CN105921179A - Palladium-supporting multilayer composite film and preparation method thereof - Google Patents
Palladium-supporting multilayer composite film and preparation method thereof Download PDFInfo
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- CN105921179A CN105921179A CN201610281804.2A CN201610281804A CN105921179A CN 105921179 A CN105921179 A CN 105921179A CN 201610281804 A CN201610281804 A CN 201610281804A CN 105921179 A CN105921179 A CN 105921179A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title abstract description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 54
- 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 27
- 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 25
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005859 coupling reaction Methods 0.000 claims abstract description 10
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 9
- 150000002940 palladium Chemical class 0.000 claims abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 114
- 229910052763 palladium Inorganic materials 0.000 claims description 57
- 150000001875 compounds Chemical class 0.000 claims description 38
- 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
- 229920000620 organic polymer Polymers 0.000 claims description 17
- 239000002897 polymer film coating Substances 0.000 claims description 15
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000010445 mica Substances 0.000 claims description 8
- 229910052618 mica group Inorganic materials 0.000 claims description 8
- 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
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000011010 flushing procedure Methods 0.000 claims description 6
- 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
- 239000007921 spray Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002120 nanofilm Substances 0.000 abstract 1
- 238000001338 self-assembly Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 20
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000003949 imides Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 3
- 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
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-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
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 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
- 238000002474 experimental method Methods 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- -1 temperature Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
-
- B01J35/59—
-
- 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
-
- 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
-
- 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
-
- 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
- B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
-
- 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
- B01J2231/4266—Sonogashira-type, i.e. RY + HC-CR' triple bonds, in which R=aryl, alkenyl, alkyl and R'=H, alkyl or aryl
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
Abstract
The invention discloses a palladium-supporting multilayer composite film and a preparation method thereof. According to the invention, a layer of organic high-molecular film is sprayed onto the surface of a substrate; the substrate is repeatedly soaked in a palladium salt water solution and a fluorenone pyridine solution; and the multilayer composite film is formed with a self-assembly manner. The preparation process of the film substrate is simple, and the performance of the film is stable. The film assists in highly effectively catalyzing a carbon-carbon coupling reaction, and can be repeatedly used, such that catalyst consumption is reduced, and environment pollution is reduced. The film can be widely applied in the field of catalysis.
Description
Technical field
The invention belongs to film catalyst field, be specifically related to a kind of supported palladium multi-layer compound film for catalyzed coupling reaction
Substrate and preparation method thereof.
Background technology
The biphenol compound built by carbon carbon coupling reaction is widely present in daily life, such as agricultural chemicals,
Pharmaceutical chemistry, natural products, commercial dyes, liquid crystal material and functional material etc., therefore, carbon carbon coupling reaction is organic
The research heat in the fields such as one of most important means in synthetic reaction, the most always catalytic chemistry, organic chemistry and materials chemistry
Point.The cross-coupling reaction of transition metal or its complex catalysis is to build one of most important means of biphenyl structural, simultaneously certain
Be difficult to the reaction realized a bit by common synthesizing mean, employing transition metal or its complex compound then can be warmer as catalyst
Complete under the conditions of with.Metal Pd or its complex compound are that being employed is the most also one of maximally efficient catalyst, a side
Face be because palladium catalyst have catalytic efficiency high, selectively the best, to substrate compatible wide, that functional group tolerance is good etc. is excellent
Point；On the other hand, being because us can be by changing the series reaction bars such as part, solvent, temperature, alkali and additive
Part, thus realize the conversion not planting between valence state of palladium.
In recent years, homogeneous palladium catalysts and heterogeneous palladium catalyzed be obtained for the biggest development, homogeneous palladium catalysts is due to instead
The advantages such as middle reaction condition gentleness, excellent catalytic effect, the highest, generation accessory substance is less are answered to be used widely, but
Owing to it is difficult to separate from product, the shortcomings such as service life of catalyst is low limit its application, as Zhao Xiuhua et al. is open
A kind of spiral shell fluorenes pyridine palladium nano-particles and preparation method thereof (CN103951611A), catalytic efficiency is high, but is not easily recycled profit
With.Heterogeneous catalysis is prone to from product separate, and can be recycled for multiple times, but catalytic efficiency does not has homogeneous palladium
Catalyst is good, and required reaction temperature is high, therefore, limits application industrially.In conjunction with existing homogeneous palladium catalysts
With the pluses and minuses of heterogeneous palladium catalyst, the present invention designs and has synthesized a kind of supported palladium multi-layer compound film substrate.This catalysis
Agent i.e. has the advantage of homogeneous palladium catalysts, solves catalyst Recycling simultaneously, at homogeneous and heterogeneous catalysis
Between erected a bridge block.
Summary of the invention
The technical problem to be solved is, for the deficiencies in the prior art, it is provided that one is prepared simply, low cost also
And carbon-carbon bond coupling reaction is had to the supported palladium multi-layer compound film of high catalytic efficiency.
The present invention solves that the technical scheme that above-mentioned technical problem is used is: a kind of can efficient catalytic carbon carbon coupling reaction
The preparation method of supported palladium multi-layer compound film, comprises the following steps:
(1) with high pressure vacuum rifle at clean substrate surface one layer of organic polymer film coating of spraying, then blow with nitrogen stream
Dry；
(2) substrate scribbling organic polymer film coating is dipped in the palladium salt aqueous solution, takes out after 25～45min, use
Distilled water cleans the palladium ion that surface is free, dries up with nitrogen stream afterwards, this substrate is placed on the third of Fluorenone pyridine the most again
Soaking 25～45min in ketone solution, taking-up distilled water flushing also dries up with nitrogen stream, i.e. forms one layer at substrate surface and bears
Carry the laminated film of palladium Fluorenone pyridine；
(3) in step (2), surface is formed on the substrate of one layer of supported palladium Fluorenone pyridine laminated film, uses high pressure vacuum rifle
Spray one layer of organic polymer film coating again；
(4) repeat step (2) and (3) repeatedly, form multi-layer compound film at substrate surface, be described supported palladium many
Layer laminated film；
Preferably, any one during described substrate is monocrystalline silicon piece, mica sheet, quartz plate；
Preferably, any one during described organic polymer is polyimides or polystyrene；
Preferably, entitled the 2 of described Fluorenone pyridine, 7-bis-(4-pyridine)-9-Fluorenone, its molecular formula is C23H14N2O, structure
Formula is as follows:
Preferably, described palladium salt is any one in palladium nitrate or palladium, and in the palladium salt aqueous solution, the concentration of palladium ion is
0.05～0.1mmol/L；
Preferably, described Fluorenone pyridine is 0.05～0.1mmol/L in the concentration of acetone soln.
Preferably, described supported palladium multi-layer compound film can be as catalyst efficient catalytic carbon-carbon bond coupling reaction.
The present invention also provides for a kind of supported palladium multi-layer compound film, and described supported palladium multi-layer compound film is according to above-mentioned supported palladium
The preparation method of multi-layer compound film prepares.
Pyridine, five-membered ring, phenyl ring and the C=O bond contained in Fluorenone pyridine organic ligands defines delocalization big π key so that end
Yl pyridines nitrogen-atoms and palladium ion form specific coordinate bond, the big pi-electron of delocalization and the d electron interaction of palladium ion, change
The valence shell level structure of palladium, thus increase the catalysis activity of palladium.
Compared with prior art, advantages of the present invention is as follows:
(1) described organic ligand Fluorenone Pyridine Molecules symmetrical configuration, 9 exist C=O bond, this to part electronics from
Territory property produces unique impact, thus the electronic energy level structure of part is produced impact, thus the compound formed has uniqueness
Physicochemical properties.
(2) electron delocalization of described Fluorenone pyridine is strong and has symmetry, can be with Metal Palladium ion at two different directions
It is coordinated, the multi-layer compound film stable performance of formation.
(3) multi-layer compound film prepared shows higher catalysis activity in catalysis carbon carbon coupling reaction, makes the reaction yield can
Reach more than 85%, it is possible to recycle repeatedly and catalytic efficiency is without being decreased obviously, have broad application prospects at catalytic field.
Accompanying drawing explanation
Fig. 1 be the embodiment of the present invention 1 circulation experiment in the ultraviolet-visible spectrum of supported palladium multi-layer compound film.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
(1) a strata acid imide organic polymer film coating is sprayed, so with high pressure vacuum rifle at clean monocrystalline silicon sheet surface
Dry up with nitrogen stream afterwards；(2) monocrystalline silicon piece scribbling polyimides organic polymer film coating is dipped into palladium water-soluble
In liquid (concentration of palladium ion is 0.05mmol/L), take out after 25min, clean, with distilled water, the palladium ion that surface is free, it
Dry up with nitrogen stream afterwards, this monocrystalline silicon piece soaked in the acetone soln (0.05mmol/L) of Fluorenone pyridine 25min the most again,
Taking-up distilled water flushing is clean and dries up with nitrogen stream, i.e. forms answering of one layer of supported palladium Fluorenone pyridine at monocrystalline silicon sheet surface
Close film；(3) in step (2), surface is formed on the monocrystalline silicon piece of one layer of supported palladium Fluorenone pyridine laminated film, with height
Pressure vacuum gun sprays a strata acid imide organic polymer film coating again；(4) step (2) and (3) is repeated repeatedly,
Monocrystalline silicon sheet surface forms multi-layer compound film, is described supported palladium multi-layer compound film.
Embodiment 2
(1) a strata styrene organic polymer film coating is sprayed, so with high pressure vacuum rifle in clean mica sheet surface
Dry up with nitrogen stream afterwards；(2) mica sheet scribbling polystyrene organic polymer film coating is dipped into palladium nitrate aqueous solution
In (concentration of palladium ion is 0.1mmol/L), take out after 45min, clean, with distilled water, the palladium ion that surface is free, use afterwards
Nitrogen stream dries up, the most again by the leaching in the acetone soln (concentration of Fluorenone pyridine is 0.1mmol/L) of Fluorenone pyridine of this mica sheet
Bubble 45min, taking-up distilled water flushing is clean and dries up with nitrogen stream, i.e. forms one layer of supported palladium Fluorenone in mica sheet surface
The laminated film of pyridine；(3) in step (2), surface is formed on the mica sheet of one layer of supported palladium Fluorenone pyridine laminated film,
A strata styrene organic polymer film coating is sprayed again with high pressure vacuum rifle；(4) step (2) and (3) is repeated repeatedly,
Form multi-layer compound film in mica sheet surface, be described supported palladium multi-layer compound film.
Embodiment 3
(1) with using the high pressure vacuum rifle quartz plate surface spraying one strata acid imide organic polymer film coating in cleaning, so
Dry up with nitrogen stream afterwards；(2) quartz plate scribbling polyimides organic polymer film coating is dipped into palladium nitrate aqueous solution
In (concentration of palladium ion is 0.08mmol/L), take out after 30min, clean, with distilled water, the palladium ion that surface is free, afterwards
Dry up with nitrogen stream, the most again by this quartz plate at the acetone soln (concentration of Fluorenone pyridine is 0.07mmol/L) of Fluorenone pyridine
Middle immersion 35min, taking-up distilled water flushing is clean and dries up with nitrogen stream, i.e. forms one layer of supported palladium on quartz plate surface
The laminated film of Fluorenone pyridine；(3) in step (2), surface forms the quartz of one layer of supported palladium Fluorenone pyridine laminated film
On sheet, spray a strata acid imide organic polymer film coating again with high pressure vacuum rifle；(4) step (2) and (3) is repeated
Repeatedly, form multi-layer compound film on quartz plate surface, be described supported palladium multi-layer compound film.
With embodiment 1, as a example by embodiment 2, and the supported palladium multi-layer compound film of embodiment 3 preparation, it is catalyzed carbon-carbon bond coupling
Reaction:
The supported palladium multi-layer compound film using above-described embodiment 1 preparation carries out catalytic reaction: by 1.0mmol 4-iodobenzene ether,
1.2mmol phenyl boric acid and 2.0mmol Na2CO3Put in reaction vessel, add 4mL water, 3mL ethanol, then will
The supported palladium multi-layer compound film substrate of embodiment 1 preparation is put in reaction vessel, with the palladium MULTILAYER COMPOSITE loaded on substrate
Film, as catalyst, reacts 4h at 90 DEG C, and productivity is 99%.Reaction equation is as follows:
Circular response: after above-mentioned reaction terminates, takes out substrate and with distilled water flushing, nitrogen fluidized drying；This substrate is put into
Fill 1.0mmol 4-iodobenzene ether, 1.2mmol phenyl boric acid and 2.0mmol Na2CO3, 4mL water and 3mL ethanol
In reaction vessel, at 90 DEG C, react 4h, obtain productivity 97%；Repeating aforesaid operations, the circulation catalysis being this substrate is real
Testing, this substrate 5 gained productivity of circulation remain above 90%, and (Fig. 1 is this supported palladium multi-layer compound film after every time recycling
The ultraviolet-visible spectrum spectrogram of substrate).
The supported palladium multi-layer compound film using above-described embodiment 2 preparation carries out catalytic reaction, and reaction condition is: by 1.0mmol
4-bromobenzene, 1.5mmol styrene and 2.0mmol K2CO3Put in reaction vessel, add 7mL N, N-dimethyl formyl
Reaction in amine (DMF), the supported palladium multi-layer compound film substrate then embodiment 2 prepared is put in reaction vessel, with base
The palladium multi-layer compound film loaded on sheet, as catalyst, reacts 16h at 140 DEG C, and productivity is 86%.Reactional equation
Formula is as follows:
The supported palladium multi-layer compound film using above-described embodiment 3 preparation carries out catalytic reaction, and reaction condition is: by 1.0mmol
4-iodobenzene, 1.2mmol phenylacetylene and 2.0mmol K2CO3Put in reaction vessel, add in 7mL ethanol, then will
The supported palladium multi-layer compound film substrate of embodiment 3 preparation is put in reaction vessel, with the palladium MULTILAYER COMPOSITE loaded on substrate
Film, as catalyst, reacts 10h at 80 DEG C, and productivity is 90%.Reaction equation is as follows:
Claims (3)
1. the preparation method of a supported palladium multi-layer compound film, it is characterised in that the system of described supported palladium multi-layer compound film
Preparation Method comprises the following steps:
(1) with high pressure vacuum rifle at clean substrate surface one layer of organic polymer film coating of spraying, then blow with nitrogen stream
Dry；
(2) substrate scribbling organic polymer film coating is dipped in the palladium salt aqueous solution, takes out after 25～45min, use
Distilled water cleans the palladium ion that surface is free, dries up with nitrogen stream afterwards, this substrate is placed on the third of Fluorenone pyridine the most again
Soaking 25～45min in ketone solution, taking-up distilled water flushing also dries up with nitrogen stream, i.e. forms one layer at substrate surface and bears
Carry the laminated film of palladium Fluorenone pyridine；
(3) in step (2), surface is formed on the substrate of one layer of supported palladium Fluorenone pyridine laminated film, uses high pressure vacuum rifle
Spray one layer of organic polymer film coating again；
(4) repeat step (2) and (3) repeatedly, form multi-layer compound film at substrate surface, be described supported palladium many
Layer laminated film；
Described substrate is any one in monocrystalline silicon piece, mica sheet, quartz plate；
Described organic polymer is any one in polyimides or polystyrene；
Entitled the 2 of described Fluorenone pyridine, 7-bis-(4-pyridine)-9-Fluorenone, its molecular formula is C23H14N2O；
Described palladium salt is any one in palladium nitrate or palladium, and in the palladium salt aqueous solution, the concentration of palladium ion is 0.05～0.1
mmol/L；
Described Fluorenone pyridine is 0.05～0.1mmol/L in the concentration of acetone soln.
2. the preparation method of a supported palladium multi-layer compound film as claimed in claim 1, it is characterised in that described load
Palladium multi-layer compound film can be as catalyst efficient catalytic carbon-carbon bond coupling reaction.
3. a supported palladium multi-layer compound film, it is characterised in that supported palladium multilayer according to claim 1 and 2 is multiple
The preparation method closing film prepares.
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| CN108705838A (en) * | 2018-05-29 | 2018-10-26 | 中新科技集团股份有限公司 | A kind of preparation method of laminated film |
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| WO2009071997A2 (en) * | 2007-12-06 | 2009-06-11 | Centre National De La Recherche Scientifique (C.N.R.S.) | Iron and copper catalytic systems for cross-coupling reactions |
| CN103127954A (en) * | 2013-01-28 | 2013-06-05 | 宁波大学 | Preparation method of multi-layer composite film capable of catalyzing C-C key coupling reaction |
| CN103934022A (en) * | 2013-12-04 | 2014-07-23 | 宁波大学 | Palladium composite multilayered film |
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2016
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| WO2009071997A2 (en) * | 2007-12-06 | 2009-06-11 | Centre National De La Recherche Scientifique (C.N.R.S.) | Iron and copper catalytic systems for cross-coupling reactions |
| CN103127954A (en) * | 2013-01-28 | 2013-06-05 | 宁波大学 | Preparation method of multi-layer composite film capable of catalyzing C-C key coupling reaction |
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| CN108705838A (en) * | 2018-05-29 | 2018-10-26 | 中新科技集团股份有限公司 | A kind of preparation method of laminated film |
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