WO2022083795A1 - 一种金属配位卟啉基共轭聚合物及其制备方法与在光催化降解有机污染物中的应用 - Google Patents
一种金属配位卟啉基共轭聚合物及其制备方法与在光催化降解有机污染物中的应用 Download PDFInfo
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- WO2022083795A1 WO2022083795A1 PCT/CN2021/139074 CN2021139074W WO2022083795A1 WO 2022083795 A1 WO2022083795 A1 WO 2022083795A1 CN 2021139074 W CN2021139074 W CN 2021139074W WO 2022083795 A1 WO2022083795 A1 WO 2022083795A1
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- WIPO (PCT)
- Prior art keywords
- porphyrin
- metal
- conjugated polymer
- coordination
- reaction
- Prior art date
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- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 71
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 25
- 239000002184 metal Substances 0.000 title claims abstract description 25
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000013033 photocatalytic degradation reaction Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 3
- 230000001699 photocatalysis Effects 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- JDMIEZMXBAUTSW-UHFFFAOYSA-N 4-[4-(4-formylphenyl)-2,1,3-benzothiadiazol-7-yl]benzaldehyde Chemical compound O=Cc1ccc(cc1)-c1ccc(-c2ccc(C=O)cc2)c2nsnc12 JDMIEZMXBAUTSW-UHFFFAOYSA-N 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- REPFNYFEIOZRLM-UHFFFAOYSA-N chembl376444 Chemical compound C1=CC(N)=CC=C1C(C1=CC=C(N1)C(C=1C=CC(N)=CC=1)=C1C=CC(=N1)C(C=1C=CC(N)=CC=1)=C1C=CC(N1)=C1C=2C=CC(N)=CC=2)=C2N=C1C=C2 REPFNYFEIOZRLM-UHFFFAOYSA-N 0.000 claims description 17
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000004729 solvothermal method Methods 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 238000005859 coupling reaction Methods 0.000 claims description 8
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 claims description 7
- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 claims description 6
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- 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 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- 229960001541 benzthiazide Drugs 0.000 claims description 2
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical group O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 2
- FXSRQZATDVOERQ-UHFFFAOYSA-N C.Cl.Cl.Cl Chemical compound C.Cl.Cl.Cl FXSRQZATDVOERQ-UHFFFAOYSA-N 0.000 claims 1
- FODIZZXWLNCFBV-UHFFFAOYSA-N C=1C=CNC=1.N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound C=1C=CNC=1.N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 FODIZZXWLNCFBV-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 3
- 238000000862 absorption spectrum Methods 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 239000000178 monomer Substances 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 15
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical group CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- 238000002329 infrared spectrum Methods 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 229960001701 chloroform Drugs 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- NUSORQHHEXCNQC-UHFFFAOYSA-N [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NUSORQHHEXCNQC-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000012467 final product Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- FVHZCBQLLFLQAG-UHFFFAOYSA-N 5,10,15,20-tetrakis(4-nitrophenyl)-21,23-dihydroporphyrin Chemical compound [O-][N+](=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)[N+]([O-])=O)c2ccc([nH]2)c(-c2ccc(cc2)[N+]([O-])=O)c2ccc(n2)c(-c2ccc(cc2)[N+]([O-])=O)c2ccc1[nH]2 FVHZCBQLLFLQAG-UHFFFAOYSA-N 0.000 description 4
- 125000003172 aldehyde group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000002071 nanotube Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical group O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 3
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000000944 Soxhlet extraction Methods 0.000 description 3
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 description 3
- YIYFFLYGSHJWFF-UHFFFAOYSA-N [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YIYFFLYGSHJWFF-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 159000000021 acetate salts Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- -1 triphenylphosphino Chemical group 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229940057499 anhydrous zinc acetate Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Definitions
- the invention belongs to the field of organic conjugated polymer functional materials, and at the same time relates to the field of photocatalytic oxidation, in particular to an organic conjugated polymer based on a porphyrin structure, a preparation method thereof, and a method for photocatalytic removal of organic pollutants in water bodies. application.
- photocatalysis can convert clean solar energy into electrical energy and chemical energy, and at the same time generate a variety of active species under light conditions to degrade various organic pollutants in water and photooxidize them into non-toxic substances.
- the photocatalytic technology can fully utilize sunlight at room temperature, has the advantages of low cost and no pollution, and has broad application prospects in the treatment of organic pollutants in water.
- photocatalytic materials are mainly divided into two categories: inorganic semiconductors and organic photocatalytic materials.
- inorganic semiconductor photocatalysts have the characteristics of good catalytic activity and wide application environment, most of them are metal-based semiconductor materials. These materials are not only expensive, but also aggravate metal ion pollution.
- organic photocatalytic materials will become more ideal candidates in the field of photocatalysis because of their rich variety, easy regulation of molecular structure, and wide spectral response range.
- the purpose of the present invention is to provide a metal-coordination porphyrin-based conjugated polymer photocatalytic material and a preparation method thereof, which can effectively remove organic pollutants in water through photocatalytic reaction.
- the organic photocatalytic material constructed by the present invention on the one hand, porphyrin has a large conjugated ring structure, and the formed conjugated polymer has a wide response range to the solar spectrum (200-800 nm); on the other hand, the introduction of coordinating metals improves the charge separation efficiency in the polymer, and at the same time exposes more metal active sites, generates more active species with stronger oxidizing properties, and enhances the photocatalytic performance of polymer materials. Photocatalytic degradation performance of organic pollutants.
- the porphyrin-based conjugated polymer constructed in the present invention has the shape of a hollow nanotube, which promotes the adsorption of organic pollutants in water and the surface catalytic reaction thereof.
- the present invention adopts the following specific technical scheme: a metal-coordination porphyrin-based conjugated polymer, the preparation method of which is as follows: in an inert atmosphere, metal-coordination porphyrin (MTAPP) and 4,7- Bis(4-formylphenyl)-2,1,3-benzothiadiazole (BT) was polymerized by solvothermal reaction to obtain the final metal-coordinated porphyrin-based conjugated polymer (MTAPP-BT).
- MTAPP metal-coordination porphyrin
- BT 4,7- Bis(4-formylphenyl)-2,1,3-benzothiadiazole
- a method for removing organic pollutants in water comprising the following steps: (1) in an inert atmosphere, metal-coordination porphyrin (MTAPP) and 4,7-bis(4-formylphenyl)-2,1, 3-benzothiadiazole (BT) was polymerized by solvothermal reaction to obtain the final metal-coordination porphyrin-based conjugated polymer (MTAPP-BT); (2) the obtained metal-coordination porphyrin-based conjugated polymer was The photocatalytic material is added to the water containing organic pollutants and treated with light to achieve the removal of organic pollutants in the water.
- MTAPP metal-coordination porphyrin
- BT 4,7-bis(4-formylphenyl)-2,1, 3-benzothiadiazole
- 5,10,15,20-tetrakis(4-nitrophenyl)-porphyrin is synthesized by using 4-nitrobenzaldehyde and pyrrole, and then the nitro group is reduced by a reducing agent in concentrated hydrochloric acid to obtain 5,10,15,20-tetrakis(4-nitrophenyl)-porphyrin.
- the palladium-catalyzed coupling reaction between 4-formylbenzeneboronic acid and 4,7-dibromo-2,1,3-benzothiadiazole is used to obtain 4,7-bis(4-formylbenzene) base)-2,1,3-benzothiadiazole; preferably, the coupling reaction is carried out in a basic environment, a nitrogen atmosphere, and a solvent.
- the metal-coordination porphyrin and 4,7-bis(4-formylphenyl)-2,1,3-benzothiadiazole are used as raw materials, and the solvothermal method is used to obtain the Porphyrin-based conjugated polymer photocatalytic materials.
- the molar ratio of 4-nitrobenzaldehyde and pyrrole is 1:1 to 1.2, preferably 1:1;
- the single solvent is propionic acid, and the catalyst is acetic anhydride, preferably propionic acid and acetic anhydride
- the volume ratio is 10: 0.3 ⁇ 0.6, preferably 10: 0.4;
- the temperature of the synthesis reaction is 140 ⁇ 160 ° C, and the time is 30 ⁇ 60 min; in the recrystallization step, the solvent is pyridine, and the temperature is 115 ⁇ 125 °C, the time is 60 ⁇ 90 min;
- the dosage ratio of 5,10,15,20-tetrakis(4-nitrophenyl)-porphyrin, concentrated hydrochloric acid and reducing agent is 2g:150 ⁇ 200 mL: 8-10 g, the reducing agent is stannous chloride, the reaction temperature is 70-90 °C, and the reaction time is 30-60 min; concentrated am
- sodium carbonate or cesium carbonate is selected as the Lewis base to provide an alkaline environment, preferably cesium carbonate;
- the molar ratio of 7-dibromo-2,1,3-benzothiadiazole and 4-formylbenzeneboronic acid is 1:2 ⁇ 3, preferably 1:2.5;
- the solvent is anhydrous toluene/absolute ethanol, the volume ratio It is 5:3 ⁇ 4;
- the palladium catalyst is tetrakis(triphenylphosphino)palladium, and the amount is 18 ⁇ 22% of the weight of 4,7-dibromo-2,1,3-benzothiadiazole; coupling reaction
- the temperature ranged from 75 to 85 °C and the time ranged from 12 to 24 h.
- the molar ratio of the metal-coordination porphyrin and 4,7-bis(4-formylphenyl)-2,1,3-benzothiadiazole is: 1: 2 ⁇ 3, preferably 1: 2.5;
- the solvent is o-dichlorobenzene/n-butanol, and the volume ratio is 1: 1;
- the catalyst is the acetic acid solution of 3 ⁇ 6 mol/L, preferably 6 mol/L;
- the temperature was 100-140 °C, and the time was 48-96 h; after the reaction was completed, Soxhlet extraction was used for purification operation, the solvents were dioxane and acetone, and the washing time was 12-36 h.
- the organic pollutants are phenolic pollutants; the light treatment is visible light treatment or simulated visible light treatment.
- the metal-coordination porphyrin-based conjugated polymer organic photocatalytic material disclosed in the present invention has the advantages of stable skeleton, abundant raw material sources, low cost, and diversified synthesis and modification methods.
- the metal-coordination porphyrin-based conjugated polymer organic photocatalytic material disclosed in the present invention has the shape of hollow nanotubes, and the larger specific surface area provides a large number of active sites, thereby promoting its effect on organic pollutants in water.
- the adsorption and surface catalytic reaction can improve the photocatalytic efficiency.
- the metal-coordination porphyrin-based conjugated polymer organic photocatalytic material disclosed in the present invention has a wide light response range (200-800 nm), and is a good visible light photocatalytic material.
- the metal-coordination porphyrin-based conjugated polymer organic photocatalytic material disclosed in the present invention has improved internal charge separation efficiency due to the introduction of coordinating metals, and exposes more metal active sites simultaneously, resulting in more and more oxidizing properties.
- the active species enhance the photocatalytic degradation performance of organic pollutants.
- Fig. 1 is the infrared spectrum of the metal-coordinated porphyrin-based conjugated polymer in Example 3 (a), Example 4 (b), Example 5 (c) and Example 6 (d).
- Example 2 is a transmission electron microscope photograph of the metal-coordinated porphyrin-based conjugated polymer in Example 3(a), Example 4(b), Example 5(c) and Example 6(d).
- FIG. 3 is a diagram showing the effect of the copper porphyrin-based conjugated polymer (CuTAPP-BT) organic photocatalytic material obtained in Example 5 for degrading bisphenol A in water.
- CuTAPP-BT copper porphyrin-based conjugated polymer
- the preparation method of the metal-coordination porphyrin-based conjugated polymer is as follows: metal-coordination porphyrin (MTAPP), 4,7-bis(4-formylphenyl)-2,1,3-benzothiazide Synthesis of oxadiazole (BT) monomer; then in inert atmosphere, the final metal-coordination porphyrin-based conjugated polymer (MTAPP-BT) was obtained by solvothermal reaction polymerization.
- MTAPP metal-coordination porphyrin
- BT oxadiazole
- a metal-coordination porphyrin-based conjugated polymer photocatalytic material the preparation method of which is as follows: (1) First, 5,10,15,20-tetrakis(4- Nitrophenyl)-porphyrin, after recrystallization and purification, dissolved in concentrated hydrochloric acid to reduce the nitro group with a reducing agent to obtain 5,10,15,20-tetrakis(4-aminophenyl)-porphyrin; under nitrogen protection , 5,10,15,20-tetra(4-aminophenyl)-porphyrin reacts with metal acetate in a mixed solvent under reflux, and after recrystallization and purification, the corresponding metal-coordination porphyrin monomer is obtained.
- Step (1) is as follows: under a nitrogen atmosphere, 4-nitrobenzaldehyde is added to the flask, and propionic acid and acetic anhydride are added thereto. Then heat up to 140 ⁇ 160 °C and reflux, add pyrrole to it, and continue the reflux reaction for 30 ⁇ 60 min, after the reaction was naturally cooled to room temperature, the precipitate was collected and washed with ultrapure water and methanol, and dried under vacuum. The obtained powder was dissolved in pyridine and refluxed for 30-60 After min, the reaction mixture was cooled to 0 °C and placed in the refrigerator for 5–6 h.
- the precipitate was collected by filtration and washed with acetone to obtain a dark purple solid powder; the dark purple solid powder was dissolved in concentrated hydrochloric acid, and a concentrated hydrochloric acid solution in which stannous chloride was dissolved was added dropwise. Stir at room temperature for 1–3 h, then stir at 70–90 °C for 30–60 min, and cool to 0 °C. The green solid was obtained by suction filtration, and the pH value was adjusted to 9-10 with concentrated ammonia water to obtain a crude product.
- TAPP 5,10,15,20-tetrakis(4-aminophenyl)-porphyrin
- TAPP 5,10,15,20-tetrakis(4-aminophenyl)-porphyrin
- Step (2) is as follows: add aqueous cesium carbonate solution to a single-necked flask and degas with N 2 . Then, anhydrous toluene/anhydrous ethanol, 4-formylbenzeneboronic acid, 4,7-dibromo-2,1,3-benzothiadiazole and tetrakis(triphenylphosphino)palladium were added successively, Degas twice. The reaction was carried out under reflux at 75 ⁇ 85 °C for 12 ⁇ 24 h. After the reaction, the mixed system was poured into water and extracted with chloroform for three times. The organic solvent was removed by a rotary evaporator to obtain a crude product.
- Step (3) is as follows: add metal-coordination porphyrin, 4,7-bis(4-formylphenyl)-2,1,3-benzothiadiene into a 10 mL ground Shrek reaction tube in turn azole, o-dichlorobenzene/n-butanol, acetic acid as catalyst, ultrasonic dispersion 10 ⁇ 15 After degassing for 30 minutes, the reaction tube was placed at 100 ⁇ 140 The reaction was carried out under reduced pressure at °C for 48-96 h.
- the raw materials involved in the present invention are all commercially available products, and the specific operation methods are all conventional techniques; unless otherwise specified, the preparations are all carried out in a conventional environment.
- Embodiment 1 The present invention firstly synthesizes a metal-coordinated porphyrin monomer, and the specific steps are as follows: 11 g of 4-nitrobenzaldehyde, 300 mL of propionic acid and 12 mL of acetic anhydride are sequentially added to a 500 mL three-necked flask. Then, under a nitrogen atmosphere, the temperature was raised to 150 °C and refluxed, and 5 mL of pyrrole was added to it, and the reflux reaction was continued for 30 min. After the reaction was naturally cooled to room temperature, the black precipitate was collected, washed with ultrapure water and methanol, and vacuumed at 60 °C. Dry in the oven for 12 h.
- the obtained powder was dissolved in 35 mL of pyridine, refluxed for 60 min, cooled to 0 °C and placed in a refrigerator for 6 h.
- the precipitate was collected by filtration and washed with acetone until the filtrate was colorless to obtain a dark purple solid powder, which was dried in a vacuum oven at 60 °C for 12 h.
- the crude product was purified by Soxhlet extraction with chloroform, and the organic solvent was removed by rotary evaporation to obtain a bright purple crystalline solid powder, 5,10,15,20-tetrakis(4-aminophenyl)-porphyrin (TAPP). Dry in a vacuum oven at 60 °C. It can be seen from the infrared spectrum that 1616, 1510 and 1465 cm -1 are vibrational absorptions of the benzene ring and pyrrole ring, and 979 cm -1 corresponds to the NH stretching vibration in the porphyrin ring, which proves the existence of the porphyrin ring. The sharp peak at 3200-3400 cm -1 corresponds to the stretching vibration of the amino group.
- Embodiment 2 Synthesis of 4,7-bis(4-formylphenyl)-2,1,3-benzothiadiazole (BT) monomer, the specific steps are as follows: add 9 mL to a 100 mL single-necked flask 6 mol/L cesium carbonate aqueous solution and degassed with N 2 for 20 min.
- BT 4,7-bis(4-formylphenyl)-2,1,3-benzothiadiazole
- Example 3 Preparation of porphyrin-based conjugated polymer (TAPP-BT), the specific steps are as follows: 33.0 mg of 5,10,15,20-tetrakis(4- Aminophenyl)-porphyrin, 34.5 mg 4,7-bis(4-formylphenyl)-2,1,3-benzothiadiazole, o-dichlorobenzene/n-butanol (1/1 by volume) , a total of 4 mL), 0.4 mL of 6 mol/L acetic acid aqueous solution as a catalyst, ultrasonically dispersed for 15 min, degassed for 30 min, the reaction tube was decompressed to 50 mtorr by an oil pump in a liquid nitrogen bath, and returned to room temperature at 120 °C.
- TAPP-BT porphyrin-based conjugated polymer
- the reaction was carried out for 72 h. After the end, it was naturally cooled to room temperature, and the precipitate was collected by filtration and washed three times with acetone, and then extracted with dioxane and acetone for 24 h to remove unreacted monomers. The final product obtained is the porphyrin group.
- the conjugated polymer was dried in a vacuum oven at 100 °C for 12 h. Its infrared spectrum is shown in Figure 1(a), and its TEM photo is shown in Figure 2(a).
- Example 4 Preparation of zinc porphyrin-based conjugated polymer (ZnTAPP-BT), the specific steps are as follows: 37.0 mg of 5,10,15,20-tetra(4 -Aminophenyl)-porphyrin zinc, 34.5 mg 4,7-bis(4-formylphenyl)-2,1,3-benzothiadiazole, o-dichlorobenzene/n-butanol (v/v 1 /1, total 4 mL), 0.4 mL of 6 mol/L acetic acid aqueous solution as catalyst, ultrasonically dispersed for 15 min, degassed for 30 min, the reaction tube was decompressed to 50 mtorr by oil pump in a liquid nitrogen bath, and returned to normal temperature at 120 mtorr The reaction was carried out at °C for 72 h.
- Example 5 Preparation of copper porphyrin-based conjugated polymer (CuTAPP-BT), the specific steps are as follows: 36.0 mg of 5,10,15,20-tetrakis(4) were added to a 10 mL ground-mouth Shrek reaction tube in turn -Aminophenyl)-porphyrin copper, 34.5 mg 4,7-bis(4-formylphenyl)-2,1,3-benzothiadiazole, o-dichlorobenzene/n-butanol (volume ratio 1 /1, total 4 mL), 0.4 mL of 6 mol/L acetic acid aqueous solution as catalyst, ultrasonically dispersed for 15 min, degassed for 30 min, the reaction tube was decompressed to 50 mtorr by an oil pump in a liquid nitrogen bath, and returned to room temperature at 120 mtorr The reaction was carried out at °C for 72 h.
- CuTAPP-BT copper porphyrin-based conjugated polymer
- Example 6 Preparation of iron porphyrin-based conjugated polymer (FeTAPP-BT), the specific steps are as follows: 36.6 mg of 5,10,15,20-tetrakis(4) were sequentially added to a 10 mL ground-mouth Shrek reaction tube -Aminophenyl)-porphyrin iron, 34.5 mg 4,7-bis(4-formylphenyl)-2,1,3-benzothiadiazole, o-dichlorobenzene/n-butanol (v/v 1 /1, total 4 mL), 0.4 mL of 6 mol/L acetic acid aqueous solution as catalyst, ultrasonically dispersed for 15 min, degassed for 30 min, the reaction tube was decompressed to 50 mtorr by oil pump in a liquid nitrogen bath, and returned to normal temperature at 120 mtorr The reaction was carried out at °C for 72 h.
- the base conjugated polymer was dried in a vacuum oven at 100 °C for 12 h. Its infrared spectrum is shown in Figure 1(d), and its TEM photo is shown in Figure 2(d). It can be seen from the infrared spectrum that the characteristic peak at 1000 cm -1 corresponds to Fe-N in the iron porphyrin-based polymer.
- Example 7 Photocatalytic degradation experiment of bisphenol A in water by metal-coordination porphyrin-based conjugated polymer organic photocatalytic material: Weigh 25 mg of the above Example 3, Example 4, Example 5 or Example 6 The obtained porphyrin-based conjugated polymer organic photocatalytic material was placed in 50 mL of bisphenol A aqueous solution with a concentration of 15 mg/L, and stirred for 1 h in the dark to achieve the adsorption-desorption equilibrium. After equilibration, the prepared photocatalytic material was irradiated with a 300 W xenon lamp cold light source, and the degradation experiment was started, and 1 mL was sampled every 30 min.
- the signal intensity at nm wavelength was calculated to obtain the concentration of bisphenol A in the corresponding water sample, and the residual concentration of bisphenol A in the corresponding water sample was obtained by referring to the standard curve.
- 3 is a graph showing the relationship between the concentration and time of residual bisphenol A obtained by photocatalytic degradation of bisphenol A in water using the copper porphyrin-based conjugated polymer organic photocatalytic material (CuTAPP-BT) obtained in Example 5. It can be seen that the removal rate of bisphenol A in the aqueous solution reached more than 99% after 60 minutes of illumination under the condition of adding CuTAPP-BT organic photocatalytic material and applying light.
- Example 5 Compared with the photocatalytic effects of other porphyrin-based conjugated polymer organic photocatalytic materials obtained in Example 3, Example 4 and Example 6, the organic photocatalytic material obtained in Example 5 has the best effect.
- Table 1 shows the removal rate of bisphenol A in the aqueous solution after 60 minutes of illumination with different catalysts using the same experimental method described above.
- the invention discloses a visible light-responsive organic photocatalytic material based on a porphyrin structure conjugated polymer.
- a visible light-responsive organic photocatalytic material based on a porphyrin structure conjugated polymer.
- 5,10,15,20-tetrakis(4-aminophenyl)-porphyrin monomers were synthesized, and then the corresponding metalloporphyrin monomers were obtained by coordinating with metal acetate salts.
- 4,7-bis(4-formylphenyl)-2,1,3-benzothiadiazole monomer was synthesized by palladium-catalyzed coupling reaction.
- a novel metal-coordinated porphyrin-based conjugated polymer organic photocatalytic material was obtained by polymerizing the metal-coordination porphyrin monomer and the benzothiadiazole monomer by a solvothermal method.
- the hollow nanotube morphology of metal-coordination porphyrin-based conjugated polymers provides a large specific surface area and abundant active sites to promote the adsorption and surface catalysis of organic pollutants by the composite photocatalyst .
- metal coordination introduces a large number of metal active sites, which can accelerate the intramolecular charge transfer and separation efficiency, thereby improving the photocatalytic efficiency.
- the present invention constructs a metal-coordination porphyrin-based conjugated polymer organic photocatalytic material with visible light response.
- This design is not only conducive to charge transfer and separation efficiency, but also improves the reduction of organic pollutants.
- Molecular adsorption capacity while also providing a large number of surface metal catalytic active sites.
- the copper porphyrin-based conjugated polymer organic photocatalytic material (CuTAPP-BT) prepared above showed effective degradation of bisphenol A in water.
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Abstract
Description
Claims (10)
- 一种金属配位卟啉基共轭聚合物,其特征在于,所述金属配位卟啉基共轭聚合物的制备方法如下:在惰性气氛中,将金属配位卟啉与4,7-二(4-甲酰基苯基)-2,1,3-苯并噻二唑通过溶剂热反应得到金属配位卟啉基共轭聚合物。
- 根据权利要求1所述金属配位卟啉基共轭聚合物,其特征在于,利用4-硝基苯甲醛与吡咯合成反应得到5,10,15,20-四(4-硝基苯基)-卟啉,再于浓盐酸中还原反应得到5,10,15,20-四(4-氨基苯基)-卟啉,然后在氮气保护下,5,10,15,20-四(4-氨基苯基)-卟啉与醋酸金属盐在混合溶剂中回流反应,得到金属配位卟啉。
- 根据权利要求2所述金属配位卟啉基共轭聚合物,其特征在于,4-硝基苯甲醛与吡咯的摩尔比为1∶1~1.2;合成反应的温度为140~160 ℃,时间为30~60 min;还原反应中,还原剂为氯化亚锡,反应温度为70~90 ℃,时间为30~60 min;醋酸金属盐为一水合醋酸铜、无水醋酸锌或者醋酸铁水合物;5,10,15,20-四(4-氨基苯基)-卟啉与醋酸金属盐的摩尔比为1∶2~4;混合溶剂为N,N-二甲基甲酰胺与三氯甲烷;回流反应的温度为80~90 ℃,时间为12~36 h。
- 根据权利要求1所述金属配位卟啉基共轭聚合物,其特征在于,利用4-甲酰基苯硼酸、4,7-二溴-2,1,3-苯并噻二唑之间的钯催化偶联反应获得4,7-二(4-甲酰基苯基)-2,1,3-苯并噻二唑。
- 根据权利要求4所述金属配位卟啉基共轭聚合物,其特征在于,偶联反应在碱性环境、氮气氛围、溶剂中进行;偶联反应的温度为75~85 ℃,时间为12~24 h。
- 根据权利要求1所述金属配位卟啉基共轭聚合物,其特征在于,金属配位卟啉与4,7-二(4-甲酰基苯基)-2,1,3-苯并噻二唑的摩尔比为1∶2~3;溶剂为邻二氯苯/正丁醇;溶剂热的温度为100~140 ℃,时间为48~96 h。
- 权利要求1所述金属配位卟啉基共轭聚合物在降解水体有机污染物中的应用。
- 一种去除水体有机污染物的方法,其特征在于,包括以下步骤:(1)在惰性气氛中,将金属配位卟啉(MTAPP)及4,7-二(4-甲酰基苯基)-2,1,3-苯并噻二唑(BT)通过溶剂热反应聚合得到最终的金属配位卟啉基共轭聚合物(MTAPP-BT);(2)将所得的金属配位卟啉基共轭聚合物光催化材料加入含有有机污染物的水中,光照处理,实现水中有机污染物的去除。
- 根据权利要求8所述去除水体有机污染物的方法,其特征在于,以金属配位卟啉与4,7-二(4-甲酰基苯基)-2,1,3-苯并噻二唑为原料,在催化剂下,通过溶剂热法获得所述卟啉基共轭聚合物光催化材料。
- 根据权利要求8所述去除水体有机污染物的方法,其特征在于,有机污染物为酚类污染物。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102206328A (zh) * | 2010-03-31 | 2011-10-05 | 海洋王照明科技股份有限公司 | 含苯并噻二唑单元卟啉共聚物、其制备方法和应用 |
CN102417586A (zh) * | 2010-09-28 | 2012-04-18 | 海洋王照明科技股份有限公司 | 金属卟啉-苯并噻二唑有机半导体材料及其制备方法和应用 |
CN102453234A (zh) * | 2010-10-28 | 2012-05-16 | 海洋王照明科技股份有限公司 | 金属卟啉-噻吩并噻二唑有机半导体材料及其制备方法和应用 |
CN107021939A (zh) * | 2017-04-25 | 2017-08-08 | 苏州大学 | 基于苯并噻二唑的d‑a‑a型近红外发光化合物及其应用 |
CN107899618A (zh) * | 2017-10-23 | 2018-04-13 | 中山大学 | 一种基于大环化合物光敏染料与二氧化钛的杂化材料及其制备方法和在光催化中的应用 |
CN112111070A (zh) * | 2020-10-20 | 2020-12-22 | 苏州大学 | 一种金属配位卟啉基共轭聚合物及其制备方法与在光催化降解有机污染物中的应用 |
-
2020
- 2020-10-20 CN CN202011128871.3A patent/CN112111070B/zh active Active
-
2021
- 2021-12-17 WO PCT/CN2021/139074 patent/WO2022083795A1/zh active Application Filing
- 2021-12-17 US US17/912,539 patent/US20230132599A1/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102206328A (zh) * | 2010-03-31 | 2011-10-05 | 海洋王照明科技股份有限公司 | 含苯并噻二唑单元卟啉共聚物、其制备方法和应用 |
CN102417586A (zh) * | 2010-09-28 | 2012-04-18 | 海洋王照明科技股份有限公司 | 金属卟啉-苯并噻二唑有机半导体材料及其制备方法和应用 |
CN102453234A (zh) * | 2010-10-28 | 2012-05-16 | 海洋王照明科技股份有限公司 | 金属卟啉-噻吩并噻二唑有机半导体材料及其制备方法和应用 |
CN107021939A (zh) * | 2017-04-25 | 2017-08-08 | 苏州大学 | 基于苯并噻二唑的d‑a‑a型近红外发光化合物及其应用 |
CN107899618A (zh) * | 2017-10-23 | 2018-04-13 | 中山大学 | 一种基于大环化合物光敏染料与二氧化钛的杂化材料及其制备方法和在光催化中的应用 |
CN112111070A (zh) * | 2020-10-20 | 2020-12-22 | 苏州大学 | 一种金属配位卟啉基共轭聚合物及其制备方法与在光催化降解有机污染物中的应用 |
Non-Patent Citations (3)
Title |
---|
LI ZIPING; ZHI YONGFENG; SHAO PENGPENG; XIA HONG; LI GUOSHENG; FENG XIAO; CHEN XIONG; SHI ZHAN; LIU XIAOMING: "Covalent organic framework as an efficient, metal-free, heterogeneous photocatalyst for organic transformations under visible light", APPLIED CATALYSIS B. ENVIRONMENTAL, vol. 245, 1 January 1900 (1900-01-01), AMSTERDAM, NL , pages 334 - 342, XP085680064, ISSN: 0926-3373, DOI: 10.1016/j.apcatb.2018.12.065 * |
LIN SONG, CHRISTIAN S. DIERCKS, YUE-BIAO ZHANG, NIKOLAY KORNIENKO, EVA M. NICHOLS, YINGBO ZHAO, AUBREY R. PARIS, DOHYUNG KIM, PEID: "Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water", SCIENCE, vol. 349, no. 6253, 11 September 2015 (2015-09-11), pages 1205 - 1208, XP055923909 * |
SHEN RUI, ZHU WEI, YAN XIAODONG, LI TAO, LIU YONG, LI YUNXING, DAI SIYUAN, GU ZHI-GUO: "A porphyrin porous organic polymer with bicatalytic sites for highly efficient one-pot tandem catalysis", CHEMICAL COMMUNICATIONS, vol. 55, no. 6, 13 December 2018 (2018-12-13), UK , pages 822 - 825, XP055923912, ISSN: 1359-7345, DOI: 10.1039/C8CC08918C * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114854034A (zh) * | 2022-05-27 | 2022-08-05 | 武汉大学 | 一种钴酞菁和金属卟啉偶联的共价有机框架聚合物材料、制备方法及其应用 |
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CN115634717B (zh) * | 2022-10-31 | 2024-04-30 | 江南大学 | 一种用于光催化分解水产氢的双金属COF-CdS复合光催化剂及其制备方法 |
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