CN104907095B - 一种催化氧化用多功能集成多孔基固态材料的制备方法 - Google Patents
一种催化氧化用多功能集成多孔基固态材料的制备方法 Download PDFInfo
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- CN104907095B CN104907095B CN201510188869.8A CN201510188869A CN104907095B CN 104907095 B CN104907095 B CN 104907095B CN 201510188869 A CN201510188869 A CN 201510188869A CN 104907095 B CN104907095 B CN 104907095B
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 34
- 230000003647 oxidation Effects 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 28
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000013110 organic ligand Substances 0.000 claims abstract description 8
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 6
- 238000000975 co-precipitation Methods 0.000 claims abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 3
- 150000003624 transition metals Chemical class 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 25
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 17
- 235000019441 ethanol Nutrition 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 14
- -1 4,4 '-difluorodiphenyl methylmethanes Chemical class 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 claims description 4
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 4
- CRZQGDNQQAALAY-UHFFFAOYSA-N Methyl benzeneacetate Chemical compound COC(=O)CC1=CC=CC=C1 CRZQGDNQQAALAY-UHFFFAOYSA-N 0.000 claims description 4
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical class CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 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
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical class CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 claims description 3
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- GEZMEIHVFSWOCA-UHFFFAOYSA-N (4-fluorophenyl)methanol Chemical class OCC1=CC=C(F)C=C1 GEZMEIHVFSWOCA-UHFFFAOYSA-N 0.000 claims description 2
- 150000000215 1-octanols Chemical class 0.000 claims description 2
- 125000002927 2-methoxybenzyl group Chemical group [H]C1=C([H])C([H])=C(C(OC([H])([H])[H])=C1[H])C([H])([H])* 0.000 claims description 2
- FQHYQCXMFZHLAE-UHFFFAOYSA-N 25405-85-0 Chemical compound CC1(C)C2(OC(=O)C=3C=CC=CC=3)C1C1C=C(CO)CC(C(C(C)=C3)=O)(O)C3C1(O)C(C)C2OC(=O)C1=CC=CC=C1 FQHYQCXMFZHLAE-UHFFFAOYSA-N 0.000 claims description 2
- QDHRSLFSDGCJFX-UHFFFAOYSA-N 3-fluorobenzyl alcohol Chemical class OCC1=CC=CC(F)=C1 QDHRSLFSDGCJFX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- BNUDRLITYNMTPD-UHFFFAOYSA-N acetic acid;zirconium Chemical compound [Zr].CC(O)=O BNUDRLITYNMTPD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 claims description 2
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001588 bifunctional effect Effects 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
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- PQANGXXSEABURG-UHFFFAOYSA-N cyclohex-2-en-1-ol Chemical class OC1CCCC=C1 PQANGXXSEABURG-UHFFFAOYSA-N 0.000 claims description 2
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 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
- GQKZBCPTCWJTAS-UHFFFAOYSA-N methoxymethylbenzene Chemical compound COCC1=CC=CC=C1 GQKZBCPTCWJTAS-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims 2
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 230000004913 activation Effects 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims 1
- MVZXTUSAYBWAAM-UHFFFAOYSA-N iron;sulfuric acid Chemical compound [Fe].OS(O)(=O)=O MVZXTUSAYBWAAM-UHFFFAOYSA-N 0.000 claims 1
- BYOBIQOEWYNTMM-UHFFFAOYSA-N manganese;nitric acid Chemical compound [Mn].O[N+]([O-])=O BYOBIQOEWYNTMM-UHFFFAOYSA-N 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
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- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims 1
- 239000001301 oxygen Substances 0.000 abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 13
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 150000007530 organic bases Chemical class 0.000 abstract description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 description 9
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- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
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- KVQMUHHSWICEIH-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical class N1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 KVQMUHHSWICEIH-UHFFFAOYSA-N 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910016874 Fe(NO3) Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000013178 MIL-101(Cr) Substances 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
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- 239000010949 copper Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
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- 230000007704 transition Effects 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- WIOZZYWDYUOMAY-UHFFFAOYSA-N 2,5-diaminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=C(N)C=C1C(O)=O WIOZZYWDYUOMAY-UHFFFAOYSA-N 0.000 description 1
- 125000006497 3-methoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C(OC([H])([H])[H])=C1[H])C([H])([H])* 0.000 description 1
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种催化氧化用多功能集成多孔基固态材料的制备方法,属于复合材料领域。首先制备得到具有碱性功能或可修饰碱性的有机配体,进而将其与具有催化活性的过渡金属源进行水热/共沉淀反应,得到多催化功能集成的金属有机骨架催化材料,并首次将其应用于以分子氧为氧源的苄基氧化、醇氧化体系中。本发明开发了一种多功能集成催化材料制备的方法;所制备的催化材料有效的将催化活性中心与碱性功能集成,解决了绿色分子氧氧源难以激活的问题,以及避免因催化体系需额外借助均相有机碱实现C‑H键脱H过程中造成的难以回收、污染严重等问题;首次将该催多功能集成化材料应用于以分子氧为氧源的催化氧化体系,实现了无碱条件下高效催化氧化体系的建立。
Description
技术领域
本发明属于复合材料领域,具体涉及一种绿色催化氧化用多功能集成金属有机骨架材料的制备方法。
背景技术
催化氧化反应是将化工原料转化为工业产品的核心技术,相比于传统的有机氧化过程,催化氧化过程具有反应时间短、选择性高、副产物少等诸多优点,因此被广泛应用于精细化工、有机合成等多个领域。催化氧化反应可以提升化工产品的附加值,在绿色化工研究及工业应用中占有非常重要的地位。例如,将正己醇通过催化氧化转化成正己醛,可使产品附加值提高多倍,在化工生产中具有重要的经济意义。此外,烃类的选择催化氧化产物如环氧化物等还是极具商业价值的有机中间体。
当前,以资源节约、环境友好、条件温和及原子经济为目标的催化过程研究中,氧源是催化氧化体系最为关键的构成因素之一。如何实现氧源绿色化是构建全绿色催化体系的核心问题。分子氧作为一种气态氧源,广泛地存在于空气之中,廉价易得,原料分子中的氧原子百分之百地转变成产物,不产生副产物或废物,实现废物的“零排放”,是氧化反应中公认的最理想氧源。然而,传统的氧化用催化剂存在着难以活化分子氧,或分子氧利用率偏低等问题。且通常催化氧化体系需借助额外的碱性助剂,如:吡啶或氨类衍生物等,实现对烷烃、烯烃及醇类的氧化,易造成环境污染且增加回收成本。因此,通过对催化剂进行目标性设计,从而实现催化氧化活性中心与碱性功能同时在催化材料上的集成,最终在无碱性助剂的条件下,实现铜催化中心惰性分子氧高效活化,以及分子氧催化氧化高效执行。
发明内容
本发明提出一种有效将催化活性中心与有机碱功能等催化功能集成,制备新型功能化绿色催化氧化用催化材料的新方法,有效解决氧化体系中需额外加入均相有机碱,造成浪费与污染的问题,满足我国对绿色、低碳生产方式的迫切需求。
本发明的技术方案是:
本发明的技术方案主要包括以下三方面:
1)含碱类功能基团有机配体的制备:
通过磺化、硝化、酯化、亲核取代、碳-氢活化(C-H活化),铃木偶联反应(Suzuki),施蒂勒偶联反应(Stille),布赫瓦尔德-哈特维希偶联反应(Buchwald-Hartwig)或赫克偶联反应(Heck)反应等有机化学手段,对有机配体,如1,4-对苯二甲酸、4,4’-联吡啶、2,2’-联吡啶、酒石酸等进行官能团修饰和接枝,得到具有碱性或可修饰碱性的配体单元待用;
2)双功能化新型金属有机骨架催化材料的制备:
将过渡金属源与上述所制备的具有碱性的有机配体溶解于有机溶剂中,通过共沉淀法或水热法,控制反应温度与反应时间,直接制备具有催化活性位点与碱性双功能集成的金属有机骨架催化材料;或者是获得催化活性位点集成的金属有机骨架催化材料,再通过合成后修饰手段引入碱性第二功能。
3)以分子氧为氧源的催化氧化性能测试:
将上述两类催化材料分别应用于以分子氧为氧源的苄基氧化、醇类氧化体系中。具体步骤如下:分别称取一定量的上述催化剂和自由基添加剂于25mL的圆底烧瓶中,再分别加入一定量的有机溶剂和底物后将体系密封,抽真空3次,通入氧气,将装置置于一定温度的油浴中反应,产物经过滤后,滤液由GC-MS气相色谱质谱联用仪分析,硝基苯作为内标物,测定催化反应的转化率和选择性。
步骤1)中所制备出的具有碱性配体包括:2-氨基对苯二甲酸,2,2'-联吡啶-5,5'-二羧酸,5,5’-二甲基-2,2’-联吡啶,2,4,6-三(4-羧基苯基)-1,3,5-三嗪,偶氮苯-4,4-二羧酸,2,5-二氨基对苯二甲酸,4-(4-吡啶基)苯甲酸,四(4-羧苯基)卟吩,1,2-二(4-吡啶基)乙烯,1,2-二吡啶乙炔,2,4,6-三(4-吡啶基)-1,3,5-三嗪,1,4-双[(1H-咪唑-1-基)甲基]苯中的一种或几种。
步骤2)中所述的金属源包括:硝酸铜,氯化铜,硫酸铜,醋酸铜,硝酸铁,氯化铁,硫酸铁,醋酸铁,硝酸铝,氯化铝,硫酸铝,醋酸铝,硝酸铬,氯化铬,硫酸铬,醋酸铬,硝酸锆,氯化锆,硫酸锆,醋酸锆,硝酸锌,氯化锌,硫酸锌,醋酸锌,硝酸镍,氯化镍,硫酸镍,醋酸镍,硝酸钴,氯化钴,硫酸钴,醋酸钴,硝酸锰,氯化锰,硫酸锰,醋酸锰,硝酸钛,氯化钛等其中的一种。
有机溶剂包括:无水乙醇,无水甲醇,正丁醇,异丙醇,水,二氯甲烷,三氯甲烷,二氯乙烷,四氢呋喃,乙腈,甲苯,1,4-二氧六环,N,N-二甲基甲酰胺,N,N-二乙基甲酰胺,二甲基亚砜等其中的一种或几种。
步骤3)中所述的底物包括:芴、4,4′-二氟二苯基甲烷,乙基苯,2-氟乙苯,3-氟乙苯,4-氟乙苯,2-甲氧基乙苯,3-甲氧基乙苯,4-甲氧基乙苯,苯乙酸甲酯,苄基甲基醚,2-乙基噻吩,1,2,3,4-四氢萘,苯甲醇,2-氟苯甲醇,3-氟苯甲醇,4-氟苯甲醇,2-甲氧基苯甲醇,3-甲氧基苯甲醇,4-甲氧基苯甲醇,2-甲基苯甲醇,3-甲基苯甲醇,4-甲基苯甲醇,2-噻吩甲醇,环戊醇,肉桂醇,异戊烯醇,2-环己烯醇,1-辛醇,1-苯基乙醇,1,2-二苯基甲醇中的一种或几种。
有机溶剂包括:无水乙醇,无水甲醇,正丁醇,异丙醇,水,二氯甲烷,三氯甲烷,二氯乙烷,四氢呋喃,乙腈,甲苯,1,4-二氧六环,N,N-二甲基甲酰胺,N,N-二乙基甲酰胺,二甲基亚砜等其中的一种或几种。
本发明在于提供一种多功能集成催化氧化用材料的制备方法,设计制备集过渡金属催化氧化活性中心,碱性功能基团等于一体的新型催化氧化用材料。创新性的将催化活性中心与碱性等功能高效集成,解决反应体系中绿色分子氧氧源难以被催化剂激活,以及避免因催化体系需额外借助均相有机碱实现去质子化过程中,造成的碱性助剂难以再次利用、污染严重等问题,并将其首次应用于以分子氧为氧源的催化氧化体系,全面实现催化氧化体系的高效化、去碱化及绿色化。
本发明的优点在于:1)开发了一种新型多功能集成催化材料的制备方法;2)所制备的催化材料有效的将过渡金属催化活性中心与碱性功能集成,解决了长期以来绿色分子氧氧源难以激活的问题,有效避免因催化体系需额外借助均相有机碱而造成的难以回收、污染严重等问题;3)首次将该多功能集成催化材料应用于以分子氧为氧源的催化氧化体系,创新性的构筑了无碱条件下的高效催化氧化体系。
附图说明
图1为本发明实施案例1得到的新型铜基绿色催化氧化用双功能金属有机骨架催化材料Cr-MIL-101-NH-CH2CH2NH2。
具体实施方式
下面结合具体的实施方式对本发明的技术方案做进一步说明。
实施案例1
1)将8mmol的九水合硝酸铬,8mmol的2-氨基对苯二甲酸,20mmol的NaOH加入到60mL的水中,搅拌5分钟至完全分散,再将上述混合液转移至100mL的反应釜中,置于150℃烘箱中,保温12小时后,用去离子水洗涤2次,再用10mL的N,N-二甲基甲酰胺浸泡半天,离心,用甲醇洗涤3次,得到Cr-MIL-101(NH2)。
2)常温下,将0.6mmol步骤1)中制备的Cr-MIL-101(NH2)与6mL的CHCl3溶剂加入到25mL的圆底烧瓶中,搅拌至完全分散,再向其中加入0.9mmol的氮丙啶,将圆底烧瓶置于45℃的油浴中,持续加热6小时后,离心,将10mL的CHCl3加入到所得的固体中,浸泡两天后,离心,将得到的固体置于80℃真空烘箱中干燥12小时。
3)分别称量0.5mol%的上述催化剂和0.5eq的2-(10-羧癸基)-2-己基-4,4'-二甲基-3-噁唑烷基氧基,自由基装入至25mL的圆底烧瓶中,分别加入5mL的乙腈和1mmol的芴后将体系密封,抽真空3次,通入氧气,将装置置于40℃的油浴中反应12h后,产物经过滤后,滤液由GC-MS气相色谱质谱联用仪分析,硝基苯作为内标物,芴的转化率为85%,其中9-芴酮的选择性大于99%。具体反应式如下:
实施案例2
1)将27mmol的5,5’-二甲基-2,2’-联吡啶加入到125mL 95%的浓硫酸中并持续搅拌,缓慢加入82mmol的重铬酸钾,控制加入速度于20分钟加完,搅拌至温度降为35℃,将上述溶液倒入800mL的冰水中冷却,过滤,用去离子水洗涤5次,然后用丙酮洗涤3次,60℃真空干燥12h,得到2,2'-联吡啶-5,5'-二羧酸配体。将2,2'-联吡啶-5,5'-二羧酸配体,与盐酸水溶液混合搅拌,得到2,2'-联吡啶-5,5'-二羧酸盐酸盐。
2)常温下,将0.2mmol的九水合硝酸铁溶解于20mL的N,N-二甲基甲酰胺中,搅拌至完全溶解,再向其中加入0.2mmol的2,2'-联吡啶-5,5'-二羧酸盐酸盐至完全溶解,再加入6mmol的苯甲酸,将上述混合溶液超声10分钟后转移至100mL的聚四氟反应釜中,再置于102℃的烘箱中保温3天。过滤后用0.5M NaOH溶液浸泡12h,再用DMF洗涤3次后,将沉淀物浸泡在乙醇中半天,过滤后再浸泡于乙醇中,反复3次,在40℃下干燥12h后得到最终产物。
3)分别称量0.5mol%的上述催化剂和0.5eq的2-(10-羧癸基)-2-己基-4,4'-二甲基-3-噁唑烷基氧基,自由基装入至25mL的圆底烧瓶中,分别加入5mL的乙腈和1mmol的苯甲醇后将体系密封,抽真空3次,通入氧气,将装置置于50℃的油浴中反应12h后,产物经过滤后,滤液由GC-MS气相色谱质谱联用仪分析,硝基苯作为内标物,苯甲醇的转化率为99%,其中苯甲醛的选择性大于99%。具体反应式如下:
实施案例3
1)将58g的65%的浓硝酸稀释于131mL的水中,向其中加入35g的2,4,6-三(4-甲苯基)-4,4’,4”-三嗪,溶解后将混合液转移至聚四氟反应釜中,加热至220℃,并保温5h,乙醚洗涤5次,得到2,4,6-三(4-羧基苯基)-1,3,5-三嗪配体待用。
2)常温下,将0.2mmol的九水合硝酸铁溶解于20mL的N,N-二甲基甲酰胺中,搅拌至完全溶解,再向其中加入0.2mmol的2,4,6-三(4-羧基苯基)-1,3,5-三嗪配体至完全溶解,再加入6mmol的醋酸,将上述混合溶液超声10分钟后转移至100mL的聚四氟反应釜中,再置于120℃的烘箱中保温3天。过滤后用DMF洗涤3次后,将沉淀物浸泡在乙醇中半天,过滤后再浸泡于乙醇中,反复3次,在40℃下干燥12h后得到最终产物。
3)分别称量0.5mol%的上述催化剂和0.5eq的2-(10-羧癸基)-2-己基-4,4'-二甲基-3-噁唑烷基氧基,自由基装入至25mL的圆底烧瓶中,分别加入5mL的乙腈和1mmol的1-苯基乙醇后将体系密封,抽真空3次,通入氧气,将装置置于45℃的油浴中反应15h后,产物经过滤后,滤液由GC-MS气相色谱质谱联用仪分析,硝基苯作为内标物,1-苯基乙醇的转化率为89%,其中苯乙酮的选择性大于99%。具体反应式如下:
Claims (3)
1.一种催化氧化用多功能集成多孔基固态材料的制备方法,其特征在于包括以下步骤:
1)含Brønsted碱类功能基团有机配体的制备:
通过碳-氢活化、Suzuki、Stille、Buchwald-Hartwig或Heck有机化学手段,对有机配体进行官能团修饰和接枝,得到具有Brønsted碱性或可修饰Brønsted碱性的有机配体单元待用;有机配体包括1,4-对苯二甲酸、2,2’-联吡啶;
2)双功能化金属有机骨架催化材料的制备:
将过渡金属源与上述所制备的具有Brønsted碱性的或可修饰Brønsted碱性的有机配体溶解于有机溶剂中,通过共沉淀法或水热法,控制反应温度与反应时间,直接制备具有催化活性位点与Brønsted碱性双功能集成的金属有机骨架催化材料;或者是获得催化活性位点集成的金属有机骨架催化材料,再通过合成后修饰手段引入Brønsted碱性第二功能;
其中,步骤1)中所制备出的具有Brønsted碱性配体包括:2-氨基对苯二甲酸,2,2'-联吡啶-5,5'-二羧酸,5,5’-二甲基-2,2’-联吡啶,偶氮苯-4,4-二羧酸,2,5-二氨基对苯二甲酸,4-(4-吡啶基)苯甲酸,四(4-羧苯基)卟吩。
2.如权利要求1所述一种催化氧化用多功能集成多孔基固态材料的制备方法,其特征在于步骤2)中所述的金属源包括:硝酸铜,氯化铜,硫酸铜,醋酸铜,硝酸铁,氯化铁,硫酸铁,醋酸铁,硝酸铬,氯化铬,硫酸铬,醋酸铬,硝酸锆,氯化锆,硫酸锆,醋酸锆,硝酸锌,氯化锌,硫酸锌,醋酸锌,硝酸镍,氯化镍,硫酸镍,醋酸镍,硝酸钴,氯化钴,硫酸钴,醋酸钴,硝酸锰,氯化锰,硫酸锰,醋酸锰,硝酸钛,氯化钛中的一种;
有机溶剂包括:无水乙醇,无水甲醇,正丁醇,异丙醇,二氯甲烷,三氯甲烷,二氯乙烷,四氢呋喃,乙腈,甲苯,1,4-二氧六环,N,N-二甲基甲酰胺,N,N-二乙基甲酰胺,二甲基亚砜其中的一种或几种。
3.如权利要求1所述一种催化氧化用多功能集成多孔基固态材料的制备方法,其特征在于所述催化氧化的底物包括:芴、4,4′-二氟二苯基甲烷,乙基苯,2-氟乙苯,3-氟乙苯,4-氟乙苯,2-甲氧基乙苯,3-甲氧基乙苯,4-甲氧基乙苯,苯乙酸甲酯,苄基甲基醚,2-乙基噻吩,1,2,3,4-四氢萘,苯甲醇,2-氟苯甲醇,3-氟苯甲醇,4-氟苯甲醇,2-甲氧基苯甲醇,3-甲氧基苯甲醇,4-甲氧基苯甲醇,2-甲基苯甲醇,3-甲基苯甲醇,4-甲基苯甲醇,2-噻吩甲醇,环戊醇,肉桂醇,异戊烯醇,2-环己烯醇,1-辛醇,1-苯基乙醇,1,2-二苯基甲醇中的一种或几种;
有机溶剂包括:无水乙醇,无水甲醇,正丁醇,异丙醇,二氯甲烷,三氯甲烷,二氯乙烷,四氢呋喃,乙腈,甲苯,1,4-二氧六环,N,N-二甲基甲酰胺,N,N-二乙基甲酰胺,二甲基亚砜其中的一种或几种。
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