CN106732781A - The primary reconstruction preparation method of Tetraploid rice/zinc oxide composite membrane nano material - Google Patents
The primary reconstruction preparation method of Tetraploid rice/zinc oxide composite membrane nano material Download PDFInfo
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- CN106732781A CN106732781A CN201610994174.3A CN201610994174A CN106732781A CN 106732781 A CN106732781 A CN 106732781A CN 201610994174 A CN201610994174 A CN 201610994174A CN 106732781 A CN106732781 A CN 106732781A
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- tetraphenylporphyrin
- zinc oxide
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 239000012528 membrane Substances 0.000 title claims abstract description 24
- 235000007164 Oryza sativa Nutrition 0.000 title claims abstract description 16
- 235000009566 rice Nutrition 0.000 title claims abstract description 16
- 208000035199 Tetraploidy Diseases 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 11
- 240000007594 Oryza sativa Species 0.000 title 1
- 239000000463 material Substances 0.000 claims abstract description 27
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011521 glass Substances 0.000 claims abstract description 16
- 241000209094 Oryza Species 0.000 claims abstract description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 238000004528 spin coating Methods 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- 230000001699 photocatalysis Effects 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 12
- 238000007146 photocatalysis Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007857 degradation product Substances 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000004471 Glycine Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical class N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000011162 ammonium carbonates Nutrition 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- 150000003233 pyrroles Chemical class 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 3
- 235000013904 zinc acetate Nutrition 0.000 claims description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 238000001228 spectrum Methods 0.000 abstract description 7
- 239000005416 organic matter Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000000975 dye Substances 0.000 abstract description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 abstract description 2
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 23
- 238000011065 in-situ storage Methods 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 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 description 7
- 229940043267 rhodamine b Drugs 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 150000004032 porphyrins Chemical class 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000593 degrading effect Effects 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000003403 water pollutant Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- -1 Hydroxyl free radical Chemical class 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000040710 Chela Species 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
- 239000013543 active substance Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LGZXYFMMLRYXLK-UHFFFAOYSA-N mercury(2+);sulfide Chemical compound [S-2].[Hg+2] LGZXYFMMLRYXLK-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The present invention discloses a kind of primary reconstruction preparation method of Tetraploid rice/zinc oxide composite membrane nano material.Its step is：1）Synthesize nest like ZnO nano membrane material on ITO electro-conductive glass；2）Synthesis tetraphenylporphyrin（H2TPP）；3）Tetraphenylporphyrin is dissolved in chloroform solvent；4）Will attach to the ZnO nano membrane material above ITO electro-conductive glass and be immersed in H2In TPP solution, uniform spin coating attachment is realized immediately；5）It is placed in tube furnace and is calcined in nitrogen.In preparation process, Tetraploid rice（ZnTPP）Primary reconstruction is formed on ZnO surfaces, interface cleanness, chemical bonding, the good stability of obtained organic matter and composite material of inorganic matter, not only widen the visible absorption frequency spectrum of composite, the separative efficiency of photogenerated charge can be improved simultaneously, photocatalytic degradation efficiency is greatly improved, and shows hydrophobicity and the obvious selectivity to organic dyestuff.
Description
Technical field
The invention belongs to the preparation field of nano-functional material, and in particular to a kind of Tetraploid rice/zinc oxide is combined
The primary reconstruction preparation method of film nano material.
Background technology
In numerous ambient water pollutant abatement technologies, photocatalysis oxidation technique is with its room temperature deep reaction and catalytic condition letter
The special performance such as single and turn into a kind of ambient water pollutant abatement technology with broad prospect of application.At present, mainly with nanometer half
To there is ZnO small sizes, bigger serface and surface in conductor ZnO substantial amounts of as photochemical catalyst, as a result of nanometer technology
Dangling bonds, and be fully contacted with water pollutant, catalytic rate is not only increased, reaction temperature is reduced, and also method is simple, easy
OK.But the ZnO of routine is wide as a kind of band gap（3.37eV）Semi-conducting material, its absorption spectrum is located at ultraviolet region, photoproduction electricity
Lotus is easily combined, while ZnO photocatalyst is without selectivity, the extensive use of the technology is subject to a certain degree of restriction.Mesh
Before, it is recognized that ZnO photocatalytic mechanisms be：When irradiation energy is more than its energy gap, photohole has very strong electronics
Ability, with strong oxidizing property, can be with the OH in the oxygen and water in air-With reference to generation OH（Hydroxyl free radical）, it can be with oxygen
Change includes the various organic matters of bio-refractory, and is allowed to permineralization.
How to improve the quantum yield of photochemical catalyst, widen light absorbing frequency band and degradation selectivity target degradation product into
It is the research focus of current world photocatalysis field.Light-catalysed over-all quantum efficiency is determined by two critical process：First, photic
Electronics and the competition for recombining and being captured in hole；Second, trapped electron and hole are recombined between interface
The competition of electric charge transfer.In recent years, to improve photocatalysis quantum efficiency, most of researchs are concentrated mainly on the surface of photochemical catalyst
It is modified, including surface chela and, surface metal is co-deposited and transient metal doped etc., but there is quantum efficiency increase rate
It is limited（~2 times）, conversion ratio is low (about 80%), and light application time is more long（A few hours）, there is selectivity to related degradation product.
The main method for expanding photoresponse scope is surface sensitization, mainly using infusion process, by Photoactive compounds
Absorption or physical absorption are learned on ZnO, to expand excitation wavelength range, increases the efficiency of light-catalyzed reaction, but because it is used
Infusion process, Photoactive compounds are combined with ZnO with a kind of surface physics effect, there is crystal boundary between two kinds of materials, when light is lived
Property material can only make electric charge and energy transmission between two kinds of materials receive a fixed limit under the light irradiation of certain spectral range
System, photosensitizer and quantum efficiency are influenceed by certain.
At present, the research emphasis of many photochemical catalysts are placed on the degradation efficiency for how improving photocatalytic pollutant degradation, but
It is to lack research in the sequencing and its selectivity of different catalysates of degrading in photochemical catalyst.How catalyst is made
One time, target product of effectively and rapidly degrading, rather than " making no exception " ground all organic matters of degrading, by more researchs
Pay attention to and favor.Semiconductor oxidation photocatalyst is generally believed that it is, without selectivity, to be urged according to light in pollutant is processed
Change the free radical mechanism of reaction, that is, substrate to be degraded is existed without selection including strong oxidizer hydroxyl radical free radical fast-attack
The characteristics of property.The photocatalysis to selectively of metal oxide semiconductor material is improved, at present mainly can be by following several ways
Footpath：（1）Strengthen the attraction that catalyst treats catalytic substrate；（2）It is modified by catalyst surface, to strengthen catalyst
Treat the attraction of degraded substrate in surface；（3）Catalyst surface is modified so that the material that need not be degraded is from catalyst
Surface separates；（4）Catalyst is doped in itself.
In recent years, researchers are obtained by changing substitution base species and number on porphyrin intermetallic metal and its chow ring
There is the macromolecular derivatives of porphyrin of good characteristic to some, the various demands of people can be met.Metalloporphyrins
(Porphyrin）The plane macrocycle molecule of the π-electron system with height conjugation, it has good light, heat endurance, its
In visible region（400~700nm）There is strong absorption, make it in catalyst（Including photochemical catalyst）, photocell, dyestuff, light note
The aspects such as record material, biomedical material have excellent characteristic.Therefore, Metalloporphyrins are called 21st century
New material, related basic and applied research turns into recent study focus.By with hydrophilic or hydrophobic substituent metal
Metalloporphyrin complex is respectively attached to ZnO nano film surface, rings widening spectrum on ZnO nano particle as optical active substance
Should, to improve lighting efficiency, photoelectric transformation efficiency, photocatalytic activity and photocatalysis to selectively.
The situ synthesis techniques of organic/inorganic composite are have specific physical, change in inorganic substrate surface fabricated in situ
Learn the new method of property material.The technology is to utilize target inorganic and organic respective presoma, through a series of short range physics, is changed
The molecular level organic/inorganic composite presoma that course of reaction is formed is learned, during the course of the reaction, is formed due to organic matter skeleton
The presence of " cage ", limits ZnO molecules and makees migration at a distance, the collision probability with porphyrin macromolecular is increased, due to anti-
The size of " cage " is smaller during answering, and reduction is constantly shunk with the carrying out of process, through certain heat treatment, easily forms gold
Belong to the monomer of metalloporphyrin complex, as fabricated in situ main Connotation.And, the method can avoid Metalloporphyrins from easily being formed
The unfavorable factors such as dimerization, form uniform nano composite material.
The content of the invention
It is not enough it is an object of the invention to be directed to prior art, a kind of Tetraploid rice/zinc oxide composite membrane is provided and is received
The primary reconstruction preparation method of rice material.Composite of the invention by Tetraploid rice on ZnO surfaces it is in situ from
Assembling is formed, and obtains interface cleanness, chemical bonding, the good stability of organic matter and composite material of inorganic matter, is not only widened multiple
The visible absorption frequency spectrum of condensation material, improves the separative efficiency of photogenerated charge, greatly improves photocatalytic degradation efficiency.Meanwhile,
There is hydrophobic phenyl ring on tetraphenylporphyrin chow ring so that composite photo-catalyst shows hydrophobicity, in organic mixing of degrading
In liquid, obvious selectivity is shown to organic dyestuff such as hydrophobic phenol.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of primary reconstruction preparation method of Tetraploid rice/zinc oxide composite membrane nano material, it is concretely comprised the following steps：
（1）Synthesize nest like ZnO nano membrane material on ITO electro-conductive glass（ZnO NAs）；
（2）Synthesize tetraphenylporphyrin with Adler methods（H2TPP, belongs to metal-free porphyrin）；
（3）0.05g tetraphenylporphyrins are taken in beaker, chloroform is dropwise added dropwise under agitation, until tetraphenylporphyrin
It is completely dissolved, forms tetraphenylporphyrin solution；
（4）By step（1）The nest like ZnO nano membrane material being attached on ITO electro-conductive glass of synthesis is immersed in step（3）
To tetraphenylporphyrin solution in, impregnate 1s, then taking out to be placed on carries out rotation 30s on spin coating instrument, rotary speed is
1000r/min；
（5）By step（4）ITO electro-conductive glass after spin coating is placed in tube furnace, and 2h is calcined at 500 DEG C in nitrogen, is made
Tetraploid rice/zinc oxide composite membrane nano material（ZnTPP/ZnO NAs）；
Step（1）Described in the synthesis step of nest like ZnO nano membrane material be：Weigh the water that 0.5g PVP are dissolved in 30mL
In, it is then respectively adding 0.2g glycine, 0.2g zinc acetates and 0.2g Na2SO4, and stir to form solution A, in addition, claiming
Take during 0.19g ammonium carbonates are dissolved in 20mL water and form solution B；Then under conditions of stirring, solution B is slowly dropwise added drop-wise to
Mixed solution is formed in solution A；Then the ITO that will be cleaned up is put into ptfe autoclave, then will be above-mentioned
Mixed solution is added in reactor, then reactor is placed in chamber type electric resistance furnace, 3h is reacted under conditions of 180 DEG C, after cooling
ITO in reactor is taken out, is placed in baking oven after being adsorbed with distilled water and is dried 12h at 80 DEG C, obtain precursor Zn
(OH)2, then presoma is calcined into 2h at 500 DEG C, finally obtain the nest like ZnO nano film being attached on ITO electro-conductive glass
Material.
Step（2）Described in the synthesis step of tetraphenylporphyrin be：To equipped with reflux, constant pressure funnel three
Add 60mL propionic acid, 20mL nitrobenzene and 3.85mL benzaldehydes, agitating heating in mouthful flask, i.e. temperature when drop starts backflow
140 DEG C, stirring is lower to instill 2.1mL pyrroles and 15mL nitrobenzene mixed liquors by constant pressure funnel, continues the state in backflow
Lower reaction 4h, overnight, suction filtration is dried to obtain crude product for cooling and standings after reaction stopping, and purification obtains tetraphenylporphyrin.
The beneficial effects of the present invention are：
（1）Obtained composite photo-catalyst of the invention（ZnTPP/ZnO NAs）Walked by three-step approach and synthesized, metalloporphyrin center gold
Category is directly provided by inorganic substrates, and in the original location in building-up process, it is without metal tetraphenylporphyrin (H2TPP hydrogen on), by Zn (II)
Displacement, and be closely chemically bonded (ZnTPP) by being chemically bound in inorganic substrates, be not simple physical absorption, with
Traditional synthesis technique is different；
（2）Microstructure with nano hybridization in the structure of ZnTPP/ZnO NAs, can fully eliminate organic matter with inorganic matter
It is separated and phase boundary, to improve the effect of the strong interface between inorganic matrix and organic matter, gives full play to two kinds of groups of different attribute
The cooperative effect of part；
（3）The present invention forms chemical bonding by the dangling bonds of inorganic part with organic moiety, not only increases photochemical catalyst
Quantum yield, makes the light absorbing frequency of composite be widened to visible region by ultraviolet region, solves ZnO as one kind
Broad-band gap（3.37eV）The narrower problem of semi-conducting material absorption spectrum；Meanwhile, photogenerated charge can be by between ZnO and ZnTPP
Chemical bond, realizes efficiently separating for photogenerated charge.It is of particular importance that based on the phenyl ring on ZnTPP complex chow rings, with compared with
Strong hydrophobicity, specific can adsorb the hydrophobicity toxic target thing treated in degradation product, be capable of achieving visible light-responded, high selection
Property and high efficiency photocatalysis.
Brief description of the drawings
Fig. 1 is the flow chart of fabricated in situ ZnTPP/ZnO NAs；
Fig. 2 is ZnO NAs and ZnTPP/ZnO NAs fabricated in situ materials（500 DEG C, 2h sintering）X-ray diffractogram；
Fig. 3 is ZnO NAs（a）With ZnTPP/ZnO NAs（b）Scanning electron microscope (SEM) photograph；
Fig. 4 is fabricated in situ ZnTPP/ZnO NAs composites（500 DEG C, 2h sintering）UV-Vis DRS spectrum；
Fig. 5 is fabricated in situ ZnTPP/ZnO NAs composites（500 DEG C, 2h sintering）CHCl3Ultraviolet-visible after extraction is inhaled
Receive spectrum；
Fig. 6 fabricated in situ ZnTPP/ZnO NAs composites（500 DEG C, 2h sintering）CDCl3H after extraction1NMR nuclear-magnetisms are total to
Shake spectrogram；
Fig. 7 is the change procedure of ZnTPP sensitization ZnO NAs membrane materials and water surface contact angle, figure（a）It is without sensitization plays pure
ZnO NAs membrane materials and the change procedure of water surface contact angle, scheme（b）It is ZnO NAs membrane materials and water meter after ZnTPP sensitizations
The change procedure of face contact angle；
Fig. 8 is fabricated in situ ZnTPP/ZnO NAs（500 DEG C, 2h sintering）The sunlight photocatalysis degradation rhodamine B of photochemical catalyst
（RhB）And phenol（PL）Degraded figure（76~85 milliwatts of illuminance/square centimeter, 25 DEG C）；
Fig. 9 is fabricated in situ ZnTPP/ZnO NAs（500 DEG C, 2h sintering）The sunlight photocatalysis degradation rhodamine B of photochemical catalyst
（RhB）And phenol（PL）Mixed solution degraded figure（76~85 milliwatts of illuminance/square centimeter, 25 DEG C）.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment
A kind of primary reconstruction preparation method of Tetraploid rice/zinc oxide composite membrane nano material, its specific steps
For：
（1）ITO electro-conductive glass is cleaned by ultrasonic with cleaning agent, acetone, ethanol and deionized water respectively, every time at intervals of
10min, is then placed on 80 DEG C of drying for standby in baking oven；
（2）Weigh 0.5g PVP to be dissolved in the water of 30mL, be then respectively adding 0.2g glycine, 0.2g zinc acetates and 0.2g
Na2SO4, and stir to form solution A, in addition, weigh during 0.19g ammonium carbonates are dissolved in 20mL water forming solution B；Then exist
Under conditions of stirring, solution B is slowly dropwise added drop-wise in solution A and forms mixed solution；Then the ITO that will be cleaned up is put into
To in ptfe autoclave, then poured into reactor by above-mentioned mixed solution, then reactor is placed in box resistance
In stove, 3h is reacted under conditions of 180 DEG C, take out the ITO in reactor after after temperature cooling, adsorb rearmounted with distilled water
12h is dried at 80 DEG C in baking oven, precursor Zn (OH) is now formed2, then presoma is calcined into 2h at 500 DEG C, finally
Obtain the nest like ZnO being attached on ITO electro-conductive glass（ZnO NAs）Nano-sized membrane；
（3）To equipped with addition 60mL propionic acid, 20mL nitrobenzene, 3.85mL in reflux, the there-necked flask of constant pressure funnel
Benzaldehyde, agitating heating, drop starts i.e. about 140 DEG C of temperature during backflow, and stirring is lower new by constant pressure funnel instillation 2.1mL
Pyrroles and 15mL nitrobenzene mixed liquors are steamed, 4h is reacted in continuation in the state of backflow, and reaction is cooled in being stood in refrigerator after stopping
Overnight, Buchner funnel suction filtration is used, baking oven the inside is placed on and is dried to obtain crude product tetraphenylporphyrin；
（4）By step（3）The crude product of gained（4g）It is substantially soluble in chloroform（500mL）In, the 35mL that addition there are about 1g DDQ does
Dry benzene, mixture is stirred at reflux 3h, and yellow solution is filtered with the glass sand for being covered with activated alumina（60g Al2O3With CH2Cl2
After mixing, paved in organdy funnel, cover a filter paper）, filter cake CH2Cl2Washing, washing lotion and filtrate merge, and are concentrated into
30mL, adds 6mL methyl alcohol, is cooled to room temperature, is filtrated to get high-purity tetraphenylporphyrin（H2TPP）；
（5）The tetraphenylporphyrin of 0.05g is taken out in beaker, chloroform is dropwise added dropwise under agitation, until tetraphenyl
Porphyrin is completely dissolved, and forms tetraphenylporphyrin solution；
（6）Take step（2）The ITO electro-conductive glass pieces of the attachment Nano-ZnO Films material of synthesis, are fully immersed in tetraphenylporphyrin molten
Liquid, takes out the speed being placed on spin coating instrument with 1000r/min and at the uniform velocity rotates 30s at once；
（7）ITO electro-conductive glass pieces after spin coating are placed in tube furnace in N2In it is lower 500 DEG C calcining 2h, be made nano compound light
Catalyst Z nTPP/ZnO NAs.
The flow chart of above-mentioned fabricated in situ ZnTPP/ZnO NAs is as shown in Figure 1.
First, the structural characterization of ZnTPP/ZnO NAs：
（1）Fabricated in situ ZnTPP/ZnO NAs composite film materials, knowable to the Figure of description 2 and accompanying drawing 3, photochemical catalyst
Principal crystalline phase is ZnO, and is hexagonal system structure and nest like structure.
（2）In the product for differentiating fabricated in situ, to there is object Tetraploid rice（ZnTPP）Presence, wherein
H2The chemical structural formula of TPP, ZnTPP is respectively：
Composed using powder UV-Vis DRS（Figure of description 4）、CHCl3Uv-visible absorption spectrum after solvent extraction
（Figure of description 5）And CDCl3H after extraction1Nuclear magnetic resonance spectrogram is characterized（Figure of description 6）, in accompanying drawing 4
Composite photo-catalyst is significantly improved to the utilization rate of visible ray in the visible-range of 400-700nm, the suction of 419nm in accompanying drawing 5
It is the B bands of ZnTPP to receive peak（Also known as Soret bands）, this feature peak is stronger so that therefore composite catalyst shows Chinese red,
547nm（β absorption bands）And 584nm（α absorption bands）It is the Q bands of metalloporphyrin, after metal-free porphyrin forms metal porphyrinses,
Four absworption peaks of visible ray merge into 2, and the Soret bands near ultraviolet band absorb and still exist, simply the position of Soret bands
Have blue shift or red shift.For different metals, it is seen that the position of two absworption peaks in area and relative intensity show as different
Feature, therefore metal porphyrinses can uniquely be confirmed according to the uv-visible absorption spectra of compound；Accompanying drawing 6 is
The nmr spectrum of composite catalyst, top right plot tetraphenylporphyrin nmr spectrum, spectrogram is pyrrole ring at 8.98ppm
The resonance absorbing peak of upper 8 hydrogen, 8.26ppm is 8 resonance absorbing peaks of hydrogen on four phenyl ring ortho positions, and 7.99-7.65ppm is four
12 resonance absorbing peaks of hydrogen between individual phenyl ring in contraposition, its volume ratio is 2:2:3.Compared with tetraphenylporphyrin ,-
Do not occur two formants of H of N-H keys on pyrrole ring at 2.74ppm, composed with UV-vis（Accompanying drawing 4）With reference to can determine that hydrogen is former
Son is replaced by zinc ion, forms metal complex（ZnTPP）.
2nd, hydrophobicity and photocatalysis performance are tested
1. hydrophobicity.By contact angle instrument, ZnO and ZnTPP/ZnO composite tables are respectively dropped into by distilling water droplet
Face, at the same 5 after recording, 10, in 15s drop and interfacial contact angle change dynamic process（Accompanying drawing 7）, it is seen that ZnO NAs
Surface shows hydrophily, and the interfacial contact angle of ZnTPP/ZnO NAs composites is all higher than ZnO NAs, shows brighter
Aobvious hydrophobicity.
2. photocatalysis performance.In sunshine degradation of dye（Selection organic pollution is rhodamine B（RhB）AR
And phenol（PL）AR）Photocatalytic degradation experiment in, experiment condition be environment temperature be 25 DEG C, irradiation level be 76~
85mW/cm2, step is as follows：
（a）Prepare certain density rhodamine B (phenol, rhodamine B and phenol mixed solution) aqueous solution (1 × 10-6mol/L)。
（b）The ito glass piece of ZnO NAs and ZnTPP/ZnO NAs composites is taken respectively（2cm×2cm）, it is placed in 40mL
Rhodamine B (phenol, rhodamine B and phenol mixed solution) aqueous solution (1 × 10-6Mol/L) bottom, the quartz with air-filled pore
In cup.
（c）Tested through sunlight photocatalysis degradation, 4 milliliters of solution degraded were taken every 30 minutes, take about 3 milliliters of upper stratas
Solution after centrifugation, for the measurement of ultraviolet-visible spectrum.
（d）In ultraviolet-visible light spectrometry, with the molar absorptivity intensity at the principal absorption wavelength for treating degradation product as light
The criterion of catalytic degradation, and the photochemical catalyst situation for preparing pure ZnO NAs with same method is compared.
From explanation accompanying drawing 8 and accompanying drawing 9, through the photochemical catalyst of the ZnTPP/ZnO NAs of fabricated in situ, not only visible
Can be with degradable organic pollutant under light, not only rate of photocatalytic oxidation is greatly improved, and the degradation rate of independent degradation of phenol can
It is pure zinc oxide up to 95.73%（31.62%）3.03 times, while in mixed solution ZnTPP/ZnO NAs degraded PL
（56.4%）It is RhB（16.84%）3.35 times, to hydrophobic degradation product（PL）Show selectivity.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modification, should all belong to covering scope of the invention.
Claims (5)
1. the primary reconstruction preparation method of a kind of Tetraploid rice/zinc oxide composite membrane nano material, it is characterised in that：Its
Concretely comprise the following steps：
（1）Synthesize nest like ZnO nano membrane material on ITO electro-conductive glass；
（2）Synthesize tetraphenylporphyrin with Adler methods；
（3）0.05g tetraphenylporphyrins are taken in beaker, chloroform is dropwise added dropwise under agitation, until tetraphenylporphyrin
It is completely dissolved, forms tetraphenylporphyrin solution；
（4）By step（1）The nest like ZnO nano membrane material being attached on ITO electro-conductive glass of synthesis is immersed in step（3）
To tetraphenylporphyrin solution in, impregnate 1s, then take out to be placed on spin coating instrument and rotated；
（5）By step（4）ITO electro-conductive glass after spin coating is placed in tube furnace, and 2h is calcined at 500 DEG C in nitrogen, is made
Tetraploid rice/zinc oxide composite membrane nano material.
2. the primary reconstruction preparation side of Tetraploid rice according to claim 1/zinc oxide composite membrane nano material
Method, it is characterised in that：Step（1）Described in the synthesis step of nest like ZnO nano membrane material be：Weigh 0.5g PVP molten
In the water of 30mL, 0.2g glycine, 0.2g zinc acetates and 0.2g Na are then respectively adding2SO4, and stir to form solution
A, in addition, weigh during 0.19g ammonium carbonates are dissolved in 20mL water forming solution B；Then it is under conditions of stirring, solution B is slow
Dropwise it is added drop-wise in solution A and forms mixed solution；Then the ITO that will be cleaned up is put into ptfe autoclave, so
It is added in reactor by above-mentioned mixed solution afterwards, then reactor is placed in chamber type electric resistance furnace, is reacted under conditions of 180 DEG C
3h, takes out the ITO in reactor after cooling, is placed in baking oven after being adsorbed with distilled water and dries 12h at 80 DEG C, before obtaining
Body Zn (OH)2, then presoma is calcined into 2h at 500 DEG C, finally obtain the nest like ZnO being attached on ITO electro-conductive glass
Nano-sized membrane.
3. preparation method according to claim 1, it is characterised in that：Step（2）Described in tetraphenylporphyrin synthesis
Step is：To equipped with addition 60mL propionic acid, 20mL nitrobenzene and 3.85mL in reflux, the there-necked flask of constant pressure funnel
Benzaldehyde, agitating heating, drop starts i.e. 140 DEG C of temperature during backflow, and stirring is lower by constant pressure funnel instillation 2.1mL pyrroles
With 15mL nitrobenzene mixed liquors, continuation reacts 4h in the state of backflow, reaction stop after cooling and standings overnight, suction filtration is dry
To crude product, purify and obtain tetraphenylporphyrin.
4. preparation method according to claim 1, it is characterised in that：Step（4）Middle rotary speed is 1000r/min, rotation
Turn the time for 30s.
5. Tetraploid rice obtained in preparation method according to claim 1/zinc oxide composite membrane nano material should
With, it is characterised in that：Tetraphenylporphyrin/zinc oxide surface shows hydrophobicity, is treated for selective photocatalysis degraded hydrophobicity
Degradation product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108456908A (en) * | 2018-02-08 | 2018-08-28 | 北京航空航天大学 | A kind of preparation and application of the porphyrin based on self assembly/alumina composite nanochannel film |
| CN109647529A (en) * | 2018-12-21 | 2019-04-19 | 福州大学 | A method of ZnO/ZIF-CN/Ag nanocomposite is synthesized based on ZIF-8 |
| CN110804190A (en) * | 2019-11-05 | 2020-02-18 | 东莞行渡科技有限公司 | Preparation method of hydrophilic-hydrophobic water molecule self-assembled micelle embedded with aromatic amide fragment and supermolecule photocatalytic assembly |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368294A (en) * | 2007-08-15 | 2009-02-18 | 中国科学院化学研究所 | Surface finished zinc oxide nanometer stick array and preparation method thereof |
| CN101997084A (en) * | 2010-09-10 | 2011-03-30 | 江苏大学 | CuPc/ZnO organic/inorganic compound solar battery and preparation method thereof |
| CN106000471A (en) * | 2016-06-03 | 2016-10-12 | 河南大学 | Zinc oxide-porphyrin core-shell nanorod composite material and preparation method thereof |
-
2016
- 2016-11-11 CN CN201610994174.3A patent/CN106732781B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368294A (en) * | 2007-08-15 | 2009-02-18 | 中国科学院化学研究所 | Surface finished zinc oxide nanometer stick array and preparation method thereof |
| CN101997084A (en) * | 2010-09-10 | 2011-03-30 | 江苏大学 | CuPc/ZnO organic/inorganic compound solar battery and preparation method thereof |
| CN106000471A (en) * | 2016-06-03 | 2016-10-12 | 河南大学 | Zinc oxide-porphyrin core-shell nanorod composite material and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| YUVARAJ SIVALINGAM等: "The light modulation of the interaction of l-cysteine with porphyrins coated ZnO nanorods", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
| ZHIZHONG HAN等: "Synthesis and photocatalytic application of oriented hierarchical ZnO flower-rod architectures", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| 孙绪利等: "四苯基卟啉的合成与表征", 《科技视界》 * |
| 李景泉: "金属卟啉/TiO2纳米复合材料的制备、表征及光催化研究", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技I辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108456908A (en) * | 2018-02-08 | 2018-08-28 | 北京航空航天大学 | A kind of preparation and application of the porphyrin based on self assembly/alumina composite nanochannel film |
| CN108456908B (en) * | 2018-02-08 | 2019-08-27 | 北京航空航天大学 | A kind of preparation and application of the porphyrin based on self assembly/alumina composite nanochannel film |
| CN109647529A (en) * | 2018-12-21 | 2019-04-19 | 福州大学 | A method of ZnO/ZIF-CN/Ag nanocomposite is synthesized based on ZIF-8 |
| CN110804190A (en) * | 2019-11-05 | 2020-02-18 | 东莞行渡科技有限公司 | Preparation method of hydrophilic-hydrophobic water molecule self-assembled micelle embedded with aromatic amide fragment and supermolecule photocatalytic assembly |
| CN110804190B (en) * | 2019-11-05 | 2021-10-29 | 东莞行渡科技有限公司 | Preparation method of hydrophilic-hydrophobic water molecule self-assembled micelle embedded with aromatic amide fragment and supermolecule photocatalytic assembly |
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