CN106582881A - 具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂及其制备和应用 - Google Patents
具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂及其制备和应用 Download PDFInfo
- Publication number
- CN106582881A CN106582881A CN201611108640.XA CN201611108640A CN106582881A CN 106582881 A CN106582881 A CN 106582881A CN 201611108640 A CN201611108640 A CN 201611108640A CN 106582881 A CN106582881 A CN 106582881A
- Authority
- CN
- China
- Prior art keywords
- niobium hydroxide
- mellow
- fragrant
- niobium
- visible light
- 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.)
- Pending
Links
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 title claims abstract description 77
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000011941 photocatalyst Substances 0.000 title abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 16
- 231100000719 pollutant Toxicity 0.000 claims abstract description 16
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 11
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 9
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims abstract description 7
- 229940012189 methyl orange Drugs 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229960003742 phenol Drugs 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 31
- 238000001228 spectrum Methods 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 17
- 206010013786 Dry skin Diseases 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000003643 water by type Substances 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 238000006298 dechlorination reaction Methods 0.000 claims description 5
- SIRPHJCQZYVEES-UHFFFAOYSA-N 1-methylbenzimidazole-2-carbaldehyde Chemical compound C1=CC=C2N(C)C(C=O)=NC2=C1 SIRPHJCQZYVEES-UHFFFAOYSA-N 0.000 claims description 4
- FNAWJOBKLWLHTA-UHFFFAOYSA-N [4-(trifluoromethyl)benzoyl] 4-(trifluoromethyl)benzoate Chemical compound C1=CC(C(F)(F)F)=CC=C1C(=O)OC(=O)C1=CC=C(C(F)(F)F)C=C1 FNAWJOBKLWLHTA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- OIGWAXDAPKFNCQ-UHFFFAOYSA-N p-Isopropylbenzyl alcohol Natural products CC(C)C1=CC=C(CO)C=C1 OIGWAXDAPKFNCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims 1
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 claims 1
- 239000010955 niobium Substances 0.000 abstract description 53
- 230000001699 photocatalysis Effects 0.000 abstract description 19
- 238000007146 photocatalysis Methods 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 229910052758 niobium Inorganic materials 0.000 abstract description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 abstract description 9
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 230000005855 radiation Effects 0.000 abstract description 4
- 238000006482 condensation reaction Methods 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 229960004217 benzyl alcohol Drugs 0.000 abstract 1
- 239000011651 chromium Substances 0.000 abstract 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 238000006042 reductive dechlorination reaction Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- 230000015556 catabolic process Effects 0.000 description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 16
- 239000000975 dye Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000011521 glass Substances 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- 229910052724 xenon Inorganic materials 0.000 description 10
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000000356 contaminant Substances 0.000 description 9
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 238000010189 synthetic method Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 229910000484 niobium oxide Inorganic materials 0.000 description 5
- 229940067107 phenylethyl alcohol Drugs 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- -1 transition-metal cations Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-OUBTZVSYSA-N Ammonia-15N Chemical compound [15NH3] QGZKDVFQNNGYKY-OUBTZVSYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 4
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000007540 photo-reduction reaction Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 229910019804 NbCl5 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 238000007539 photo-oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- MOOUWXDQAUXZRG-UHFFFAOYSA-N 4-(trifluoromethyl)benzyl alcohol Chemical compound OCC1=CC=C(C(F)(F)F)C=C1 MOOUWXDQAUXZRG-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910003378 NaNbO3 Inorganic materials 0.000 description 1
- 229910003256 NaTaO3 Inorganic materials 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- JJIUCEJQJXNMHV-UHFFFAOYSA-N VX nerve agent Chemical group CCOP(C)(=O)SCCN(C(C)C)C(C)C JJIUCEJQJXNMHV-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 150000002822 niobium compounds Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002351 wastewater 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
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
本发明属于光催化剂合成技术领域,具体一种具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂及其制备和应用。本发明采用五氯化铌为铌源,在一定温度下水解首先制得氢氧化铌,然后以芳醇为有机溶剂,使上述氢氧化铌在溶剂热条件下与芳醇分子发生缩合反应,所得固体物经离心分离、洗涤、干燥后得到表面嫁接芳醇的氢氧化铌。本发明制得的表面嫁接芳醇的氢氧化铌为黄色粉末,能有效吸收可见光,在可见光照射下对污染物罗丹明B、甲基橙、苯酚降解,苯甲醇选择性氧化制备苯甲醛,重金属离子六价铬Cr(VI)还原与氯酚类污染物还原脱氯等反应均表现出极好的催化活性,并且无毒、高效、不易失活、适用范围广,在光催化领域具有良好的应用前景。
Description
技术领域
本发明属于光催化剂合成技术领域,具体涉及一种具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂及其制备和应用。
背景技术
半导体光催化技术是一种新型的环境治理技术,它利用太阳能作为驱动力,产生电子-空穴对,利用具有强氧化能力的空穴能将难降解的污染物完全分解,或者利用光生电子还原去除废水中的有毒重金属离子,而且大多数半导体光催化剂化学性质稳定,在使用过程中不会产生新的污染,半导体光催化技术的发展为深度处理环境污染提供了有效途径(M.R.Hoffmann,et al.Environmental applications of semiconductorphotocatalysis,Chemical Reviews,1995,95,69-96;X.C.Wang,et al.Advances inphotocatalysis in China,Chinese Journal of Catalysis,2013,524-535;A.Komano,etal.Titanium dioxide photocatalytic decomposition of ethyl-S-dimethylaminoethyl methylphosph-onothiolate(VX)in aqueous phase,AppliedCatalysis B:Environmental,2013,134-135,19-25)。同时,异相光催化还可用于有机化合物的选择性合成领域,光催化选择性氧化-还原反应体系通常在简单温和的条件下即可进行,避免了传统有机合成中所使用的复杂步骤和苛刻条件,为有机合成提供了一种绿色途径(徐艺军,等.光催化选择性氧化还原体系在有机合成中的研究进展,中国科学:化学,2011,41,1097-1111;S.Higashimoto,et al.Effect of surface treatment on theselective photocatalytic oxidation of benzyl alcohol into benzaldehyde byO2on TiO2under visible light,Topics in Catalysis,2010,53,578-583;许宜铭,等.氟离子对二氧化钛选择性光催化氧化环己烷的影响,化学学报,2010,68,471-475)。
目前用于污染物去除与选择性合成的光催化剂多为TiO2基材料,这是由于TiO2具有光稳定性好、成分简单、易制备且无毒等优点。但是,TiO2的带隙能是3.2eV,对应着387nm的光,这意味着它只能吸收太阳光谱中仅占3-5%的紫外光。为了拓展TiO2在可见光区的响应,各种过渡金属阳离子或者阴离子掺杂型TiO2光催化材料应运而生,但是金属离子掺杂易在TiO2的禁带中引入深杂质能级,成为电子和空穴的复合中心,并存在热不稳定性因素(V.Stengl,et al.Ge4+doped TiO2for stoichiometric degradation of warfareagents,Journal of Hazardous Materials,2012,227-228,62-67;沈忠,等.模拟太阳光下鍺掺杂纳米TiO2对化学毒剂的降解性能,无机材料学报,2016,31,427-433);而阴离子掺杂,如N、S等则削弱了空穴的氧化能力,而且通常的合成方法可引入的离子掺杂量较低,对可见光吸收性能的改善有限(T.C.Jagadale,et al.N-doped TiO2nanoparticle basedvisible light photocatalyst by modified peroxide sol-gel method,Journal ofPhysical Chemistry C,2008,112,14595-14602;Y.S.Jiang,et al.Improved visible-light photocatalytic activity of NaTaO3with perovskite-like structure viasulfur anion doping,Applied Catalysis B:Environmental,2015,166-167,104-111)。最近,有研究报道在TiO2表面嫁接金属离子如Cu(II)、Fe(III)可有效改善TiO2的可见光吸收特性与光催化性能(M.Miyauchi,et al. Visible-light-sensitive photocatalysts:nanocluster-grafted titanium dioxide for indoor environmental remediation,Journal of Physical Chemistry Letters,2016,7,75-84)。
除了TiO2基光催化材料,含铌化合物是另一类绿色光催化剂,因其环境友好、高的稳定性与催化性能,近年来受到研究者们的广泛关注。目前对碱金属铌酸盐和晶态氧化铌光催化剂的研究相对较多(T.Tanaka,et al.Synthesis of niobium oxidenanoparticles with plate morphology utilizing solvothermal reaction and theirperformances for selective photooxidation,Applied Catalysis B:Environmental,2016,182,469-475;K.J.Zhu,et al.Modified solvothermal strategy forstraightforward synthesis of cubic NaNbO3nanowires with enhancedphotocatalytic H2evolution,Journal of Physical Chemistry C,2015,119,25956-25964),而对无定型氢氧化铌的光催化研究相对较少。近来有研究报道相对于传统的晶态氧化物,无定型氧化物或氢氧化物及其复合催化剂在可见光照射下显示出更高的光催化活性,这主要归因于无定型氧化物优异的电子迁移能力、高的比表面积及由此产生的强吸附能力(Q.Wang,et al.Synergistic photosensitized removal of Cr(VI)and RhodamineB dye on amorphous TiO2under visible light irradiation,Journal of HazardousMaterials,2013,247,135-144)。而且,相对于晶型氧化铌,无定型氢氧化铌含有大量的缺陷或表面羟基,可与嫁接分子间形成丰富的化学键,如此得到的表面改性催化剂可见光吸收性能好、光催化活性稳定。为了得到光吸收与氧化性能优异的可见光催化剂,以五氯化铌为铌源,经由水解反应首先制得无定型氢氧化铌Nb(OH)5,然后以芳醇为有机溶剂,通过溶剂热条件下的缩合反应,制得表面嫁接芳醇的Nb(OH)5,本发明的这一可见光催化剂及其制备方法尚未见报道。
发明内容
本发明的目的是提供一种具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂及其制备和应用。
具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂,其氢氧化铌与芳醇分子间以-Nb-O-C-键相连接。
具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂的制备方法,包括以下步骤:
(1)向去离子水中加入五氯化铌,将得到的五氯化铌混合液置于带有冷凝回流装置的油浴中进行水解反应,然后将所得固体物离心分离、水洗并干燥后首先制得氢氧化铌粉末;
(2)将步骤(1)制得的氢氧化铌粉末加入到芳醇溶剂中,超声分散后,将所得混合悬浮液转移至带有聚四氟乙烯内衬的不锈钢反应釜中,密封后置于干燥箱中进行溶剂热反应;
(3)反应釜室温冷却后,先将所得沉淀物离心分离、然后用正己烷洗涤3次、丙酮洗涤3次,所得固体物于60℃干燥后即制得表面嫁接芳醇的氢氧化铌可见光催化剂。
进一步,所述的步骤(1)中五氯化铌的量为体积份每100份去离子水中加入重量份0.5~3份五氯化铌。
进一步,所述的步骤(1)中所用油浴装置的温度为110~150℃,加热时间为3~9h。
进一步,所述的步骤(2)中所用的芳醇溶剂可以为:苯甲醇BA、4-甲氧基苯甲醇MBA、2-苯乙醇2-PEA、1-苯乙醇1-PEA、4-异丙基苯甲醇IPBA与4-(三氟甲基)苯甲醇TFBA中的任一种。
进一步,所述的步骤(2)中氢氧化铌的加入量为体积份每50份芳醇溶剂中加入重量份为0.5~2份的Nb(OH)5。
进一步,所述的步骤(2)中溶剂热反应的温度为120~180℃,溶剂热反应时间为8~24h。
通过调节五氯化铌的水解温度与时间、所用芳醇分子结构、氢氧化铌用量与溶剂热温度等制备条件可控制表面嫁接芳醇氢氧化铌可见光催化剂的组成、光吸收性能与光催化活性。
具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂在污染物罗丹明B、甲基橙、苯酚降解,苯甲醇选择性氧化制备苯甲醛,Cr(VI)还原与氯酚类污染物还原脱氯等方面的应用。
有益效果:
(1)本发明经由溶剂热条件下的缩合反应,氢氧化铌与芳醇分子间以-Nb-O-C-键相连接,与通过物理吸附作用的染料敏化可见光催化剂相比,如此制得的表面嫁接芳醇的氢氧化铌具有更高的稳定性。
(2)本发明的制备方法中所用芳醇既为有机溶剂,同时也是氢氧化铌表面嫁接的有机配体,更重要的是芳醇分子结构的多样化使得所制表面嫁接芳醇氢氧化铌的光吸收性能与光催化活性更加易于调控。
(3)本发明所制表面嫁接芳醇光催化剂中的氢氧化铌为无定型结构,具有优异的电荷迁移能力、高的比表面积及由此产生的强吸附能力。
(4)本发明在光催化反应中,表面嫁接芳醇的氢氧化铌吸收可见光发生电荷迁移,一方面形成表面有机芳醇自由基,可降解染料、苯酚等有机污染物,通过调控溶剂等实验条件还可用于选择性合成;另一方面注入氢氧化铌的光电子可用于重金属污染物Cr(VI)还原或氯酚类污染物的还原脱氯。因此,本发明所制备的表面嫁接芳醇的氢氧化铌具有广谱光催化性能,既可用于光氧化反应,也可用于光还原体系。
本发明的表面嫁接芳醇的氢氧化铌具有广谱可见光催化活性,在可见光照射下对污染物罗丹明B、甲基橙、苯酚的光氧化降解,苯甲醇的选择性氧化,Cr(VI)的光还原去除与氯酚类污染物的还原脱氯,均表明出良好的催化效果。本发明所制备表面嫁接芳醇的氢氧化铌用于光降解污染物或光还原Cr(VI)的反应条件为:浓度为20mg/L的污染物溶液50mL加入一玻璃反应器中,然后再加入所制光催化剂50mg,室温搅拌下可见光照射0.2~4h,污染物的去除率高于96%。本发明所制备表面嫁接芳醇的氢氧化铌用于苯甲醇选择性氧化的反应条件为:10mL乙腈与10mg所制光催化剂加入到一玻璃反应器中,然后再加入0.5mmol苯甲醇,密封反应器,室温搅拌下可见光照射4~8h,苯甲醇的转化率高于94%,生成目标产物苯甲醛的选择性均大于98%。本发明所制备表面嫁接芳醇的氢氧化铌用于氯酚还原脱氯的反应条件为:40mL去离子水、10mL甲醇与50mg所制光催化剂加入一玻璃反应器中,然后再加入一定量的氯酚浓溶液,使氯酚的初始浓度为20mg/L,并通氮气15分钟,室温搅拌下可见光照射1~5h,氯酚中氯离子的脱除率高达95%以上。其中所用可见光源可以是配有420nm截止型滤光片的300W氙灯、300W卤钨灯或太阳光。
附图说明
图1为实施例1中表面嫁接苯甲醇BA的氢氧化铌[用Nb(OH)5-BA表示]与空白氢氧化铌的红外光谱图,其中-Nb-O-C-键的出现表明芳醇与氢氧化铌间的成功键合。
图2为实施例2中表面嫁接4-甲氧基苯甲醇MBA的氢氧化铌[用Nb(OH)5-MBA表示]的透射电镜图片,表明氢氧化铌-MBA颗粒分布均匀,大小约为10~15nm。
图3为实施例2中表面嫁接4-甲氧基苯甲醇MBA的氢氧化铌[用Nb(OH)5-MBA表示]与空白氢氧化铌的紫外-可见吸收光谱图,表明所制备的氢氧化铌-MBA具有明显的可见光吸收。
图4为实施例3中表面嫁接1-苯乙醇(1-PEA)的氢氧化铌[用Nb(OH)5-1-PEA表示]降解苯酚的循环使用效果图。
具体实施方式
以下结合具体实施例,对本发明作进一步说明:
实施例1:
具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂的制备方法,包括以下步骤:
向100mL去离子水中加入2g NbCl5,将所得混合液置于带有冷凝回流装置的130℃油浴中反应6h,反应结束后,所得固体物经离心分离、蒸馏水洗涤3次、60℃干燥制得白色Nb(OH)5粉末;然后将制得的1.5g的氢氧化铌加入到80mL苯甲醇BA中,并超声分散30分钟,将所得混合悬浮液转移至带有聚四氟乙烯内衬的不锈钢反应釜中,密封后置于干燥箱中在150℃条件下进行溶剂热处理12h;反应釜室温冷却后,将所得沉淀物离心分离、分别用正己烷与丙酮各洗涤3次,60℃干燥后即制得淡黄色的表面嫁接苯甲醇BA的氢氧化铌,可用Nb(OH)5-BA表示。
将浓度为20mg/L的染料污染物罗丹明B溶液50mL加入一玻璃反应器中,然后再加入所制光催化剂Nb(OH)5-BA 50mg,室温搅拌下经配有420nm滤光片的300W氙灯照射0.2h,污染物罗丹明B的降解率为97.6%。
对比例1
具体过程与实施例1相同,只是用乙醇代替苯甲醇作为溶剂热处理的有机溶剂,制得表面嫁接乙醇的氢氧化铌[用Nb(OH)5-乙醇表示]。同样,用配有420nm滤光片的300W氙灯照射0.2h,染料污染物罗丹明B的降解率仅为23.8%。明显低于实施例1中Nb(OH)5-BA光催化体系罗丹明B的降解率97.6%。
对比例2
具体过程与实施例1相同,只是用苯代替苯甲醇作为溶剂热处理的有机溶剂,制得表面苯改性的氢氧化铌[用Nb(OH)5-苯表示]。同样,用配有420nm滤光片的300W氙灯照射0.2h,染料污染物罗丹明B的降解率仅为11.2%。明显低于实施例1中Nb(OH)5-BA光催化体系罗丹明B的降解率97.6%。
对比例3
不经过NbCl5的水解反应,直接由NbCl5与苯甲醇进行溶剂热处理制备表面嫁接苯甲醇的NbCl5,其具体步骤为:2gNbCl5加入到80mL苯甲醇中,超声分散30分钟后,将所得混合液转移至带有聚四氟乙烯内衬的不锈钢反应釜中,密封后于干燥箱中150℃反应12h;室温冷却后,将所得沉淀物离心分离、分别用正己烷与丙酮各洗涤3次,60℃干燥后制得表面嫁接苯甲醇的NbCl5[用NbCl5-BA表示]。
经过配有420nm滤光片的300W氙灯照射0.2h,染料污染物罗丹明B的降解率仅为32.5%。明显低于实施例1中Nb(OH)5-BA光催化体系罗丹明B的降解率97.6%。
对比例4
采用结晶五氧化二铌Nb2O5为铌源,直接与苯甲醇进行溶剂热处理制备表面嫁接苯甲醇的Nb2O5,其具体步骤为:2g Nb2O5加入到80mL苯甲醇中,超声分散30分钟后,将所得混合液转移至带有聚四氟乙烯内衬的不锈钢反应釜中,密封后于干燥箱中150℃反应12h;室温冷却后,将所得沉淀物离心分离、分别用正己烷与丙酮各洗涤3次,60℃干燥后制得表面嫁接苯甲醇的Nb2O5[用Nb2O5-BA表示]。
经过配有420nm滤光片的300W氙灯照射0.2h,染料污染物罗丹明B的降解率仅为20.3%。明显低于实施例1中Nb(OH)5-BA光催化体系罗丹明B的降解率97.6%。
表1对比例1~4和实施例1中的各种催化剂可见光照射下降解罗丹明B的效果比较
从表1可看出,光催化剂的结构组成与制备方法对污染物罗丹明B的降解率影响很大。
实施例2:
具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂的制备方法,包括以下步骤:
向100mL去离子水中加入1gNbCl5,将所得混合液置于带有冷凝回流装置的150℃油浴中反应3h,反应结束后,所得固体物经离心分离、蒸馏水洗涤3次、60℃干燥制得白色氢氧化铌粉末;然后将2.4g制得的氢氧化铌加入到60mL4-甲氧基苯甲醇MBA中,并超声分散30分钟,将所得混合悬浮液转移至带有聚四氟乙烯内衬的不锈钢反应釜中,密封后置于干燥箱中在120℃条件下进行溶剂热处理24h;反应釜室温冷却后,将所得沉淀物离心分离、分别用正己烷与丙酮各洗涤3次,60℃干燥后即制得黄色的表面嫁接4-甲氧基苯甲醇MBA的氢氧化铌,可用Nb(OH)5-MBA表示。
将浓度为20mg/L的染料污染物甲基橙溶液50mL加入一玻璃反应器中,然后再加入所制光催化剂Nb(OH)5-MBA 50mg,室温搅拌下经300W卤钨灯照射1h,染料污染物甲基橙的降解率可达97.0%。
实施例3:
具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂的制备方法,包括以下步骤:
向100mL去离子水中加入3gNbCl5,将所得混合液置于带有冷凝回流装置的110℃油浴中反应9h,反应结束后,所得固体物经离心分离、蒸馏水洗涤3次、60℃干燥制得白色氢氧化铌粉末;然后将0.5g制得的氢氧化铌加入到50mL1-苯乙醇1-PEA中,超声分散30分钟,将所得混合悬浮液转移至带有聚四氟乙烯内衬的不锈钢反应釜中,密封后置于干燥箱中在180℃条件下进行溶剂热处理8h;反应釜室温冷却后,将所得沉淀物离心分离、分别用正己烷与丙酮各洗涤3次,60℃干燥后即制得黄色的表面嫁接1-苯乙醇(1-PEA)的氢氧化铌,可用Nb(OH)5-1-PEA表示。
将浓度为20mg/L的有机污染物苯酚溶液50mL加入一玻璃反应器中,然后再加入所制光催化剂Nb(OH)5-1-PEA 50mg,室温搅拌下经配有420nm滤光片的300W氙灯照射1.5h,污染物苯酚的降解率可达98.2%。
把体系中的Nb(OH)5-1-PEA光催化剂通过离心过滤分离出来进行第二次循环反应。把分离出的Nb(OH)5-1-PEA催化剂重新加入浓度为20mg/L的苯酚溶液50mL中,然后用配有420nm滤光片的300W 氙灯照射1.5h,苯酚的降解率为97.5%。
这样的催化剂循环使用重复进行五次,实验结果如图4。
实施例4:
具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂的制备方法,包括以下步骤:
向100mL去离子水中加入0.5g氢氧化铌,将所得混合液置于带有冷凝回流装置的140℃油浴中反应5h,反应结束后,所得固体物经离心分离、蒸馏水洗涤3次、60℃干燥制得白色氢氧化铌粉末;然后将1g制得的氢氧化铌加入到50mL 2-苯乙醇2-PEA中,超声分散30分钟,将所得混合悬浮液转移至带有聚四氟乙烯内衬的不锈钢反应釜中,密封后置于干燥箱中在140℃条件下进行溶剂热处理15h;反应釜室温冷却后,将所得沉淀物离心分离、分别用正己烷与丙酮各洗涤3次,60℃干燥后即制得黄色的表面嫁接2-苯乙醇(2-PEA)的氢氧化铌,可用Nb(OH)5-2-PEA表示。
将10mL乙腈与10mg所制光催化剂Nb(OH)5-2-PEA加入到一玻璃反应器中,然后再加入0.5mmol苯甲醇,密封反应器,室温搅拌下经由300W卤钨灯照射4h,苯甲醇氧化为苯甲醛的转化率为98%。
实施例5
具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂的制备方法,包括以下步骤:
向100mL去离子水中加入1.5g氢氧化铌,将所得混合液置于带有冷凝回流装置的140℃油浴中反应5h,反应结束后,所得固体物经离心分离、蒸馏水洗涤3次、60℃干燥制得白色氢氧化铌粉末;然后将2g制得的氢氧化铌加入到70mL 4-异丙基苯甲醇IPBA中,超声分散30分钟,将所得混合悬浮液转移至带有聚四氟乙烯内衬的不锈钢反应釜中,密封后置于干燥箱中在160℃条件下进行溶剂热处理12h;反应釜室温冷却后,将所得沉淀物离心分离、分别用正己烷与丙酮各洗涤3次,60℃干燥后即制得黄色的表面嫁接4-异丙基苯甲醇IPBA的Nb(OH)5,可用Nb(OH)5-IPBA表示。
将浓度为20mg/L的重金属离子Cr(VI)溶液50mL加入一玻璃反应器中,然后再加入所制光催化剂Nb(OH)5-IPBA 50mg,室温搅拌下经300W卤钨灯照射2h,重金属离子Cr(VI)的去除率可达97.0%。
实施例6
具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂的制备方法,包括以下步骤:
向100mL去离子水中加入2.5g氢氧化铌,将所得混合液置于带有冷凝回流装置的120℃油浴中反应7h,反应结束后,所得固体物经离心分离、蒸馏水洗涤3次、60℃干燥制得白色氢氧化铌粉末;然后将1.6g制得的氢氧化铌加入到80mL4-(三氟甲基)苯甲醇TFBA中,超声分散30分钟,将所得混合悬浮液转移至带有聚四氟乙烯内衬的不锈钢反应釜中,密封后置于干燥箱中在170℃条件下进行溶剂热处理10h;反应釜室温冷却后,将所得沉淀物离心分离、分别用正己烷与丙酮各洗涤3次,60℃干燥后即制得黄色的表面嫁接4-(三氟甲基)苯甲醇TFBA的氢氧化铌,可用Nb(OH)5-TFBA表示。
将40mL去离子水、10mL甲醇与50mg所制光催化剂Nb(OH)5-TFBA加入一玻璃反应器中,然后再加入一定量的2,4-二氯苯酚浓溶液,使2,4-二氯苯酚的初始浓度为20mg/L,并通氮气15分钟,室温搅拌下经配有420nm滤光片的300W氙灯照射1.5h,2,4-二氯苯酚中氯离子的脱除率可达95.6%。
实施例7
采用实施例1中的合成方法制备Nb(OH)5-BA光催化剂。
将50mg所制光催化剂Nb(OH)5-BA加入到浓度为20mg/L的50mL Cr(VI)溶液中,室温搅拌下经300W卤钨灯照射1.5h,重金属离子Cr(VI)的去除率可达96.4%。
实施例8
采用实施例2中的合成方法制备Nb(OH)5-MBA光催化剂。
将50mg所制光催化剂Nb(OH)5-MBA加入到40mL去离子水与10mL甲醇的混合溶液中,然后再加入一定量的2,4,6-三氯苯酚浓溶液,使2,4,6-三氯苯酚的初始浓度为20mg/L,并通氮气15分钟,室温搅拌下经配有420nm滤光片的300W氙灯照射1.2h,2,4,6-三氯苯酚中氯离子的脱除率可达96.0%。
实施例9
采用实施例6中的合成方法制备Nb(OH)5-TFBA光催化剂。
将50mg所制光催化剂Nb(OH)5-TFBA加入到浓度为20mg/L的50mL甲基橙溶液中,室温搅拌下经300W卤钨灯照射2h,染料污染物甲基橙的降解率为96.2%。
实施例10
采用实施例2中的合成方法制备Nb(OH)5-MBA光催化剂。
将10mg所制光催化剂Nb(OH)5-MBA加入到10mL乙腈中,并加入0.5mmol苯甲醇,然后密封反应器并将其放到太阳光下,选择光照充足的上午九点到下午五点时间段,在搅拌的情况下照射反应8h,结束反应,苯甲醇经由光催化氧化选择性生成苯甲醛的转化率为94.5%。
实施例11
采用实施例3中的合成方法制备Nb(OH)5-1-PEA光催化剂。
将浓度为20mg/L的有机污染物苯酚溶液50mL加入一玻璃反应器中,然后再加入所制光催化剂Nb(OH)5-1-PEA 50mg,密封反应器并将其放到太阳光下,选择光照充足的上午九点到下午五点时间段,在搅拌的情况下照射反应4h,污染物苯酚的降解率为96.1%。
实施例12
采用实施例1中的合成方法制备Nb(OH)5-BA光催化剂。
将50mg所制光催化剂Nb(OH)5-BA加入到40mL去离子水与10mL甲醇的混合溶液中,然后再加入一定量的2,4-二氯苯酚浓溶液,使2,4-二氯苯酚的初始浓度为20mg/L,密封反应器并通氮气15分钟,然后将其放到太阳光下,选择光照充足的上午九点到下午五点时间段,在搅拌的情况下照射反应5h,2,4-二氯苯酚中氯离子的脱除率可达95.2%。
虽然,上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述,但在本发明基础上,可以对之作一些修改或改进,这对本领域技术人员而言是显而易见的。因此,在不偏离本发明精神的基础上所做的这些修改或改进,均属于本发明要求保护的范围。
Claims (8)
1.具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂,其特征在于,氢氧化铌与芳醇分子间是以-Nb-O-C-键相连接。
2.具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂的制备方法,其特征在于,包括以下步骤:
(1) 向去离子水中加入五氯化铌,将得到的五氯化铌混合液置于带有冷凝回流装置的油浴中进行水解反应,然后将所得固体物离心分离、水洗并干燥后首先制得氢氧化铌粉末;
(2) 将步骤(1)制得的氢氧化铌粉末加入到芳醇溶剂中,超声分散后,将所得混合悬浮液转移至带有聚四氟乙烯内衬的不锈钢反应釜中,密封后置于干燥箱中进行溶剂热反应;
(3) 反应釜室温冷却后,先将所得沉淀物离心分离、然后用正己烷洗涤3次、丙酮洗涤3次,所得固体物于60℃干燥后即制得表面嫁接芳醇的氢氧化铌可见光催化剂。
3.根据权利要求2所述的具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂的制备方法,其特征在于,所述的步骤(1)中五氯化铌的加入量为体积份每100份去离子水中加入重量份0.5~3份五氯化铌。
4.根据权利要求2所述的具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂的制备方法,其特征在于,所述的步骤(1)中所用油浴装置的温度为110~150℃,加热时间为3~9h。
5.根据权利要求2所述的具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂的制备方法,其特征在于,所述的步骤(2)中所用的有机溶剂芳醇可以为:苯甲醇BA、4-甲氧基苯甲醇MBA、2-苯乙醇2-PEA、1-苯乙醇1-PEA、4-异丙基苯甲醇IPBA与4-(三氟甲基)苯甲醇TFBA中的任一种。
6.根据权利要求2所述的具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂的制备方法,其特征在于,所述的步骤(2)中氢氧化铌的加入量为体积份每50份芳醇溶剂中加入重量份0.5~2份氢氧化铌。
7.根据权利要求2所述的具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂的制备方法,其特征在于,所述的步骤(2)中溶剂热处理的温度为120~180℃,溶剂热反应时间为8~24h。
8.权利要求1与2所述的具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂在污染物罗丹明B、甲基橙、苯酚降解,苯甲醇选择性氧化制备苯甲醛,Cr(VI)还原与氯酚类污染物还原脱氯等方面的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611108640.XA CN106582881A (zh) | 2016-12-06 | 2016-12-06 | 具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂及其制备和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611108640.XA CN106582881A (zh) | 2016-12-06 | 2016-12-06 | 具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂及其制备和应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN106582881A true CN106582881A (zh) | 2017-04-26 |
Family
ID=58596579
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611108640.XA Pending CN106582881A (zh) | 2016-12-06 | 2016-12-06 | 具有广谱催化性能的表面嫁接芳醇的氢氧化铌可见光催化剂及其制备和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106582881A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116078440A (zh) * | 2023-01-17 | 2023-05-09 | 中山大学 | 一种高效吸附降解苯甲醛的多孔光催化凝胶及其制备方法和应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101456585A (zh) * | 2009-01-04 | 2009-06-17 | 武汉理工大学 | 一种尿素改性的高光催化活性二氧化钛空心微球的原位自转变制备方法 |
CN103540318A (zh) * | 2013-10-11 | 2014-01-29 | 上海大学 | 稀土配合物嫁接的发光二氧化钛介孔微球的制备方法 |
CN105709793A (zh) * | 2016-01-26 | 2016-06-29 | 苏州大学 | 硫化镉纳米粒子修饰的五氧化二铌纳米棒/氮掺杂石墨烯复合光催化剂、制备方法与应用 |
-
2016
- 2016-12-06 CN CN201611108640.XA patent/CN106582881A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101456585A (zh) * | 2009-01-04 | 2009-06-17 | 武汉理工大学 | 一种尿素改性的高光催化活性二氧化钛空心微球的原位自转变制备方法 |
CN103540318A (zh) * | 2013-10-11 | 2014-01-29 | 上海大学 | 稀土配合物嫁接的发光二氧化钛介孔微球的制备方法 |
CN105709793A (zh) * | 2016-01-26 | 2016-06-29 | 苏州大学 | 硫化镉纳米粒子修饰的五氧化二铌纳米棒/氮掺杂石墨烯复合光催化剂、制备方法与应用 |
Non-Patent Citations (1)
Title |
---|
SARINA SARINA ET AL.: "Driving selective aerobic oxidation of alkyl aromatics by sunlight on alcohol grafted metal hydroxides", 《CHEMICAL SCIENCE》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116078440A (zh) * | 2023-01-17 | 2023-05-09 | 中山大学 | 一种高效吸附降解苯甲醛的多孔光催化凝胶及其制备方法和应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Sharma et al. | Carbon quantum dot supported semiconductor photocatalysts for efficient degradation of organic pollutants in water: a review | |
Sharma et al. | Microwave assisted fabrication of La/Cu/Zr/carbon dots trimetallic nanocomposites with their adsorptional vs photocatalytic efficiency for remediation of persistent organic pollutants | |
Han et al. | Tailored titanium dioxide photocatalysts for the degradation of organic dyes in wastewater treatment: a review | |
CN101791565B (zh) | 一种TiO2@石墨相氮化碳异质结复合光催化剂及其制备方法 | |
CN102580742B (zh) | 一种活性炭负载氧化亚铜光催化剂及其制备方法 | |
Tian et al. | 0D/3D coupling of g-C3N4 QDs/hierarchical macro-mesoporous CuO-SiO2 for high-efficiency norfloxacin removal in photo-Fenton-like processes | |
CN105664979B (zh) | 一种纳米介孔微球状Ln-Bi5O7I光催化剂及其制备方法 | |
Min et al. | Sonodegradation and photodegradation of methyl orange by InVO4/TiO2 nanojunction composites under ultrasonic and visible light irradiation | |
CN104801328B (zh) | 一种低温制备TiO2/g‑C3N4复合光催化剂的方法 | |
CN106732524A (zh) | 一种α/β‑氧化铋相异质结光催化剂及其制法和用途 | |
KR102042995B1 (ko) | 도핑된 이산화 티타늄, 이의 제조 방법, 및 이를 포함하는 촉매 | |
CN102380366B (zh) | 铋、硅共掺杂的纳米二氧化钛光催化剂及其制备、应用 | |
Behpour et al. | Considering photocatalytic activity of N/F/S-doped TiO2 thin films in degradation of textile waste under visible and sunlight irradiation | |
CN109967074A (zh) | 一种银负载的二氧化钛光催化剂的制备方法与应用 | |
CN106914268B (zh) | 一种石墨烯复合纳米材料及其制备方法和应用 | |
CN109395761A (zh) | 一种氮掺杂BiOIO3光催化剂的制备方法及其应用 | |
CN105148964A (zh) | 一种三维还原氧化石墨烯-Mn3O4/MnCO3纳米复合材料及其制备方法 | |
CN106745470A (zh) | 一种改性粉煤灰沸石负载混合稀土掺杂TiO2催化降解去除蒽的方法 | |
CN105148972A (zh) | 可见光条件下还原水中硝态氮的新型催化剂的制备方法及其应用 | |
Prabhavathy et al. | Visible light-induced Silver and Lanthanum co-doped BiVO4 nanoparticles for photocatalytic dye degradation of organic pollutants | |
Zhu et al. | Heterogeneous activation of persulfate by Bi2MoO6–CuS composite for efficient degradation of orange II under visible light | |
CN106914266A (zh) | 一种快速降解污染物的g‑C3N4复合光催化剂及其制备方法 | |
CN107469822A (zh) | 高效电子转移Cu修饰C/TiO2光催化还原材料的制备方法 | |
CN108722445B (zh) | 一种超薄卤氧化铋基固溶体光催化剂及其制备方法和应用 | |
CN106807413A (zh) | 一种具有等离子体表面共振效应的Ag@AgBr/CaTiO3光催化剂及其制备方法 |
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 | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170426 |
|
RJ01 | Rejection of invention patent application after publication |