CN110951088A - 锆基金属有机骨架材料、制备及作为除铬剂的用途 - Google Patents
锆基金属有机骨架材料、制备及作为除铬剂的用途 Download PDFInfo
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- CN110951088A CN110951088A CN201911278842.2A CN201911278842A CN110951088A CN 110951088 A CN110951088 A CN 110951088A CN 201911278842 A CN201911278842 A CN 201911278842A CN 110951088 A CN110951088 A CN 110951088A
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- Prior art keywords
- zirconium
- organic framework
- chromium
- metal salt
- solution
- Prior art date
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- 239000011651 chromium Substances 0.000 title claims abstract description 42
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 27
- 239000013096 zirconium-based metal-organic framework Substances 0.000 title claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims description 37
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000013110 organic ligand Substances 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 64
- 239000002184 metal Substances 0.000 claims description 64
- 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 56
- 239000012266 salt solution Substances 0.000 claims description 54
- 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 44
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 40
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910001867 inorganic solvent Inorganic materials 0.000 claims description 6
- 239000003049 inorganic solvent Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000007146 photocatalysis Methods 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000001784 detoxification Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- 238000013329 compounding Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000012621 metal-organic framework Substances 0.000 abstract description 26
- 230000009467 reduction Effects 0.000 abstract description 18
- 238000006722 reduction reaction Methods 0.000 abstract description 18
- 239000000203 mixture Substances 0.000 abstract description 11
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 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 description 20
- 238000002156 mixing Methods 0.000 description 19
- 150000003754 zirconium Chemical class 0.000 description 14
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 239000011941 photocatalyst Substances 0.000 description 10
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 9
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 9
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- 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 description 8
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 150000003751 zinc Chemical class 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910007746 Zr—O Inorganic materials 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 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 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 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
- 150000000703 Cerium Chemical class 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000013082 iron-based metal-organic framework Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Images
Classifications
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- 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
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- 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
- C02F1/30—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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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Abstract
本发明涉及一种锆基金属有机骨架材料,其由金属离子或团簇与有机配体自组装连接而成,所述金属离子或团簇为锆或者为锆与铜、铝、锌、钴、铁、铈的复合。本发明提供的锆基金属有机骨架,通过可见光范围内有机分子官能团的光激发,为Zr3+‑Zr4+反应提供源源不断的电子,Zr3+‑Zr4+产生的光激发电子向Cr(VI)转移,导致Cr(VI)‑Cr(III)的还原,从而促进催化还原反应,六价铬最终光催化还原脱毒成铬(Ⅲ)并被金属有机骨架的孔道吸附去除。本发明提供了一种通过羟基改性金属有机骨架来处理污水的设计思路。本发明提供的除铬剂工艺简单,材料便宜,易于大量运用于设备工艺中。
Description
技术领域
本发明涉及锆基金属有机骨架材料、制备及作为除铬剂的用途。
背景技术
金属有机骨架材料是一种新型多孔材料,由有机配体和金属离子或团簇自组装连接而成,具有比表面积大,孔隙率高,孔径和表面性质可调,金属节点丰富,热稳定性和化学稳定性高,合成方便廉价等优点。使其在气体储存、分离、多相催化等众多领域都拥有诱人的应用前景,近些年,金属有机骨架材料用作光催化剂已经引起了众多科学家的兴趣,通过对有机连接物的合理改性,增加活性催化位点,可以实现更高效的利用太阳能,进而有效去除水体中的污染物。
铬(Ⅵ)是污染物中最常见的重金属污染物,通过工业废水和肥料释放到环境中,铬(Ⅵ)在整个酸度和碱度的范围内都可以稳定存在,对生物系统具有高毒害作用,其易于穿透细胞壁,是各种癌症疾病的来源。因此,去除工业废水中的铬是关系到环境和人类健康的重要课题。目前主要采用化学沉淀、电解还原、吸附法、光催化法去除,其中吸附法和光催化法最为简单易于操作,但吸附法吸附效果极低;目前,六价铬光催化还原脱毒成铬(Ⅲ)是一个重要的研究方向,并且铬(Ⅲ)在饮用水中的含量对人体健康无害,且其在中性或碱性溶液中容易形成不溶性沉淀,易于除去。当前,光催化法除铬(Ⅵ)所采用的光催化剂多为纳米氧化物,且常见的纳米氧化物有ZrO2,ZnO,Fe2O3,CdS,TiO2,其光催化能力大小比较为ZrO2>ZnO>Fe2O3>CdS>TiO2,但现有纳米氧化物光催化剂存在易于团聚、光响应范围小等问题。
而用金属有机框架代替纳米氧化物作为光催化剂,通过在合成过程中改性有机或无机组分来实现MOF的带隙的调节,从而允许可见光活化的光催化。如Cleaning up:MOFphotocatalysts for chromium reduction,By Sophia Lloyd Posted on March 18,2015,Advanced Science提到:日本研究人员已经开发出一种基于金属有机骨架材料的光催化剂,用于将Cr(VI)还原为Cr(III),其是由铁基金属有机框架组成,并经胺基官能化,所述材料对较低浓度(8ppm)的铬(Ⅵ)需要较长的时间才能降解完全,对高浓度的铬(Ⅵ)的处理并未可知。又如,文章--Robust photocatalytic reduction of Cr(VI)on UiO-66-NH2(Zr/Hf)metalorganic framework membrane under sunlight irradiation By Xue-DongDu Posted on September 11,2018,Chemical Engineering提到利用UiO-66-NH2(Zr/Hf)膜作为光催化剂还原Cr(VI),文献中的材料需要用α-Al2O3作为载体,合成复杂,不利于大量生产,且其对Cr(VI)的还原能力较弱,文章中只对于5ppm的Cr(VI)进行还原,且需要120min还原完全,还原效率较低。
发明内容
本发明选用光催化能力较强的锆基金属有机骨架,针对现有纳米氧化物光催化剂存在的易于团聚、光响应范围小以及其他光催化剂的催化活性不高和催化效率低等问题,提供了一种锆基金属有机骨架材料、制备及作为除铬剂的用途,能够维持氧化物中Zr-O官能团的纳米尺度,而且能够将Zr-O纳米团簇的高催化还原活性和有机分子光激发活性很好的结合起来。通过羟基助色基团改性有机配体,使光催化剂的光响应范围拓宽到可见光区,实现对六价铬在可见光范围内光催化还原。
本发明所述的锆基金属有机骨架材料,由金属离子或团簇与有机配体自组装连接而成,所述金属离子或团簇为锆或者为锆与铜、铝、锌、钴、铁、铈的复合,优选锆;所述有机配体为2-羟基对苯二甲酸或2,5-二羟基对苯二甲酸
本发明所述的锆基金属有机骨架材料的制备方法,其是将金属盐溶液和有机配体溶液混合水热反应得到;
上述所述锆基金属有机骨架材料的制备方法中,优选的,所述金属盐溶液所用溶剂为有机溶剂与无机溶剂的复合,所述有机溶剂为甲醇、N,N-二甲基甲酰胺(DMF)、二氯甲烷、二甲基亚砜(DMSO)或N-甲基吡咯烷酮,所述无机溶剂为盐酸、硝酸、磷酸或硫酸,有机溶剂和无机溶剂混合的体积比为1:0.1~1:10。
上述所述锆基金属有机骨架材料的制备方法中,优选的,所述金属盐溶液的浓度为0.01~5mol/L。
上述所述锆基金属有机骨架材料的制备方法中,优选的,所述有机配体溶液所用溶剂为甲醇、乙醇、N,N-二甲基甲酰胺(DMF)、二氯甲烷、二甲基亚砜(DMSO)或N-甲基吡咯烷酮。
上述所述锆基金属有机骨架材料的制备方法中,优选的,所述有机配体溶液的浓度为0.01~5mol/L。
上述所述锆基金属有机骨架材料的制备方法中,优选的,所述金属盐溶液与有机配体溶液的体积比为1:0.1~1:10。
上述所述锆基金属有机骨架材料的制备方法中,优选的,所述水热反应温度为60-150℃,反应时间为1h-24h。
本发明所述的锆基金属有机骨架材料可作为除铬剂应用,其主要用于光催化还原铬(Ⅵ)成铬(Ⅲ),优选的,其可用于含铬(Ⅵ)水体的脱毒处理。
需要说明的是,本发明中所述金属盐溶液的金属盐可以为锆盐,所述锆盐可以为硝酸锆、硫酸锆、氯化锆,磷酸锆、醋酸锆中的至少一种。
或者,所述金属盐溶液的金属盐也可以为锆盐和铜盐的混合盐,所述锆盐为硝酸锆、硫酸锆、氯化锆,磷酸锆、醋酸锆中的至少一种,所述铜盐为硝酸铜、硫酸铜、氯化铜,磷酸铜、醋酸铜中的至少一种。
或者,所述金属盐溶液的金属盐为锆盐和铝盐的混合盐,所述锆盐为硝酸锆、硫酸锆、氯化锆,磷酸锆、醋酸锆中的至少一种,所述铝盐为硝酸铝、硫酸铝、氯化铝,磷酸铝、醋酸铝中的至少一种。
或者,所述金属盐溶液的金属盐为锆盐和锌盐的混合盐,所述锆盐为硝酸锆、硫酸锆、氯化锆,磷酸锆、醋酸锆中的至少一种,所述锌盐为硝酸锌、硫酸锌、氯化锌,磷酸锌、醋酸锌中的至少一种。
或者,所述金属盐溶液的金属盐为锆盐和钴盐的混合盐,所述锆盐为硝酸锆、硫酸锆、氯化锆,磷酸锆、醋酸锆中的至少一种,所述锌盐为硝酸钴、硫酸钴、氯化钴,磷酸钴、醋酸钴中的至少一种。
或者,所述金属盐溶液的金属盐为锆盐和铁盐的混合盐,所述锆盐为硝酸锆、硫酸锆、氯化锆,磷酸锆、醋酸锆中的至少一种,所述锌盐为硝酸铁、硫酸铁、氯化铁,磷酸铁、醋酸铁中的至少一种。
或者,所述金属盐溶液的金属盐为锆盐和铈盐的混合盐,所述锆盐为硝酸锆、硫酸锆、氯化锆,磷酸锆、醋酸锆中的至少一种,所述锌盐为硝酸铈、硫酸铈、氯化铈,磷酸铈、醋酸铈中的至少一种。
本发明的锆基MOF中Zr-O簇中Zr3+/Zr4+具有较低的还原电势,具有更高的光催化还原铬(Ⅵ)的能力。本发明的锆基金属有机骨架光催化剂具有更高的催化活性和催化效率,能够快速降解低浓度以及高浓度(5-25ppm)的铬(Ⅵ)。同时,本发明涉及的光催化材料易于合成,操作简单,且光催化降解能力较强。
本发明提供的锆基金属有机骨架,通过有机配体支撑分隔,避免了金属氧化物团聚引起的催化性能下降,通过可见光范围内有机分子官能团的光激发,为Zr3+-Zr4+反应提供源源不断的电子,Zr3+-Zr4+产生的光激发电子向Cr(VI)转移,导致Cr(VI)-Cr(III)的还原。从而促进催化还原反应,六价铬最终光催化还原脱毒成铬(Ⅲ)并被金属有机骨架的孔道吸附去除。金属有机骨架的热稳定性避免了离子散失所引起的二次污染,并且提供了一种通过羟基改性金属有机骨架来处理污水的设计思路。本发明提供的除铬剂工艺简单,材料便宜,易于大量运用于设备工艺中。
附图说明
图1是本发明制备的金属有机骨架除铬剂的X射线衍射图,其中模拟峰为金属有机骨架模拟标准峰。
图2是本发明制备的金属有机骨架除铬剂的扫描电镜图,该SEM照片清晰地显示出了目标产物是由小于300nm的球状颗粒构成。
图3是本发明制备出的金属有机骨架除铬剂光催化还原Cr(VI)的反应曲线。
具体实施方式
以下结合附图和具体实施例对本发明作进一步详细说明。
实施例一
(1)金属盐溶液的配制:将0.01mol的硝酸锆,加入DMF:硝酸=1:0.1,总体积1L溶解,配制成金属盐溶液;
(2)2-羟基对苯二甲酸溶液的配制:将1mol的2-羟基对苯二甲酸,加入1L的DMF溶液溶解,配置成1mol/L的2-羟基对苯二甲酸溶液;
(3)金属有机骨架的制备:将配制好的金属盐溶液和2-羟基对苯二甲酸溶液按照体积比1:1混合,然后加入到100ml具塞锥形瓶中,放入烘箱,80℃条件下加热12h,然后用去离子水和乙醇洗涤数遍,自然风干即可得到粉末状的除铬剂。
图1是使用X射线衍射仪(XRD)对除铬剂进行表征,该图证明合成的目标产物X射线衍射峰与模拟的X射线衍射标准峰一致。X射线衍射峰也显示出没有明显的结晶度损失,强度没有降低。
图2是使用扫描电镜(SEM)对除铬剂进行表征,SEM图片表明,目标产物的微观形貌为球形,平均粒径约为100nm左右。
图3是将除铬剂分别置于浓度为20ppm、8ppm的含Cr(VI)水溶液中所测得的浓度时间曲线。测试的条件为:温度为25度,pH为7,光还原反应装置置于300w氙灯照射下(以无光照参比)。可见,目标产物对铬的去除效率很高。
实施例二
(1)金属盐溶液的配制:将0.1mol的硫酸锆,加入二氯甲烷:盐酸=1:1,总体积1L溶解,配制成金属盐溶液;
(2)2,5-二羟基对苯二甲酸溶液的配制:将3mol的2,5-对苯二甲酸,加入1L的二氯甲烷溶液溶解,配置成3mol/L的2,5-对苯二甲酸溶液;
(3)金属有机骨架的制备:将配制好的金属盐溶液和2,5-二羟基对苯二甲酸溶液溶液按照体积比1:0.6混合,然后加入到100ml具塞锥形瓶中,放入烘箱,100℃条件下加热10h,然后DMF洗涤数遍,自然风干即可得到粉末状的除铬剂。
实施例三
(1)金属盐溶液的配制:将3mol的氯化锆,加入甲醇:硫酸=1:5,总体积1L溶解,配制成金属盐溶液;
(2)2,5-二羟基对苯二甲酸的配制:将5mol的2,5-二羟基对苯二甲酸,加入1L的甲醇溶液溶解,配置成5mol/L的2,5-二羟基对苯二甲酸;
(3)金属有机骨架的制备:将配制好的金属盐溶液和2,5-二羟基对苯二甲酸溶液按照体积比1:10混合,然后加入到100ml具塞锥形瓶中,放入烘箱,130℃条件下加热15h,然后二氯甲烷洗涤数遍,自然风干即可得到粉末状的除铬剂。
实施例四
(1)金属盐溶液的配制:将3mol的磷酸锆,加入DMSO:硫酸=1:10,总体积1L溶解,配制成金属盐溶液;
(2)2-羟基对苯二甲酸的配制:将1mol的2-羟基对苯二甲酸,加入1L的DMSO溶液溶解,配置成1mol/L的2-羟基对苯二甲酸;
(3)金属有机骨架的制备:将配制好的金属盐溶液和2-羟基对苯二甲酸溶液按照体积比1:9混合,然后加入到100ml具塞锥形瓶中,放入烘箱,150℃条件下加热24h,然后乙醇洗涤数遍,自然风干即可得到粉末状的除铬剂。
实施例五
(1)金属盐溶液的配制:将0.03mol的硝酸锆和0.07mol硝酸铜,加入DMF:磷酸=1:3,总体积1L溶解,配制成金属盐溶液;
(2)2,5-二羟基对苯二甲酸的配制:将4mol的2,5-对苯二甲酸,加入1L的DMF溶液溶解,配置成4mol/L的2,5-对苯二甲酸;
(3)金属有机骨架的制备:将配制好的金属盐溶液和2,5-二羟基对苯二甲酸溶液按照体积比1:4混合,然后加入到100ml具塞锥形瓶中,放入烘箱,110℃条件下加热18h,然后乙醇洗涤数遍,自然风干即可得到粉末状的除铬剂。
实施例六
(1)金属盐溶液的配制:将1mol的氯化锆和4mol硝酸锌,加入DMSO:盐酸=1:0.8,总体积1L溶解,配制成金属盐溶液;
(2)2-羟基对苯二甲酸的配制:将2mol2-羟基对苯二甲酸的,加入1L的DMSO溶液溶解,配置成为2mol/L的2-羟基对苯二甲酸;
(3)金属有机骨架的制备:将配制好的金属盐溶液和2-羟基对苯二甲酸溶液按照体积比1:0.7混合,然后加入到100ml具塞锥形瓶中,放入烘箱,90℃条件下加热24h,然后二氯甲烷洗涤数遍,自然风干即可得到粉末状的除铬剂。
实施例七
(1)金属盐溶液的配制:将1mol的氯化锆和4mol硝酸锌,加入N-甲基吡咯烷酮:盐酸=1:0.8,总体积1L溶解,配制成金属盐溶液;
(2)2,5-二羟基对苯二甲酸的配制:将0.5mol的2,5-二羟基对苯二甲酸,加入1L的N-甲基吡咯烷酮溶液溶解,配置成0.5mol/L的2,5-二羟基对苯二甲酸;
(3)金属有机骨架的制备:将配制好的金属盐溶液和2,5-二羟基对苯二甲酸溶液按照体积比1:0.7混合,然后加入到100ml具塞锥形瓶中,放入烘箱,90℃条件下加热24h,然后二氯甲烷洗涤数遍,自然风干即可得到粉末状的除铬剂。
实施例八
(1)金属盐溶液的配制:将0.8mol的磷酸锆和1mol硫酸铁,加入甲醇:硝酸=1:3,总体积1L溶解,配制成金属盐溶液;
(2)2-羟基对苯二甲酸的配制:将1mol的2-羟基对苯二甲酸,加入1L的DMSO溶液溶解,配置成1mol/L的2-羟基对苯二甲酸;
(3)金属有机骨架的制备:将配制好的金属盐溶液和2-羟基对苯二甲酸溶液按照体积比1:2混合,然后加入到100ml具塞锥形瓶中,放入烘箱,100℃条件下加热24h,然后去离子水洗涤数遍,自然风干即可得到粉末状的除铬剂。
实施例九
(1)金属盐溶液的配制:将3mol的氯化锆和5mol硫酸锌,加入乙醇:盐酸=1:9,总体积1L溶解,配制成金属盐溶液;
(2)2-羟基对苯二甲酸的配制:将0.2mol的2-羟基对苯二甲酸,加入1L的乙醇溶液溶解,配置成0.2mol/L的2-羟基对苯二甲酸溶液;
(3)金属有机骨架的制备:将配制好的金属盐溶液和2-羟基对苯二甲酸溶液按照体积比1:6混合,然后加入到100ml具塞锥形瓶中,放入烘箱,80℃条件下加热14h,然后二氯甲烷洗涤数遍,自然风干即可得到粉末状的除铬剂。
实施例十
(1)金属盐溶液的配制:将1mol的氯化锆和4mol硝酸锌,加入N-甲基吡咯烷酮:盐酸=1:0.8,总体积1L溶解,配制成金属盐溶液;
(2)2,5-二羟基对苯二甲酸的配制:将0.5mol的2,5-二羟基对苯二甲酸,加入1L的DMSO溶液溶解,配置成1mol/L的2,5-二羟基对苯二甲酸;
(3)金属有机骨架的制备:将配制好的金属盐溶液和2,5-二羟基对苯二甲酸溶液按照体积比1:0.7混合,然后加入到100ml具塞锥形瓶中,放入烘箱,90℃条件下加热10h,然后二氯甲烷洗涤数遍,自然风干即可得到粉末状的除铬剂。
实施例十一
(1)金属盐溶液的配制:将2mol的氯化锆和2mol氯化锌,加入DMF:盐酸=1:6,总体积1L溶解,配制成金属盐溶液;
(2)2-羟基对苯二甲酸的配制:将2mol的2-羟基对苯二甲酸,加入1L的DMF溶液溶解,配置成2mol/L的2-羟基对苯二甲酸;
(3)金属有机骨架的制备:将配制好的金属盐溶液和2-羟基对苯二甲酸溶液按照体积比1:1混合,然后加入到100ml具塞锥形瓶中,放入烘箱,100℃条件下加热24h,然后二氯甲烷洗涤数遍,自然风干即可得到粉末状的除铬剂。
实施例十二
(1)金属盐溶液的配制:将1mol的氯化锆,0.5mol氯化锌和0.5mol硝酸铜,加入DMSO:盐酸=1:3,总体积1L溶解,配制成金属盐溶液;
(2)2,5-二羟基对苯二甲酸的配制:将2mol的2,5-二羟基对苯二甲酸,加入1L的DMSO溶液溶解,配置成2mol/L的2,5-二羟基对苯二甲酸;
(3)金属有机骨架的制备:将配制好的金属盐溶液和2,5-二羟基对苯二甲酸溶液按照体积比1:8混合,然后加入到100ml具塞锥形瓶中,放入烘箱,120℃条件下加热18h,然后二氯甲烷洗涤数遍,自然风干即可得到粉末状的除铬剂。
实施例十三
(1)金属盐溶液的配制:将2mol的硝酸锆,0.1mol硝酸铈和1mol硝酸铁,加入N-甲基吡咯烷酮:盐酸=1:1,总体积1L溶解,配制成金属盐溶液;
(2)2-羟基对苯二甲酸的配制:将0.9mol的2-羟基对苯二甲酸,加入1L的DMSO溶液溶解,配置成0.9mol/L的2-羟基对苯二甲酸;
(3)金属有机骨架的制备:将配制好的金属盐溶液和2-羟基对苯二甲酸溶液按照体积比1:10混合,然后加入到100ml具塞锥形瓶中,放入烘箱,140℃条件下加热12h,然后二氯甲烷洗涤数遍,自然风干即可得到粉末状的除铬剂。
Claims (10)
1.锆基金属有机骨架材料,由金属离子或团簇与有机配体自组装连接而成,所述金属离子或团簇为锆或者为锆与铜、铝、锌、钴、铁、铈的复合;所述有机配体为2-羟基对苯二甲酸或2,5-二羟基对苯二甲酸。
2.权利要求1所述锆基金属有机骨架材料的制备方法,其特征在于:将金属盐溶液和有机配体溶液混合水热反应得到。
3.如权利要求2所述锆基金属有机骨架材料的制备方法,其特征在于:所述金属盐溶液所用溶剂为有机溶剂与无机溶剂的复合,所述有机溶剂为甲醇、N,N-二甲基甲酰胺、二氯甲烷、二甲基亚砜或N-甲基吡咯烷酮,所述无机溶剂为盐酸、硝酸、磷酸或硫酸,有机溶剂和无机溶剂体积比为1:0.1~1:10。
4.如权利要求3所述锆基金属有机骨架材料的制备方法,其特征在于:所述金属盐溶液的浓度为0.01~5mol/L。
5.如权利要求2所述锆基金属有机骨架材料的制备方法,其特征在于:所述有机配体溶液所用溶剂为甲醇、乙醇、N,N-二甲基甲酰胺、二氯甲烷、二甲基亚砜或N-甲基吡咯烷酮。
6.如权利要求5所述锆基金属有机骨架材料的制备方法,其特征在于:所述有机配体溶液的浓度为0.01~5mol/L。
7.如权利要求2所述锆基金属有机骨架材料的制备方法,其特征在于:所述金属盐溶液与有机配体溶液的体积比为1:0.1~1:10。
8.如权利要求2所述锆基金属有机骨架材料的制备方法,其特征在于:所述水热反应温度为60-150℃,反应时间为1h-24h。
9.权利要求1所述的或者由权利要求2-8任一项所述制备方法得到的锆基金属有机骨架材料作为除铬剂的用途,其特征在于:光催化还原铬(Ⅵ)成铬(Ⅲ)。
10.如权利要求9所述用途,其特征在于:用于含铬(Ⅵ)水体的脱毒处理。
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