CN112604714B - 一种cof@mof/m/l复合材料及其制备方法 - Google Patents
一种cof@mof/m/l复合材料及其制备方法 Download PDFInfo
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- CN112604714B CN112604714B CN202011354582.5A CN202011354582A CN112604714B CN 112604714 B CN112604714 B CN 112604714B CN 202011354582 A CN202011354582 A CN 202011354582A CN 112604714 B CN112604714 B CN 112604714B
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- mof
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- chiral
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 20
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 19
- 239000013110 organic ligand Substances 0.000 claims abstract description 18
- 239000011258 core-shell material Substances 0.000 claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims abstract description 8
- 239000012917 MOF crystal Substances 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims abstract description 4
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 57
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000011259 mixed solution Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- -1 2, 5-diamino-p-benzenePhthalic acid Chemical compound 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000002955 isolation Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
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- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- YONLFQNRGZXBBF-ZIAGYGMSSA-N (2r,3r)-2,3-dibenzoyloxybutanedioic acid Chemical compound O([C@@H](C(=O)O)[C@@H](OC(=O)C=1C=CC=CC=1)C(O)=O)C(=O)C1=CC=CC=C1 YONLFQNRGZXBBF-ZIAGYGMSSA-N 0.000 claims description 3
- YONLFQNRGZXBBF-KBPBESRZSA-N (2s,3s)-2,3-dibenzoyloxybutanedioic acid Chemical compound O([C@H](C(=O)O)[C@H](OC(=O)C=1C=CC=CC=1)C(O)=O)C(=O)C1=CC=CC=C1 YONLFQNRGZXBBF-KBPBESRZSA-N 0.000 claims description 3
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 claims description 3
- YSIIHTHHMPYKFP-UHFFFAOYSA-N 2,5-dimethoxyterephthalaldehyde Chemical compound COC1=CC(C=O)=C(OC)C=C1C=O YSIIHTHHMPYKFP-UHFFFAOYSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- IPHJVOCATFFPSZ-UHFFFAOYSA-N 3-bromo-2-tert-butylimidazo[1,2-a]pyridine Chemical compound C1=CC=CN2C(Br)=C(C(C)(C)C)N=C21 IPHJVOCATFFPSZ-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- IIKNTCGCRNEFET-UHFFFAOYSA-N c1cc2cc3ccc([nH]3)c(-c3ccccc3)c3ccc(cc4ccc(cc1n2)[nH]4)n3 Chemical compound c1cc2cc3ccc([nH]3)c(-c3ccccc3)c3ccc(cc4ccc(cc1n2)[nH]4)n3 IIKNTCGCRNEFET-UHFFFAOYSA-N 0.000 claims description 3
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 3
- 235000018417 cysteine Nutrition 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- GAWAYYRQGQZKCR-UWTATZPHSA-N (2r)-2-chloropropanoic acid Chemical compound C[C@@H](Cl)C(O)=O GAWAYYRQGQZKCR-UWTATZPHSA-N 0.000 claims description 2
- IWYDHOAUDWTVEP-SSDOTTSWSA-N (R)-mandelic acid Chemical compound OC(=O)[C@H](O)C1=CC=CC=C1 IWYDHOAUDWTVEP-SSDOTTSWSA-N 0.000 claims description 2
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 2
- IWYDHOAUDWTVEP-ZETCQYMHSA-N (S)-mandelic acid Chemical compound OC(=O)[C@@H](O)C1=CC=CC=C1 IWYDHOAUDWTVEP-ZETCQYMHSA-N 0.000 claims description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- PIWMYUGNZBJTID-UHFFFAOYSA-N 2,5-dihydroxyterephthalaldehyde Chemical compound OC1=CC(C=O)=C(O)C=C1C=O PIWMYUGNZBJTID-UHFFFAOYSA-N 0.000 claims description 2
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 2
- QPBGNSFASPVGTP-UHFFFAOYSA-N 2-bromoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Br)=C1 QPBGNSFASPVGTP-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- KYERQSUZHFINIE-UHFFFAOYSA-N 4-[2,4,5-tris(4-formylphenyl)phenyl]benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC(C=2C=CC(C=O)=CC=2)=C(C=2C=CC(C=O)=CC=2)C=C1C1=CC=C(C=O)C=C1 KYERQSUZHFINIE-UHFFFAOYSA-N 0.000 claims description 2
- MSFXUHUYNSYIDR-UHFFFAOYSA-N 4-[4,6-bis(4-carboxyphenyl)-1,3,5-triazin-2-yl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=NC(C=2C=CC(=CC=2)C(O)=O)=NC(C=2C=CC(=CC=2)C(O)=O)=N1 MSFXUHUYNSYIDR-UHFFFAOYSA-N 0.000 claims description 2
- GGWRKPJRGMCLQA-UHFFFAOYSA-N 4-[[4,6-bis(4-aminophenoxy)-1,3,5-triazin-2-yl]oxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=NC(OC=2C=CC(N)=CC=2)=NC(OC=2C=CC(N)=CC=2)=N1 GGWRKPJRGMCLQA-UHFFFAOYSA-N 0.000 claims description 2
- LNHGLSRCOBIHNV-UHFFFAOYSA-N 4-[tris(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 LNHGLSRCOBIHNV-UHFFFAOYSA-N 0.000 claims description 2
- SNLFYGIUTYKKOE-UHFFFAOYSA-N 4-n,4-n-bis(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 SNLFYGIUTYKKOE-UHFFFAOYSA-N 0.000 claims description 2
- DZLGZIGLHCRIMF-UHFFFAOYSA-N 4-pyridin-4-ylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=NC=C1 DZLGZIGLHCRIMF-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 2
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
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- XEBCWEDRGPSHQH-YUMQZZPRSA-N dipropan-2-yl (2s,3s)-2,3-dihydroxybutanedioate Chemical compound CC(C)OC(=O)[C@@H](O)[C@H](O)C(=O)OC(C)C XEBCWEDRGPSHQH-YUMQZZPRSA-N 0.000 claims description 2
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Abstract
本发明公开了一种COF@MOF/M/L复合材料，包括有COF包覆MOF晶体材料合成的具有核壳结构的COF@MOF材料，所述COF@MOF材料的MOF先进行合成后金属离子交换后，再进行配体交换，形成同时具有金属离子和手性配体的COF@MOF/M/L复合材料。同时公开了该COF@MOF/M/L复合材料的制备方法。本发明的COF@MOF/M/L复合材料，具有核壳结构的COF@MOF材料的特性；同时引入了铜或铁等有高效催化降解功能的金属离子和L‑乳酸或组氨酸等手性功能有机配体，使得MOF的节点上具有单原子催化的高催化活性，并且利用手性‑手性相互作用，有效识别cis‑氟氯菊脂、cis‑氯菊脂等手性毒性污染物，能够有选择性将手性污染物快速、高效、彻底的催化降解为无毒物质。
Description
技术领域
本发明属于复合材料技术领域，具体涉及一种COF@MOF/M/L复合材料及其制备方法。
背景技术
新型纳米多孔材料是21世纪以来发展为迅速的三维多孔材料之一，其中为大家熟知的金属有机骨架材料(MOF)。近十年来，共价有机骨架材料(COF)也开始崭露头角，在气体吸附、化学分离、催化、化学传感、光电和储能等领域表现出了强大的应用潜力。
美国加州大学体系的Pingyun Feng和Xianhui Bu教授团队开发了一种集成的COF@MOF协同装配策略，通过MOF:[(M3-(OH)1-x(O)x(COO)6]型和COF:[B3O3(py)3]型叠加。采用这种策略，acs构型框架的配位驱动组装与COF框架的缩合反应同时发生，并协同作用于一个C3对称的三聚体硼氧化合物分子(tpb)中。吉林大学的裘式纶教授课题组与法国国家科学研究中心的Valentin Valtchev教授证明了MOF可以生长在共价有机骨架(COF)膜上用于制造COF@MOF复合膜。合成的COF@MOF复合膜对H2/CO2混合气体的分离选择性高于单独的COF和MOF。COF@MOF复合膜在H2/CO2气体对混合分离中，超过了聚合物膜的罗伯逊上界，远高于各自的分离值及COF-300,Zn2(bdc)2(dabco)和ZIF-8膜。南京师范大学兰教授通过将NH2-UiO-66共价结合固定在TpPa-1-COF表面，合成了一种具有高表面积、多孔骨架和高结晶度的MOF/COF杂化材料。由此得到的多孔多孔混合材料在可见光照射下表现出的光催化H2演化。中山大学的李教授课题组报导了一种介孔MOFs:NH2-MIL-101(Fe)为核心，生成具有介孔COFs:NUT-COF-1(NTU)为外壳的新多孔核壳材料。通过共价连接工艺，复合材料NH2-MIL-101(Fe)@NTU具有良好的结晶度和分级孔隙度，并探讨了MOFs与COFs在多相催化中的协同作用。新加坡南洋理工大学的张华教授课题组将MOFs与COFs相结合，形成了一种的MOF@COF核-壳杂化材料，即:合成了具有高结晶度和分级孔结构的NH2-MIL-68@TPA-COF。NH2-MIL-68@TPA-COF作为一种的可见光驱动光催化剂，在降解有机污染物方面具有广阔的应用前景。韩国浦航科技大学博士后Dong-Pyo Kim等人报道了一种的光催化平台：一种金属掺杂的核-壳结构的MOFs@COFs(Pd/TiATA@LZU1)。这种MOF@COF使用含NH2基的MOFs可以直接生长在COF外壳，而不需要额外的功能化步骤。可见，COF@MOF复合材料的多孔核壳结构，在节能分离技术、光催化H2、分离、能量转化和其他催化领域具有广阔的应用前景。
但是，现有的COF@MOF复合材料对有害物质的去除率还不高，用途单一，存在提升空间。尤其是对手性有害物质，其去除率只有50％左右。因此，有必要对COF@MOF复合材料进一步研究改进，有针对性的提高其作用效果以及进一步拓展其用途。
发明内容
为了进一步研究COF@MOF复合材料，本发明采用的技术方案是：一种COF@MOF/M/L复合材料，包括有COF包覆MOF晶体材料合成的具有核壳结构的COF@MOF材料，其中M代表金属离子，L代表手性配体，所述COF@MOF材料的MOF先进行合成后金属离子交换后，再进行配体交换，形成同时具有金属离子和手性配体的COF@MOF/M/L复合材料。
COF@MOF/M/L复合材料的制备方法，一定比例的金属离子盐Ⅰ和MOF有机配体溶于一定量的有机溶剂Ⅰ中，在一定温度和压力或微波超声条件下反应一段时间，然后洗涤、干燥，获得MOF晶体材料；将MOF晶体材料溶于含有COF有机配体Ⅰ前驱体溶液中，加热搅拌或超声分散一段时间形成混合溶液，然后向混合溶液中加入COF有机配体Ⅱ前驱体溶液和适量调节剂，在一定温度和压力或微波超声条件下反应一段时间，然后洗涤、干燥，获得具有核壳结构的COF@MOF材料；将一定量的金属离子盐Ⅱ溶于有机溶剂Ⅰ中，向其中加入所述COF@MOF材料，并加入一定含量调节剂形成混合溶液，将混合溶液置于微波反应器中进行微波反应，然后置于摇床上振荡，重复进行微波-振荡3-5个循环，反应结束后进行洗涤、冷冻干燥得到离子交换型具有核壳结构的COF@MOF/M复合材料；将一定量的手性有机配体溶于有机溶剂Ⅱ中，向其中加入COF@MOF/M复合材料，将混合溶液置于隔离交换沉降池中，超声微波反应后静置，抽取反应液的上清液，在上清液中注入手性配体溶液，重复5-8次，离心分离产物，并洗涤干燥，得到COF@MOF/M/L复合材料。
作为上述技术方案的优选，所述金属离子盐Ⅰ为铝、铬、钛、锆、锌、钴或钙的硝酸盐、氯化盐、硫酸盐或醋酸盐中的任一种或多种的混合物。
作为上述技术方案的优选，所述MOF有机配体为对苯二甲酸、均三苯甲酸、2-氨基对苯二甲酸、2-羟基对苯二甲酸、4-[1,2,4]噻唑-4-苯甲酸、2-甲基咪唑、2-溴对苯二甲酸、2,5-二羟基对苯二甲酸、2,2'-联吡啶-5,5'-二羧酸、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、
中的任意一种。
作为上述技术方案的优选，所述COF有机配体Ⅰ为均苯三甲醛、对苯二甲醛、四(4-甲酰基苯)甲烷、四醛基苯基卟啉、3,3',5,5'-四醛基联苯、1,2,4,5-四(4-甲酰基苯基)苯、2,2'-联吡啶-5,5'-二甲醛、2,5-二羟基对苯二甲醛、2,5-二甲氧基苯-1,4-二甲醛、2,6-萘二羧醛、
作为上述技术方案的优选，所述COF有机配体Ⅱ前驱体溶液为苯二胺、蜜勒胺、1,3,5-三氨基苯、联苯二胺、5,15-(氨苯基)-10,20-苯基卟啉、四(4-氨基苯基)甲烷、三(4-氨基苯基)胺、5,5'-二氨基-2,2'-联吡啶、2,4,6-三(4-氨基苯氧基)-1,3,5-三嗪、1,3,5-三(4-氨基苯基)苯、4,4,4,4-甲乙烷四基四苯胺、
中的任意一种。
作为上述技术方案的优选，所述调节剂为甲酸、乙酸、苯甲酸、乙二酸、氢氟酸、氢氰酸或三氟乙酸。
作为上述技术方案的优选，所述金属离子盐Ⅱ为铜、钴、铁、镍、镁或锰的硝酸盐、氯化盐、硫酸盐或醋酸盐中的任一种或多种的混合物。
作为上述技术方案的优选，所述有机溶剂Ⅰ为无水甲醇、无水乙醇、丙酮、正己烷、乙酸乙酯、N,N-二甲基甲酰胺、N,N-二乙基甲酰胺、二氯甲烷、三氯甲烷、四氯甲烷、石油醚、四氢呋喃、吡啶、吡咯、乙腈、甲苯、1,4-二氧六环中的任意一种或多种的混合物；有机溶剂Ⅱ为无水甲醇、无水乙醇、丙酮、正己烷、乙酸乙酯、N,N-二甲基甲酰胺、N,N-二乙基甲酰胺、二氯甲烷、三氯甲烷、四氯甲烷、石油醚、四氢呋喃、吡啶、吡咯、乙腈、甲苯、1,4-二氧六环中的任意一种或多种的混合物。
作为上述技术方案的优选，所述手性有机配体为S-扁桃酸、R-扁桃酸、D-(+)-对甲基二苯甲酰酒石酸(一水物)、L-(-)-对甲基二苯甲酰酒石酸(一水物)、D-(+)-对甲基二苯甲酰酒石酸(无水物)、L-(-)-对甲基二苯甲酰酒石酸(无水物)、D-(+)-二苯甲酰酒石酸(一水物)、D-酒石酸二异丙酯L-(-)-二苯甲酰酒石酸(一水物)、D-(+)-二苯甲酰酒石酸(无水物)、L-(-)-二苯甲酰酒石酸(无水物)、右旋樟脑磺酸、左旋樟脑磺酸、R-2-氯丙酸S-2-氯丙酸、L-乳酸、组氨酸、谷氨酸、酪氨酸、半胱氨酸、联二萘酚(BINOL)、1,1'-联萘-2,2'-双二苯膦(BINAP)或
本发明的有益效果是：本发明提供了一种COF@MOF/M/L复合材料及其制备方法，该复合材料具有核壳结构的COF@MOF材料的特性；同时引入了铜或铁等有高效催化降解功能的金属离子和L-乳酸或组氨酸等手性功能有机配体，使得MOF的节点上具有单原子催化的高催化活性，并且利用手性-手性相互作用，有效识别cis-氟氯菊脂、cis-氯菊脂等手性毒性污染物，能够有选择性将手性污染物快速、高效、彻底的催化降解为无毒物质。
附图说明
图1是实施例1、2、3的反应原理图；
图2是COF@MOF/M/L-1复合材料的扫描电镜图；
图3是COF@MOF/M/L-2复合材料的扫描电镜图；
图4是COF@MOF/M/L-3复合材料的扫描电镜图。
具体实施方式
下面将结合附图对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
在本发明的描述中，需要说明的是，术语“中心”、“上”、“下”、“左”、“右”、“竖直”、“水平”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。此外，术语“第一”、“第二”、“第三”仅用于描述目的，而不能理解为指示或暗示相对重要性。
实施例1
COF@MOF/M/L-1复合材料
将4.0mmol的九水合硝酸铬，1.25mmol的2-羟基对苯二甲酸溶于25ml DMF中，超声分散5min，在80℃冷凝回流条件下反应24h，反应后自然冷却到室温，离心分离产物，用DMF和甲醇洗涤三次，在65℃烘箱中干燥5h，获得MOF-1样品；将5mg MOF-1样品溶于的均苯三甲醛的DMF溶液中(2M，5mL)，超声分散5min，超声分散过程中滴入对苯二胺的1,4-二氧六环(2M，5mL)溶液，超声分散1h，然后将混合溶液置于封管中，在60℃下反应24h，离心分离产物，得到的固体产物用甲醇洗涤三次，并在60℃下真空干燥2h，获得COF@MOF-1；将0.5mg的CoCl2溶于15mL的DMF中，再向其中加入140mg的COF@MOF-1，将混合溶液在室温下置于摇床上振荡30min，再放入微波反应器中，通过控制微波功率，使得混合溶液进行局部微波反应中反应30min，重复进行振荡-微波3个循环，然后搅拌18h，离心分离产物，获得COF@MOF/M-1；配制10mM的D-半胱氨酸的DMF溶液，向其中加入COF@MOF/M-1(80mg)，将混合溶液置于隔离交换沉降池中，超声微波反应1h后静置30min，然后抽取反应液上清液2mL，注入新鲜的2mL 10mM的半胱氨酸溶液，重复超声微波-静置-抽取5～8次，离心分离产物，并用DMF和甲醇洗涤，冷冻干燥24h，获得COF@MOF/M/L-1样品。COF@MOF/M/L-1样品的扫描电镜图如图2所示。
实施例2
将3.8mmol的氯化钴，1.15mmol的偶氮苯-4,4-二羧酸于20mL DMF中，超声分散，将混合溶液置于反应釜中，120℃下反应15h，自然冷却到室温，离心分离产物，甲醇洗涤三次，在55℃烘箱中干燥8h，获得MOF-2样品；将8mg MOF-2样品溶于的2,2'-联吡啶-5,5'-二甲醛的1,4-二氧六环溶液中(1.75M，8mL)，超声分散5min，并滴入0.1mL 1M的乙酸溶液，超声分散过程中滴入4,4,4,4-甲乙烷四基四苯胺(2M，3mL)溶液，超声分散1h，然后将混合溶液置于封管中，在100℃下反应24h，离心分离产物，得到的固体产物用甲醇和1,4-二氧六环洗涤三次，并在60℃下真空干燥8h，获得COF@MOF-2；将0.8mg的硝酸铜溶于20mL的DMF中，再向其中加入120mg的COF@MOF-2，将混合溶液在室温下置于摇床上振荡20min，再放入微波反应器中，通过控制微波功率，使得混合溶液进行局部微波反应中反应20min，重复进行振荡-微波5个循环，然后搅拌20h，离心分离产物，获得COF@MOF/M-2；配制8mM的酪氨酸的DMF溶液，向其中加入COF@MOF/M-2(40mg)，将混合溶液置于隔离交换沉降池中，超声微波反应2h后静置30min，然后抽取反应液上清液2mL，注入新鲜的2mL 8mM的酪氨酸溶液，重复超声微波-静置-抽取5～8次，离心分离产物，并用丙酮和甲醇洗涤，冷冻干燥24h，获得COF@MOF/M/L-2样品。COF@MOF/M/L-2样品的扫描电镜图如图3所示。
实施例3
将5.2mmol的氯化铁，1.8mmol的2-甲基咪唑溶于30mL DMF/去离子水(1:0.2)中，超声分散过程中滴入醋酸溶液(0.02mL，1M)，将混合溶液置于反应釜中，140℃下反应20h，自然冷却到室温，离心分离产物，甲醇洗涤三次，在80℃烘箱中干燥5h，获得MOF-3样品；将7mg MOF-3样品溶于2,5-二甲氧基苯-1,4-二甲醛的DMF溶液中(1.5M，10mL)，超声分散5min，并滴入0.1mL 1M的氢氟酸溶液，超声分散过程中滴入5,15-(氨苯基)-10,20-苯基卟啉的DMF(2M，3mL)溶液，超声分散30min，然后将混合溶液置于封管中，在110℃下反应48h，离心分离产物，得到的固体产物用DMF洗涤三次，并在60℃下真空干燥8h，获得COF@MOF-3；将0.5mg的硝酸银溶于25mL的DMF中，再向其中加入110mg的COF@MOF-3，将混合溶液在室温下置于摇床上振荡40min，再放入微波反应器中，通过控制微波功率，使得混合溶液进行局部微波反应中反应40min，重复进行振荡-微波5个循环，然后搅拌28h，离心分离产物，获得COF@MOF/M-3；配制12mM的甘氨酸的甲醇溶液，向其中加入COF@MOF/M-3(60mg)，将混合溶液置于隔离交换沉降池中，超声微波反应5h后静置2h，然后抽取反应液上清液2mL，注入新鲜的2mL 12mM的甘氨酸溶液，重复超声微波-静置-抽取5～8次，离心分离产物，并用甲醇和丙酮洗涤三次，冷冻干燥24h，获得COF@MOF/M/L-3样品。COF@MOF/M/L-3样品的扫描电镜图如图4所示。
苯乙烯的催化降解试验：利用光催化反应装置进行苯乙烯的催化降解试验，将催化剂悬挂在固定反应器中，将系统抽成真空，在通入适量苯乙烯，装置中气体循环速度为1.25L/min，当系统中苯乙烯浓度保持不变时，达到吸附平衡，打开LED(8W)光源，进行光催化反应，每隔1h检测反应系统中苯乙烯的浓度，并计算反应后浓度与初始浓度之比C/C0。
联苯菊脂降解性能测试方法：配置浓度为0.20mg/L的联苯菊脂水溶液5mL，置于石英玻璃管中，加入0.5mg的自制COF@MOF材料，在9W的LED灯下进行降解，每隔15min测定溶液中联苯菊脂浓度并计算降解率[降解率＝(初始浓度-反应后浓度)/初始浓度×100％]
实施例1、2、3的反应过程原理如图1所示。将上述实施例1、2、3制得COF@MOF/M/L复合材料进行结构和性能分析，的与现有分子筛进行性能对比，对比结果如下表所示：
由各样品的扫描电镜图可知，样品中均能够清洗的观察到纳米级的多孔结构，纳米颗粒大小均匀，孔道大小及分布均匀，可见样品中均具有完整、稳定的核壳结构。从上表可知，制备过程中MOF、COF@MOF均具备很大的比表面积和孔容，核壳结构对苯乙烯和手性有害物质联苯菊酯均具有一定的去除效果，这是多孔、高比表面积的核壳结构产生的作用，从效果上进一步佐证了MOF、COF@MOF结构的存在。但是单纯MOF、COF@MOF结构的对苯乙烯的去除率并不高，对于手性有害物质联苯菊酯的去除率更是在60％以下。而通过金属离子M的引入，形成的COF@MOF/M复合材料，其比表面积、孔容和平均孔径略有降低，表面明金属离子M的引入对核壳结构影响较小，但是对苯乙烯的去除率提高明显，达到了99％左右。这是具有高效催化降解功能的金属离子M在MOF的节点上进一步形成了单原子催化的高催化活性造成的。而COF@MOF/M复合材料用作手性有害物质联苯菊酯的去除时，相对于MOF和COF@MOF材料，其去除效果并没有提高，反而略有降低，这是由于COF@MOF/M复合材料比表面积、孔容和平均孔径略有降低造成的，而金属离子M无法有效识别手性有害物质，对联苯菊酯不产生去除作用。但是当手性配体L引入后，利用利用手性-手性相互作用，形成的COF@MOF/M/L复合材料对联苯菊酯的去除率显著提高。同时，手性配体L的引入并没用影响材料对苯乙烯的去除效果。综上所述，采用本发明制得的COF@MOF/M/L复合材料，能够同时用于苯乙烯等一般有害物质的去除和手性有害物质联苯菊酯等的去除，且具有很高的去除效果。
值得一提的是，本发明专利申请涉及的微波反应器、摇床、高温高压反应釜、隔离交换沉降池等技术特征应被视为现有技术，这些技术特征的具体结构、工作原理以及可能涉及到的控制方式、空间布置方式采用本领域的常规选择即可，不应被视为本发明专利的发明点所在，本发明专利不做进一步具体展开详述。
以上详细描述了本发明的较佳具体实施例，应当理解，本领域的普通技术人员无需创造性劳动就可以根据本发明的构思做出诸多修改和变化，因此，凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案，皆应在由权利要求书所确定的保护范围内。
Claims (4)
1.COF@MOF/M/L复合材料的制备方法，其特征在于，一定比例的金属离子盐Ⅰ和MOF有机配体溶于一定量的有机溶剂Ⅰ中，在一定温度和压力或微波超声条件下反应一段时间，然后洗涤、干燥，获得MOF晶体材料；将MOF晶体材料溶于含有COF有机配体Ⅰ前驱体溶液中，加热搅拌或超声分散一段时间形成混合溶液，然后向混合溶液中加入COF有机配体Ⅱ前驱体溶液和适量调节剂，在一定温度和压力或微波超声条件下反应一段时间，然后洗涤、干燥，获得具有核壳结构的COF@MOF材料；将一定量的金属离子盐Ⅱ溶于有机溶剂Ⅰ中，向其中加入所述COF@MOF材料，并加入一定含量调节剂形成混合溶液，将混合溶液置于微波反应器中进行微波反应，然后置于摇床上振荡，重复进行微波-振荡3-5个循环，反应结束后进行洗涤、冷冻干燥得到离子交换型具有核壳结构的COF@MOF/M复合材料；将一定量的手性有机配体溶于有机溶剂Ⅱ中，向其中加入COF@MOF/M复合材料，将混合溶液置于隔离交换沉降池中，超声微波反应后静置，抽取反应液的上清液，在上清液中注入手性配体溶液，重复5-8次，离心分离产物，并洗涤干燥，得到COF@MOF/M/L复合材料；
所述金属离子盐Ⅰ为铝、铬、钛、锆、锌、钴或钙的硝酸盐、氯化盐、硫酸盐或醋酸盐中的任一种或多种的混合物；
所述金属离子盐Ⅱ为铜、钴、铁、镍、镁或锰的硝酸盐、氯化盐、硫酸盐或醋酸盐中的任一种或多种的混合物；
所述MOF有机配体为对苯二甲酸、均三苯甲酸、2-氨基对苯二甲酸、2-羟基对苯二甲酸、4-[1,2,4]噻唑-4-苯甲酸、2-甲基咪唑、2-溴对苯二甲酸、2,5-二羟基对苯二甲酸、2,2'-联吡啶-5,5'-二羧酸、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、
中的任意一种；
所述COF有机配体Ⅰ为均苯三甲醛、对苯二甲醛、四(4-甲酰基苯)甲烷、四醛基苯基卟啉、3,3',5,5'-四醛基联苯、1,2,4,5-四(4-甲酰基苯基)苯、2,2'-联吡啶-5,5'-二甲醛、2,5-二羟基对苯二甲醛、2,5-二甲氧基苯-1,4-二甲醛、2,6-萘二羧醛、
中的任意一种；
所述COF有机配体Ⅱ前驱体溶液为苯二胺、蜜勒胺、1,3,5-三氨基苯、联苯二胺、5,15-(氨苯基)-10,20-苯基卟啉、四(4-氨基苯基)甲烷、三(4-氨基苯基)胺、5,5'-二氨基-2,2'-联吡啶、2,4,6-三(4-氨基苯氧基)-1,3,5-三嗪、1,3,5-三(4-氨基苯基)苯、4,4,4,4-甲乙烷四基四苯胺、
中的任意一种；
所述手性有机配体为S-扁桃酸、R-扁桃酸、D-(+)-对甲基二苯甲酰酒石酸、L-(-)-对甲基二苯甲酰酒石酸、D-(+)-二苯甲酰酒石酸、D-酒石酸二异丙酯、L-(-)-二苯甲酰酒石酸、右旋樟脑磺酸、左旋樟脑磺酸、R-2-氯丙酸、S-2-氯丙酸、L-乳酸、组氨酸、谷氨酸、酪氨酸、半胱氨酸、联二萘酚、1,1'-联萘-2,2'-双二苯膦或
2.如权利要求1所述的COF@MOF/M/L复合材料的制备方法，其特征在于，所述调节剂为甲酸、乙酸、苯甲酸、乙二酸、氢氟酸、氢氰酸或三氟乙酸。
3.如权利要求1所述的COF@MOF/M/L复合材料的制备方法，其特征在于，所述有机溶剂Ⅰ为无水甲醇、无水乙醇、丙酮、正己烷、乙酸乙酯、N,N-二甲基甲酰胺、N,N-二乙基甲酰胺、二氯甲烷、三氯甲烷、四氯甲烷、石油醚、四氢呋喃、吡啶、吡咯、乙腈、甲苯、1,4-二氧六环中的任意一种或多种的混合物；有机溶剂Ⅱ为无水甲醇、无水乙醇、丙酮、正己烷、乙酸乙酯、N,N-二甲基甲酰胺、N,N-二乙基甲酰胺、二氯甲烷、三氯甲烷、四氯甲烷、石油醚、四氢呋喃、吡啶、吡咯、乙腈、甲苯、1,4-二氧六环中的任意一种或多种的混合物。
4.一种COF@MOF/M/L复合材料，其特征在于，由权利要求1-3中任意一项的COF@MOF/M/L复合材料的制备方法制得。
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