CN109126893A - 一种碳氧化钛-金属有机框架复合材料及制备方法和应用 - Google Patents
一种碳氧化钛-金属有机框架复合材料及制备方法和应用 Download PDFInfo
- Publication number
- CN109126893A CN109126893A CN201811171056.8A CN201811171056A CN109126893A CN 109126893 A CN109126893 A CN 109126893A CN 201811171056 A CN201811171056 A CN 201811171056A CN 109126893 A CN109126893 A CN 109126893A
- Authority
- CN
- China
- Prior art keywords
- titanium
- composite material
- oxidation
- mil
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 title claims abstract description 29
- 230000003647 oxidation Effects 0.000 title claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 20
- 239000003245 coal Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000002086 nanomaterial Substances 0.000 claims abstract description 8
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000013049 sediment Substances 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- 238000005119 centrifugation Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- 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 compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 9
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- 239000001119 stannous chloride Substances 0.000 claims description 9
- 235000011150 stannous chloride Nutrition 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000013110 organic ligand Substances 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005642 Oleic acid Substances 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 230000005484 gravity Effects 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 238000002372 labelling Methods 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052603 melanterite Inorganic materials 0.000 claims description 2
- 239000002073 nanorod Substances 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims 1
- 239000002070 nanowire Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 46
- 239000013206 MIL-53 Substances 0.000 abstract description 12
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 229910021392 nanocarbon Inorganic materials 0.000 abstract description 5
- 239000005416 organic matter Substances 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 239000013144 Fe-MIL-100 Substances 0.000 abstract description 4
- 239000013179 MIL-101(Fe) Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 25
- 239000012621 metal-organic framework Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000013177 MIL-101 Substances 0.000 description 3
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- MYLBTCQBKAKUTJ-UHFFFAOYSA-N 7-methyl-6,8-bis(methylsulfanyl)pyrrolo[1,2-a]pyrazine Chemical compound C1=CN=CC2=C(SC)C(C)=C(SC)N21 MYLBTCQBKAKUTJ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000013291 MIL-100 Substances 0.000 description 1
- 239000013292 MIL-100(Cr) Substances 0.000 description 1
- 239000013178 MIL-101(Cr) Substances 0.000 description 1
- 239000012922 MOF pore Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 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 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ZNKMCMOJCDFGFT-UHFFFAOYSA-N gold titanium Chemical compound [Ti].[Au] ZNKMCMOJCDFGFT-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000013337 mesoporous metal-organic framework Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- WCJNRJDOHCANAL-UHFFFAOYSA-N n-(4-chloro-2-methylphenyl)-4,5-dihydro-1h-imidazol-2-amine Chemical compound CC1=CC(Cl)=CC=C1NC1=NCCN1 WCJNRJDOHCANAL-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 229910001258 titanium gold Inorganic materials 0.000 description 1
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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
-
- 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
- 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
- B01J35/33—Electric or magnetic properties
-
- 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
-
- 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
-
- 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
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- 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
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种碳氧化钛‑金属有机框架复合材料及制备方法和应用,其材料中以Fe金属中心的MIL‑53(Fe)、MIL‑100(Fe)或MIL‑101(Fe)为框架,与纳米碳材料形成插入、点缀、包裹、交替或混合的复合结构,最后再将二氧化钛纳米颗粒或一维纳米结构以包裹或表面联接的复合方式实现三元材料的制备。该材料是通过共价键的方式结合,金属有机框架和纳米碳材料均具有大的比表面积和强的吸附能力;纳米碳材料在该体系中能够转移半导体的电子,阻碍电子与空穴的复合,从而提高光催化性能。同时,金属有机框架与二氧化钛均是具有半导体结构的光催化材料,可以高效的降解分解有机物。本发明的复合材料,能够有效处理金属离子浓度较高的有机废水。
Description
技术领域
本发明涉及复合材料及制备和应用,尤其是一种碳氧化钛-金属有机框架复合材料及制备方法和在光电催化净化中的应用。
背景技术
MOF全称为Metal-Organic Framework,是指一类新型金属无机材料与有机高分子单体的原子级别复合物。这类材料具有发达的纳米级孔道,单位MOF材料其孔道为1-3纳米。通过大量单位MOF聚合形成的三维网络框架结构具有相对较大的比表面积,能用于吸附、储存大量气体分子;在水中吸附有机物、不同尺寸的基团和离子等。通过调整MOF孔道尺寸、形状及结构可进一步筛选不同的分子,MOF的自身静电荷还能捕捉附近的分子,例如PM2.5等。MOFs材料分为微孔、介孔、和大孔。介孔材料的尺寸范围为2-50 nm,这一尺寸相当于典型有机物分子大小(除了聚合物)。因此,介孔MOF材料是特别有前途的吸附剂,用于许多领域。常见的金属-有机骨架材料主要有6大类,包括:IRMOF系列材料、ZIF系列材料、CPL系列材料、MIL系列材料、PCN系列材料和UiO系列材料,目前已制备的MOF材料超过五千多种,从理论上计算能够制备出来的MOF种类没有上限。
MOF材料除了可以吸附气体分子,也可以吸附水中的物质,从而应用与水净化等应用领域,因此它在水中的稳定性至关重要。MOFs材料由于配位键较弱,极易在水气存在下水解而发生骨架坍塌,金属和配体检的连接配合物遇水又会水解,因此许多MOFs在水中是不稳定的,稳定的MOFs材料才能用于水的净化。在不同的材料体系中MIL系列材料,在水中是相对最稳定的。MIL材料系统列是使用不同的过渡金属和琥珀酸、戊二酸等二羧酸配体合成,主要包括MIL-100,MIL-101,MIL-125,MIL-43,MIL-47,MIL-53和MIL-88类型,其中在水中最稳定的是MIL-100(Cr),MIL-101(Cr),MIL-101(Al),其次较稳定的是MIL-X(Fe),包括MIL-53(Fe)、MIL-100(Fe)和MIL-101(Fe)等。一般,MIL-53(Fe)、MIL-100(Fe)和MIL-101(Fe)都会经过300摄氏度以上的焙烧活化,去除了有机杂质,且是孔道中的小分子跑出,比表面积和孔隙率提高的同时,Fe会通过小分子的离开暴露出来,一部分的三价铁能够转变成二价铁,这对不饱和气体小分子的吸附分离式及其有利的。
MOF材料最大的优势是吸附,在水净化中除了抓取水中污染物,更重要的是通过有效的方法去除污染物。目前,最普遍的是通过膜过滤结合生物降解技术等方法,现有方法存在膜易堵塞、分解周期长、吸附效率低等一系列的问题,特别是处理高有机、高盐含量等复杂污水体系,传统方法具有非常大的局限性和处理困难。因此,一种光催化结合电催化的水净化处理技术被提出了,如专利CN201610373986.6, CN201620512520.5所述,该技术主要采用了氧化钛基材料为光催化降解主体;采用铝、铁金属等为电催化氧化剂,大大的提高了复杂污水系统的污染物降解效率和能力,从而实现污水的快速净化。
发明内容
本发明的目的是提供一种碳氧化钛-金属有机框架复合材料的制备方法,制得的纳米复合的MOF材料具有良好的物理吸附和光电催化性能,可以用于光电催化净化领域。
本发明中MIL材料中M代表Fe金属,MIL后面的数字是Yaghi【Takayabu Y N,Iguchi T, Kachi M, et al. Design and Synthesis of an Exceptionally Stable andHighly Porous Metal-Organic Framework [J]. Nature, 1999, 402: 276-279.】提出的一种MOF材料模拟系统中的序号。本发明所制备的复合材料中以Fe为金属中心的MIL-53(Fe)、MIL-100(Fe)或MIL-101(Fe)为框架,与纳米碳结构材料形成插入、点缀、包裹、交替或混合的复合机构,最后再将二氧化钛纳米颗粒或一维纳米结构以包裹或表面联接的复合方式实现三元材料的复合制备。
实现本发明目的的具体技术方案是:
一种碳氧化钛-金属有机框架复合材料的制备方法,该方法包括以下具体步骤:
步骤1:选取纳米结构含碳材料,将其在分析纯强酸:水的体积比为1:2~1的溶液中,超声分散,边搅拌边加热至90℃,搅拌0.5~1小时,降温后用清水清洗离心;将离心沉淀物放入体积比为4~2:3~1的分析纯HCL和H2O的溶液中,浸泡0.5~2小时后,清洗离心取出;50~60℃干燥得粉末待用;所述强酸为分析纯HNO3或者H2SO4;所述纳米结构含碳材料为纯碳纳米管、石墨烯、氧化石墨烯或石墨型氮化碳g-C3N4;
步骤2:取步骤1得到的粉末分散于浓度为0.05~5mol/L的氯化亚锡水溶液中,浸泡时间6~12小时,用水清洗离心后取出沉淀物待用;所述粉末与氯化亚锡的质量比为0.2:0.2~0.8;
步骤3:溶液1:取步骤2得到的沉淀物加入二甲基甲酰胺DMF,沉淀物与DMF的质量比1:5~10;搅拌30min;
预备溶液1:取0.5~1g 铁盐;所述铁盐为FeCl3· 6H2O、Fe2(SO4)3或其中一种与FeSO4·7H2O的混合物,其中,FeCl3· 6H2O与FeSO4·7H2O或Fe2(SO4)3与FeSO4·7H2O的质量比为7:3~9:1;
预备溶液2:取有机配体混合物;所述有机配体混合物由有机配体与DMF混合而成,有机配体与DMF的比重是:0.3~0.6g:30~60ml;所述有机配体是均苯三甲酸H3BTC、乙二胺四乙酸EDTA和对苯二甲酸H2BDC中的一种;
将上述预备溶液1、预备溶液2与溶液1混合,用磁力搅拌1~2h,使溶液均匀;将所得溶液倒入聚四氟乙烯的水热釜中,100-150 oC条件下反应15-24h,自然冷却至室温,并用DMF和无水乙醇各洗涤3次,50-80 oC干燥后得粉末产物,将该产物标记为CMFe,通过含量控制,产物中复合的含碳材料质量比为1-8%;
步骤4:将步骤3制得的粉末分散到无水乙醇中,加入钛醇盐作为钛源,通过不断搅拌经水解缩聚反应形成均匀溶胶,经烘干,煅烧后获得碳氧化钛-金属有机框架复合材料;煅烧温度为350~450℃;其中,在加入钛醇盐的同时加入油酸和十二胺,钛醇盐与油酸质量比为1:8~12,钛醇盐与十二胺的质量比为3~2:1,并边搅拌边升温至280℃,使复合材料中的氧化钛是以二氧化钛纳米棒或管或线形式生长;当油酸和十二胺的质量低于上述范围,复合材料中的氧化钛是以二氧化钛颗粒形式生长;所述钛醇盐为钛酸四丁酯。
一种上述方法制得的碳氧化钛-金属有机框架复合材料。
一种上述方法制得的碳氧化钛-金属有机框架复合材料在光电催化净化中的应用。
本发明所制得的材料通过丝网印刷、喷涂、刮涂等工艺在不同衬底上制备成薄膜,膜厚5-20微米,该薄膜可以用于光电水净化、光电气净化等应用。另外,在步骤4中浸入酸洗后的不锈钢网,形成包有上述碳氧化钛-金属有机框架复合材料的网板;或者通过丝网印刷工艺在不锈钢板上印制上述碳氧化钛-金属有机框架复合材料的膜层;包裹了碳氧化钛-金属有机框架复合材料金属基板可以直接作为光电催化电极板应用于光电催化净化系统。
本发明所得的是三元复合材料,材料的复合通过共价键的方式结合,金属有机框架和纳米碳结构材料均具有大的比表面积和强的吸附能力;同时,金属有机框架与二氧化钛均是具有半导体结构的光催化材料,可以高效的降解分解有机物另外纳米碳材料在该体系中可以转移半导体的电子,阻碍电子与空穴的复合,从而提高光催化性能。本发明中优先复合纳米碳材料和金属有机框架为支架,因此生成的二氧化钛颗粒或棒不易团聚,使得光催化效能的发挥更加高效。
本发明采用基于MOF(Fe)-碳-氧化钛复合材料,进一步提升了光电催化系统中光催化系统的效率,并将去离子技术相结合,有效处理金属离子浓度较高的有机废水。对于MIL材料体系中例如MIL-X(Cr)等以重金属原子为中心的MOFs材料,在具有电场作用的水中,不可避免Cr等重金属离子的逸出,《污水综合排放标准》2018最新标准中提出一类污染物中的重金属的排放限值为总Cr 0.5mg/L;总Ni0.1 mg/L;总Cd0.01 mg/L,六价Cr0.1 mg/L等。排入环境水体的第二类污染物中金属含量的相关排放限值为Cu0.2 mg/L;Zn1.0 mg/L;Mn1.0 mg/L;Fe2.0 mg/L。根据要求,含有重金属的MOFs材料都具有二次污染的风险,不适合与水处理的应用,而要求未对Al的含量提出要求。另外,在光电催化技术的应用中,Fe可以用于催化聚合和催化还原,最终通过气泡悬浮刮除或者还原-絮凝-沉淀等过程以固体废弃物的方式与水分离。鉴于以上材料和水处理技术,本发明提出了一种由碳-二氧化钛复合的MIL-X(Fe)金属有机框架复合材料,并应用于光电催化净化领域。
附图说明
图1为MIL-53(Fe)的通用结构图;
图2为g-C3N4扫描电镜照片图;
图3为MIL-53(Fe)扫描电镜照片图;
图4为CM53Fe-X扫描电镜照片图;
图5MIL101Fe的通用结构图。
具体实施方式
实施例1
称取一定量片状g-C3N4在分析纯HNO3:水的体积比为1:2的溶液中,超声分散,边搅拌边加热至90℃,搅拌0.5小时,降温后用清水清洗离心;将离心沉淀物放入体积比为2∶3的分析纯HCL和H2O的溶液中,浸泡0.5小时后,清洗离心取出;50~60℃干燥得粉末;将干燥所得粉末在0.1mol/L氯化亚锡水溶液浸泡6小时后,离心烘干取出,加入到10ml DMF中,搅拌30min,得溶液1。再取0.54g(2mmol)FeCl3· 6H2O和0.33g(2mmol)对苯二甲酸(H2BDC),30.88ml(0.56mol)DMF 于烧杯中,混合均匀,得溶液2,将上述两份溶液混合,用磁力搅拌机机械搅拌1h,使溶液均匀;将所得溶液放入水热釜中,150oC条件下反应15h,自然冷却至室温,并用DMF和无水乙醇各洗涤3次,150oC干燥过夜,最终产物为黄棕色。用此方法通过控制g-C3N4质量可以合成一系列不同掺碳比例的MIL-53(Fe)样品,样品标记为CM53(Fe)-X,X为掺碳比例;其扫描电镜照片如图4所示。
MIL-53(Fe)是由链状的Fe (Ⅲ)八面体通过对苯二甲基基团(O2C-C6H4-CO2) 桥联形成的三维空间网状结构的材料。MIL-53(Fe)的通用化学式是MⅢ(OH)·[O2C-C6H4-CO2]·x(solv),其结构如图1所示,扫描电镜照片如图3所示。
将CM53(Fe)-X材料分散到12ml无水乙醇中,加入0.4ml钛酸正丁酯,搅拌5min后再向其中加入0.6ml氢氟酸溶液并迅速加入2mlTiCl3溶液,然后将上述混合液导入聚四氟乙烯反应釜内,180摄氏度反应24小时。冷却降到室温后,用乙醇和水清洗样品3次,最后在60摄氏度条件下干燥5小时得到三元的复合材料粉末。将粉末以10-15%的质量比例混合入丝网印刷浆料中(乙基纤维素与松油醇的6%的混合溶剂),研磨均匀后在不锈钢网上印制厚度为6-18um的膜层,经350摄氏度烧结1小时后,制得光电催化电极板。在光电催化系统中,可用于阴极,在电流作用下除了还原金属离子,可以大量吸附有机物,增加了光催化分解的辅助作用,使得水净化效率大大增强。
实施例2
取100g的多壁碳纳米管,用体积比为1∶2的分析纯HNO3:水溶液超声分散,然后边搅拌边加热至90℃,浸泡1小时后用去离子水离心清洗3次。将离心沉淀物放入体积比为2∶1的HCL和H2O的溶液中,浸泡0.5小时后,清洗离心取出。低温60℃干燥成粉末待用。
选取上述粉末分散于氯化亚锡水溶液中,粉末与氯化亚锡的质量比为0.2g∶0.4g,浸泡时间8小时后,完成表面敏化,用水清洗离心后取出沉淀物待用。
称量沉淀物5g,分散到20ml二甲基甲酰胺DMF中;搅拌30min,获得混合均匀的溶液1。取1g 铁盐,铁盐是Fe2(SO4)3与FeSO4·7H2O的混合物,混合物质量比为7∶3;0.5g的均苯三甲酸H3BTC,混合在50ml DMF中,搅拌均匀后得到溶液2。将上述2种溶液互混,用磁力搅拌2h,使溶液均匀。将所得溶液倒入聚四氟乙烯的水热釜中,150oC条件下反应24h,自然冷却至室温,并用DMF和无水乙醇各洗涤3次,150oC干燥后得粉末产物CM100Fe-X。
取1g上述粉末产物与10 mL 钛酸四丁酯和100 mL 油酸共同加入锥形瓶中, 室温下剧烈磁力搅拌1 h, 用注射器将4 mL十二胺注入锥形瓶(1 mL/min), 再在室温下剧烈搅拌24 h,保证溶液中各成分混合均匀。将溶液导入较大的反应容器中,将经HCl(10%)浸泡过2小时的不锈钢网置于上述溶液中。在搅拌的情况下,通过加热圈将溶液温度升高到280℃,反应0.5h后,自然冷却至室温。在不锈钢网上面附着的膜层即为所需的三元复合材料。基于不锈钢网的碳氧化钛-金属有机框架复合材料的膜层可应用于可见光催化分解VOCs,碳纳米管和有机金属框架的高吸附能力,再通过氧化钛的复合,大大提高了气体净化效率。另外,MIL-100Fe含有不饱和金属位点,除了物理吸附,还有酸碱反应和氢键作用,因此不会出现坍塌现象,在应用中比较稳定可以应用于CDMI等去离子水的制备系统。
实施例3
石墨烯表面含有羧基、环氧基、羟基等极性官能团,可以为MOFs材料的生长提供诸多的结合位点。石墨烯是片状的,在合成MOF材料的过程中加入石墨烯材料,可以获得片层结构间夹杂MOF的复合材料。石墨烯的环氧基与MOF材料的金属中心进行反应可以制成交替结构的复合材料,吸附NH3和NO2。
将CVD生长的少层石墨烯分散,用体积比为1∶2的分析纯HSO4∶水溶液超声分散,然后边搅拌边加热至90℃,浸泡1小时后用去离子水离心清洗3次。将离心沉淀物放入体积比为4∶3的HCL和H2O的溶液中,浸泡0.5小时后,清洗离心取出。低温60℃干燥等粉末待用。将上述粉末放入氯化亚锡水溶液中(1mol/l),碳材料与氯化亚锡的质量比为1∶1,浸泡时间6小时,用水清洗离心后取出沉淀物待用。
将5g沉淀物放入0.68g的FeCl3· 6H2O(2.45mmol),0.21g对苯二甲酸(H2BDC)和15mlDMF的混合溶液,超声处理15min,使之混合均匀。
将上述混合溶液倒入聚四氟乙烯反应釜中,在110℃下加热20小时,降到室温后,用无水乙醇洗涤2次,将产物过滤,经70℃干燥30min。随后在真空条件下150℃干燥8h,去除吸附在孔道中的乙醇分子,得到比表面积在2500以上的CMIL-101(Fe)。
MIL-101(Fe)的通用结构如图5所示,与MIL-53(Fe)一样,也还有Fe原子。本结构中Fe原子与OH根连接,更有利与光电催化应用效果。
将0.05mol的钛酸四丁酯溶于100ml无水乙醇中,搅拌20分钟,然后加入0.1gCMIL-101(Fe)材料,超声1小时,使之完全分散。在缓慢滴入20mlpH值为2的硝酸水溶液,陈化12小时,使钛酸四丁酯完全水解, CMIL-101(Fe)表面负载的二氧化钛颗粒层。用水洗涤过滤后,至于80℃烘箱内干燥,最后在450℃条件下煅烧2小时,自然冷却后,研磨得到三元的TiO2-CMIL-101(Fe)复合材料。
在电催化系统的阴极基板表面涂敷上述材料,可同时实现催化聚合和催化氧化分解两种功能,对于高浓有机废水,因其透光性较差,主要采用电催化为主的工艺进行预处理;在电场与催化材料的共同作用下,较大分子量的有机物或含有钙、镁等离子的团聚体较大、较重时,会从水中直接沉积至催化反应室的底部,到一定量时可通过底部的出泥口排出。
Claims (3)
1.一种碳氧化钛-金属有机框架复合材料的制备方法,其特征在于,该方法包括以下具体步骤:
步骤1:选取纳米结构含碳材料,将其在分析纯强酸:水的体积比为1:2~1的溶液中,超声分散,边搅拌边加热至90℃,搅拌0.5~1小时,降温后用清水清洗离心;将离心沉淀物放入体积比为4~2:3~1的分析纯HCL和H2O的溶液中,浸泡0.5~2小时后,清洗离心取出;50~60℃干燥得粉末待用;所述强酸为分析纯HNO3或者H2SO4;所述纳米结构含碳材料为纯碳纳米管、石墨烯、氧化石墨烯或石墨型氮化碳g-C3N4;
步骤2:取步骤1得到的粉末分散于浓度为0.05~5mol/L的氯化亚锡水溶液中,浸泡时间6~12小时,用水清洗离心后取出沉淀物待用;所述粉末与氯化亚锡的质量比为0.2:0.2~0.8;
步骤3:溶液1:取步骤2得到的沉淀物加入二甲基甲酰胺DMF,沉淀物与DMF的质量比1:5~10;搅拌30min;
预备溶液1:取0.5~1g 铁盐;所述铁盐为FeCl3· 6H2O、Fe2(SO4)3或其中一种与FeSO4·7H2O的混合物,其中,FeCl3· 6H2O与FeSO4·7H2O或Fe2(SO4)3与FeSO4·7H2O的质量比为7:3~9:1;
预备溶液2:取有机配体混合物;所述有机配体混合物由有机配体与DMF混合而成,有机配体与DMF的比重是:0.3~0.6g:30~60ml;所述有机配体是均苯三甲酸H3BTC、乙二胺四乙酸EDTA和对苯二甲酸H2BDC中的一种;
将上述预备溶液1、预备溶液2与溶液1混合,用磁力搅拌1~2h,使溶液均匀;将所得溶液倒入聚四氟乙烯的水热釜中,100-150oC条件下反应15-24h,自然冷却至室温,并用DMF和无水乙醇各洗涤3次,50-80oC干燥后得粉末产物,将该产物标记为CMFe,通过含量控制,产物中复合的含碳材料质量比为1-8%;
步骤4:将步骤3制得的粉末分散到无水乙醇中,加入钛醇盐作为钛源,通过不断搅拌经水解缩聚反应形成均匀溶胶,经烘干,煅烧后获得碳氧化钛-金属有机框架复合材料;煅烧温度为350~450℃;其中,在加入钛醇盐的同时加入油酸和十二胺,钛醇盐与油酸质量比为1:8~12,钛醇盐与十二胺的质量比为3~2:1,并边搅拌边升温至280℃,复合材料中的氧化钛是以二氧化钛纳米棒、纳米管或纳米线形式生长;当油酸和十二胺的质量低于上述范围,复合材料中的氧化钛是以二氧化钛颗粒形式生长;所述钛醇盐为钛酸四丁酯。
2.一种权利要求1所述方法制得的碳氧化钛-金属有机框架复合材料。
3.一种权利要求2所述碳氧化钛-金属有机框架复合材料在光电催化净化中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811171056.8A CN109126893B (zh) | 2018-10-09 | 2018-10-09 | 一种碳氧化钛-金属有机框架复合材料及制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811171056.8A CN109126893B (zh) | 2018-10-09 | 2018-10-09 | 一种碳氧化钛-金属有机框架复合材料及制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109126893A true CN109126893A (zh) | 2019-01-04 |
CN109126893B CN109126893B (zh) | 2021-03-26 |
Family
ID=64810936
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811171056.8A Active CN109126893B (zh) | 2018-10-09 | 2018-10-09 | 一种碳氧化钛-金属有机框架复合材料及制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109126893B (zh) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109622062A (zh) * | 2019-01-16 | 2019-04-16 | 南京工程学院 | 一种改性钒酸铋光催化剂及其制备方法 |
CN110615501A (zh) * | 2019-09-26 | 2019-12-27 | 常熟理工学院 | 一种垃圾渗滤液的处理方法 |
CN111530426A (zh) * | 2020-05-11 | 2020-08-14 | 上海纳米技术及应用国家工程研究中心有限公司 | 结构可伸缩的Zn/MIL-88(Al)复合吸附剂的制备方法及其产品和应用 |
CN111617805A (zh) * | 2020-06-04 | 2020-09-04 | 吉林大学 | 光Fenton催化剂、其制备方法、其应用及水处理剂 |
CN111841074A (zh) * | 2020-07-29 | 2020-10-30 | 杭州职业技术学院 | 一种多孔膜保护纳米材料固相微萃取装置及其应用 |
CN111974459A (zh) * | 2020-09-03 | 2020-11-24 | 宜兴国际环保城科技发展有限公司 | 一种管式自由基催化剂及其制备方法 |
CN112408492A (zh) * | 2020-11-23 | 2021-02-26 | 上海纳米技术及应用国家工程研究中心有限公司 | 用于甲醛检测的金属氧化物修饰氮缺陷复合材料的制备方法及其产品和应用 |
WO2021258233A1 (zh) * | 2020-06-22 | 2021-12-30 | 苏州楚捷新材料科技有限公司 | 高可见光响应的MOFs光催化材料的制备方法 |
CN114002201A (zh) * | 2021-11-09 | 2022-02-01 | 山西聚微天成科技有限公司 | 一种高灵敏性离子检测装置及其应用 |
CN114042476A (zh) * | 2021-11-15 | 2022-02-15 | 杭州师范大学 | MOF-TiO2/石墨烯量子点纳米复合光催化剂的制备方法 |
CN114460150A (zh) * | 2022-02-09 | 2022-05-10 | 福州市第二医院(福建省福州中西医结合医院、福州市职业病医院) | 一种基于MOFs复合材料的无标记DNA光电化学检测方法 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001014053A1 (en) * | 1999-08-23 | 2001-03-01 | Georgetown University | Catalytic system and method for reducing perchlorate ion |
CN101733134A (zh) * | 2008-11-21 | 2010-06-16 | 北京工业大学 | 燃料电池催化剂的制备方法 |
US20140051898A1 (en) * | 2009-07-29 | 2014-02-20 | Us Government As Represented By The Secretary Of Department Of The Navy | Diesel and Jet Fuels Based on the Oligomerization of Butene |
CN103771504A (zh) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | 一种二氧化钛光催化剂的合成方法 |
CN104722335A (zh) * | 2015-01-30 | 2015-06-24 | 湖南大学 | 石墨型氮化碳-金属有机框架复合光催化剂及其制备方法和应用 |
WO2015195510A1 (en) * | 2014-06-18 | 2015-12-23 | California Institute Of Technology | Highly active mixed-metal catalysts made by pulsed-laser ablation in liquids |
CN106582859A (zh) * | 2016-12-21 | 2017-04-26 | 湘潭大学 | 一种负载型类沸石咪唑骨架材料的制备方法及其在环己烷氧化反应中的应用 |
CN106694007A (zh) * | 2016-12-19 | 2017-05-24 | 中国科学院山西煤炭化学研究所 | 一种单分散金属原子/石墨烯复合催化剂及其制备方法和应用 |
CN108097317A (zh) * | 2017-12-08 | 2018-06-01 | 北京林业大学 | 一种采用g-C3N4/MIL-125(Ti)催化剂对噻吩类硫化物光催化氧化的方法 |
CN108525685A (zh) * | 2017-03-01 | 2018-09-14 | 中国科学院理化技术研究所 | 一种单分散或负载型的含磷金属化合物作为催化剂的储氢材料水解释氢体系 |
-
2018
- 2018-10-09 CN CN201811171056.8A patent/CN109126893B/zh active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001014053A1 (en) * | 1999-08-23 | 2001-03-01 | Georgetown University | Catalytic system and method for reducing perchlorate ion |
CN101733134A (zh) * | 2008-11-21 | 2010-06-16 | 北京工业大学 | 燃料电池催化剂的制备方法 |
US20140051898A1 (en) * | 2009-07-29 | 2014-02-20 | Us Government As Represented By The Secretary Of Department Of The Navy | Diesel and Jet Fuels Based on the Oligomerization of Butene |
CN103771504A (zh) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | 一种二氧化钛光催化剂的合成方法 |
WO2015195510A1 (en) * | 2014-06-18 | 2015-12-23 | California Institute Of Technology | Highly active mixed-metal catalysts made by pulsed-laser ablation in liquids |
CN104722335A (zh) * | 2015-01-30 | 2015-06-24 | 湖南大学 | 石墨型氮化碳-金属有机框架复合光催化剂及其制备方法和应用 |
CN106694007A (zh) * | 2016-12-19 | 2017-05-24 | 中国科学院山西煤炭化学研究所 | 一种单分散金属原子/石墨烯复合催化剂及其制备方法和应用 |
CN106582859A (zh) * | 2016-12-21 | 2017-04-26 | 湘潭大学 | 一种负载型类沸石咪唑骨架材料的制备方法及其在环己烷氧化反应中的应用 |
CN108525685A (zh) * | 2017-03-01 | 2018-09-14 | 中国科学院理化技术研究所 | 一种单分散或负载型的含磷金属化合物作为催化剂的储氢材料水解释氢体系 |
CN108097317A (zh) * | 2017-12-08 | 2018-06-01 | 北京林业大学 | 一种采用g-C3N4/MIL-125(Ti)催化剂对噻吩类硫化物光催化氧化的方法 |
Non-Patent Citations (2)
Title |
---|
LIANJIE LING ET AL.: "Preparation of a Novel Ternary Composite of TiO2/", 《CATALYSIS LETTERS》 * |
钱敏: "纳米碳材料的制备及其薄膜透明导电和场发射性能的研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109622062A (zh) * | 2019-01-16 | 2019-04-16 | 南京工程学院 | 一种改性钒酸铋光催化剂及其制备方法 |
CN109622062B (zh) * | 2019-01-16 | 2021-06-04 | 南京工程学院 | 一种改性钒酸铋光催化剂及其制备方法 |
CN110615501B (zh) * | 2019-09-26 | 2022-02-11 | 常熟理工学院 | 一种垃圾渗滤液的处理方法 |
CN110615501A (zh) * | 2019-09-26 | 2019-12-27 | 常熟理工学院 | 一种垃圾渗滤液的处理方法 |
CN111530426A (zh) * | 2020-05-11 | 2020-08-14 | 上海纳米技术及应用国家工程研究中心有限公司 | 结构可伸缩的Zn/MIL-88(Al)复合吸附剂的制备方法及其产品和应用 |
CN111530426B (zh) * | 2020-05-11 | 2022-09-02 | 上海纳米技术及应用国家工程研究中心有限公司 | 结构可伸缩的Zn/MIL-88(Al)复合吸附剂的制备方法及其产品和应用 |
CN111617805A (zh) * | 2020-06-04 | 2020-09-04 | 吉林大学 | 光Fenton催化剂、其制备方法、其应用及水处理剂 |
CN111617805B (zh) * | 2020-06-04 | 2023-02-03 | 吉林大学 | 光Fenton催化剂、其制备方法、其应用及水处理剂 |
WO2021258233A1 (zh) * | 2020-06-22 | 2021-12-30 | 苏州楚捷新材料科技有限公司 | 高可见光响应的MOFs光催化材料的制备方法 |
CN111841074A (zh) * | 2020-07-29 | 2020-10-30 | 杭州职业技术学院 | 一种多孔膜保护纳米材料固相微萃取装置及其应用 |
CN111974459B (zh) * | 2020-09-03 | 2022-11-04 | 宜兴国际环保城科技发展有限公司 | 一种管式自由基催化剂及其制备方法 |
CN111974459A (zh) * | 2020-09-03 | 2020-11-24 | 宜兴国际环保城科技发展有限公司 | 一种管式自由基催化剂及其制备方法 |
CN112408492A (zh) * | 2020-11-23 | 2021-02-26 | 上海纳米技术及应用国家工程研究中心有限公司 | 用于甲醛检测的金属氧化物修饰氮缺陷复合材料的制备方法及其产品和应用 |
CN112408492B (zh) * | 2020-11-23 | 2023-02-14 | 上海纳米技术及应用国家工程研究中心有限公司 | 用于甲醛检测的金属氧化物修饰氮缺陷复合材料的制备方法及其产品和应用 |
CN114002201A (zh) * | 2021-11-09 | 2022-02-01 | 山西聚微天成科技有限公司 | 一种高灵敏性离子检测装置及其应用 |
CN114042476A (zh) * | 2021-11-15 | 2022-02-15 | 杭州师范大学 | MOF-TiO2/石墨烯量子点纳米复合光催化剂的制备方法 |
CN114460150A (zh) * | 2022-02-09 | 2022-05-10 | 福州市第二医院(福建省福州中西医结合医院、福州市职业病医院) | 一种基于MOFs复合材料的无标记DNA光电化学检测方法 |
CN114460150B (zh) * | 2022-02-09 | 2023-04-11 | 福州市第二医院(福建省福州中西医结合医院、福州市职业病医院) | 一种基于MOFs复合材料的无标记DNA光电化学检测方法 |
Also Published As
Publication number | Publication date |
---|---|
CN109126893B (zh) | 2021-03-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109126893A (zh) | 一种碳氧化钛-金属有机框架复合材料及制备方法和应用 | |
Li et al. | TiO2 nanoparticles anchored onto the metal–organic framework NH2-MIL-88B (Fe) as an adsorptive photocatalyst with enhanced fenton-like degradation of organic pollutants under visible light irradiation | |
Areerob et al. | Enhanced sonocatalytic degradation of organic dyes from aqueous solutions by novel synthesis of mesoporous Fe3O4-graphene/ZnO@ SiO2 nanocomposites | |
Li et al. | Photo-Fenton degradation of amoxicillin via magnetic TiO2-graphene oxide-Fe3O4 composite with a submerged magnetic separation membrane photocatalytic reactor (SMSMPR) | |
Soltani et al. | Ultrasonically induced ZnO–biosilica nanocomposite for degradation of a textile dye in aqueous phase | |
Saputra et al. | Egg-shaped core/shell α-Mn2O3@ α-MnO2 as heterogeneous catalysts for decomposition of phenolics in aqueous solutions | |
Liu et al. | Surfactant-free synthesis of octahedral ZnO/ZnFe2O4 heterostructure with ultrahigh and selective adsorption capacity of malachite green | |
Wang et al. | Highly-dispersed Fe2O3@ C electrode materials for Pb2+ removal by capacitive deionization | |
Zhou et al. | Efficient degradation of tetracycline by a novel nanoconfinement structure Cu2O/Cu@ MXene composite | |
Gangadhar et al. | Application of nanomaterials for the removal of pollutants from effluent streams | |
JP5167418B2 (ja) | 炭素触媒及びその用途 | |
Xu et al. | A 3D porous structured cellulose nanofibrils-based hydrogel with carbon dots-enhanced synergetic effects of adsorption and photocatalysis for effective Cr (VI) removal | |
Chen et al. | Studies on the photocatalytic performance of cuprous oxide/chitosan nanocomposites activated by visible light | |
CN108031433A (zh) | 一种介孔硅酸钙负载纳米零价铁复合材料的制备方法 | |
Saroyan et al. | Degradation of endocrine disruptor, bisphenol-A, on an mixed oxidation state manganese oxide/modified graphite oxide composite: A role of carbonaceous phase | |
Zhao et al. | MOFs-derived MnOx@ C nanosheets for peroxymonosulfate activation: Synergistic effect and mechanism | |
Alavi et al. | Ultrasound and modulation assisted synthesis of {[Cu2 (BDC-NH2) 2 (dabco)] DMF. 3H2O} nanostructures; New precursor to prepare nanorods and nanotubes of copper (II) oxide | |
Alavi et al. | Ultrasound assisted synthesis of {[Cu2 (BDC) 2 (dabco)]. 2DMF. 2H2O} nanostructures in the presence of modulator; new precursor to prepare nano copper oxides | |
Li et al. | Self-cleaning photocatalytic PVDF membrane loaded with NH2-MIL-88B/CDs and Graphene oxide for MB separation and degradation | |
CN108654586A (zh) | 一种石墨化介孔碳-TiO2复合光催化材料及其制备方法与应用 | |
Wang et al. | Preparation and photocatalytic application of magnetic Fe2O3/SBA-15 nanomaterials | |
Zhang et al. | Enhanced visible-light photocatalytic H2 production of hierarchical g-C3N4 hexagon by one-step self-assembly strategy | |
Li et al. | Metal-organic frameworks (MOFs) as efficient catalysts for electro-Fenton (EF) reactions: Current progress and prospects | |
CN107983295A (zh) | 核壳结构铁铜双金属材料及其制备方法和应用 | |
CN111018037B (zh) | 一种基于聚丙烯腈纳米薄膜复合物的去除水中重金属汞离子的方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |