CN106334579A - Recoverable ligand-free mesoporous polymer palladium catalyst and synthetic method and application thereof - Google Patents
Recoverable ligand-free mesoporous polymer palladium catalyst and synthetic method and application thereof Download PDFInfo
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- CN106334579A CN106334579A CN201610711604.6A CN201610711604A CN106334579A CN 106334579 A CN106334579 A CN 106334579A CN 201610711604 A CN201610711604 A CN 201610711604A CN 106334579 A CN106334579 A CN 106334579A
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- mesoporous polymer
- palladium catalyst
- palladium
- recyclable
- catalyst
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 184
- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 88
- 229920000642 polymer Polymers 0.000 title claims abstract description 61
- 238000010189 synthetic method Methods 0.000 title claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 43
- 238000006722 reduction reaction Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 27
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims abstract description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims abstract description 13
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000021286 stilbenes Nutrition 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000012736 aqueous medium Substances 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- 238000007341 Heck reaction Methods 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 24
- 238000007306 functionalization reaction Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- -1 methoxyl group Chemical group 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 239000002736 nonionic surfactant Substances 0.000 claims description 13
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 235000019270 ammonium chloride Nutrition 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 238000003837 high-temperature calcination Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000005011 phenolic resin Substances 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 229920000428 triblock copolymer Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229920000359 diblock copolymer Polymers 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 14
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 45
- 239000000243 solution Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 239000013335 mesoporous material Substances 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 230000014509 gene expression Effects 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000001338 self-assembly Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 229910052756 noble gas Inorganic materials 0.000 description 4
- 150000002835 noble gases Chemical class 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- ZWINLZAYDMUOAE-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-(2-hexadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical group CCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ZWINLZAYDMUOAE-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000000935 solvent evaporation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HNUQMTZUNUBOLQ-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-(2-octadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO HNUQMTZUNUBOLQ-UHFFFAOYSA-N 0.000 description 2
- JKXYOQDLERSFPT-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-octadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO JKXYOQDLERSFPT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000006193 liquid solution 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
- 229920003986 novolac Polymers 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009736 wetting 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
- B01J31/02—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
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/647—2-50 nm
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a recoverable ligand-free mesoporous polymer palladium catalyst and a synthetic method and application thereof. The catalyst has a two-dimensional hexagonal ordered mesostructure. specific surface area is 250-380 m<2>/g; pore diameter is 3.0-7.0 nm; mass content of a functional phase transfer agent is 8.5-13 wt%; mass content of metal palladium is 1-5 wt%; and particle size of palladium particles is 3-5 nm. The preparation comprises the following steps: adding a surfactant and hydrochloric acid into an organic solvent, stirring and reacting, successively adding a silicon source, quaternary ammonium salt and a carbon source, continuously stirring and reacting; carrying out a thermosetting reaction, and then carrying out high-temperature calcining to prepare a functional mesoporous polymer carrier; and mixing the functional mesoporous polymer carrier and a palladium source, stirring, carrying out suction filtration, washing, carrying out vacuum drying, and carrying out a reduction reaction. The catalyst is applied in aqueous medium catalysis of a Heck reaction between bromobenzene and styrene for generation of stilbene. In comparison with the prior art, the method of the invention is simple; and the catalyst is efficient and stable, can be recycled for many times and has a wide application prospect in the field of industrial catalysis.
Description
Technical field
The invention belongs to mesoporous material preparing technical field, it is related to a kind of catalyst and its synthetic method and application, especially
It is to be related to a kind of recyclable no part mesoporous polymer palladium catalyst and its synthetic method and application.
Background technology
It is big that meso-porous carbon material has a specific surface area, the advantages of high stability and aperture are homogeneous, is led to mesoporous carbon for carrier
Later mode of loading prepares the extensive concern that metallic catalyst has caused scientist.But, meso-porous carbon material is originally as lazy
Property adhesion between carrier, and noble metal very weak, thus obtained catalyst has that metal particle size is larger, distribution
The problems such as be easy to run off in uneven, easy reunion, course of reaction.Therefore, prepare efficient, stable catalyst particularly important.
Certain avtive spot can be introduced by surface-functionalized in material with carbon element, thus can expand mesoporous carbon materials further
Material is in absorption and the application separating, sense, be catalyzed etc. field.At present, people are generally by preparing carbon-silica composite material,
The hydroxyl grafting functional group recycling silica surface to enrich, obtains the composite of sense dough.But this method exists
Not enough as follows: silica support is unstable, decomposition, the functional group's skewness introducing, content easily under alkaline hot conditionss
Low, time-consuming, process is loaded down with trivial details etc..Therefore, research and develop a kind of method of one-step synthesis method sense dough mesoporous polymer have important
Research Significance and economic worth.
The Chinese invention patent of Application No. 201110309914.2 disclose a kind of mesoporous carbon-supported palladium catalyst and
Its preparation method and purposes, described catalyst is made up of active component pd and carrier, and used carrier is mesoporous carbon, the pore volume of mesoporous carbon
For 1.5-2.5ml/g, specific surface area is 1000-2000m2/ g, channel diameter is 2-12nm, and mesoporous rate is 80-100%；Activity
The weight percentage of component pd is 1-5%.Preparation method comprises the following steps: palladium liquid is added to by (1) under agitation
In the mesoporous carbon suspension infiltrating in advance, 20-40 DEG C is stirred to obtain mixed liquor；Described palladium liquid is selected from the halogenation of the palladium of solubility
The aqueous solution of any one of thing, nitrate, the coordination compound of acetate, the acid of chlorine palladium or palladium ammonia；Described mesoporous carbon suspension is
Refer in advance by carrier mesoporous carbon deionized water complete wetting, infiltration solid-to-liquid ratio is 1:2-20；(2) with alkali liquor adjust mixed liquor to
Ph=10-12, stirring reaction；(3) add reducing agent, reducing agent consumption is 1-10 times of theoretical amount, is warming up to 60-100 DEG C,
Reduction 1-3 hour；Described reducing agent is selected from one of formic acid, sodium formate, formaldehyde, hydrazine hydrate or hydrogen；(4) it is cooled to room
Temperature, adjusts solution ph=5-6 with acid solution, separates solid, and deionized water cyclic washing is clean；Described acid solution is hydrochloric acid solution；
(5) solid sucking filtration is fallen to dripless, obtain mesoporous carbon carried palladium catalyst, the wet storage of band is standby.Due to meso-porous carbon material
This is very weak as the adhesion between inert carrier, and noble metal, and what the back loading method that above-mentioned patent is adopted was obtained urges
Agent has that metal particle size is larger, skewness, the problems such as easily reunite, be easy to run off in course of reaction.Ask for above-mentioned
Topic, the present invention is modified quaternary ammonium salt on polymeric material using solvent evaporation induced self-assembly method, and passes through ion exchange
Method introduces palladium material, and reduction obtains the Polymeric palladium catalyst with high stability.Quaternary ammonium salt in polymer support can not only
Enough anchor Pd nano particle, part can also be served as in catalytic process.Catalyst of the present invention is in aqueous medium bromobenzene and styrene
Higher catalysis activity is shown in heck reaction, reusable more than 12 times.
Content of the invention
The purpose of the present invention is exactly the catalysis in order to overcome the defect of above-mentioned prior art presence to provide a kind of good stability
The high recyclable no part mesoporous polymer palladium catalyst of activity and its application.
Another object of the present invention is exactly to overcome the defect of above-mentioned prior art presence to provide one kind simply easy
OK, with low cost, the synthetic method of the recyclable no part mesoporous polymer palladium catalyst of favorable repeatability.
The purpose of the present invention can be achieved through the following technical solutions:
Recyclable no part mesoporous polymer palladium catalyst, this catalyst is one kind no part, containing functionalization phase transfer
The mesoporous polymer loaded palladium catalyst of agent, has the ordered mesostructure of two-dimentional six sides, and specific surface area is 250-380m2/ g,
Aperture is 3.0-7.0nm, and the weight/mass percentage composition of functionalization consisting of phase-transferring agent is 8.5-13%, and the weight/mass percentage composition of Metal Palladium is
1-5%, the particle diameter of palladium granule is 3-5nm.
Described functionalization consisting of phase-transferring agent is quaternary ammonium salt.
The synthetic method of recyclable no part mesoporous polymer palladium catalyst, the method specifically includes following steps:
(1) surfactant, hydrochloric acid are added in organic solvent, at 20-40 DEG C, stirring reaction 10-30 minute, then according to
Secondary addition silicon source, quaternary ammonium salt and carbon source, at 20-40 DEG C, continue stirring reaction 60-180 minute；
(2) after organic solvent volatilizees completely, carry out thermosetting reaction at 40-100 DEG C, the response time is 12-36 hour；
(3) it is transferred in tube furnace, in atmosphere of inert gases, high-temperature calcination, remove surfactant, prepared functionalization
Mesoporous polymer carrier；
(4) palladium source is mixed with the mesoporous polymer carrier of functionalization, at room temperature stir 6-12 hour, by sucking filtration,
Washing, vacuum drying, then carry out reduction reaction, that is, described recyclable no part mesoporous polymer palladium catalyst is obtained.
Surfactant described in step (1) is nonionic surfactant, and described organic solvent includes c1-c4's
One or more of alcohols, toluene, oxolane, chloroform, dichloromethane or ether, described silicon source include organosilan or
One of inorganic silane or two kinds, described quaternary ammonium salt includes octadecyldimethyl [3- (methoxyl group silicon substrate) propyl group] chlorination
One of ammonium or octadecyldimethyl [3- (ethyl-silicone) propyl group] ammonium chloride or two kinds, described carbon source is relatively point
Son measures a rank phenolic resin for 300-500.
Described c1-c4Alcohols include methanol, ethanol, normal propyl alcohol, n-butyl alcohol, preferred alcohol.
Described nonionic surfactant include poly(ethylene oxide)-poly(propylene oxide) triblock copolymer or alkane-
One of poly(ethylene oxide) diblock copolymer.
Described poly(ethylene oxide)-poly(propylene oxide) triblock copolymer or alkane-poly(ethylene oxide) di-block copolymer
The formula of thing can be expressed as eocpodeoc、cah2a+1eob, wherein, a numerical range is 12-18, and b numerical range is 5-25, c
Numerical range is 20-135, and d numerical range is 50-135.
Described nonionic surfactant is selected from brij56 (c16h33eo10)、brij76(c18h37eo10)、brij78
(c16h33eo20)、p123(eo20po70eo20)、f127(eo106po70eo106)、f108(eo132po50eo132) one of or several
Kind.
In described silicon source, inorganic silane and the mass ratio of organosilan are 1.5:0.5,1:1 or 0.5:1.
The condition of the high-temperature calcination described in step (3) is: it is warming up to 275-350 DEG C with the heating rate of 1-5 DEG C/min,
Calcining at constant temperature 5-10 hour.
Described noble gases are high pure nitrogen or argon, and purity is 99.999%.
Palladium source described in step (4) is pdcl2Or na2pdcl4One of, the condition of described reduction reaction is:
In the mixed gas of hydrogen and nitrogen, the temperature of reduction reaction is controlled to be 200-300 DEG C, the time of reduction reaction is 2-5 hour.
Preferably, in described reduction reaction, the ratio of hydrogen and nitrogen is 1:4 or 1:5.
The application of recyclable no part mesoporous polymer palladium catalyst, described catalyst is applied to aqueous medium catalysis bromobenzene
React with cinnamic heck and generate stilbene.
With block copolymer as template, water soluble phenol resin (pf) is presoma to the present invention, tetraethyl orthosilicate
(teos) it is inorganic silicon source, and be introduced directly into octadecyldimethyl [3- (methoxyl group silicon substrate) propyl group] ammonium chloride for organosilicon
Source, the method using solvent evaporation induced self-assembly synthesizes the mesoporous carbon silica composite material that quaternary ammonium salt is modified.And by from
Sub- exchange process introduces palladium material, and reduction obtains the Polymeric palladium catalyst with high stability.Quaternary ammonium salt in polymer support
Pd nano particle can not only be anchored, part can also be served as in catalytic process.This catalyst is in aqueous medium bromobenzene and benzene second
Higher catalysis activity and excellent stability is shown in alkene heck reaction.
The present invention is self-assembly of orderly meso-hole structure using the volatilization induction nonionic surfactant of organic solvent,
Quaternary ammonium salt is introduced surfactant self-assembly system, obtains the mesoporous polymer carrier of quaternary ammonium salt functionalization, then pass through ion
Exchange process introduces palladium species, and reduction obtains the mesoporous polymer palladium catalyst with high stability.
In the present invention, in initial solution, comprise phenol, triblock copolymer eo20po70eo20(p123), teos, organic
Silane, hydrochloric acid and ethanol, mass ratio be phenol/formaldehyde/p123/teos (y1)/organosilan (y2)/hydrochloric acid/ethanol=
0.61:0.39:1.2:y1:y2:1.0:5.0, preferably y1:y2=2.87:0.82,2.66:0.99 or 2.78:1.18.
In the present invention, preparing specifically comprising the following steps that of Metal Palladium of introducing by ion exchange will be containing saturation Metal Palladium
The mesoporous polymer carrier of the aqueous solution of salt or ethanol solution 2.0～4.0ml and 0.3～0.6g functionalization is stirred at room temperature
6-12 hour, sucking filtration, it is dried.
Mass concentration in aqueous solution or ethanol solution for the described metal palladium salt is 0.01-0.1g/ml.
Compared with prior art, the invention has the characteristics that:
1) present invention obtains the mesoporous poly- of quaternary ammonium salt consisting of phase-transferring agent functionalization using the method for solvent evaporation induced self-assembly
Compound material, further with ion exchange, Metal Palladium is supported in mesopore orbit, and reduction obtains with high catalytic activity
Recyclable no part mesoporous polymer palladium catalyst with stability；
2) catalyst being obtained has a high-sequential mesoscopic structure, high specific surface area (250-380m2/ g), homogeneous hole
Footpath (3-7nm), the Pd nano particle (3-5nm) of high functionalization consisting of phase-transferring agent content (8.5-13.0wt%) and high dispersive, surely
Qualitative good, catalysis activity is high.
Brief description
Fig. 1 is the mesoporous polymer palladium catalyst of the different quaternary ammonium salt contents that embodiment 2, embodiment 3 and embodiment 5 synthesize
X-ray diffraction (xrd) spectrogram, wherein, a is low angle diagram, and b is wide-angle diffraction figure；
Fig. 2 is the mesoporous material 11.5oddma-mp (a, b), pd/11.5oddma-mp modifying through quaternary ammonium salt in embodiment 3
(c, d), transmission electron microscope (tem) image of pd/11.5oddma-mp-12run (e, f)；
Fig. 3 is through quaternary ammonium salt in the mesoporous material pd/8.5oddma-mp and embodiment 3 modifying through quaternary ammonium salt in embodiment 2
X-ray photoelectron spectroscopy (xps) table of mesoporous material pd/11.5oddma-mp and pd/11.5oddma-mp-12run modifying
Levy figure, wherein, a and b is respectively n 1s and pd 3d track xps collection of illustrative plates.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
The synthesis of novolak resin precursor liquid solution.Detailed process is as follows: weighs the quality of flask and magneton, accurately adds
8.0g phenol, heating in water bath under the conditions of 42～45 DEG C, so that phenol is melted completely, transparent shape.1.7g 20% by preparation
Naoh solution be added dropwise in phenol solution.Then formalin 14.2g of Deca 37wt% is little in 70 DEG C of condensing refluxes 1
When.Backflow finishes, and is cooled to room temperature, and solution is adjusted to neutrality, vacuum decompression under the conditions of 45～50 DEG C with 2mol/l hcl
Distill to anhydrous state, naturally cool to room temperature.Weigh product quality, be formulated as 20wt% ethanol solution, after stirring from
The heart, gained supernatant is phenolic resin precursor, referred to as pf.
Embodiment 2
Pd content is 1wt%, and n content is the synthesis of the mesoporous polymer palladium catalyst of recyclable no part of 8.5wt%.
By 2.4g p123,2.0g hydrochloric acid is dissolved in 10.0g ethanol and stirs 15min, 3.74g tetraethyl orthosilicate, 1.65g at 40 DEG C
Stirring 15 minutes at octadecyldimethyl [3- (trimethoxy silicon substrate) propyl group] 40 DEG C of (oddma) ammonium chloride 5.0g ethanol, so
20% pf solution is added to be mixed together continuation stirring 2 hours afterwards.By mixed liquor film, volatilize 5～8 hours at room temperature, then
Put in baking oven 100 DEG C of hot polymerizations 24 hours.Knifing, calcines under high pure nitrogen atmosphere for 330 DEG C and obtains final product order mesoporous material in 5 hours
Material, is labeled as 8.5oddma-mp (weight/mass percentage composition of the oddma functional group that 8.5 expressions record) through elementary analysiss.Will
2.0ml 0.05g/ml na2pdcl4Stir 6 hours under ethanol solution and 0.3g 8.5oddma-mp room temperature condition, then will mix
Compound filters, and is washed with deionized for several times, 100 DEG C of dried in vacuum overnight, is the condition of 1:5 in hydrogen and nitrogen volume ratio
Under, in tube furnace, 200 DEG C reduce 3 hours, and heating rate is 1 DEG C/min.Gained catalyst is designated as pd/8.5oddma-mp.icp
Record palladium catalyst content and be about 1wt%；It is 8.5wt% that elementary analysiss record n content；The aperture of material is 4.0nm, specific surface
For 260m2/g；As shown in figure 1, xrd collection of illustrative plates proves that mesoporous polymer catalyst is two-dimentional hexagonal structure, palladium particle diameter is about 4nm.
In the present embodiment, the x-ray photoelectron spectroscopy (xps) of the mesoporous material pd/8.5oddma-mp modifying through quaternary ammonium salt
As shown in figure 3, wherein, a and b is respectively n 1s and pd 3d track xps collection of illustrative plates.
In 50ml flask add 0.108ml (1.5mmol) bromobenzene and, 0.174ml (1.5mmol) styrene, 0.1g should
Catalyst carries out being heated to reflux stirring, and cools down, with acetone dilute reaction solution, centrifugation catalyst after reaction certain time.With
Gas chromatogram is analyzed.The yield of the stilbene obtaining is 80%.
Embodiment 3
Pd content is 1wt%, and n content is the conjunction of the mesoporous polymer palladium catalyst of recyclable no part of 11.5wt%
Become.By 2.4g p123,2.0g hydrochloric acid is dissolved in 10.0g ethanol and stirring 15 minutes at 40 DEG C, 3.74g tetraethyl orthosilicate,
1.87g stirring 45 points at octadecyldimethyl [3- (trimethoxy silicon substrate) propyl group] 40 DEG C of (oddma) ammonium chloride 5.0g ethanol
Clock, the pf solution being subsequently adding 20% is mixed together continuation stirring 2 hours.By mixed liquor film, volatilization 5～8 is little at room temperature
When, place in baking oven 100 DEG C of hot polymerizations 48 hours.Knifing, calcines under high pure nitrogen atmosphere for 275 DEG C and obtains final product within 5 hours orderly Jie
Porous materials, are labeled as 11.5oddma-mp (weight/mass percentage composition of the oddma functional group that 11.5 expressions record) through elementary analysiss.
By 4.0ml 0.05g/ml na2pdcl4Stir 6 hours under ethanol solution and 0.3g 11.5oddma-mp room temperature condition, then will
Mixture filters, and is washed with deionized for several times, 100 DEG C of dried in vacuum overnight, is the condition of 1:4 in hydrogen and nitrogen volume ratio
Under, 200 DEG C of reductase 12 hours in tube furnace, heating rate is 1 DEG C/min.Gained catalyst is designated as pd/11.5oddma-mp.icp
Record palladium catalyst content and be about 1wt%；It is 11.5wt% that elementary analysiss record n content；The aperture of material is 5.0nm, compares table
Face is 380m2/g；As shown in figure 1, xrd collection of illustrative plates proves that mesoporous polymer catalyst is two-dimentional hexagonal structure, palladium particle diameter is about
3nm.
In 50ml flask add 0.108ml (1.5mmol) bromobenzene and, 0.174ml (1.5mmol) styrene, 0.1g's
This catalyst carries out being heated to reflux stirring, and cools down, with acetone dilute reaction solution, centrifugation catalyst after reaction certain time.
It is analyzed with gas chromatogram.The yield of the stilbene obtaining is 85%.The catalyst being centrifugally separating to obtain is reused
12 times, gained catalyst is designated as pd/11.5oddma-mp-12run, is analyzed with gas chromatogram, obtains the product of stilbene
Rate is 88%.
In the present embodiment, through quaternary ammonium salt modify mesoporous material 11.5oddma-mp (a, b) pd/11.5oddma-mp (c,
D), the tem figure of (e, f) pd/11.5oddma-mp-12run, respectively along the tem figure in (a, c, e) and (b, d, f) direction, specifically
Refer to Fig. 2.In the present embodiment, the mesoporous material pd/11.5oddma-mp, pd/11.5oddma-mp- that modify through quaternary ammonium salt
As shown in figure 3, wherein, a and b is respectively n 1s and pd 3d track xps collection of illustrative plates to the x-ray photoelectron spectroscopy (xps) of 12run.
Embodiment 4
Pd content is 2wt%, and n content is the conjunction of the mesoporous polymer palladium catalyst of recyclable no part of 11.5wt%
Become.By 2.4g p123,2.0g hydrochloric acid is dissolved in 10.0g ethanol and stirring 15 minutes at 40 DEG C, 3.744g tetraethyl orthosilicate,
45 points are stirred at 1.652g octadecyldimethyl [3- (trimethoxy silicon substrate) propyl group] 40 DEG C of (oddma) ammonium chloride 5.0g ethanol
Clock, the pf solution being subsequently adding 20% is mixed together continuation stirring 2 hours.By mixed liquor film, volatilization 5～8 is little at room temperature
When, place in baking oven 100 DEG C of hot polymerizations 48 hours.Knifing, calcines under high pure nitrogen atmosphere for 350 DEG C and obtains final product within 5 hours orderly Jie
Porous materials, are labeled as 11.5oddma-mp (weight/mass percentage composition of the oddma functional group that 11.5 expressions record) through elementary analysiss.
By 4.0ml 0.05g/ml na2pdcl4Ethanol solution and stirring under 0.3g 11.5oddma-mp room temperature condition 12 hours, then
Mixture is filtered, is washed with deionized for several times, 100 DEG C of dried in vacuum overnight, are the bar of 1:5 in hydrogen and nitrogen volume ratio
Under part, in tube furnace, 200 DEG C reduce 3 hours, and heating rate is 1 DEG C/min.Gained catalyst is designated as 2pd/11.5oddma-mp.
Icp records palladium catalyst content and is about 1wt%；It is 8.5wt% that elementary analysiss record n content；The aperture of bet material is 6.0nm,
Specific surface is 375m2/g；Palladium particle diameter is about 3.5nm.
In 50ml flask add 0.108ml (1.5mmol) bromobenzene and, 0.174ml (1.5mmol) styrene, 0.05g's
This catalyst carries out being heated to reflux stirring, and cools down, with acetone dilute reaction solution, centrifugation catalyst after reaction certain time.
It is analyzed with gas chromatogram.The yield of the stilbene obtaining is 88%.
Embodiment 5
Pd content is 1wt%, and n content is the conjunction of the mesoporous polymer palladium catalyst of recyclable no part of 13.0wt%
Become.By 2.4g p123,2.0g hydrochloric acid is dissolved in 10.0g ethanol and stirring 45 minutes at 40 DEG C, 3.744g tetraethyl orthosilicate,
30 points are stirred at 2.448g octadecyldimethyl [3- (trimethoxy silicon substrate) propyl group] 40 DEG C of (oddma) ammonium chloride 5.0g ethanol
Clock, the pf solution being subsequently adding 20% is mixed together continuation stirring 6 hours.By mixed liquor film, volatilization 5～8 is little at room temperature
When, place in baking oven 100 DEG C of hot polymerizations 48 hours.Knifing, calcines under high pure nitrogen atmosphere for 350 DEG C and obtains final product within 5 hours orderly Jie
Porous materials, are labeled as 13.0oddma-mp (weight/mass percentage composition of the oddma functional group that 13.0 expressions record) through elementary analysiss.
By 2.0ml 0.05g/ml na2pdcl4Stir 8 hours under ethanol solution and 0.3g 13.0oddma-mp room temperature condition, then will
Mixture filters, and is washed with deionized for several times, 80 DEG C of dried in vacuum overnight, is the condition of 1:4 in hydrogen and nitrogen volume ratio
Under, in tube furnace, 200 DEG C reduce 3 hours, and heating rate is 1 DEG C/min.Gained catalyst is designated as pd/13.0oddma-mp.icp
Record palladium catalyst content and be about 1wt%；It is 13.0wt% that elementary analysiss record n content；The aperture of bet material is about 7.0nm,
Specific surface is 380m2/g；As shown in figure 1, xrd collection of illustrative plates proves that mesoporous polymer catalyst is two-dimentional hexagonal structure, palladium particle diameter is about
For 3nm.
In 50ml flask add 0.108ml (1.5mmol) bromobenzene and, 0.174ml (1.5mmol) styrene, 0.1g should
Catalyst carries out being heated to reflux stirring, and cools down, with acetone dilute reaction solution, centrifugation catalyst after reaction certain time.With
Gas chromatogram is analyzed.The yield of the stilbene obtaining is 88%.The catalyst being centrifugally separating to obtain is reused 12
Secondary, it is analyzed with gas chromatogram.The yield obtaining stilbene is 88%.
Embodiment 6
Pd content is 2wt%, and n content is the conjunction of the mesoporous polymer palladium catalyst of recyclable no part of 13.0wt%
Become.By 2.4g p123,2.0g hydrochloric acid is dissolved in 10.0g ethanol and stirring 45 minutes at 40 DEG C, 3.744g tetraethyl orthosilicate,
2.448g stirring 30 points at octadecyldimethyl [3- (trimethoxy silicon substrate) propyl group] 40 DEG C of (oddma) ammonium chloride 5.0g ethanol
Clock, the pf solution being subsequently adding 20% is mixed together continuation stirring 6 hours.By mixed liquor film, volatilization 5～8 is little at room temperature
When, place in baking oven 100 DEG C of hot polymerizations 48 hours.Knifing, calcines under high pure nitrogen atmosphere for 350 DEG C and obtains final product within 5 hours orderly Jie
Porous materials, are labeled as 13.0oddma-mp (weight/mass percentage composition of the oddma functional group that 13.0 expressions record) through elementary analysiss.
By 4.0ml 0.05g/ml na2pdcl4Stir 8 hours under ethanol solution and 0.3g 13.0oddma-mp room temperature condition, then will
Mixture filters, and is washed with deionized for several times, 80 DEG C of dried in vacuum overnight, is the condition of 1:4 in hydrogen and nitrogen volume ratio
Under, in tube furnace, 200 DEG C reduce 3 hours, and heating rate is 1 DEG C/min.Gained catalyst is designated as 2pd/13.0oddma-mp.
Icp records palladium catalyst content and is about 2wt%；It is 13.0wt% that elementary analysiss record n content；The aperture of bet material is about
6.0nm, specific surface is 352m2/g；Xrd spectrogram proves that mesoporous polymer catalyst is two-dimentional hexagonal structure, and palladium particle diameter is about
3.8nm.
In 50ml flask add 0.108ml (1.5mmol) bromobenzene and, 0.174ml (1.5mmol) styrene, 0.05g should
Catalyst carries out being heated to reflux stirring, and cools down, with acetone dilute reaction solution, centrifugation catalyst after reaction certain time.With
Gas chromatogram is analyzed.The yield of the stilbene obtaining is 90%.
Embodiment 7
The synthetic method of recyclable no part mesoporous polymer palladium catalyst in the present embodiment, the method specifically includes following
Step:
(1) surfactant, hydrochloric acid are added in organic solvent, at 20 DEG C, stirring reaction 30 minutes, sequentially add
Silicon source, quaternary ammonium salt and carbon source, at 20 DEG C, continue stirring reaction 180 minutes；
(2) after organic solvent volatilizees completely, carry out thermosetting reaction at 40 DEG C, the response time is 36 hours；
(3) it is transferred in tube furnace, in atmosphere of inert gases, high-temperature calcination, remove surfactant, prepared functionalization
Mesoporous polymer carrier；
(4) palladium source is mixed with the mesoporous polymer carrier of functionalization, stir 6 hours at room temperature, by sucking filtration, wash
Wash, be vacuum dried, then carry out reduction reaction, that is, described recyclable no part mesoporous polymer palladium catalyst is obtained.
In step (1), surfactant is nonionic surfactant, and this nonionic surfactant is by brij56
(c16h33eo10) and p123 (eo20po70eo20)、f127(eo106po70eo106) mix for 1:1:2 in molar ratio.
Organic solvent includes ethanol, oxolane, chloroform and ether.
Silicon source is mixed for 1.5:0.5 by the mass ratio of inorganic silane and organosilan.
Quaternary ammonium salt is octadecyldimethyl [3- (methoxyl group silicon substrate) propyl group] ammonium chloride.
The a rank phenolic resin that carbon source is 300 for relative molecular weight.
In step (3), the condition of high-temperature calcination is: is warming up to 275 DEG C with the heating rate of 1 DEG C/min, calcining at constant temperature 10
Hour.Noble gases are high pure nitrogen, and purity is 99.999%.
In step (4), palladium source is pdcl2, the condition of reduction reaction is: in the mixed gas with nitrogen for the hydrogen, controls
The temperature of reduction reaction is 200 DEG C, and the time of reduction reaction is 5 hours.In reduction reaction, the ratio of hydrogen and nitrogen is 1:4.
The catalyst of the present embodiment synthesis is one kind no part, the mesoporous polymer supported palladium containing functionalization consisting of phase-transferring agent
Catalyst, has the ordered mesostructure of two-dimentional six sides, and specific surface area is 250m2/ g, aperture is 3.0nm, functionalization phase transfer
The weight/mass percentage composition of agent is 8.5%, and the weight/mass percentage composition of Metal Palladium is 1%, and the particle diameter of palladium granule is 3nm.Catalyst should
It is catalyzed bromobenzene for aqueous medium and cinnamic heck reaction generates stilbene.
Embodiment 8
The synthetic method of recyclable no part mesoporous polymer palladium catalyst in the present embodiment, the method specifically includes following
Step:
(1) surfactant, hydrochloric acid are added in organic solvent, at 40 DEG C, stirring reaction 10 minutes, sequentially add
Silicon source, quaternary ammonium salt and carbon source, at 40 DEG C, continue stirring reaction 60 minutes；
(2) after organic solvent volatilizees completely, carry out thermosetting reaction at 100 DEG C, the response time is 12 hours；
(3) it is transferred in tube furnace, in atmosphere of inert gases, high-temperature calcination, remove surfactant, prepared functionalization
Mesoporous polymer carrier；
(4) palladium source is mixed with the mesoporous polymer carrier of functionalization, stir 12 hours at room temperature, by sucking filtration, wash
Wash, be vacuum dried, then carry out reduction reaction, that is, described recyclable no part mesoporous polymer palladium catalyst is obtained.
In step (1), surfactant is nonionic surfactant, and this nonionic surfactant is by brij56
(c16h33eo10) and p123 (eo20po70eo20)、f108(eo132po50eo132) mix for 1:1:3 in molar ratio.
Organic solvent includes normal propyl alcohol, oxolane, dichloromethane and ether.
Silicon source is mixed for 1:1 by the mass ratio of inorganic silane and organosilan.
Quaternary ammonium salt is octadecyldimethyl [3- (ethyl-silicone) propyl group] ammonium chloride.
The a rank phenolic resin that carbon source is 500 for relative molecular weight.
In step (3), the condition of high-temperature calcination is: is warming up to 350 DEG C with the heating rate of 5 DEG C/min, calcining at constant temperature 5 is little
When.Noble gases are high pure nitrogen, and purity is 99.999%.
In step (4), palladium source is na2pdcl4, the condition of reduction reaction is: in the mixed gas with nitrogen for the hydrogen, control
The temperature of reduction reaction processed is 300 DEG C, and the time of reduction reaction is 2 hours.In reduction reaction, the ratio of hydrogen and nitrogen is 1:5.
The catalyst of the present embodiment synthesis is one kind no part, the mesoporous polymer supported palladium containing functionalization consisting of phase-transferring agent
Catalyst, has the ordered mesostructure of two-dimentional six sides, and specific surface area is 380m2/ g, aperture is 7.0nm, functionalization phase transfer
The weight/mass percentage composition of agent is 13%, and the weight/mass percentage composition of Metal Palladium is 5%, and the particle diameter of palladium granule is 5nm.Catalyst is applied
It is catalyzed bromobenzene in aqueous medium and cinnamic heck reaction generates stilbene.
Embodiment 9
The synthetic method of recyclable no part mesoporous polymer palladium catalyst in the present embodiment, the method specifically includes following
Step:
(1) surfactant, hydrochloric acid are added in organic solvent, at 35 DEG C, stirring reaction 15 minutes, sequentially add
Silicon source, quaternary ammonium salt and carbon source, at 35 DEG C, continue stirring reaction 90 minutes；
(2) after organic solvent volatilizees completely, carry out thermosetting reaction at 80 DEG C, the response time is 24 hours；
(3) it is transferred in tube furnace, in atmosphere of inert gases, high-temperature calcination, remove surfactant, prepared functionalization
Mesoporous polymer carrier；
(4) palladium source is mixed with the mesoporous polymer carrier of functionalization, stir 8 hours at room temperature, by sucking filtration, wash
Wash, be vacuum dried, then carry out reduction reaction, that is, described recyclable no part mesoporous polymer palladium catalyst is obtained.
In step (1), surfactant is nonionic surfactant, and this nonionic surfactant is by brij76
(c18h37eo10) and brij78 (c16h33eo20)、f108(eo132po50eo132) mix for 1:1:3 in molar ratio.
Organic solvent includes n-butyl alcohol, toluene, oxolane, dichloromethane and ether.
Silicon source is mixed for 0.5:1 by the mass ratio of inorganic silane and organosilan.
Quaternary ammonium salt is octadecyldimethyl [3- (ethyl-silicone) propyl group] ammonium chloride.
The a rank phenolic resin that carbon source is 400 for relative molecular weight.
In step (3), the condition of high-temperature calcination is: is warming up to 320 DEG C with the heating rate of 3 DEG C/min, calcining at constant temperature 7 is little
When.Noble gases are high-purity argon gas, and purity is 99.999%.
In step (4), palladium source is na2pdcl4, the condition of reduction reaction is: in the mixed gas with nitrogen for the hydrogen, control
The temperature of reduction reaction processed is 240 DEG C, and the time of reduction reaction is 3 hours.In reduction reaction, the ratio of hydrogen and nitrogen is 1:5.
The catalyst of the present embodiment synthesis is one kind no part, the mesoporous polymer supported palladium containing functionalization consisting of phase-transferring agent
Catalyst, has the ordered mesostructure of two-dimentional six sides, and specific surface area is 320m2/ g, aperture is 4.0nm, functionalization phase transfer
The weight/mass percentage composition of agent is 11%, and the weight/mass percentage composition of Metal Palladium is 3%, and the particle diameter of palladium granule is 4nm.Catalyst is applied
It is catalyzed bromobenzene in aqueous medium and cinnamic heck reaction generates stilbene.
The above-mentioned description to embodiment is to be understood that and use invention for ease of those skilled in the art.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
, according to the announcement of the present invention, the improvement made without departing from scope and modification all should be the present invention's for field technique personnel
Within protection domain.
Claims (10)
1. recyclable no part mesoporous polymer palladium catalyst is it is characterised in that this catalyst is one kind no part, containing functional
Change the mesoporous polymer loaded palladium catalyst of consisting of phase-transferring agent, there is the ordered mesostructure of two-dimentional six sides, specific surface area is 250-
380m2/ g, aperture is 3.0-7.0nm, and the weight/mass percentage composition of functionalization consisting of phase-transferring agent is 8.5-13%, the quality hundred of Metal Palladium
Content is divided to be 1-5%, the particle diameter of palladium granule is 3-5nm.
2. recyclable no part mesoporous polymer palladium catalyst according to claim 1 is it is characterised in that described function
Change consisting of phase-transferring agent is quaternary ammonium salt.
3. as claimed in claim 1 recyclable no part mesoporous polymer palladium catalyst synthetic method it is characterised in that should
Method specifically includes following steps:
(1) surfactant, hydrochloric acid are added in organic solvent, at 20-40 DEG C, stirring reaction 10-30 minute, then add successively
Enter silicon source, quaternary ammonium salt and carbon source, at 20-40 DEG C, continue stirring reaction 60-180 minute；
(2) after organic solvent volatilizees completely, carry out thermosetting reaction at 40-100 DEG C, the response time is 12-36 hour；
(3) it is transferred in tube furnace, in atmosphere of inert gases, high-temperature calcination, remove surfactant, Jie of prepared functionalization
Pore polymer carrier；
(4) palladium source is mixed with the mesoporous polymer carrier of functionalization, at room temperature stir 6-12 hour, by sucking filtration, washing,
Vacuum drying, then carry out reduction reaction, that is, described recyclable no part mesoporous polymer palladium catalyst is obtained.
4. recyclable no part mesoporous polymer palladium catalyst according to claim 3 synthetic method it is characterised in that
Surfactant described in step (1) is nonionic surfactant, and described organic solvent includes c1-c4Alcohols, first
One or more of benzene, oxolane, chloroform, dichloromethane or ether, described silicon source includes organosilan or inorganic silicon
One of alkane or two kinds, described quaternary ammonium salt includes octadecyldimethyl [3- (methoxyl group silicon substrate) propyl group] ammonium chloride or ten
One of eight alkyl dimethyls [3- (ethyl-silicone) propyl group] ammonium chloride or two kinds, described carbon source for relative molecular weight is
The a rank phenolic resin of 300-500.
5. recyclable no part mesoporous polymer palladium catalyst according to claim 4 synthetic method it is characterised in that
Described nonionic surfactant includes poly(ethylene oxide)-poly(propylene oxide) triblock copolymer or alkane-polycyclic oxygen second
One of alkane diblock copolymer.
6. recyclable no part mesoporous polymer palladium catalyst according to claim 5 synthetic method it is characterised in that
Described nonionic surfactant is selected from c16h33eo10、c16h33eo20、c18h37eo10、eo20po70eo20、eo106po70eo106、
eo132po50eo132One or more of.
7. recyclable no part mesoporous polymer palladium catalyst according to claim 4 synthetic method it is characterised in that
In described silicon source, inorganic silane and the mass ratio of organosilan are 1.5:0.5,1:1 or 0.5:1.
8. recyclable no part mesoporous polymer palladium catalyst according to claim 3 synthetic method it is characterised in that
The condition of the high-temperature calcination described in step (3) is: is warming up to 275-350 DEG C with the heating rate of 1-5 DEG C/min, calcining at constant temperature
5-10 hour.
9. recyclable no part mesoporous polymer palladium catalyst according to claim 3 synthetic method it is characterised in that
Palladium source described in step (4) is pdcl2Or na2pdcl4One of, the condition of described reduction reaction is: in hydrogen and nitrogen
In the mixed gas of gas, the temperature of reduction reaction is controlled to be 200-300 DEG C, the time of reduction reaction is 2-5 hour.
10. as claimed in claim 1 the application of recyclable no part mesoporous polymer palladium catalyst it is characterised in that described
Catalyst be applied to aqueous medium catalysis bromobenzene and cinnamic heck reaction generate stilbene.
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| CN110152730A (en) * | 2019-04-29 | 2019-08-23 | 上海师范大学 | A kind of functional ordered mesopore Polymer-supported palladium catalyst and preparation method thereof |
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| CN107774246A (en) * | 2017-09-29 | 2018-03-09 | 兰州大学 | The preparation method and applications of loaded palladium catalyst in a kind of hollow nanometer capsule core |
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| CN108675262A (en) * | 2018-05-07 | 2018-10-19 | 南京大学 | A method of catalysis formic acid hydrogen manufacturing |
| CN110152730A (en) * | 2019-04-29 | 2019-08-23 | 上海师范大学 | A kind of functional ordered mesopore Polymer-supported palladium catalyst and preparation method thereof |
| CN110075900A (en) * | 2019-04-30 | 2019-08-02 | 上海师范大学 | The mesoporous carbon-silica catalyst material and preparation method and application of supported palladium |
| CN110075900B (en) * | 2019-04-30 | 2022-12-16 | 上海师范大学 | Palladium-loaded mesoporous carbon-silicon dioxide catalyst material, and preparation method and application thereof |
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