CN114082447A - 一种咪唑类离子液体单原子催化剂的制备方法及其应用 - Google Patents
一种咪唑类离子液体单原子催化剂的制备方法及其应用 Download PDFInfo
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- CN114082447A CN114082447A CN202111365207.5A CN202111365207A CN114082447A CN 114082447 A CN114082447 A CN 114082447A CN 202111365207 A CN202111365207 A CN 202111365207A CN 114082447 A CN114082447 A CN 114082447A
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- Prior art keywords
- ionic liquid
- imidazole
- monatomic catalyst
- monatomic
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 49
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000005859 coupling reaction Methods 0.000 claims abstract description 5
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 claims abstract description 4
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 claims abstract description 4
- 229920000831 ionic polymer Polymers 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 12
- 125000002883 imidazolyl group Chemical group 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 7
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 150000001450 anions Chemical group 0.000 claims description 4
- -1 cyano, amino Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 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
- 150000003839 salts Chemical class 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000005349 anion exchange Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- CYJQCYXRNNCURD-UHFFFAOYSA-N 2,8-dimethyl-1,3,4,4a,5,9b-hexahydropyrido[4,3-b]indole Chemical compound N1C2=CC=C(C)C=C2C2C1CCN(C)C2 CYJQCYXRNNCURD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 229960000359 chromic chloride Drugs 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 229950010754 dicarbine Drugs 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 2
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- CALMYRPSSNRCFD-UHFFFAOYSA-J tetrachloroiridium Chemical compound Cl[Ir](Cl)(Cl)Cl CALMYRPSSNRCFD-UHFFFAOYSA-J 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- JNVLJWBOAWSXKO-UHFFFAOYSA-K trichloronickel Chemical compound Cl[Ni](Cl)Cl JNVLJWBOAWSXKO-UHFFFAOYSA-K 0.000 claims description 2
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000006880 cross-coupling reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical group FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- 229910003244 Na2PdCl4 Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- UNJHYXSLULDQRA-UHFFFAOYSA-M 2-(3-ethenylimidazol-1-ium-1-yl)acetonitrile bromide Chemical compound [Br-].C=C[N+]=1C=CN(CC#N)C=1 UNJHYXSLULDQRA-UHFFFAOYSA-M 0.000 description 1
- REXUYBKPWIPONM-UHFFFAOYSA-N 2-bromoacetonitrile Chemical compound BrCC#N REXUYBKPWIPONM-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005232 molecular self-assembly Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
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Abstract
本发明提供了一种咪唑类离子液体单原子催化剂的制备方法及其应用，结合咪唑类离子液体对单原子金属强的卡宾配位能力，在咪唑类离子液体中引入双键，通过交联共聚，采用预聚合/配位或预配位/聚合方法，在聚离子液体表面锚定单原子金属，制备一系列单原子催化剂。通过本发明的方法合成构筑结构稳定、反应活性高、选择性高、易分离的多相单原子催化剂，实现对金属的最大化利用，其应用于催化交叉偶联反应(Suzuki‑Miyaura反应，Sonogashira偶联反应、Heck偶联等反应中能够在更温和和更环保的反应条件下进行，对催化交叉偶联反应具有更高的催化效率和产物选择性。
Description
技术领域
本发明属于化学领域，涉及负载型单原子多相催化剂，具体涉及一种基于联咪唑离子液体单体单原子催化剂的制备方法及其在交叉偶联反应中的应用。
背景技术
单原子催化已成为多相催化领域中最活跃的新领域。作为一种特殊的负载型金属催化剂，单原子催化剂专指载体上所有金属组分都以单原子分散的形式存在。越来越多的研究结果表明，单原子催化剂由于具有特殊的结构，因而呈现出显著不同于常规纳米催化剂的活性、选择性和稳定性。单原子催化剂中一个关键的科学问题是单原子在载体上的稳定机制。因此，载体的设计与制备至关重要。总结单原子的催化活性、选择性、稳定性与其局域结构和电子性质的关联，可得到以下几点结论：(1)提高单原子的活性位点密度(负载量)非常重要，这可以从调变载体材料的表面性质入手。(2)与活性相比，单原子催化剂在反应的选择性控制方面表现出更大的优势。(3)越来越多的证据表明单原子催化剂要比相应的纳米催化剂更加稳定，主要是因为金属单原子与载体表面的非金属原子形成较强的共价键。
聚离子液体(PILs)是由离子液体通过一定的聚合方法得到的聚合物，具有广泛的可设计性，其结构中含有有机阳离子(含有杂原子磷、硫、氮的有机物质)和无机阴离子(Cl-、Br-、I-、BF4 -、PF6 -、NTf2、TFSI-、H2PO4、NO3 -、C2H5COO-等)。聚离子液体不仅具有离子液体的特点，还具有相对更好的机械稳定性、安全性及分子自组装性能，且更易回收循环利用。采用聚离子液体合成负载型单原子催化剂的研究在聚合和催化领域具有重要意义。
发明内容
本发明的目的在于提供一种构筑结构稳定、反应活性高、选择性高、易分离的咪唑类离子液体多相单原子催化剂。
为了实现上述目的，本发明采用的技术方案如下：一种咪唑类离子液体单原子催化剂，所述单原子催化剂具有式(Ⅰ)或(Ⅱ)所示的结构单元；
其中，M＝Pd、Rh、Ru、Mn、Fe、Co、Ni或Cu；n,m均为整数；
R1、R2为C1-C10的烷基、烷氧基、羟基、氰基、氨基、硝基、卤代或苯基。
进一步的，所述催化剂中金属的负载量为0～10wt％。
本发明的另一目的在于提供一种负载型咪唑类离子液体单原子催化剂的制备方法，简单、高效、稳定。
本发明采用的技术方案如下：所述催化剂是由单分散金属原子均匀地与咪唑单卡宾或双卡宾配位在聚离子液体衬底材料表面构成，具体为：以聚咪唑类离子液体为载体，与多种金属盐M以双卡宾或单卡宾原位络合，通过预聚合/配位或预配位/聚合得到；
采用所述预聚合/配位时，采用如下反应：
其中，a,b,c,d均为整数；X-为Cl-、Br-、I-、BF4 -、PF6 -、NTf2、TFSI-、H2PO4、NO3 -或C2H5COO-。
采用所述预配位/聚合时，采用如下反应：
其中，a,b,c,d均为整数；X-为Cl-、Br-、I-、BF4 -、PF6 -、NTf2、TFSI-、H2PO4、NO3 -或C2H5COO-。
优选的，所述聚咪唑类离子液体载体，通过以下步骤得到：
S1.分别称取一定量的N-乙烯基咪唑和卤代化合物，反应得到含咪唑环的卤代离子液体单体；
S2.含咪唑环的卤代离子液体单体在交联剂、引发剂作用下交联聚合即得。
优选地，上述交联剂为二甲基丙烯酸乙二醇酯(EGDMA)或二乙烯苯(DVB)。
优选地，上述引发剂为过硫酸钾、偶氮二异丁腈、偶氮二异庚腈、过氧化苯甲酰/N，N-二甲基苯胺或过硫酸铵。
本发明中通过阴离子取代反应实现阴离子交换，离子液体单体的基本结构单元如式(Ⅰ)所示；
其中，取代基R1为C1-C10的烷基或烷氧基、羟基、氰基、氨基、硝基、卤代或苯基；
阴离子X-＝Cl-、Br-、I-、BF4 -、PF6 -、NTf2、TFSI-、H2PO4、NO3 -或C2H5COO-。
优选的，所述金属盐为三氯化钒、三氯化铬、硫酸锰、三氯化铁、二氯化钴、三氯化镍、二氯化铜、硝酸锌、钼酸铵、三氯化钌、六氯铑酸钠、四氯钯酸钠、四氯钯酸钾、硝酸银、四氯化铱、六氯铂酸、四氯金酸、氯化铟或四氯化锡。
本发明的再一目的在于提供一种应用方法，采用上述方法制备的咪唑类离子液体单原子催化剂在温和条件下Suzuki-Miyaura反应，Sonogashira偶联反应、Heck偶联反应中的应用，应用于交叉偶联反应条件温和，实现偶联反应的高效、经济和绿色合成。
本发明所涉及的催化反应可以用以下通式(Ⅰ)(Ⅱ)(Ⅲ)表示：
所述单原子金属在聚离子液体表面地负载量为0～11wt％。
与现有技术相比，本发明的有益效果是：
1.本发明的负载型单原子催化剂既减小了贵金属用量，又提高了原子利用率，可以根据应用需求通过与聚离子液体载体的相互作用调控单原子电子结构，本发明简单可控，合成的负载型多相催化剂在聚合和催化领域具有重要意义。
2.本发明的基于联咪唑离子液体单体单原子催化剂，为结构稳定、反应活性高、选择性高、易分离的多相单原子催化剂，通过结合咪唑类离子液体对单原子金属强的卡宾配位能力，在咪唑类离子液体中引入双键，通过交联共聚，采用预聚合/配位或预配位/聚合两种技术，在聚离子液体表面锚定单原子金属，制备出一系列单原子催化剂。
3.本发明催化剂能实现对金属的最大化利用，提高催化效率，使在Suzuki-Miyaura反应，Sonogashira偶联反应、Heck偶联等催化反应中能够在更温和、更环保的反应条件下进行，对催化交叉偶联反应具有更高的催化效率和产物选择性。
附图说明
图1.使用动态光散射测定的聚离子液体载体颗粒的大小图；
图2.Pd单原子负载型多相催化剂的XPS谱图。
具体实施方式
下面结合具体实施例对本发明做进一步的解释和说明，但并不限制于本发明内容。
实施例1
N-乙烯基联咪唑类离子液体单体的合成：将稍过量的N-乙烯基咪唑(4.00g,42.5mmol)与1,4-二溴丁烷(4.75g,20mmol)溶于5mL甲醇，60℃搅拌24小时后，在100mL乙醚中沉降，所得产物在真空干燥箱中室温干燥过夜，即得到离子液体单体。
聚咪唑类离子液体载体的合成：将上述离子液体单体(1.98g,4.9mmol)，与交联剂二甲基丙烯酸乙二醇酯EGDMA(0.194g,0.98mmol)，引发剂偶氮二异丁腈(0.021g,0.13mmol)溶于50mL甲醇溶液，70℃交联聚合24小时。反应结束后，在150mL乙醚中沉降，产物分别使用四氢呋喃、乙醚和水洗涤，50℃真空干燥24小时，即得聚离子液体载体。
咪唑类离子液体单原子催化剂的合成：将上述聚离子液体载体，与等摩尔的Na2PdCl4，室温搅拌24小时后，依次加入10mL、5摩尔NaOAc和5mL甲醇，用20mL乙醇和水抽滤三次，80℃干燥24小时，即得Pd单原子负载型多相催化剂。
实施例2
一种负载型单原子多相催化剂的制备方法，所述催化剂是由单分散钯原子与咪唑环卡宾配位均匀的负载在交联聚离子液体表面构成，其制备方法为：
将稍过量的N-乙烯基咪唑(4.00g,42.5mmol)与1,4-二溴丁烷(4.75g,20mmol)溶于5mL甲醇，60℃搅拌24小时后，在100mL乙醚中沉降，所得产物在真空干燥箱中室温干燥过夜，即得到离子液体单体1,4-butanediyl-3,3’-bis-1-vinylimidazolium dibromide([BVIm]Br)。将所得离子液体单体(1.98g,4.9mmol)，与交联剂二甲基丙烯酸乙二醇酯EGDMA(0.194g,0.98mmol)，引发剂偶氮二异丁腈(0.021g,0.13mmol)溶于50mL甲醇溶液，70℃交联聚合24小时。反应结束后，在150mL乙醚中沉降，产物分别使用四氢呋喃、乙醚和水洗涤，50℃真空干燥24小时，即得聚离子液体载体。将所得聚离子液体作为载体，与等摩尔的Na2PdCl4，室温搅拌24小时后，依次加入10mL、5摩尔NaOAc和5mL甲醇，用20mL乙醇和水抽滤三次，80℃干燥24小时，即得钯负载单原子多相催化剂。
实施例3
一种负载型单原子多相催化剂的制备方法，所述催化剂是由单分散钯原子与咪唑环卡宾配位均匀的负载在交联聚离子液体表面构成，其制备方法为：
将N-乙烯基咪唑(6.21g,66mmol)与溴乙腈(7.2g,60mmol)溶于5mL甲醇，室温搅拌6小时后，在100mL乙醚中沉降，所得产物在真空干燥箱中室温干燥过夜，即得到离子液体单体1-cyanomethyl-3-vinylimidazolium bromide(CMVImBr)。通过与双三氟甲烷磺酰亚胺锂(LiNTf2)进行阴离子交换，即得离子液体单体CMVImNTf2。将所得离子液体单体(10g)，引发剂偶氮二异丁腈(0.2g)溶于100mL DMSO溶液，惰性气体保护，75℃交联聚合24小时。反应结束后，在过量四氢呋喃中沉降，产物使用乙醇洗涤，60℃真空干燥过夜，即得聚离子液体。将所得聚离子液体作为载体，与等摩尔的K2PdCl4，室温搅拌24小时后，依次加入10mL、5摩尔NaOAc和5mL甲醇，用20mL乙醇和水抽滤三次，80℃干燥24小时，即得钯负载单原子多相催化剂。
实施例4
一种负载型单原子多相催化剂的制备方法，所述催化剂是由单分散银原子与咪唑环卡宾配位均匀的负载在交联聚离子液体表面构成，其制备方法为：
将N-乙烯基咪唑(9.4g,100mmol)与溴乙酸(13.9g,100mmol)溶于50mL丙酮，室温搅拌24小时后，在乙醚中沉降，所得产物在真空干燥箱中室温干燥过夜，即得到离子液体单体1-carboxymethyl-3-vinylimidazolium bromide(CAVImBr)。将所得离子液体单体(10g)，引发剂偶氮二异庚腈(0.2g)溶于100mL DMSO溶液，惰性气体保护，75℃交联聚合24小时。反应结束后，在过量四氢呋喃中沉降，产物使用乙醇洗涤，60℃真空干燥过夜，即得聚离子液体。将所得聚离子液体作为载体，与等摩尔的硝酸银，室温搅拌24小时后，抽滤洗涤，80℃干燥24小时，即得银负载单原子多相催化剂。
实施例5
一种负载型单原子多相催化剂的制备方法，所述催化剂是由单分散钴原子与咪唑环卡宾配位均匀的负载在交联聚离子液体表面构成，其制备方法为：
将稍过量的N-乙烯基咪唑(4.00g,42.5mmol)与1,4-二溴丁烷(4.75g,20mmol)溶于5mL甲醇，60℃搅拌24小时后，在100mL乙醚中沉降，所得产物在真空干燥箱中室温干燥过夜，即得到离子液体单体1,4-butanediyl-3,3’-bis-1-vinylimidazolium dibromide([BVIm]Br)。将所得离子液体单体(1.98g,4.9mmol)，与交联剂二乙烯苯DVB(0.194g,0.98mmol)，引发剂偶氮二异丁腈(0.021g,0.13mmol)溶于50mL甲醇溶液，70℃交联聚合24小时。反应结束后，在150mL乙醚中沉降，产物分别使用四氢呋喃、乙醚和水洗涤，50℃真空干燥24小时，即得聚离子液体载体。将所得聚离子液体作为载体，与等摩尔的Na2PdCl4，室温搅拌24小时后，依次加入10mL、5摩尔NaOAc和5mL甲醇，用20mL乙醇和水抽滤三次，80℃干燥24小时，即得钴负载单原子多相催化剂。
Claims (10)
1.一种咪唑类离子液体单原子催化剂，其特征在于：所述单原子催化剂具有式(Ⅰ)或(Ⅱ)所示的结构单元；
其中，M＝Pd、Rh、Ru、Mn、Fe、Co、Ni或Cu；
m、n均为整数；
R1、R2为C1-C10的烷基、烷氧基、羟基、氰基、氨基、硝基、卤代或苯基。
2.根据权利要求1所述的一种咪唑类离子液体单原子催化剂，其特征在于：所述催化剂中金属的负载量为0～11wt％。
3.一种根据权利要求1或2所述的咪唑类离子液体单原子催化剂的制备方法，其特征在于：是以聚咪唑类离子液体为载体，与多种金属盐M以双卡宾或单卡宾原位络合，通过预聚合/配位或预配位/聚合得到的单原子负载型多相催化剂。
4.根据权利要求3所述的一种咪唑类离子液体单原子催化剂的制备方法，其特征在于：所述预聚合/配位，采用如下反应：
其中，a,b,c,d均为整数；X-为Cl-、Br-、I-、BF4 -、PF6 -、NTf2、TFSI-、H2PO4、NO3 -或C2H5COO-。
5.根据权利要求3所述的一种咪唑类离子液体单原子催化剂的制备方法，其特征在于：所述预配位/聚合时，采用如下反应：
其中，a,b,c,d均为整数；X-为Cl-、Br-、I-、BF4 -、PF6 -、NTf2、TFSI-、H2PO4、NO3 -或C2H5COO-。
6.根据权利要求4或5所述的一种咪唑类离子液体单原子催化剂的制备方法，其特征在于：所述聚咪唑类离子液体载体，通过以下步骤得到：
S1.分别称取一定量的N-乙烯基咪唑和卤代化合物，反应得到含咪唑环的卤代离子液体单体；
S2.含咪唑环的卤代离子液体单体在交联剂、引发剂作用下交联聚合即得。
7.根据权利要求6所述的一种咪唑类离子液体单原子催化剂的制备方法，其特征在于：通过阴离子取代反应实现阴离子交换，离子液体单体的基本结构单元如式(Ⅰ)所示；
其中，取代基R1为C1-C10的烷基或烷氧基、羟基、氰基、氨基、硝基、卤代或苯基；
阴离子X-＝Cl-、Br-、I-、BF4 -、PF6 -、NTf2、TFSI-、H2PO4、NO3 -或C2H5COO-。
8.根据权利要求4、5或7所述的一种咪唑类离子液体单原子催化剂的制备方法，其特征在于：所述金属盐为三氯化钒、三氯化铬、硫酸锰、三氯化铁、二氯化钴、三氯化镍、二氯化铜、硝酸锌、钼酸铵、三氯化钌、六氯铑酸钠、四氯钯酸钠、四氯钯酸钾、硝酸银、四氯化铱、六氯铂酸、四氯金酸、氯化铟或四氯化锡。
9.一种咪唑类离子液体单原子催化剂是由单分散金属原子均匀地与咪唑单卡宾或双卡宾配位在聚离子液体衬底材料表面构成。
10.根据权利要求8所述方法制备的咪唑类离子液体单原子催化剂在温和条件下Suzuki-Miyaura反应，Sonogashira偶联反应、Heck偶联反应中的应用。
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