CN107308990B - 一种TiO2/卟啉/MOFs超薄异质体的制备方法 - Google Patents
一种TiO2/卟啉/MOFs超薄异质体的制备方法 Download PDFInfo
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- CN107308990B CN107308990B CN201710409307.0A CN201710409307A CN107308990B CN 107308990 B CN107308990 B CN 107308990B CN 201710409307 A CN201710409307 A CN 201710409307A CN 107308990 B CN107308990 B CN 107308990B
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 52
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 67
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002135 nanosheet Substances 0.000 claims abstract description 39
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- -1 porphyrin compound Chemical class 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 7
- 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 6
- 238000011068 loading method Methods 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- NVJHHSJKESILSZ-UHFFFAOYSA-N [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NVJHHSJKESILSZ-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
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- 238000001035 drying Methods 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 235000015110 jellies Nutrition 0.000 claims description 4
- 239000008274 jelly Substances 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- 239000002064 nanoplatelet Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 38
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 20
- 239000001569 carbon dioxide Substances 0.000 abstract description 19
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 230000009467 reduction Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 230000002093 peripheral effect Effects 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 2
- 230000031700 light absorption Effects 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- 230000010354 integration Effects 0.000 abstract 1
- 239000004408 titanium dioxide Substances 0.000 description 8
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- 230000003595 spectral effect Effects 0.000 description 6
- 239000013207 UiO-66 Substances 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 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 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010586 diagram Methods 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
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- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 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 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 1
- RAADBCJYJHQQBI-UHFFFAOYSA-N 2-sulfoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(S(O)(=O)=O)=C1 RAADBCJYJHQQBI-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 240000001414 Eucalyptus viminalis Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000010521 absorption reaction Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 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
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 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
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 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
- 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
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper 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
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-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
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- QUMITRDILMWWBC-UHFFFAOYSA-N nitroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 QUMITRDILMWWBC-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- FZHCFNGSGGGXEH-UHFFFAOYSA-N ruthenocene Chemical compound [Ru+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 FZHCFNGSGGGXEH-UHFFFAOYSA-N 0.000 description 1
- 238000010942 self-nucleation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 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 1
Images
Classifications
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B01J35/39—
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
Abstract
本发明公开了一种TiO2/卟啉/MOFs超薄异质体的制备方法，属于无机有机复合功能材料制备技术领域。本发明以TiO2超薄纳米片为模板，利用卟啉化合物外围的羧基、羟基等官能团将其锚固在TiO2超薄纳米片表面，进而利用卟啉化合物的剩余外围羧基、羟基等官能团吸附金属离子，通过金属有机骨架层层自组装的手段实现在卟啉化合物外层MOFs包覆，以获得催化活性高效稳定的TiO2/卟啉/MOFs超薄异质体。本发明的优点在于：1)创新性地利用TiO2、卟啉、MOFs进行超薄异质体催化区/光吸收区/吸附区的层级构筑和功能集成，开发得到一种性能优异的光催化还原二氧化碳用新型催化材料；2)基于卟啉和MOFs材料可调控的结构和功能特性，实现对TiO2/卟啉/MOFs超薄异质体的性能优化。
Description
技术领域
本发明属于无机有机复合功能材料制备技术领域，特别涉及一种TiO2/卟啉/MOFs超薄异质体（即MOFs负载于卟啉敏化的TiO2纳米片上）的制备方法。
背景技术
实现二氧化碳的资源化和能源化，将其转化为可再生能源和高附加值的产品，不仅能帮助解决石化资源日益溃乏的问题，且有益于缓解大气中二氧化碳浓度过高所造成的温室效应等环境问题。目前研究二氧化碳的转化途径主要有：热化学转化、电化学转化以及光催化转化。相较于需要热能、电能等高能动力源的热化学、电化学转化，光催化转化的动力源为来源于太阳光或者其他人造光，来源广泛且不受能源短缺的限制，具有低成本、无污染的优点，因而得到广泛的研究。
在众多光催化还原二氧化碳的材料中，二氧化钛具有成本低、催化活性高、化学稳定性高、抗氧化能力强、安全无毒等特点，而被认为是最具潜力的光催化材料之一。然而，因二氧化钛禁带宽度相对较大，只能吸收紫外光；且不具备超大的比表面积和孔道结构，难以有效吸附二氧化碳，因此对于二氧化碳的光催化还原仍有一定的局限性，通过改变纳米粒子的形貌、结构和尺寸，以及表面敏化、半导体复合、离子掺杂、贵金属沉积等多种改性手段提高二氧化钛的光谱响应能力和催化活性，从而提高二氧化钛光催化二氧化碳还原的性能。
龙金林等人采用表面金属有机化学方法，将双环戊二烯基钌通过表面接枝的方法嫁接到二氧化钛表面，拓宽了光响应范围，从而提高了光催化还原二氧化碳的催化效率；刑宏珠等人通过溶剂热方法，以乙炔基苯甲酸为配体，四氯化锆为金属源，苯甲酸为调节剂在有机溶剂中反应得到一种新型的锆基有机金属骨架晶体材料，因其规则的孔道结构使它具有较高的吸附能力，促进了二氧化碳的光催化还原。但目前文献中鲜有同时提高光谱响应和二氧化碳捕获能力的报道。
综上所述，针对二氧化钛光谱响应范围窄及二氧化碳捕获能力差的问题，发展一种具有强光谱响应能力、高二氧化碳吸附能力，优异催化活性的光催化还原二氧化碳催化材料具有重要意义。
发明内容
本发明的目的在于解决二氧化钛光谱响应范围窄及二氧化碳捕获能力差的问题，开发一种TiO2/卟啉/MOFs复合材料的制备方法，使制得的催化材料不仅光谱响应范围宽而且二氧化碳吸附能力强及催化性能优异，并可以在二氧化碳光催化还原领域中广泛应用。
本发明的技术方案是：以TiO2超薄纳米片为模板，利用卟啉化合物外围的羧基、羟基等官能团将其锚固在TiO2超薄纳米片表面，进而利用卟啉化合物的剩余外围羧基、羟基等官能团吸附金属离子，通过金属有机骨架层层自组装的手段实现在卟啉化合物外层MOFs包覆，以获得催化活性高效稳定的TiO2/卟啉/MOFs超薄异质体。通过调节卟啉、MOFs的种类及负载量，获得系列TiO2/卟啉/MOFs超薄异质体，建立多种TiO2/卟啉/MOFs超薄异质体的构筑及调控方法。
本发明的具体制备步骤为：
先制备TiO2纳米片，再制备TiO2/卟啉/MOFs，制备过程如下：
所述的TiO2纳米片制备是将1~10mL的氢氟酸缓慢加入到5~50 mL的钛酸四丁酯中，搅拌0.5-3h后，将得到的白色胶状物转移到聚四氟乙烯高压反应釜中，随后将反应釜放在150-200 oC烘箱中反应6-48h后缓慢降至室温，取下层白色沉淀用去离子水离心洗涤数遍直至上层清液至中性，然后置于40-100 oC真空干燥烘箱中干燥即得到TiO2纳米片。
所述的金属卟啉包括四羧基苯基锌卟啉、四羧基苯基钴卟啉、四羧基苯基铜卟啉中的一种，其中优选四羧基苯基锌卟啉或四羧基苯基钴卟啉。
所述的可溶性金属盐包括硝酸铬，氯化铬，硫酸铬，醋酸铬，硝酸锆，氯化锆，硫酸锆，醋酸锆，硝酸铜，氯化铜，硫酸铜，醋酸铜，硝酸锌，氯化锌，硫酸锌，醋酸锌，硝酸镍，氯化镍，硫酸镍，醋酸镍，硝酸钴，氯化钴，硫酸钴，醋酸钴，硝酸铁，氯化铁，硫酸铁，醋酸铁，硝酸铝，氯化铝，硫酸铝，醋酸铝，硝酸锰，氯化锰，硫酸锰，醋酸锰，硝酸钛，氯化钛，硫酸钛，其中优选硝酸铬。
所述的配体包括对苯二甲酸、2,5-二羟基对苯二甲酸、2-氨基对苯二甲酸、2-磺酸基对苯二甲酸，2-硝基对苯二甲酸，均苯三甲酸、2-甲基咪唑，其中优选对苯二甲酸。
本发明的优点在于：
1.外层高孔隙率、大比表面积的MOFs层作为吸附区可有效吸附CO2分子，中间卟啉化合物作为光吸收区可有效吸收可见光并将光生电子从卟啉的导带向TiO2导带的传递，内层高活性的TiO2超薄纳米片作为催化区将富集在其表面的CO2进行高效转化。
2.可以通过调控卟啉外围取代基和配位中心金属离子提高TiO2的活性，调控MOFs孔隙率、孔径大小、开放金属位点、孔道内表面官能团等提高对CO2的吸附效率及选择性，优化TiO2/卟啉/MOFs超薄异质体的综合性能。
附图说明
图1为本发明实施例1得到的TiO2/卟啉/MOFs超薄异质体的X射线衍射图。
图2为本发明实施例1得到的TiO2/卟啉/MOFs超薄异质体的紫外-可见漫反射光谱图。
图3为本发明实施例1得到的TiO2/卟啉/MOFs超薄异质体的热重分析图。
图4为本发明实施例1得到的TiO2/卟啉/MOFs超薄异质体的扫描电镜照片。
具体实施方式
实施例1
1）TiO2纳米片的制备
取25 mL的钛酸四丁酯置于烧杯中，取5mL的氢氟酸缓慢加入烧杯中，搅拌均匀后，将得到的白色胶状物转移到100ml聚四氟乙烯高压反应釜中，随后将反应釜放在200 oC烘箱中反应20 h后缓慢降至室温。取下层白色沉淀用去离子水离心洗涤数遍直至上层清液至中性，然后置于80 oC真空干燥烘箱中干燥即得到TiO2纳米片。
2）TiO2/卟啉/MOFs的制备
TiO2/卟啉/MOFs制备过程如下：
取上述TiO2纳米片 0.1g 置于浓度为1 M的四羧基苯基钴卟啉的DMF溶液中，放在超声波清洗机中超声30min，使TiO2纳米片充分分散，随后在常温下磁力搅拌6h。然后将上述分散液抽滤得到金属卟啉修饰的TiO2纳米片；
将得到的金属卟啉修饰的TiO2纳米片分散到5 ml 浓度为1 M 的硝酸铬溶液中，超声30min后磁力搅拌6h，经过抽滤装置分离后得到吸附金属离子的TiO2/卟啉超薄异质体；
将得到的铬离子修饰的TiO2/卟啉超薄异质体分散到10 ml 浓度为1 M 的对苯二甲酸溶液中，超声30min后，120°C反应12h的条件下，在TiO2/卟啉超薄异质体表面生产相应的MOFs层即TiO2/卟啉/MOFs，重复
步骤两次，得到负载量不同的TiO2/卟啉/MOFs复合材料。
如图1所示，5~8°为UiO-66 X射线衍射特征峰，20~80°为TiO2X射线衍射特征峰，表明TiO2/ZnTCPP (四羧基苯基锌卟啉)/ UiO-66 (MOFs)超薄异质体的成功合成。
如图2所示，紫外区为TiO2特征吸收峰，420nm和560nm左右为四羧基苯基锌卟啉特征吸收峰，表明卟啉的加入拓宽了TiO2的光响应范围，有助于提高光催化还原二氧化碳的催化性能。
如图3所示，TiO2/ZnTCPP/ UiO-66超薄异质体有两段热损失，100~300°C为四羧基苯基锌卟啉热分解，400~550°C为UiO-66热分解。TiO2/ZnTCPP/ UiO-66-1为敏化1次热重图，TiO2/ZnTCPP/ UiO-66-2为敏化2次热重图，从图中可得到两者负载量分别为40.07%和46.35%，表明得到负载量不同的TiO2/卟啉/MOFs复合材料。
如图4所示，纯TiO2纳米片呈薄片状，形状规则四边形。由于MOFs的生成，TiO2纳米片片层状结构越来越模糊，取而代之的是UiO-66在TiO2纳米片上自成核和团聚
实施例2
1）TiO2纳米片的制备
取25 mL钛酸四丁酯置于烧杯中，取3mL的氢氟酸缓慢加入烧杯中，搅拌均匀后，将得到的白色胶状物转移到100ml聚四氟乙烯高压反应釜中，随后将反应釜放在180 oC烘箱中反应20 h后缓慢降至室温。取下层白色沉淀用去离子水离心洗涤数遍直至上层清液至中性，然后置于80 oC真空干燥烘箱中干燥即得到TiO2纳米片。
2）TiO2/卟啉/MOFs的制备
TiO2/卟啉/MOFs制备过程如下：
取上述TiO2纳米片0.3g 置于浓度为3M的四羧基苯基锌卟啉的DMF溶液中，放在超声波清洗机中超声30min，使TiO2纳米片充分分散，随后在常温下磁力搅拌6h。然后将上述分散液抽滤得到金属卟啉修饰的TiO2纳米片；
将得到的金属卟啉修饰的TiO2纳米片分散到5 ml 浓度为5M 的硝酸锌溶液中，超声20min后磁力搅拌6h，经过抽滤装置分离后得到吸附金属离子的TiO2/卟啉超薄异质体；
将得到的锌离子修饰的TiO2/卟啉超薄异质体分散到10 ml 浓度为5M 的2-甲基咪唑溶液中，超声10min后，120°C反应24h的条件下，在TiO2/卟啉超薄异质体表面生产相应的MOFs层即得到TiO2/卟啉/MOFs。
实施例3
1）TiO2纳米片的制备
取25 mL的钛酸四丁酯置于烧杯中，取5mL的氢氟酸缓慢加入烧杯中，搅拌均匀后，将得到的白色胶状物转移到100ml聚四氟乙烯高压反应釜中，随后将反应釜放在220 oC烘箱中反应20 h后缓慢降至室温。取下层白色沉淀用去离子水离心洗涤数遍直至上层清液至中性，然后置于80 oC真空干燥烘箱中干燥即得到TiO2纳米片。
2）TiO2/卟啉/MOFs的制备
TiO2/卟啉/MOFs制备过程如下：
取上述TiO2纳米片0.5g 置于浓度为5M的四羧基苯基钴卟啉的DMF溶液中，放在超声波清洗机中超声40min，使TiO2纳米片充分分散，随后在常温下磁力搅拌12h。然后将上述分散液抽滤得到金属卟啉修饰的TiO2纳米片；
将得到的金属卟啉修饰的TiO2纳米片分散到5 ml 浓度为10M 的硝酸铜溶液中，超声40min后磁力搅拌12h，经过抽滤装置分离后得到吸附金属离子的TiO2/卟啉超薄异质体；
将得到的铜离子修饰的TiO2/卟啉超薄异质体分散到10 ml 浓度为10M 的均苯三甲酸溶液中，超声40min后，120°C反应48h的条件下，在TiO2/卟啉超薄异质体表面生产相应的MOFs层即得到TiO2/卟啉/MOFs。
Claims (2)
1.一种TiO2/卟啉/MOFs超薄异质体的制备方法，其特征在于，先制备TiO2纳米片，再制备TiO2/卟啉/MOFs，TiO2/卟啉/MOFs制备过程如下：
①取上述TiO2纳米片0.1～0.5g置于浓度为0.1-5M的金属卟啉DMF溶液中，放在超声波清洗机中超声5-40min，使TiO2纳米片充分分散，随后在常温下磁力搅拌2-12h，然后将上述分散液抽滤得到金属卟啉修饰的TiO2纳米片，所述的金属卟啉为四羧基苯基锌卟啉、四羧基苯基钴卟啉中的一种；
②将得到的金属卟啉修饰的TiO2纳米片分散到浓度为0.1-10M的可溶性金属盐溶液中，超声5-40min后磁力搅拌2-12h，经过抽滤装置分离后得到吸附金属离子的TiO2/卟啉超薄异质体，所述的可溶性金属盐为硝酸铬，硝酸锌，硝酸铜中的一种；
③将得到的金属离子修饰的TiO2/卟啉超薄异质体分散到浓度为0.1-10M的配体溶液中，超声5-40min后，在20-220℃下反应0.5-48h，在TiO2/卟啉超薄异质体表面生产相应的MOFs层即得到TiO2/卟啉/MOFs，所述的配体为对苯二甲酸、均苯三甲酸、2-甲基咪唑中的一种；
④重复上述①②③若干次，得到负载量不同的TiO2/卟啉/MOFs复合材料。
2.根据权利要求1所述的制备方法，其特征在于，所述TiO2纳米片的制备是将1～10mL的氢氟酸缓慢加入到5～50mL的钛酸四丁酯中，搅拌0.5-3h后，将得到的白色胶状物转移到聚四氟乙烯高压反应釜中，随后将反应釜放在150-200℃烘箱中反应6-48h后缓慢降至室温，取下层白色沉淀用去离子水离心洗涤数遍直至上层清液至中性，然后置于40-100℃真空干燥烘箱中干燥即得到TiO2纳米片。
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| CN111135870B (zh) * | 2019-12-29 | 2021-05-07 | 苏州阿德旺斯新材料有限公司 | 二氧化钛纳米带@mof复合材料及其应用 |
| WO2021135253A1 (zh) * | 2019-12-29 | 2021-07-08 | 苏州阿德旺斯新材料有限公司 | 二氧化钛纳米带@mof复合材料、其制备方法及应用 |
| CN111607808B (zh) * | 2020-05-19 | 2021-11-16 | 首都师范大学 | 一种超薄金属有机框架材料UiO-67包覆二氧化钛纳米棒的核壳结构及其制备方法 |
| CN111905824B (zh) * | 2020-08-18 | 2023-06-16 | 苏州荣格君新材料有限公司 | 一种双配体金属有机骨架光催化剂及其应用 |
| CN111871465B (zh) * | 2020-08-18 | 2023-03-21 | 苏州荣格君新材料有限公司 | 一种双配体金属有机骨架光催化剂及其制备方法 |
| CN115318339B (zh) * | 2022-08-11 | 2023-05-26 | 郑州大学 | 负载zif-67的荷叶衍生生物炭及制备方法和应用 |
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