CN107824218A - A kind of metal composite Janus nanometer sheet catalyst and its production and use - Google Patents
A kind of metal composite Janus nanometer sheet catalyst and its production and use Download PDFInfo
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- CN107824218A CN107824218A CN201711095241.9A CN201711095241A CN107824218A CN 107824218 A CN107824218 A CN 107824218A CN 201711095241 A CN201711095241 A CN 201711095241A CN 107824218 A CN107824218 A CN 107824218A
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- metal
- janus nanometer
- janus
- catalyst
- nanometer sheets
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 239000002905 metal composite material Substances 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title description 2
- 229910052751 metal Inorganic materials 0.000 claims abstract description 80
- 239000002184 metal Substances 0.000 claims abstract description 80
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 15
- 238000005859 coupling reaction Methods 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 238000001338 self-assembly Methods 0.000 claims abstract description 5
- 238000001484 Pickering emulsion method Methods 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 230000003993 interaction Effects 0.000 claims abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 229910000765 intermetallic Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 229910052763 palladium Inorganic materials 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000012188 paraffin wax Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 239000003921 oil Substances 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002923 metal particle Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 7
- -1 phenyltriethoxy silanes Alkane Chemical class 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 235000007164 Oryza sativa Nutrition 0.000 claims description 5
- 239000008346 aqueous phase Substances 0.000 claims description 5
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims description 5
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 235000009566 rice Nutrition 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims description 4
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 4
- NJSVDVPGINTNGX-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethanamine Chemical compound CCC[Si](OC)(OC)OCN NJSVDVPGINTNGX-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 230000033228 biological regulation Effects 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 229910010199 LiAl Inorganic materials 0.000 claims description 2
- 229910010084 LiAlH4 Inorganic materials 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
- 239000003502 gasoline Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 2
- 150000002892 organic cations Chemical class 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 1
- 150000003623 transition metal compounds Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 238000002360 preparation method Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002082 metal nanoparticle Substances 0.000 abstract description 3
- 150000002941 palladium compounds Chemical class 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 6
- 150000003058 platinum compounds Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000013283 Janus particle Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 description 4
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000011157 advanced composite material Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-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
- OEHNVKBOQOXOJN-UHFFFAOYSA-N 2-(4-nitrophenyl)phenol Chemical compound OC1=CC=CC=C1C1=CC=C([N+]([O-])=O)C=C1 OEHNVKBOQOXOJN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 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
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000002604 ultrasonography 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
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
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- 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 present invention prepares amphipathic Janus nanometer sheets using Pickering emulsion methods by collosol and gel and self assembly, recycles amphipathic Janus nanometer sheets side amino and the interaction fabricated in situ of metal precursor to have the metal composite Janus nanometer sheet catalyst of catalysis.Metal composite Janus nanometer sheets combine the high catalytic activity of the amphipathic structural advantage and metal nanoparticle of Janus nanometer sheets, and very high catalytic activity and repeat performance are shown in Suzuki aryl coupling reactions.Meanwhile the preparation method of metal composite Janus nanometer sheet catalyst provided by the invention is simple and easy, strong applicability.
Description
Technical field
The present invention relates to a kind of catalyst and its preparation method and application, and in particular to a kind of Metal Palladium compound Janus is received
Rice piece catalyst and its catalysis process of preparation and Suzuki aryl coupling reactions, belong to metal nano material catalyst technology neck
Domain.
Background technology
Transition metal nanoparticles are highly important because its excellent activity and selectivity occupies in catalytic field
Position.But transition metal nanoparticles, because particle diameter is small, surface energy is big, there is serious reunion tendency, it will cause metal nano
Particle-catalytic activity reduces.To improve transition metal nanoparticles agglomeration traits, protection is added generally during its preparation
Agent, although can so alleviate agglomeration traits to a certain extent, during catalytic reaction, protective agent is possible to lose
Effect, causes catalyst to reuse, or reuse efficiency is very low.Palladium nanoparticles in transition metal are efficient because of its
Catalytic activity and be widely applied prospect and greatly paid close attention to by people, palladium nano-crystal body is as a kind of important noble metal
Nano material, relative low price, and organic coupling reaction such as Suzuki, Heck and Stille can be catalyzed.Research shows,
In the presence of metal palladium catalyst is in the form of nanoscale, higher reactivity and selectivity can be shown, and nano particle
Size and shape has significant impact to its catalytic performance.
Janus was the two-sided god in ancient Roman's mythology, since French scientist Pierre-Gilles De in 1991
Gennes describes the particle (P.G.De with double properties using the words of Janus mono- first in the prize-winning speech of its Nobel
Gennes.Rev.Mod.Phys.1992,64,645-648.) after, the Janus particles that this surface has double properties just cause
People great research interests.Nanoscale Janus particles realize two kinds of differences even opposite nature on single particle
It is integrated with uniformly, in combination with the skin effect and small-size effect of nano material, showing the physics and chemically of uniqueness
Energy.Therefore, Janus nano particles have huge answer in fields such as emulsion-stabilizing, optical probe, colored display and nano-motors
With prospect (F.X.Liang, C.L.Zhang, Z.Z.Yang, Adv.Mater.2014,26,6944-6949.).
At present, the report on sheet Janus preparation method of granules is seldom.M ü ller et al., which are reported, utilizes block copolymerization
Thing self assembly prepares organic sheet Janus materials, but the raw material and assembling condition of this method needs require harsh, and has
Machine Janus components poor solvent resistance can limit its application in emulsification etc..However, the anisotropy of Janus flaky materials
There is more abundant phase behavior, not only chemical composition is non-centrosymmetrical that its pattern is also non-centrosymmetrical.Nonomura
Et al. the result of study of (Y.Nonomura, S.Komura, K.Tsujii, 2004,20,11821-11823) show：Sheet
Energy of adsorption several orders of magnitude higher than the energy of adsorption of molecular surface active agent of Janus particles；The stable emulsion ratio of sheet-like particle
The particle stabilized emulsion intercalation method of other structures is high.Compared with spherical Janus particles, the Janus pieces of anisotropic structure exist
The rotation of emulsion interface is restricted, therefore sheet-like particle is more beneficial for the stabilization of emulsion than spheric granules.If by nanogold
Category particle be supported in Janus nanometer sheets, can be had simultaneously emulsification and catalytic performance compound Janus nanometer sheet, one
Aspect can solve the problems, such as that metal nanoparticle is easily reunited, and on the other hand can then utilize the emulsibility of Janus nanometer sheets
The contact area of water-oil phase can be increased, improve catalytic activity.
The content of the invention
For problems of the prior art, urged by combining Janus nanometers chip architecture and metal Pd nano particle height
Change the advantage of activity, it is an object of the invention to provide a kind of use condition is gentle, easily realize, catalytic activity is strong, reuses
Property good and wide applicability metal composite Janus nanometer sheet catalyst preparation method and its in Suzuki catalytic reactions should
Use method.Amphipathic Janus nanometer sheets are prepared by collosol and gel and self assembly using Pickering emulsion methods, recycling is received
Rice piece side amino and the fabricated in situ that interacts of metal precursor have the metal composite Janus nanometers of catalysis
Piece.Metal composite Janus nanometer sheets combine the high catalysis of the amphipathic structural advantage and metal nanoparticle of Janus nanometer sheets
Activity, very high catalytic activity and repeat performance are shown in Suzuki aryl coupling reactions.Meanwhile the present invention provides
The preparation method based on metal composite Janus nanometer sheet catalyst it is simple, strong applicability.
According to the first embodiment provided by the invention, there is provided metal composite Janus nanometer sheet catalyst.
A kind of metal composite Janus nanometer sheet catalyst, the catalyst are to be coagulated using Pickering emulsion methods by colloidal sol
Glue and self assembly prepare amphipathic Janus nanometer sheets, recycle amphipathic Janus nanometer sheets side amino and metal precursor
The fabricated in situ that interacts has the metal composite Janus nanometer sheets of catalysis.
Preferably, the metal in the metal composite Janus nanometer sheets is nano metal particles, in nano metal particles
Metal be transition metal, be preferably palladium, the one or more in platinum, ruthenium and gold；
Preferably, the particle diameter of the nano metal particles is 1~20nm, preferably 2~15nm, more preferably 3~
10nm。
According to second of embodiment provided by the invention, there is provided one kind prepares metal composite Janus nanometer sheet catalyst
Method.
A kind of method for preparing metal composite Janus nanometer sheet catalyst prepares catalyst described in the first embodiment
Method, this method comprises the following steps：
1) the amphipathic Janus nanometer sheets that side is amino are prepared：With the HSMA (styrene-maleic anhydride copolymers of hydrolysis
Thing) it is emulsifying agent, adjust pH value, heating, as aqueous phase；With APTMS (aminopropyl trimethoxysilane), the PTES (second of phenyl three
TMOS) and TEOS (tetraethyl orthosilicate) be precursors, add in the paraffin wax of melting, heat, stirring, as oil
Phase；Oil phase and aqueous phase are mixed, high speed shear, O/W type emulsions is formed, obtains paraffin/silicon dixoide nucleocapsid structure microballoon；Using molten
Agent dissolving removes the oil phase paraffin inside microballoon；Amido modified Janus hollow balls are obtained after drying；Again with cell disruptor pair
It is amino that the hollow ball, which is crushed to obtain side, and opposite side is the amphipathic Janus nanometer sheets of phenyl；
2) synthesis of metal composite Janus nanometer sheets catalyst：The amphipathic Janus nanometer sheets of gained are dissolved in shape in solvent
Into reactant mixture, metallic compound or its metal precursor are added in the reactant mixture, utilizes metallic compound or gold
Belong to the interaction of presoma and amphipathic Janus nanometer sheets side amino so that metal is carried on the amphipathic Janus and received
On rice piece, add excessive reductant and the metal being carried in Janus nanometer sheets is reduced into 0 valency, separate, solids is washed
Wash, dry, obtain metal composite Janus nanometer sheet catalyst.
Preferably, the metal in the metal composite Janus nanometer sheets is nano metal particles, in nano metal particles
Metal be transition metal, be preferably palladium, the one or more in platinum, ruthenium and gold；
Preferably, the particle diameter of the nano metal particles is 1~20nm, preferably 2~15nm, more preferably 3~
10nm。
Preferably, metallic compound described in step 2) is transistion metal compound, metal precursor is transition metal
Presoma.Preferably, the metal in the metallic compound or metal precursor is one kind or more in palladium, platinum, ruthenium, gold
Kind.It is further preferred that the metal in the metallic compound or metal precursor is palladium or platinum.Preferably, the metallic compound
Or metal precursor is chlorine palladium acid H2PdCl4, ammonium chloropalladate salt (NH4)2PdCl4, chloroplatinic acid H2PtCl6, chloroplatinic acid ammonium salt (NH4)2PtCl6In one kind.
Preferably, reducing agent described in step 2) is in chitosan, ascorbic acid, alanate, borane derivative
It is one or more.Preferably, alanate is R2AIH、RAIH2Or ER3One kind in AlH types, wherein：E is Li or Na, R are
Alkyl group (such as LiAlH4Or LiAl [OC (Me)3]3H).Borane derivative is FBH4-nLnType borane derivative, wherein：n
For the integer in 0-4, F is organic cation, four ammonium cations, Na, Li or K, and L is alkyl, alkoxy, amine, acyl ammonia or phosphatization
Hydrogen (such as [CH3(CH2)3]4NBH3CN or NaB [OOCMe]3H).It is further preferred that the reducing agent is sodium borohydride aqueous solution.
Preferably, the solvent is ethanol.
In the present invention, TEOS in step 1)：APTMS：PTES mol ratio is 0.5~10:0.5~2:1；Preferably 1
~8:0.6~1.5:1；More preferably 2~7:0.8~1.2:1.
In the present invention, the regulations of pH described in step 1) are using acid regulation, it is preferred to use hydrochloric acid is adjusted.PH value is adjusted to 1
~5, preferably 2~4；More preferably 2.5~3.
Preferably, the concentration of the hydrochloric acid is 1~5mol/L, preferably 2~4mol/L.
In the present invention, solvent described in step 1) is ethanol, gasoline, carbon disulfide, benzene,toluene,xylene, dichloromethane
One or more in alkane, carbon tetrachloride, chloroform, tetrahydrofuran or hexamethylene.
In the present invention, step 2) is specially：Amphipathic Janus nanometer sheets obtained by step 1) are dissolved in solvent and formed instead
Mixture is answered, metallic compound or the aqueous solution of metal precursor are slowly added dropwise in the reactant mixture, it is (excellent in 10~50 DEG C
Elect 15~40 DEG C, more preferably 20~30 DEG C, such as 25 DEG C as) 3~12h of reaction (preferably 5~10h, more preferably 6~8h,
Such as 8h), there is black precipitate precipitation, add excessive NaBH4, the metal being carried in Janus nanometer sheets is reduced into 0 valency,
Then reaction stoste is centrifuged, sediment is collected, by gained precipitating solvent, H2More alternately washings of O；Solid after centrifugation is put
It is dried in vacuo in vacuum drying chamber, that is, obtains metal composite Janus nanometer sheet catalyst.
In the present invention, the solvent is ethanol；The speed that metallic compound or the aqueous solution of metal precursor is added dropwise is 1
~30mL/min；Preferably 3~20mL/min；More preferably 5~15mL/min.
In the present invention, in metallic compound or the aqueous solution of metal precursor metallic compound or metal precursor it is dense
Spend for 0.01~0.1mmol/mL；Preferably 0.02~0.08mmol/mL；More preferably 0.03~0.06mmol/mL.
In the present invention, the amount that metallic compound or the aqueous solution of metal precursor are added dropwise in the reactive mixture is 0.1
~5mL/50mg Janus nanometer sheets；Preferably 0.3~3mL/50mg Janus nanometer sheets；More preferably 0.5~2mL/50mg
Janus nanometer sheets.
In the present invention, NaBH is added4Amount to add 2~10 times of equivalents of metallic compound or metal precursor；It is excellent
Elect 3~8 times of equivalents as；More preferably 4~6 times of equivalents.
In the present invention, the centrifugal rotational speed of the centrifugation is 5000~20000rpm；Preferably 6000~15000rpm；More
Preferably 8000~12000rpm.
In the present invention, the vacuum drying temperature is 30~90 DEG C；Preferably 40~80 DEG C, more preferably 45~70
℃。
According to the third embodiment provided by the invention, there is provided according to a kind of metal composite Janus nanometer sheet catalyst
Purposes.
A kind of purposes of metal composite Janus nanometer sheet catalyst, or the use of catalyst described in the first embodiment
On the way, or according to second of embodiment methods described the purposes of the catalyst prepared, metal composite Janus nanometer sheets are catalyzed
Agent is used to be catalyzed Suzuki aryl coupling reactions.
In the present invention, the catalysis Suzuki aryl coupling reactions are specially：Metal composite Janus nanometer sheets are catalyzed
Agent is scattered in the mixed liquor of DMF and water, is added iodobenzene, phenyl boric acid, potassium carbonate, is heated under magnetic agitation, condensing reflux, is carried out
Suzuki catalytic reactions.
In the present invention, the concrete operations for preparing the amphipathic nanometer sheets of Janus containing amino are：By deionized water and benzene second
Alkene-copolymer-maleic anhydride aqueous solution is well mixed to obtain solution A, makes its pH (for example, being approximately equal to 3) with hydrochloric acid conditioning solution A,
Solution A is placed in constant temperature in 50~90 DEG C of water-bath afterwards, as aqueous phase；By tetraethyl orthosilicate, aminopropyl trimethoxysilane
It is added sequentially to phenyl-triethoxysilane in the paraffin wax of melting, is stirred at 50~90 DEG C, makes three kinds of silane examinations
Agent is well mixed in paraffin and is used as oil phase；Water-oil phase is mixed, and the high speed shear under 5000~20000rpm/min, obtain
To O/W type emulsions.O/W type emulsions are placed in mechanic whirl-nett reaction 6~24 hours in 50~90 DEG C of oil bath pans；After reaction terminates,
Centrifuged, obtain paraffin/silica core Sales structure microspheres, be washed with deionized, at 50~90 DEG C drying obtain it is white
Color powder；Deparaffnize kernel is removed with tetrahydrofuran supersound washing, amido modified Janus hollow balls are obtained after drying；Again with thin
It is amino that born of the same parents' pulverizer is crushed to obtain side to the hollow ball, and opposite side is the Janus nanometer sheets of phenyl.
In the present invention, it is H using transistion metal compound or transition metal precursor2PdCl4, by 0.1g PdCl2Add
Enter the dense HCl of 1mL, add 10mL distilled water, obtained after 40 ° of heating water baths dissolve.And H2PdCl4Dosage be Janus nanometers
0.1~2 times of nitrogen atom content, is calculated by mass percentage in piece.
The purposes of metal composite Janus nanometer sheet catalyst prepared by the present invention, metal composite Janus nanometer sheets are catalyzed
Agent is used for the coupling reaction of halogeno-benzene.
Metal composite Janus nanometer sheet catalyst prepared by the present invention combines the amphipathic and high of Janus nanometer sheets and urged
Change the nano-particles such as transition metal palladium, the platinum of activity, be advantageous to water-oil phase catalysis, formed by the effect of Janus nanometer sheets
Emulsion, the contact area of reaction is substantially increased, be advantageous to the raising of reaction efficiency, and catalyst amount is few, reaction speed
It hurry up, yield is high.
In the present invention, the metal composite Janus nanometer sheets catalyst due to the amphipathic of Janus nanometer sheets, and
By amino side uniform load Pd nano particle, its stability and catalytic efficiency are much higher by the nanometer palladium chtalyst of exclusive use
Agent.Take iodobenzene 204mg (1mmol), phenyl boric acid 184mg (1.5mmol), potassium carbonate 0.6g (4.3mmol), metal composite Janus
Nanometer sheet catalyst 25mg (0.025mol%), solvent DMF 16mL, H2O 4mL, are placed in single port bottle, under l00 DEG C of oil bath
Condensing reflux reaction 30min conversion ratios can reach 86%.Compared with existing catalyst, the catalysis of metal composite Janus nanometer sheets
Agent only needs few content (0.025mol%) just can reach higher conversion ratio.
Compared with prior art, technical scheme has following advantageous effects：
1st, the Janus nanometer sheets used in the present invention are with amphipathic characteristic, the i.e. hydrophilic opposite side oleophylic in nanometer sheet side, are adopted
Can largely it be prepared with one-step method, preparation method is relatively easy, mild condition, and flaky material can be greatly enhanced the stabilization of emulsion
Property.
2nd, the Janus nanometer sheets that metal composite Janus nanometer sheet catalyst prepared by the present invention uses, wherein containing amino one
Side can load various metals such as palladium, platinum, ruthenium, gold etc., and the metal loaded is nanoscale, is uniformly dispersed, and Size Distribution is small, increase
The avtive spot of catalyst is added；Catalyst prepared by the present invention is heterogeneous, by simply centrifuging i.e. after the completion of reaction
Can be demulsified recovery, be reused.
3rd, metal composite Janus nanometer sheet catalyst prepared by the present invention has amphipathic, particularly suitable for halogeno-benzene
Coupling reaction (i.e. Suzuki aryl coupling reaction), catalyst amount is few, and reaction speed is fast, and yield is high.
4th, metal composite Janus nanometer sheet catalyst of the invention, reclaims after catalytic reaction, is found after recycling,
By four circulations, conversion ratio of the metal composite Janus nanometer sheets catalyst to the Suzuki coupling reactions of iodobenzene-phenyl boric acid
Remain to reach more than 90%.
Thus, the metal composite Janus nanometer sheets catalyst that prepared by the present invention (such as urge by Technique of Nano Pd compound Janus nanometer sheet
Agent), using the asymmetry of Janus materials chemistries composition and aspect of performance, draw in the subregion of inorganic carrier choice of the substrates
Enter transition metal nanoparticles, realize the structure of advanced composite material (ACM).The catalyst activity is strong, selectivity is good, reaction bar
Part is gentle, reusability is good and applicability is wide, has good application value in fields such as heterogeneous catalysis.
Brief description of the drawings
Fig. 1 schemes for Metal Palladium compound Janus nanometer sheet catalyst SEM of the present invention；
Fig. 2 schemes for Metal Palladium compound Janus nanometer sheet catalyst TEM of the present invention；
Fig. 3 is Metal Palladium compound Janus nanometer sheet catalyst XRD of the present invention；
Fig. 4 schemes for Metal Palladium compound Janus nanometer sheet catalyst EDX of the present invention；
Fig. 5 schemes for metal platinum compound Janus nanometer sheet catalyst SEM of the present invention；
Fig. 6 schemes for metal platinum compound Janus nanometer sheet catalyst TEM of the present invention；
Fig. 7 is metal platinum compound Janus nanometer sheet catalyst XRD of the present invention；
Fig. 8 schemes for metal platinum compound Janus nanometer sheet catalyst EDX of the present invention；
Fig. 9 schemes for metal platinum compound Janus nanometer sheet catalyst XPS of the present invention；
Figure 10 is that Metal Palladium compound Janus nanometer sheet of the present invention is catalyzed iodobenzene-phenyl boric acid and reacts different cycle-indexes and right
Answer conversion ratio.
Embodiment
For the present invention using the hydrolysate of styrene-maleic anhydride alternate copolymer as emulsifying agent (HSMA), it synthesizes step
Suddenly according to bibliography (Z.G.Jin, Y.H.Wang, J.G.Liu, Z.Z.Yang, Polymer 2008,49:2903-2910.)
Carry out.
Embodiment 1
A kind of method for preparing metal composite Janus nanometer sheet catalyst, this method comprise the following steps：
(1) preparation of the nanometer sheets of Janus containing amino:
The 15mL styrene maleic anhydride copolymers aqueous solution (mass concentration of maleic anhydride of styrene is 10wt.%) adds
It is well mixed in 75mL distilled water, above-mentioned pH value of water solution is adjusted to 2.5 with 2mol/L hydrochloric acid, is placed in 70 DEG C of water-baths.Take 25g
The high-efficiency tissue paraffin wax of 52 DEG C of fusing point is simultaneously heated to paraffin at 70 DEG C and melted completely.Take respectively 5.2g tetraethyl orthosilicates,
0.92g aminopropyl trimethoxysilanes, 1.2g phenyl triethoxysilanes are added in the paraffin of above-mentioned melting and are well mixed.
By the mixed with water and high speed shearing emulsification dissolved with the paraffin solution of three kinds of precursors, shear rate 12000rpm, breast
The change time is 5min, forms O/W type emulsions；70 DEG C of isothermal reaction 12h.Question response system is cooled to room temperature, filters, washs, be dry
Paraffin/silicon dixoide nucleocapsid structure microballoon is obtained after dry.Above-mentioned sample is distributed in tetrahydrofuran under ultrasonication, filter,
Dry, washed three times with tetrahydrofuran, obtain the nanometer sheets of Janus containing amino.
(2) synthesis of Metal Palladium compound Janus nanometer sheet catalyst：
The Janus nanometer sheets that step (1) obtains are dissolved in ethanol and form reactant mixture, are delayed in the reactant mixture
It is slow that H is added dropwise2PdCl4, 6h is reacted in 25 DEG C, has black precipitate precipitation, adds excessive NaBH4(addition is chlorine palladium acid H2PdCl4
5 times of equivalents), the metal being carried in Janus nanometer sheets is reduced into 0 valency, then will the centrifugation of reaction stoste (centrifugal rotational speed is
Sediment 10000rpm) is collected, by gained precipitation ethanol, H2It is placed in after O more alternating washings, centrifugations 80 in vacuum drying chamber
DEG C drying, that is, obtain Metal Palladium compound Janus nanometer sheet catalyst.
Obtained Metal Palladium compound Janus nanometer sheet catalyst is detected, the result of acquisition is as Figure 1-4.
Embodiment 2
Embodiment 1 is repeated, simply with chloroplatinic acid H2PtCl6Chlorine palladium acid H in replacement step (2)2PdCl4, obtain metal platinum and answer
Close Janus nanometer sheet catalyst.
Obtained metal platinum compound Janus nanometer sheet is detected, the result of acquisition is as shown in figures 5-9.
Embodiment 3
Embodiment 1 is repeated, simply with ammonium chloropalladate salt (NH4)2PdCl4Chlorine palladium acid H in replacement step (2)2PdCl4, obtain
Metal Palladium compound Janus nanometer sheet catalyst.
Embodiment 4
Take iodobenzene 204mg, phenyl boric acid 184mg, potassium carbonate 0.6g, the Metal Palladium compound Janus nanometer sheet in embodiment 1 is urged
Agent 25mg, solvent DMF 16mL, H2O 4mL, are placed in single port bottle, and condensing reflux reacts under l00 DEG C of oil bath.Reaction is certain
After time, extract reaction solution and centrifuged with 10000rpm rotating speeds, collect supernatant liquor, determined after dilution by high-efficient liquid phase chromatogram HPLC
Reaction yield.Lower sediment is washed by ethanol, centrifuged more than 5 times, eliminates remnants phenyl boric acid and reaction product biphenyl,
Then the potassium carbonate in above removing centrifuge tube is repeated 5 times with distillation water washing, centrifugation again, it is compound to Metal Palladium to realize
The recovery of Janus nanometer sheet catalyst.The Janus nanometer sheet catalyst that recovery obtains is reused for be catalyzed iodobenzene and phenyl boric acid
Coupling reaction, repeat more than operate.Find that the Metal Palladium compound Janus nanometer sheet prepared by us is catalyzed by HPLC tests
When reacting 30min, for conversion ratio i.e. up to 86.2%, yield reaches 85.4% for agent.2h is reacted, yield is up to 90.78%.Reaction
Conversion ratio and yield are almost converted completely after 8h, continue reaction conversion ratio increase unobvious, and yield is increased slightly.And repeat to react
Conversion ratio still has more than 90% after being catalyzed 4 times, and after being catalyzed 5 times, catalytic efficiency remains in that more than 75%.Metal Palladium is compound
Janus nanometer sheets catalyst circulates 5 times HPLC yields such as Figure 10.
Embodiment 5
Metal Palladium compound Janus nanometer sheet catalyst 25mg in Example 1 adds 25mL in 50mL reaction bulbs
0.1mM paranitroanisole solution, ultrasonic disperse 2min, add 0.5mL 0.2M NaBH4The aqueous solution, continue to be placed in 25 DEG C
Emulsification 5min is carried out in ultrasound environments, UV curves is measured after being centrifuged by differential responses time sampling, it is compound to probe into Metal Palladium
Janus nanometer sheet catalyst is in emulsion system to the catalytic effect of paranitroanisole reduction reaction.When experiment shows some
Between after Metal Palladium compound Janus nanometer sheet catalyst it is undesirable to the reduction reaction catalytic effect of paranitroanisole.
Embodiment 6
Metal Palladium compound Janus nanometer sheet catalyst 25mg in Example 1 adds 25mL in 50mL reaction bulbs
1mM p-nitrophenyl phenol solutions, ultrasonic disperse 2min, add 0.5mL 0.2mol NaBH4The aqueous solution, continue to be placed in 25 DEG C of perseverances
Temperature reaction, UV curves are measured after being centrifuged by differential responses time sampling, Metal Palladium compound Janus nanometer sheet catalyst is probed into and exists
To the catalytic effect of p-nitrophenol reduction reaction in homogeneous system.Metal Palladium compound Janus is received after experiment shows some time
Rice piece catalyst is undesirable to the reduction reaction catalytic effect of p-nitrophenol.
In Suzuki aryl coupling reactions, Metal Palladium compound Janus nanometer sheet catalyst of the invention or metal platinum are answered
Close the dosage of Janus nanometer sheet catalyst, only Pd (PPh3)4The 0.1~1% of dosage, and catalytic effect is more preferably.
Metal Palladium compound Janus nanometer sheet catalyst prepared by the present invention has amphipathic, and the coupling for halogeno-benzene is anti-
Answer (Suzuki coupling reactions) that there is unique catalytic effect, catalyst amount is few, and reaction speed is fast, and yield is high.It is being catalyzed
Can reclaim after reaction, be found after recycling, by four times circulation, Metal Palladium compound Janus nanometer sheet catalyst to iodobenzene-
The conversion ratio of phenyl boric acid Suzuki coupling reactions remains to reach more than 90%.
Claims (10)
1. a kind of metal composite Janus nanometer sheet catalyst, the catalyst is to pass through collosol and gel using Pickering emulsion methods
Amphipathic Janus nanometer sheets are prepared with self assembly, recycle the phase of amphipathic Janus nanometer sheets side amino and metal precursor
Interaction fabricated in situ has the metal composite Janus nanometer sheets of catalysis.
2. catalyst according to claim 1, it is characterised in that：Metal in the metal composite Janus nanometer sheets is
Nano metal particles, the metal in nano metal particles is transition metal, preferably one kind or more in palladium, platinum, ruthenium and gold
Kind；Preferably, the particle diameter of the nano metal particles is 1~20nm, preferably 2~15nm, more preferably 3~10nm.
3. a kind of method for preparing metal composite Janus nanometer sheet catalyst or the side for preparing the catalyst of claim 1 or 2
Method, this method comprise the following steps：
1) the amphipathic Janus nanometer sheets that side is amino are prepared：It is with the HSMA (styrene-maleic anhydride copolymer) of hydrolysis
Emulsifying agent, adjust pH value, heating, as aqueous phase；With APTMS (aminopropyl trimethoxysilane), PTES (phenyltriethoxy silanes
Alkane) and TEOS (tetraethyl orthosilicate) be precursors, add in the paraffin wax of melting, heat, stirring, as oil phase；It is mixed
Oil phase and aqueous phase are closed, high speed shear, O/W type emulsions is formed, obtains paraffin/silicon dixoide nucleocapsid structure microballoon；It is molten using solvent
Solution removes the oil phase paraffin inside microballoon；It is dried to obtain amido modified Janus hollow balls；It is hollow to this with cell disruptor again
It is amino that ball, which is crushed to obtain side, and opposite side is the amphipathic Janus nanometer sheets of phenyl；
2) synthesis of metal composite Janus nanometer sheets catalyst：The amphipathic Janus nanometer sheets of gained are dissolved in solvent and formed instead
Mixture is answered, metallic compound or its metal precursor are added in the reactant mixture, before metallic compound or metal
Drive the interaction of body and amphipathic Janus nanometer sheets side amino so that metal is carried on the amphipathic Janus nanometer sheets
On, add excessive reductant and the metal being carried in Janus nanometer sheets is reduced into 0 valency, separate, solids is washed, done
It is dry, obtain metal composite Janus nanometer sheet catalyst.
4. according to the method for claim 3, it is characterised in that：Metallic compound described in step 2) is transition metal compound
Thing, metal precursor are transition metal precursor；Preferably, the metal in the metallic compound or metal precursor is
One or more in palladium, platinum, ruthenium, gold；It is further preferred that the metal in the metallic compound or metal precursor is palladium or platinum；
Preferably, the metallic compound or metal precursor are chlorine palladium acid H2PdCl4, ammonium chloropalladate salt (NH4)2PdCl4, chloroplatinic acid
H2PtCl6, chloroplatinic acid ammonium salt (NH4)2PtCl6In one kind；And/or
Reducing agent described in step 2) is the one or more in chitosan, ascorbic acid, alanate, borane derivative；Make
To be preferred, alanate R2AIH、RAIH2Or ER3One kind in AlH types, wherein：E be Li or Na, R be alkyl group (such as
LiAlH4Or LiAl [OC (Me)3]3H)；Borane derivative is FBH4-nLnType borane derivative, wherein：N is whole in 0-4
Number, F are organic cation, four ammonium cations, Na, Li or K, and L is alkyl, alkoxy, amine, acyl ammonia or hydrogen phosphide (such as [CH3
(CH2)3]4NBH3CN or NaB [OOCMe]3H)；It is further preferred that the reducing agent is sodium borohydride aqueous solution；And/or
Solvent described in step 2) is ethanol.
5. the method according to claim 3 or 4, it is characterised in that：TEOS in step 1)：APTMS：PTES mol ratio is
0.5~10:0.5~2:1；Preferably 1~8:0.6~1.5:1；More preferably 2~7:0.8~1.2:1；And/or
The regulations of pH described in step 1) are using acid regulation, it is preferred to use hydrochloric acid is adjusted；PH value is adjusted to 1~5, preferably 2~4,
More preferably 2.5~3；Preferably, the concentration of the hydrochloric acid is 1~5mol/L, preferably 2~4mol/L；And/or
Solvent described in step 1) is ethanol, gasoline, carbon disulfide, benzene,toluene,xylene, dichloromethane, carbon tetrachloride, chlorine
One or more in imitative, tetrahydrofuran or hexamethylene.
6. according to the method any one of claim 3-5, it is characterised in that：Step 2) is specially：By obtained by step 1)
Amphipathic Janus nanometer sheets, which are dissolved in solvent, forms reactant mixture, and metallic compound is slowly added dropwise in the reactant mixture
Or the aqueous solution of metal precursor, in 10~50 DEG C of (being preferably 15~40 DEG C, more preferably 20~30 DEG C, such as 25 DEG C) reactions
3~12h (being preferably 5~10h, preferably 6~8h, such as 8h), has black precipitate precipitation, adds excessive NaBH4, will be carried on
Metal in Janus nanometer sheets is reduced into 0 valency, then will reaction stoste centrifugation, collect sediment, by gained precipitating solvent,
H2More alternately washings of O；Solid after centrifugation is placed in vacuum drying chamber and is dried in vacuo, that is, obtains metal composite Janus and receives
Rice piece catalyst.
7. according to the method for claim 6, it is characterised in that：The solvent is ethanol；Metallic compound or metal is added dropwise
The speed of the aqueous solution of presoma is 1~30mL/min, preferably 3~20mL/min, more preferably 5~15mL/min；And/or
In metallic compound or the aqueous solution of metal precursor the concentration of metallic compound or metal precursor be 0.01~
0.1mmol/mL, preferably 0.02~0.08mmol/mL, more preferably 0.03~0.06mmol/mL；And/or
The amount that metallic compound or the aqueous solution of metal precursor are added dropwise in the reactive mixture is 0.1~5mL/50mg Janus
Nanometer sheet, preferably 0.3~3mL/50mg Janus nanometer sheets, more preferably 0.5~2mL/50mg Janus nanometer sheets.
8. the method according to claim 6 or 7, it is characterised in that：Add NaBH4Amount to add metallic compound or gold
Belong to 2~10 times of equivalents of presoma, more preferably preferably 3~8 times of equivalents, 4~6 times of equivalents；And/or
The centrifugal rotational speed of the centrifugation is 5000~20000rpm, preferably 6000~15000rpm, more preferably 8000~
12000rpm；And/or
The vacuum drying temperature is 30~90 DEG C, preferably 40~80 DEG C, more preferably 45~70 DEG C.
9. a kind of purposes of metal composite Janus nanometer sheet catalyst, or the purposes of the catalyst of claim 1 or 2, or
The purposes of catalyst prepared by person's method according to any one of claim 3-8, metal composite Janus nanometer sheets are used for
It is catalyzed Suzuki aryl coupling reactions.
10. purposes according to claim 9, it is characterised in that：The catalysis Suzuki aryl coupling reactions are specially：Will
Metal composite Janus nanometer sheets are scattered in the mixed liquor of DMF and water, addition iodobenzene, phenyl boric acid, potassium carbonate, under magnetic agitation
Condensing reflux is heated, carries out Suzuki catalytic reactions.
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| CN109455807A (en) * | 2018-09-18 | 2019-03-12 | 辽宁石油化工大学 | A kind of sulfur method of high sulfur content oilfield sewage |
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| CN111871440A (en) * | 2020-07-23 | 2020-11-03 | 青岛科技大学 | Method for preparing hydrogenated rosin by rosin hydrogenation and catalyst thereof |
| CN111871440B (en) * | 2020-07-23 | 2022-05-13 | 青岛科技大学 | Method for preparing hydrogenated rosin by rosin hydrogenation and catalyst thereof |
| CN113145178A (en) * | 2021-03-19 | 2021-07-23 | 浙江工业大学 | Janus structure polymer-based nano metal catalyst and preparation method and application thereof |
| CN113856758A (en) * | 2021-11-05 | 2021-12-31 | 珠海复旦创新研究院 | Metal composite Janus polymer nanoparticle catalyst and preparation method and application thereof |
| CN113856758B (en) * | 2021-11-05 | 2023-05-26 | 珠海复旦创新研究院 | Metal composite Janus polymer nanoparticle catalyst and preparation method and application thereof |
| CN114768802A (en) * | 2022-05-06 | 2022-07-22 | 南京工业大学 | Method for preparing metal nanoparticle-reduced graphene oxide MNP-rGO Janus nanosheets |
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