
A bridge block is erected.
The content of the invention
The technical problems to be solved by the invention are, in view of the shortcomings of the prior art, there is provided one kind prepares that simple, cost is low
And there is the supported palladium multi-layer compound film of high catalytic efficiency for carbon-carbon bond coupling reaction.
The present invention is that technical scheme is used by solving above-mentioned technical problem：One kind can the coupling of efficient catalytic carbon carbon it is anti-
The preparation method for the supported palladium multi-layer compound film answered, comprises the following steps：
(1) one layer of organic polymer film coating is sprayed with substrate surface of the high pressure vacuum rifle in cleaning, then uses nitrogen
Stream drying；
(2) substrate for scribbling organic polymer film coating is dipped into the palladium salt aqueous solution, taken out after 25~45min,
The free palladium ion in surface is cleaned with distilled water, is dried up afterwards with nitrogen stream, the substrate is then placed on Fluorenone pyridine again
25~45min is soaked in acetone soln, taking-up dries up with distilled water flushing and with nitrogen stream, i.e., forming one layer in substrate surface bears
Carry the laminated film of palladium Fluorenone pyridine；
(3) surface is formed on the substrate of one layer of supported palladium Fluorenone pyridine laminated film in step (2), with high pressure vacuum rifle
One layer of organic polymer film coating is sprayed again；
(4) repeat step (2) and (3) repeatedly, multi-layer compound film, as described supported palladium multilayer are formed in substrate surface
Laminated film；
Preferably, the substrate is any one in monocrystalline silicon piece, mica sheet, quartz plate；
Preferably, the organic polymer is any one in polyimides or polystyrene；
Preferably, entitled 2,7- bis- (4- pyridines) -9-Fluorenone of the Fluorenone pyridine, its molecular formula is C23H14N2O, knot
Structure formula is as follows：
Preferably, described palladium salt is any one in palladium nitrate or palladium, and palladium ion is dense in the palladium salt aqueous solution
Spend for 0.05~0.1mmol/L；
Preferably, the Fluorenone pyridine is 0.05~0.1mmol/L in the concentration of acetone soln.
Preferably, the supported palladium multi-layer compound film can be used as catalyst efficient catalytic carbon-carbon bond coupling reaction.
The present invention also provides a kind of supported palladium multi-layer compound film, and the supported palladium multi-layer compound film is according to above-mentioned negative
The preparation method for carrying palladium multi-layer compound film is prepared.
Pyridine, five-membered ring, phenyl ring and the C=O bond contained in Fluorenone pyridine organic ligands forms the big pi bond of delocalization, makes
The d electron interactions that end group pyridine nitrogen atom forms specific coordinate bond, the big pi-electron of delocalization and palladium ion with palladium ion are obtained,
Change the valence shell level structure of palladium, so as to increase the catalytic activity of palladium.
Compared with prior art, advantages of the present invention is as follows：
(1) the organic ligand Fluorenone Pyridine Molecules symmetrical configuration, C=O bond be present on 9, this is to part electronics
Delocalization produces unique influence, and so as to be had an impact to the electronic energy level structure of part, thus the compound formed is with only
Special physicochemical properties.
(2) electron delocalization of the Fluorenone pyridine is strong and has symmetry, can be different at two with metal palladium ion
Direction is coordinated, the multi-layer compound film stable performance of formation.
(3) multi-layer compound film prepared shows higher catalytic activity in carbon carbon coupling reaction is catalyzed, and produces reaction
Rate can be recycled repeatedly and catalytic efficiency is without being decreased obviously, before having wide application in catalytic field up to more than 85%
Scape.
Brief description of the drawings
Fig. 1 be the embodiment of the present invention 1 circulation experiment in supported palladium multi-layer compound film ultraviolet-visible spectrum.
Embodiment
The present invention is described in further detail with reference to embodiments.
Embodiment 1
(1) a strata acid imide organic polymer film is sprayed in the monocrystalline silicon sheet surface of cleaning with high pressure vacuum rifle to apply
Layer, is then dried up with nitrogen stream；(2) monocrystalline silicon piece for scribbling polyimides organic polymer film coating is dipped into palladium
In the aqueous solution (concentration of palladium ion is 0.05mmol/L), taken out after 25min, the free palladium ion in surface cleaned with distilled water,
Dried up with nitrogen stream, then again soak this monocrystalline silicon piece in the acetone soln (0.05mmol/L) of Fluorenone pyridine afterwards
25min, taking-up is clean with distilled water flushing and is dried up with nitrogen stream, i.e., forms one layer of supported palladium Fluorenone pyrrole in monocrystalline silicon sheet surface
The laminated film of pyridine；(3) surface is formed on the monocrystalline silicon piece of one layer of supported palladium Fluorenone pyridine laminated film in step (2), is used
High pressure vacuum rifle sprays a strata acid imide organic polymer film coating again；(4) repeat step (2) and (3) repeatedly, in monocrystalline
Silicon chip surface forms multi-layer compound film, as described supported palladium multi-layer compound film.
Embodiment 2
(1) strata styrene organic polymer film painting is sprayed in the mica sheet surface of cleaning with high pressure vacuum rifle
Layer, is then dried up with nitrogen stream；(2) mica sheet for scribbling polystyrene organic polymer film coating is dipped into palladium nitrate water
In solution (concentration of palladium ion is 0.1mmol/L), taken out after 45min, clean the free palladium ion in surface with distilled water, afterwards
Dried up with nitrogen stream, then again by this mica sheet Fluorenone pyridine acetone soln (concentration of Fluorenone pyridine is 0.1mmol/L)
Middle immersion 45min, taking-up is clean with distilled water flushing and is dried up with nitrogen stream, i.e., forms one layer of supported palladium fluorenes in mica sheet surface
The laminated film of ketone pyridine；(3) surface is formed on the mica sheet of one layer of supported palladium Fluorenone pyridine laminated film in step (2),
A strata styrene organic polymer film coating is sprayed again with high pressure vacuum rifle；(4) repeat step (2) and (3) repeatedly, in cloud
Master surface forms multi-layer compound film, as described supported palladium multi-layer compound film.
Embodiment 3
(1) applied with quartz plate surface spraying one strata acid imide organic polymer film of the high pressure vacuum rifle in cleaning
Layer, is then dried up with nitrogen stream；(2) quartz plate for scribbling polyimides organic polymer film coating is dipped into palladium nitrate water
In solution (concentration of palladium ion is 0.08mmol/L), taken out after 30min, the free palladium ion in surface is cleaned with distilled water, it
Dried up afterwards with nitrogen stream, then by this quartz plate, in the acetone soln of Fluorenone pyridine, (concentration of Fluorenone pyridine is 0.07mmol/ again
L immersion 35min in), taking-up is clean with distilled water flushing and is dried up with nitrogen stream, i.e., forms one layer of supported palladium on quartz plate surface
The laminated film of Fluorenone pyridine；(3) surface forms the quartz plate of one layer of supported palladium Fluorenone pyridine laminated film in step (2)
On, a strata acid imide organic polymer film coating is sprayed again with high pressure vacuum rifle；(4) repeat step (2) and (3) repeatedly,
Multi-layer compound film, as described supported palladium multi-layer compound film are formed on quartz plate surface.
With embodiment 1, exemplified by supported palladium multi-layer compound film prepared by embodiment 2, and embodiment 3, catalysis carbon-carbon bond is even
Connection reaction：
The supported palladium multi-layer compound film prepared using above-described embodiment 1 carries out catalytic reaction：By 1.0mmol 4- iodobenzenes
Ether, 1.2mmol phenyl boric acids and 2.0mmol Na2CO3It is put into reaction vessel, adds 4mL water, 3mL ethanol, then will implements
Supported palladium multi-layer compound film substrate prepared by example 1 is put into reaction vessel, with the palladium multi-layer compound film loaded on substrate
As catalyst, 4h, yield 99% are reacted at 90 DEG C.Reaction equation is as follows：
Circular response：After above-mentioned reaction terminates, take out substrate and dried with distilled water flushing, nitrogen stream；This substrate is put
Enter to fill 1.0mmol 4- iodobenzenes ether, 1.2mmol phenyl boric acids and 2.0mmol Na2CO3, 4mL water and 3mL ethanol reaction hold
In device, 4h is reacted at 90 DEG C, obtains yield 97%；Aforesaid operations are repeated, are the circulation Catalysis experiments of the substrate, the substrate follows
The gained yields of ring 5 times remain above 90% (Fig. 1 be the supported palladium multi-layer compound film substrate after recycling every time it is ultraviolet-can
See spectrum spectrogram).
The supported palladium multi-layer compound film prepared using above-described embodiment 2 carries out catalytic reaction, and reaction condition is：Will
1.0mmol4- bromobenzenes, 1.5mmol styrene and 2.0mmol K2CO3It is put into reaction vessel, adds 7mL N, N- dimethyl methyls
React, then supported palladium multi-layer compound film substrate prepared by embodiment 2 is put into reaction vessel, with base in acid amides (DMF)
The palladium multi-layer compound film loaded on piece reacts 16h, yield 86% as catalyst at 140 DEG C.Reaction equation is such as
Under：
The supported palladium multi-layer compound film prepared using above-described embodiment 3 carries out catalytic reaction, and reaction condition is：Will
1.0mmol4- iodobenzenes, 1.2mmol phenylacetylenes and 2.0mmol K2CO3It is put into reaction vessel, adds in 7mL ethanol, then will
Supported palladium multi-layer compound film substrate prepared by embodiment 3 is put into reaction vessel, with the palladium MULTILAYER COMPOSITE loaded on substrate
Film reacts 10h, yield 90% as catalyst at 80 DEG C.Reaction equation is as follows：
Claims (2)
1. a kind of supported palladium multi-layer compound film, it is characterised in that the preparation method of the supported palladium multi-layer compound film includes
Following steps：
(1) one layer of organic polymer Kapton coating, Ran Houyong are sprayed with substrate surface of the high pressure vacuum rifle in cleaning
Nitrogen stream dries up；
(2) substrate for scribbling organic polymer Kapton coating is dipped into the palladium salt aqueous solution, taken after 25~45min
Go out, clean the free palladium ion in surface with distilled water, dried up afterwards with nitrogen stream, the substrate is then placed on Fluorenone pyridine again
Acetone soln in soak 25~45min, taking-up dries up with distilled water flushing and with nitrogen stream, i.e., forms one layer in substrate surface
The laminated film of supported palladium Fluorenone pyridine；
(3) surface is formed on the substrate of one layer of supported palladium Fluorenone pyridine laminated film in step (2), is sprayed again with high pressure vacuum rifle
Apply one layer of organic polymer Kapton coating；
(4) repeat step (2) and (3) repeatedly, multi-layer compound film, as described supported palladium MULTILAYER COMPOSITE are formed in substrate surface
Film；
The substrate is any one in monocrystalline silicon piece, mica sheet, quartz plate；
Polyimides can also be substituted for polystyrene simultaneously described in step (1) and (3)；
Entitled 2,7- bis- (4- pyridines) -9-Fluorenone of the Fluorenone pyridine, its molecular formula is C23H14N2O；
The palladium salt is any one in palladium nitrate or palladium, in the palladium salt aqueous solution concentration of palladium ion be 0.05~
0.1mmol/L；
The Fluorenone pyridine is 0.05~0.1mmol/L in the concentration of acetone soln.
2. a kind of a kind of supported palladium multi-layer compound film as claimed in claim 1, it is characterised in that the supported palladium multilayer is answered
Catalyst efficient catalytic carbon-carbon bond coupling reaction can be used as by closing film.
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| CN103934022A (en) * | 2013-12-04 | 2014-07-23 | 宁波大学 | Palladium composite multilayered film |
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| A highly active multi-usable palladium pyridylfluorene film-based catalyst for C–C cross-coupling reactions;Xiuhua Zhao et al.;《Appl. Organometal. Chem.》;20151014;第29卷;第840–845页 * |
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