CN107115891A - A kind of mesoporous organic metal palladium catalyst and preparation method thereof - Google Patents
A kind of mesoporous organic metal palladium catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN107115891A CN107115891A CN201710474670.0A CN201710474670A CN107115891A CN 107115891 A CN107115891 A CN 107115891A CN 201710474670 A CN201710474670 A CN 201710474670A CN 107115891 A CN107115891 A CN 107115891A
- Authority
- CN
- China
- Prior art keywords
- present
- preparation
- catalyst
- mesoporous
- organic metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
- 239000002184 metal Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 49
- 230000032683 aging Effects 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002861 polymer material Substances 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 9
- 238000007306 functionalization reaction Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- XKWSQIMYNVLGBO-UHFFFAOYSA-N 5-nitro-1h-pyridin-2-one Chemical class OC1=CC=C([N+]([O-])=O)C=N1 XKWSQIMYNVLGBO-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract description 10
- 238000007184 Barbier reaction Methods 0.000 abstract description 8
- 230000004044 response Effects 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 230000001788 irregular Effects 0.000 abstract description 4
- 239000013335 mesoporous material Substances 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 4
- 239000012798 spherical particle Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000000903 blocking effect Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000012265 solid product Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000000926 separation method Methods 0.000 description 11
- 238000012545 processing Methods 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000013019 agitation Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910002666 PdCl2 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241001269238 Data Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000736199 Paeonia Species 0.000 description 2
- 235000006484 Paeonia officinalis Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- BIWQNIMLAISTBV-UHFFFAOYSA-N (4-methylphenyl)boronic acid Chemical class CC1=CC=C(B(O)O)C=C1 BIWQNIMLAISTBV-UHFFFAOYSA-N 0.000 description 1
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- -1 aryl boric acids Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- OSCBARYHPZZEIS-UHFFFAOYSA-N phenoxyboronic acid Chemical class OB(O)OC1=CC=CC=C1 OSCBARYHPZZEIS-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/51—Spheres
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a kind of mesoporous organic metal palladium catalyst and preparation method thereof.The organic metal active sites for the catalyst that the present invention is provided are embedded in the ball shaped nano short-bore road of mesoporous material hole wall, and active sites are uniformly dispersed, and do not result in duct blocking；Catalyst regular appearance and duct is shorter, is conducive to the diffusion and absorption of reactant molecule, the catalyst with irregular pattern for making its catalytic performance more traditional improves, and may be reused.From the result of embodiment, the catalyst that the present invention is obtained is spherical, and there is mesoporous presence on surface, and spherical particle diameter is about 200~400nm；The conversion ratio of the Suzuki reactions of catalysis differential responses raw material is all higher than 85%, and yield is all higher than 85%；The conversion ratio for being catalyzed Barbier reactions is maximum up to 99%, and yield reaches as high as 85%.
Description
Technical field
The present invention relates to catalyst technical field, more particularly to a kind of mesoporous organic metal palladium catalyst and its preparation side
Method.
Background technology
The reaction such as Sonogashira, Suzuki, Heck of the catalysis such as transition metal Rh, Pd, Ru is important C-C couplings
The type of reaction, there is very extensive utilization in terms of synthetic polymer, agricultural chemicals, medicine.But such reaction is to have mostly
Carried out in machine solvent, reacted organic liquid waste can not only increase production cost because of last handling process, and easily cause serious
Environmental pollution.
Water be it is a kind of be widely present clean, nontoxic material, replace organic solvent to reduce and be produced into water
This, reduces environmental pollution.However, use is homogeneous organo-metallic catalyst mostly to the reaction of aqueous medium cleaning at present, it is such to urge
The separation of agent hardly possible, recovery and reuse, easily bring heavy metal pollution to environment.Heterogeneous catalysis can realize catalyst
Reuse, but its catalytic activity and selectivity it is all relatively low.Ordered mesoporous silicon heterogeneous catalysis pattern used at present
It is irregular, and duct is longer, there is certain obstruction to the diffusion of reactant molecule, so as to influence its catalytic performance.
The content of the invention
It is an object of the invention to provide a kind of mesoporous organic metal palladium catalyst and preparation method thereof, what the present invention was provided
Catalyst regular appearance, duct is shorter, and catalytic performance is excellent.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of preparation method of mesoporous organic metal palladium catalyst, comprise the following steps：
2- hydroxyl -5- nitropyridines, formaldehyde and phenol are subjected to polymerisation in alkali lye, presoma is obtained；
The presoma and template are combined, precursor complex is obtained；
The precursor complex is subjected to hydro-thermal ageing in water, obtains being aged presoma；
The ageing presoma is calcined, mesoporous polymer material is obtained；
The mesoporous polymer material is subjected to functionalization in the solution of palladium source, mesoporous organic metal palladium catalyst is obtained.
It is preferred that, the mass ratio of the 2- hydroxyls -5- nitropyridines and phenol is (10~25):(50~70).
It is preferred that, the formaldehyde is formalin, and the mass concentration of the formalin is 35~40%；
The quality of the 2- hydroxyls -5- nitropyridines and the volume ratio of formalin are (10~25) g:(180~250)
mL。
It is preferred that, the temperature of the polymerisation is 80~90 DEG C, and the time is 0.1~1h.
It is preferred that, the mass ratio of the 2- hydroxyls -5- nitropyridines and template is (10~25):(90~100).
It is preferred that, the compound temperature is 80~90 DEG C, and the time is 15~20h.
It is preferred that, the volume ratio of precursor complex and water is (40~50) in the hydro-thermal ageing process:(130~
150)；
The temperature of the hydro-thermal ageing is 120~140 DEG C, and the time is 20~30h.
It is preferred that, the temperature of the roasting is 370~390 DEG C, and the time is 5~10h.
It is preferred that, the mass ratio in the mesoporous polymer material and palladium source is (480~520):(80~100)；
The time of the functionalization is 20~30h.
The mesoporous organic metal palladium obtained present invention also offers preparation method described in above-mentioned technical proposal any one is urged
Agent.
The invention provides a kind of mesoporous organic metal palladium catalyst.The organic metal activity for the catalyst that the present invention is provided
Position is embedded in the ball shaped nano short-bore road of mesoporous material hole wall, and active sites are uniformly dispersed, and does not result in duct blocking；Catalyst pattern
It is regular and duct is shorter, be conducive to the diffusion and absorption of reactant molecule, make its catalytic performance it is more traditional there is irregular shape
The catalyst of looks improves, and may be reused.From the result of embodiment, the catalyst that the present invention is obtained is
Spherical, there is mesoporous presence on surface, and spherical particle diameter is about 200~400nm；It is catalyzed turn of the Suzuki reactions of differential responses raw material
Rate is all higher than 85%, and yield is all higher than 85%；The conversion ratio for being catalyzed Barbier reactions is maximum up to 99%, and yield highest can
Up to 85%.
Present invention also offers a kind of preparation method of mesoporous organic metal palladium catalyst.The present invention synthesizes N and mixed first
The spherical short-bore road carrier of miscellaneous meso-porous nano, is then loaded to nano Pd particle (II) on prepared mesoporous supports using infusion process
Catalyst is made.The preparation method that the present invention is provided is simple to operate, convenient to carry out.
Brief description of the drawings
Fig. 1 is the XRD spectra of 2HP-5NG-MPNs and Pd (II) -2HP-5NG-MPNs in embodiment 1；
The TEM spectrograms that Fig. 2 is Pd (II) -2HP-5NG-MPNs in embodiment 1；
The XPS spectrum figure that Fig. 3 is Pd (II) -2HP-5NG-MPNs in embodiment 1；
Fig. 4 is the nitrogen adsorption desorption curve of 2HP-5NG-MPNs and Pd (II) -2HP-5NG-MPNs in embodiment 1；
The catalytic life test result that Fig. 5 is Pd (II) -2HP-5NG-MPNs in embodiment 1.
Embodiment
The invention provides a kind of preparation method of mesoporous organic metal palladium catalyst, comprise the following steps：
2- hydroxyl -5- nitropyridines, formaldehyde and phenol are subjected to polymerisation in alkali lye, presoma is obtained；
The presoma and template are combined, precursor complex is obtained；
The precursor complex is subjected to hydro-thermal ageing in water, obtains being aged presoma；
The ageing presoma is calcined, mesoporous polymer material is obtained；
The mesoporous polymer material is subjected to functionalization in the solution of palladium source, mesoporous organic metal palladium catalyst is obtained.
2- hydroxyl -5- nitropyridines, formaldehyde and phenol are carried out polymerisation by the present invention in alkali lye, obtain presoma.
Order by merging of the present invention to the 2- hydroxyls -5- nitropyridines, formaldehyde, phenol and alkali lye does not have any requirement, and four can
To carry out in any order.In the specific embodiment of the invention, the present invention is preferably first by 2- hydroxyl -5- nitropyridines and benzene
Phenol is mixed, and is then mixed, is finally mixed again with alkali lye with formaldehyde again；The present invention is more preferably by 2- hydroxyl -5- nitropyridines and benzene
The mixture of phenol is warming up to after 60 DEG C and mixed again with formaldehyde.
In the present invention, the formaldehyde is preferably added in the form of formalin, and the quality of the formalin is dense
Degree is preferably 35~40%, more preferably 37%.In the present invention, the quality and formaldehyde of the 2- hydroxyls -5- nitropyridines are molten
The volume ratio of liquid is preferably (10~25) g:(180~250) mL, more preferably 18g:210mL.
In the present invention, the mass ratio of the 2- hydroxyls -5- nitropyridines and phenol is preferably (10~25):(50~
70), more preferably (18~23):(55~65), most preferably 20:60.
In the present invention, the alkali lye is preferably that sodium hydrate aqueous solution, potassium hydroxide aqueous solution, sodium hydroxide ethanol are molten
Liquid or potassium hydroxide-ethanol solution；The concentration of the alkali lye is preferably 0.1~0.5M, specifically can for 0.1M, 0.2M,
0.3M, 0.4M or 0.5M.In the present invention, the quality of the 2- hydroxyls -5- nitropyridines and the volume ratio of alkali lye are preferably (10
~25) g:(1~2) L, more preferably 18g:1.5L.
In the present invention, the temperature of the polymerisation is preferably 80~90 DEG C, more preferably 85 DEG C；The polymerisation
Time be preferably 0.1~1h, more preferably 0.2~0.8h, most preferably 0.5h.In the present invention, the polymerisation is obtained
The construction unit of the presoma arrived is preferably as shown in formula I：
Obtain after the presoma, the presoma and template are combined by the present invention, obtain precursor complex.
In the present invention, the template is preferably F127 or P123, more preferably F127.The present invention does not have to the source of the template
There is particular/special requirement, using the above-mentioned template of commercial source well-known to those skilled in the art.In the present invention, it is described
Preferably addition is used template in form of an aqueous solutions；The quality of template and the volume ratio of water are excellent in the template aqueous solution
Elect (0.5~1.5) g as:(10~20) mL, more preferably 0.96g:15mL.
In the present invention, the mass ratio of the 2- hydroxyls -5- nitropyridines and template is preferably (10~25):(90~
100), more preferably (13~23):(93~98), most preferably 18:96.Template described in preferred pair of the present invention and presoma
Mixture carries out thermal agitation processing, is combined again after then thermal agitation processing product is mixed with dilution water.
In the present invention, the temperature of the thermal agitation processing is preferably 75~85 DEG C, more preferably 80 DEG C；The rotating speed of the thermal agitation processing
Preferably 300~400rpm, more preferably 320~360rpm；The time of the thermal agitation processing is preferably 1~3h, more preferably
For 1.5~2.5h, most preferably 2h.In the present invention, the thermal agitation processing procedure causes presoma to be gathered in template week
Enclose.In the present invention, the quality of the template and the volume ratio of dilution water are preferably (0.5~1.5) g:(30~70) mL, more
Preferably 0.96g:50mL.In the present invention, the thermal agitation processing product with dilution water mix that thermal agitation can be reduced
Handle the concentration of product so that mixing is more uniformly distributed.
In the present invention, the compound temperature is preferably 80~90 DEG C, more preferably 85 DEG C；The compound time is excellent
Elect 15~20h, more preferably 16~18h as.In present invention specific implementation, described be combined preferably is carried out under agitation,
The rotating speed of the stirring is preferably 300~400rpm, more preferably 320~360rpm.
Obtain after the precursor complex, the precursor complex is carried out hydro-thermal ageing by the present invention in water, is obtained
To ageing presoma.In the present invention, the precursor complex in the hydro-thermal ageing process preferably refers to that above-mentioned be combined obtains
Precursor complex product system, i.e. product mixtures；The volume of precursor complex and water in the hydro-thermal ageing process
Than being preferably (40~50):(130~150), more preferably 44:140.
In the present invention, the temperature of the hydro-thermal ageing is preferably 120~140 DEG C, more preferably 125~135 DEG C, optimal
Elect 130 DEG C as；The time of the hydro-thermal ageing is preferably 20~30h, more preferably 22~28h, most preferably 24h.In this hair
In bright, the hydro-thermal ageing enables to the precursor complex further to crosslink.
The ageing precursor product system that hydro-thermal ageing described in preferred pair of the present invention is obtained is post-processed, the post processing
Preferably comprise following steps：
Separation of solid and liquid is carried out to hydro-thermal ageing product system, solid product is obtained；
The solid product is sequentially washed and ethanol is washed；
Solid product after the washing is dried, obtains being aged presoma.
Preferred pair hydro-thermal ageing product system of the present invention carries out separation of solid and liquid, obtains solid product.The present invention is to described solid
The mode of liquid separation does not have any particular/special requirement, can open separation of solid and liquid.It is described in the specific embodiment of the invention
Separation of solid and liquid is preferably to centrifuge；The present invention does not have any particular/special requirement to the parameter of the centrifugation, can separate
Go out solid product.
Obtain after the solid product, solid product described in preferred pair of the present invention sequentially carries out washing and ethanol is washed.This hair
Bright the concrete operations mode washed to the washing and ethanol and parameter do not have any particular/special requirement, using those skilled in the art
Known washing and ethanol is washed.
Solid product after being washed described in preferred pair of the present invention is dried, and obtains being aged presoma.In the present invention, institute
State to dry and be preferably dried in vacuo；The temperature of the drying is preferably 75~85 DEG C, more preferably 80 DEG C；It is described vacuum drying
Vacuum is preferably -0.6~-0.98MPa, more preferably -0.7~-0.8MPa；The vacuum drying time is preferably 15~
20h, more preferably 16~18h.
Obtain after the ageing presoma, the present invention is calcined to the ageing presoma, obtains mesoporous polymer material
Material.It is aged after presoma is ground processing and is calcined again described in preferred pair of the present invention；Granularity after the grinding is preferably
20~100 mesh, more preferably 40~60 mesh.The present invention does not have any particular/special requirement to the embodiment of the grinding, can
It is ground to purpose granularity.
In the present invention, the temperature of the roasting is preferably 370~390 DEG C, more preferably 375~385 DEG C, is most preferably
380℃；The time of the roasting is preferably 5~10h, more preferably 6~9h, most preferably 7~8h.In the present invention, it is described
Roasting is preferably carried out under an inert atmosphere, more preferably nitrogen or argon gas.In the present invention, the roasting can slough template
Agent.
Obtain after the mesoporous polymer material, mesoporous polymer material is carried out function by the present invention in the solution of palladium source
Change, obtain mesoporous organic metal palladium catalyst.Mesoporous polymer material described in preferred pair of the present invention enters again after being ground processing
Row functionalization；Granularity after the grinding is preferably 20~100 mesh, more preferably 40~60 mesh.The present invention is to the grinding
Embodiment does not have any particular/special requirement, can be ground to purpose granularity.
In the present invention, palladium source solution is preferably the tetrahydrofuran solution in palladium source；The concentration of palladium source solution is excellent
Elect 0.5~1g as:15~25mL, more preferably 0.89g:20mL.In the present invention, the palladium source is preferably PdCl2、Pd
(OAc)2、Pd(CH3CN)2Cl2Or Pd (PPh3)2Cl2。
In the present invention, the mesoporous polymer material and the mass ratio in palladium source are preferably (480~520):(80~
100), more preferably 500:89.
In the present invention, the functionalization is preferably and the mesoporous polymer material is immersed in the solution of palladium source, in room
It is stirred under temperature.In the present invention, the time of the functionalization is preferably 20~30h, more preferably 22~26h, most preferably
For 24h.The present invention, without any particular/special requirement, is entered to the stirring using agitating mode well-known to those skilled in the art
Row.
After the product system comprising mesoporous organic metal palladium catalyst that functionalization described in preferred pair of the present invention is obtained is carried out
Processing, the post processing preferably comprises following steps：
Separation of solid and liquid is carried out to product system, solid product is obtained；
The solid product is washed；
Solid product after the washing is dried, mesoporous organic metal palladium catalyst is obtained.
Preferred pair product system of the present invention carries out separation of solid and liquid, obtains solid product.The present invention is to the separation of solid and liquid
Mode does not have any particular/special requirement, can open separation of solid and liquid.In the specific embodiment of the invention, the separation of solid and liquid
Preferably centrifuge；The present invention does not have any particular/special requirement to the parameter of the centrifugation, can isolate solid production
Thing.
Obtain after the solid product, solid product described in preferred pair of the present invention is washed.In the present invention, it is described to wash
Wash with detergent preferably organic solvent, more preferably THF.The present invention does not have to the concrete operations mode and parameter of the washing
Any particular/special requirement, is carried out using mode of washing well-known to those skilled in the art.
Solid product after being washed described in preferred pair of the present invention is dried, and obtains mesoporous organic metal palladium catalyst.
In the present invention, the drying is preferably vacuum drying；The temperature of the drying is preferably 55~65 DEG C, more preferably 60 DEG C；Institute
It is preferably -0.6~-0.98MPa to state vacuum drying vacuum, more preferably -0.7~-0.8MPa；When described vacuum drying
Between be preferably 10~20h, more preferably 12~18h.
Present invention also offers the mesoporous polymer material that preparation method described in above-mentioned technical proposal any one is obtained.
Mesoporous organic metal palladium catalyst provided with reference to embodiment the present invention and preparation method thereof carries out detailed
Explanation, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
0.18g2- hydroxyl -5- nitropyridines, 0.60g phenol are weighed first in 250mL three-necked flasks, are placed in 60 DEG C of oil
In bath.Pipetted with liquid-transfering gun 2.1mL37% formalin and be added dropwise in three-necked flask with 2- hydroxyl -5- nitropyridines,
Phenol adds 15mL0.2M sodium hydroxide solutions after being sufficiently mixed, the compound in three-necked flask then is warming up into 85 DEG C,
And 0.5h is stirred at this temperature, produce pf resin of low molecular weight (i.e. presoma).
0.96gPluronicF127 solids are dissolved in 15mL deionized waters in advance, 2- hydroxyl -5- nitropyridine work(is added
Temperature, is adjusted to 85 DEG C by the low-molecular-weight resin precursor of energyization, make whole mixed system stirred under 350rpm rotating speeds 2h it
After add the dilution of 50mL deionized waters, temperature is maintained at 85 DEG C, continues to stir and simultaneously observes.
In whole process, the color of the aqueous solution, which have passed through, gradually to be deepened, again to the process of kermesinus from yellow to brown,
Finally after 20 hours, when there is peony sediment, stop heating, during being cooled to room temperature, peony precipitation
Thing gradually dissolves, and has obtained the presoma of nano-complex.
Take above-mentioned synthesis nano-complex presoma 44mL be transferred to 250mL specifications containing polytetrafluoroethyllining lining
In water heating kettle, and 140mL deionized waters are added, the ageing reaction 24h at 130 DEG C, will be cotton-shaped in reaction tube after reaction terminates
Thing is dried respectively with deionized water and ethanol centrifuge washing 3~5 times under the conditions of 80 DEG C.After after sample drying, obtaining deep yellow
The solid of color.
By obtained solid abrasive into powder, and it is transferred in quartz boat, quartz boat is placed in 380 DEG C of nitrogen ceilings
Tubular type kiln roasting 6h under part, removes surfactant.Mesoporous polymer material is obtained after surfactant to be removed, is marked
It is designated as 2HP-5NG-MPN.
The 5g mesoporous polymer materials of above-mentioned preparation are added to 20mL dissolved with 0.89g (2.86mmol) PdCl2Tetrahydrochysene
In tetrahydrofuran solution, 24h is stirred at room temperature, then 3~4 times are washed by filtering, THF, 60 DEG C, be dried in vacuo 12h under -0.98MPa,
Prepare mesoporous organic metal palladium catalyst Pd (II) -2HP-5NG-MPNs.Load by ICP to the Pd of catalyst material
Amount is determined, and Pd load capacity is about 1wt%.
The 2HP-5NG-MPNs and Pd (II) -2HP-5NG-MPNs that the present invention is obtained to the present embodiment have carried out XRD detections,
Its result is as shown in Figure 1.As shown in Figure 1, having loaded Pd 2HP-5NG-MPN has stronger spread out in 2 θ=0.8 °~1.0 ° or so
Penetrate peak and show that Pd (the II) -2HP-5NG-MPNs prepared has orderly meso-hole structure.Compared with 2HP-5NG-MPNs, load
Pd (II) -2HP-5NG-MPNs after Pd has similar diffraction maximum, but its intensity is in a slight decrease, illustrates immobilized organic metal
The degree of order of Pd (II) sample meso-hole structures afterwards is not substantially reduced；But the peak position that goes out of its characteristic diffraction peak does not have partially substantially
Move, illustrate that organic metal Pd (II) is immobilized and the aperture of carrier is had not significant impact on carrier, this is probably to have because of immobilized
The part of machine metal Pd (II) is embedded in the hole wall of mesoporous material, without being suspended from the wall of hole.
TEM Scanning Detctions are carried out to obtained Pd (II) -2HP-5NG-MPNs, as a result as shown in Figure 2.As shown in Figure 2,
Pd (II) -2HP-5NG-MPNs samples are spherical, and there is mesoporous presence on surface, and spherical particle diameter is about 200~400nm.
XPS detections are carried out to obtained Pd (II) -2HP-5NG-MPNs, as a result as shown in Figure 3.From the figure 3, it may be seen that Pd
(II) -2HP-5NG-MPNs samples are Pd 3d occur at 337.8eV in electron binding energy5/2Occur at electronics peak, 342.1eV
Pd 3d3/2Electronics peak, with Pd3d5/2 2+And Pd3d3/2 2+Values match, and without find Pd0Electronics peak appearance, say
Bright PdCl2Valence state does not change in copolymerization extraction process, is still+divalent.
Nitrogen adsorption desorption experiment is carried out to obtained 2HP-5NG-MPNs and Pd (II) -2HP-5NG-MPNs, as a result such as Fig. 4
It is shown.As shown in Figure 4, loaded after Pd, carrier 2HP-5NG-MPNs specific surface area has certain decline, it may be possible to due to
Load after metal, channel section is blocked what is caused.
Embodiment 2
For the catalytic performance of detection gained mesoporous organic metal palladium catalyst, two kinds of C-C coupling reactions are have selected：Water is situated between
Matter Suzuki and Barbier reaction are used as probe reaction.
Suzuki reaction equations：
Suzuki reaction conditions are as follows：The mesoporous organic metal palladium containing 0.0060mmolPd is added in 50mL reaction tubes
Catalyst, 1.0mmol halogeno-benzenes, 1.2mmol phenyl boric acids, 2.0mmolK2CO3And 4.0mLH2O, and it is placed on 80 DEG C of oil bath
Middle reaction 4h reactions.Reaction terminate after, be extracted with ethyl acetate, after centrifugation, take supernatant liquor gas-chromatography (GC,
Agilent1790 quantitative analysis on), chromatogram is with N2For carrier gas, hydrogen flame (FID) detector and JWDB-5,95%- diformazan are used
Base 1- (5%)-diphenylpolysiloxane (L=15m,) chromatographic column, column temperature is 80 DEG C to 250 DEG C, heating
Speed is 10 DEG C/min, and 270 DEG C of injector temperature, detection temperature is 280 DEG C.Due to 4- methylphenylboronic acids be it is excessive, reaction
Conversion ratio and yield are determined that experiment the data obtained is acquired by many secondary responses according to halogeno-benzene and product by normalization method
Average value.All activity datas pass through the repetition of more than three times in experiment, and its error range is within ± 5%.
Catalytic performance of the catalyst of table 1 in Suzuki reactions
Reaction condition:Catalyst Pd (II) -2HP-5NG-MPNs, 1.0mmol halogenated hydrocarbons containing 0.006mmolPd (II),
1.2mol aryl boric acids, 2.0mmol potassium carbonate, 4.0mLH2Trimethylbenzene, 80 DEG C between O, 100 μ L.
As shown in table 1, as shown in Table 1, the application is obtained catalytic activity of the catalyst in Suzuki reactions in the present embodiment
To catalyst differential responses raw material Suzuki reaction conversion ratio be all higher than 85%, yield is all higher than 85%.
In order to which the life-span to catalyst tests, first it is extracted with ethyl acetate out in reaction system after every secondary response
Organic matter, then by centrifuging out catalyst, then is washed repeatedly with ethanol, water and dichloromethane equal solvent, is urged with removing
The organic matter of agent surface physics absorption, is then placed on 80 DEG C of vacuum ovens.Carried out under same reaction condition
Active testing, to investigate the service life of catalyst.
The service life of catalyst is to investigate a very important index of catalyst performance.In the present embodiment, palladium
The life-span of Pd (II) -2HP-5NG-MPNs catalyst of load is investigated by applying mechanically experiment, as a result as shown in figure 5, Pd
(II) -2HP-5NG-MPNs catalyst can repeat catalysis Suzuki reactions 8 times and keep conversion ratio and selectivity more than 90%.
Barbier reaction equations：
The specific reaction condition of Barbier reactions is as follows：Added in clean 10mL reaction bulbs and contain 0.085mmolPd
(II) mesoporous organic metal palladium catalyst, 5.0mL water, 2.0mmol dichloros stannous, 1.5mmol3- bromopropenes and 0.50mmol
Benzaldehyde, allows it to react 12h at 50 DEG C.After the organic matter in toluene extractive reaction system, first with GC-MAS to extract
Quantitative analysis is carried out, then quantitative analysis, the analysis condition of chromatogram are carried out with GC (U.S. Agilent GC1790)：Chromatographic column is non-pole
The JWDB-5 of property, 95%- dimethyl -1- (5%)-diphenylpolysiloxane (column length=15m,), with hydrogen flame
(FID) detect, detection temperature is 280 DEG C, 270 DEG C of injector temperature, using temperature programming (15 DEG C/min) by column temperature from 80 DEG C
250 DEG C are risen to, with 0.098MPa N2For carrier gas.The allyl bromide, bromoallylene used in active testing is excessive, so according to benzaldehyde
Calculate the conversion ratio of reaction.All activity datas pass through the repetition of more than three times in experiment, and its error range is ± 5%.
The group connected on present invention adjustment benzaldehyde contraposition carbon atom, catalysis is probed into by changing benzaldehyde species
Catalytic performance of the agent in different substrate B arbier reactions, as a result as shown in table 2.
Catalytic performance of the catalyst of table 2 in Barbier reactions
As shown in Table 2, the conversion ratio for the catalyst Barbier reactions that the application is obtained is maximum up to 99%, yield
Reach as high as 85%.
As seen from the above embodiment, the invention provides a kind of mesoporous organic metal palladium catalyst.What the present invention was provided urges
The organic metal active sites of agent are embedded in the ball shaped nano short-bore road of mesoporous material hole wall, and active sites are uniformly dispersed, do not resulted in
Duct is blocked；Catalyst regular appearance and duct is shorter, is conducive to the diffusion and absorption of reactant molecule, make its catalytic performance compared with
Traditional catalyst with irregular pattern improves, and may be reused.From the result of embodiment, sheet
It is spherical to invent obtained catalyst, and there is mesoporous presence on surface, and spherical particle diameter is about 200~400nm；It is catalyzed differential responses former
The conversion ratio of the Suzuki reactions of material is all higher than 85%, and yield is all higher than 85%；The conversion ratio maximum for being catalyzed Barbier reactions can
Up to 99%, yield reaches as high as 85%.
Present invention also offers a kind of preparation method of mesoporous organic metal palladium catalyst.The present invention synthesizes N and mixed first
The spherical short-bore road carrier of miscellaneous meso-porous nano, is then loaded to nano Pd particle (II) on prepared mesoporous supports using infusion process
Catalyst is made.The preparation method that the present invention is provided is simple to operate, convenient to carry out.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of mesoporous organic metal palladium catalyst, is comprised the following steps：
2- hydroxyl -5- nitropyridines, formaldehyde and phenol are subjected to polymerisation in alkali lye, presoma is obtained；
The presoma and template are combined, precursor complex is obtained；
The precursor complex is subjected to hydro-thermal ageing in water, obtains being aged presoma；
The ageing presoma is calcined, mesoporous polymer material is obtained；
The mesoporous polymer material is subjected to functionalization in the solution of palladium source, mesoporous organic metal palladium catalyst is obtained.
2. preparation method according to claim 1, it is characterised in that the matter of the 2- hydroxyls -5- nitropyridines and phenol
Amount is than being (10~25):(50~70).
3. preparation method according to claim 1 or 2, it is characterised in that the formaldehyde is formalin, the formaldehyde is molten
The mass concentration of liquid is 35~40%；
The quality of the 2- hydroxyls -5- nitropyridines and the volume ratio of formalin are (10~25) g:(180~250) mL.
4. preparation method according to claim 1, it is characterised in that the temperature of the polymerisation is 80~90 DEG C, when
Between be 0.1~1h.
5. preparation method according to claim 1, it is characterised in that the 2- hydroxyls -5- nitropyridines and template
Mass ratio is (10~25):(90~100).
6. preparation method according to claim 1 or 5, it is characterised in that the compound temperature is 80~90 DEG C, time
For 15~20h.
7. preparation method according to claim 1, it is characterised in that in the hydro-thermal ageing process precursor complex and
The volume ratio of water is (40~50):(130~150)；
The temperature of the hydro-thermal ageing is 120~140 DEG C, and the time is 20~30h.
8. preparation method according to claim 1, it is characterised in that the temperature of the roasting is 370~390 DEG C, time
For 5~10h.
9. preparation method according to claim 1, it is characterised in that the mesoporous polymer material and the mass ratio in palladium source
For (480~520):(80~100)；
The time of the functionalization is 20~30h.
10. the mesoporous organic metal palladium catalyst that preparation method described in claim 1~9 any one is obtained.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2017103363481 | 2017-05-13 | ||
| CN201710336348 | 2017-05-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107115891A true CN107115891A (en) | 2017-09-01 |
| CN107115891B CN107115891B (en) | 2019-11-05 |
Family
ID=59718610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710474670.0A Active CN107115891B (en) | 2017-05-13 | 2017-06-21 | A kind of mesoporous organic metal palladium catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107115891B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110642670A (en) * | 2018-06-26 | 2020-01-03 | 浙江中山化工集团股份有限公司 | Production method of 1- (4-chlorphenyl) -3-butene-1-ol |
| CN112625057A (en) * | 2020-12-25 | 2021-04-09 | 山东金城柯瑞化学有限公司 | Synthetic method of methyl 3-hydroxy-4- ((trimethylsilyl) ethynyl) benzoate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040192542A1 (en) * | 2003-03-31 | 2004-09-30 | Choudary Boyapati Manoranjan | Layered double hydroxides supported nanopalladium catalysts for Heck-, Suzuki, Sonogashira-, and Stille type coupling reactions of haloarenes |
| CN101455983A (en) * | 2008-12-30 | 2009-06-17 | 上海师范大学 | Preparation method of PPh2-ordered mesopore polymer-Pd(II) heterogeneous catalyst and use thereof |
| CN103554547A (en) * | 2013-10-12 | 2014-02-05 | 上海师范大学 | Amino functionalized mesoporous macromolecular small nanosphere and preparation method thereof |
| CN104231141A (en) * | 2014-08-29 | 2014-12-24 | 西安蓝晓科技新材料股份有限公司 | Amino nitrogen heterocyclic ring resin and preparation method thereof |
| CN105566589A (en) * | 2015-12-08 | 2016-05-11 | 上海师范大学 | Amino-functionalization ordered mesopore phenolic resin material and preparing method thereof |
-
2017
- 2017-06-21 CN CN201710474670.0A patent/CN107115891B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040192542A1 (en) * | 2003-03-31 | 2004-09-30 | Choudary Boyapati Manoranjan | Layered double hydroxides supported nanopalladium catalysts for Heck-, Suzuki, Sonogashira-, and Stille type coupling reactions of haloarenes |
| CN101455983A (en) * | 2008-12-30 | 2009-06-17 | 上海师范大学 | Preparation method of PPh2-ordered mesopore polymer-Pd(II) heterogeneous catalyst and use thereof |
| CN103554547A (en) * | 2013-10-12 | 2014-02-05 | 上海师范大学 | Amino functionalized mesoporous macromolecular small nanosphere and preparation method thereof |
| CN104231141A (en) * | 2014-08-29 | 2014-12-24 | 西安蓝晓科技新材料股份有限公司 | Amino nitrogen heterocyclic ring resin and preparation method thereof |
| CN105566589A (en) * | 2015-12-08 | 2016-05-11 | 上海师范大学 | Amino-functionalization ordered mesopore phenolic resin material and preparing method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110642670A (en) * | 2018-06-26 | 2020-01-03 | 浙江中山化工集团股份有限公司 | Production method of 1- (4-chlorphenyl) -3-butene-1-ol |
| CN112625057A (en) * | 2020-12-25 | 2021-04-09 | 山东金城柯瑞化学有限公司 | Synthetic method of methyl 3-hydroxy-4- ((trimethylsilyl) ethynyl) benzoate |
| CN112625057B (en) * | 2020-12-25 | 2022-12-09 | 山东金城柯瑞化学有限公司 | Synthetic method of methyl 3-hydroxy-4- ((trimethylsilyl) ethynyl) benzoate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107115891B (en) | 2019-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110016126A (en) | A kind of conjugation microporous polymer and the preparation method and application thereof | |
| CN102921466B (en) | Heterogeneous Au/Ze-MOF catalyst and preparation method and application thereof | |
| CN103949286A (en) | MOFs (Metal-Organic Frameworks)@noble metal@MOFs catalyst applicable to selective hydrogenation reaction, as well as preparation method and application thereof | |
| Van Vaerenbergh et al. | Pd nanoparticle and molecular Pd2+ leaching pathways for a strongly acid versus strongly basic resin supported Pd nanoparticle catalyst in Suzuki coupling | |
| CN110124743B (en) | Supported porous metal organic Pd catalyst and preparation method and application thereof | |
| CN101879459B (en) | Preparation method and application of Schiff base functionalized ordered mesoporous PMO material solid supported Cu(I) heterogeneous catalyst | |
| CN104923306A (en) | Magnetron separating photocatalyst used for dye sewage treatment and preparation method for magnetron separating photocatalyst | |
| CN107115891B (en) | A kind of mesoporous organic metal palladium catalyst and preparation method thereof | |
| CN107824211A (en) | The preparation method of azotized carbon nano piece catalyst and the Knoevenagel condensation reaction methods based on above-mentioned catalyst | |
| CN106582710A (en) | Method for preparing biphenyl by catalyzing Suzuki reaction through graphene-loaded palladium-copper nanocapsule | |
| CN112934267B (en) | Alkylated hydrophobic MOFs material and application thereof in cyclohexene hydration | |
| CN103394327A (en) | Silanized functionalized ionic liquid/hydrotalcite-like compound composite material, and preparation method and application thereof | |
| CN106450358A (en) | N-doped carbon nano-tube/carbon compound oxygen reduction catalyst and preparation method thereof | |
| CN106607091A (en) | Microporous polymer-nano-metal particle catalyst and its preparation method and use | |
| CN104258874A (en) | Catalyst for use in one-step preparation of imine through selective hydrogenation coupling of cyanophenyl and preparation method and application | |
| Wang et al. | A polysalen based on polyacylamide stabilized palladium nanoparticle catalyst for efficient carbonylative Sonogashira reaction in aqueous media | |
| Ncube et al. | Palladium nanoparticles supported on mesoporous silica as efficient and recyclable heterogenous nanocatalysts for the Suzuki C–C coupling reaction | |
| CN108722445A (en) | A kind of ultra-thin BiOX based solid solution photochemical catalyst and its preparation method and application | |
| CN105358481B (en) | With sulfonic carbon system solid acid | |
| CN105879910A (en) | Poly(styrene-methacrylic acid)/nano-silver composite microsphere and preparation method thereof | |
| CN105665017A (en) | Load type Pd catalyst used for Suzuky-Miyaura coupling reaction and preparation method thereof | |
| CN105879896B (en) | Cu3B2O6/g‑C3N4The preparation method of heterojunction photocatalyst and its method for degradation of methylene blue waste water from dyestuff | |
| CN104437474A (en) | Ordered mesoporous carbon material loaded platinum catalyst and application thereof to catalytic hydrogenation of aromatic nitro compound | |
| CN102755901B (en) | Preparation and application of composite solid acid catalyst used for condensation reaction | |
| CN109879265A (en) | A kind of mesoporous nitrogen-doped carbon material and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230601 Address after: 230000 floor 1, building 2, phase I, e-commerce Park, Jinggang Road, Shushan Economic Development Zone, Hefei City, Anhui Province Patentee after: Dragon totem Technology (Hefei) Co.,Ltd. Address before: No. 111, Changjiang West Road, Huaian, Jiangsu, Jiangsu Patentee before: HUAIYIN NORMAL University Effective date of registration: 20230601 Address after: No. 19-9-2-4-1, ShuangD4 Street, Dalian Economic and Technological Development Zone, Dalian, Liaoning Province, 116000 Patentee after: Dalian Zhongke Benli Technology Co.,Ltd. Address before: 230000 floor 1, building 2, phase I, e-commerce Park, Jinggang Road, Shushan Economic Development Zone, Hefei City, Anhui Province Patentee before: Dragon totem Technology (Hefei) Co.,Ltd. |