CN107200377A - The method that methyl orange is handled using ferriporphyrin/bismuth tungstate composite photocatalyst material - Google Patents
The method that methyl orange is handled using ferriporphyrin/bismuth tungstate composite photocatalyst material Download PDFInfo
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- CN107200377A CN107200377A CN201710485872.5A CN201710485872A CN107200377A CN 107200377 A CN107200377 A CN 107200377A CN 201710485872 A CN201710485872 A CN 201710485872A CN 107200377 A CN107200377 A CN 107200377A
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- China
- Prior art keywords
- ferriporphyrin
- bismuth tungstate
- methyl orange
- solution
- bismuth
- Prior art date
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 222
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 221
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 214
- 239000000463 material Substances 0.000 title claims abstract description 139
- 239000002131 composite material Substances 0.000 title claims abstract description 114
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 114
- 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 title claims abstract description 109
- 229940012189 methyl orange Drugs 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 52
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 64
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 48
- 239000011259 mixed solution Substances 0.000 claims description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 41
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 33
- 238000005286 illumination Methods 0.000 claims description 29
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 27
- 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 claims description 26
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 22
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 22
- 230000000593 degrading effect Effects 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 230000033228 biological regulation Effects 0.000 claims description 13
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 6
- 230000001186 cumulative effect Effects 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 150000003462 sulfoxides Chemical class 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 41
- 238000006731 degradation reaction Methods 0.000 abstract description 41
- 230000008901 benefit Effects 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 24
- 230000000694 effects Effects 0.000 description 23
- 230000001699 photocatalysis Effects 0.000 description 16
- 238000007146 photocatalysis Methods 0.000 description 13
- 238000006555 catalytic reaction Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 229910020350 Na2WO4 Inorganic materials 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- -1 iron porphin Quinoline class Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 150000004032 porphyrins Chemical class 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001048 orange dye Substances 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 231100000462 teratogen Toxicity 0.000 description 1
- 239000003439 teratogenic agent Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- 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
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- C02F1/72—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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- 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
-
- 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
- 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
- C02F2101/38—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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- 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
The invention discloses the method that a kind of utilization ferriporphyrin/bismuth tungstate composite photocatalyst material handles methyl orange, methyl orange is handled using ferriporphyrin/bismuth tungstate composite photocatalyst material and hydrogen peroxide, wherein ferriporphyrin/bismuth tungstate composite photocatalyst material includes ferriporphyrin and bismuth tungstate, and ferriporphyrin is supported on bismuth tungstate.The inventive method has the advantages that the simple to operate, cycle is short, easily recycled and reused, degradation efficiency is high, can not only quickly and efficiently be degraded methyl orange under acid and solutions of weak acidity, simultaneously under strongly alkaline conditions also being capable of fast degradation methyl orange, effective fast degradation to methyl orange is realized, there is good application prospect in the processing of actual Methyl Orange in Wastewater.
Description
Technical field
The invention belongs to the advanced oxidation process field of dyestuff, it is related to one kind and is urged using bionical material/semiconductors coupling light
Change the method for material process methyl orange, and in particular to one kind utilizes ferriporphyrin/bismuth tungstate composite photocatalyst material processing methyl orange
Method.
Background technology
Methyl orange has 10%~20% to be discharged into water environment as a kind of common dyes during its use, and contains
The wastewater toxicity of methyl orange dye is high, containing carcinogenic, mutagenesis, teratogen；Colourity is high, suppresses the light of plant in aquatic system
Cooperation is used；COD value is high, can cause water eutrophication.Based on above-mentioned harm, waste water containing methyl orange dye is current water technology
On the problem for needing processing badly that faces.Conventional processing method has absorption method, membrane separation process, common oxidizing process, bioanalysis etc., but
It is that these methods have the shortcomings that technological process is complicated, equipment requirement is high, cost is high, destruction microenvironment.Photocatalytic degradation method is
A kind of advanced oxidation processes, can effectively degrade methyl orange under the irradiation of sunshine, and the recyclable recycling of catalysis material, will not
Remain in waste water and secondary pollution is caused to environment.However, the waste water containing methyl orange is generally in alkalescence, and pH value change is greatly.
In existing light catalytic treatment method, most catalysis material could only degrade in acid condition more than 90% methyl
Orange.Therefore, pH strong adaptabilities are developed and has the extremely vast scientific research work of novel photocatalysis material of efficient degradation effect to methyl orange
The concern of author, handles methyl orange significant using catalysis material.
The content of the invention
The technical problem to be solved in the invention be overcome the deficiencies in the prior art there is provided a kind of simple to operate, cycle it is short,
Easily recycle and reuse, the method that utilization ferriporphyrin that degradation efficiency is high/bismuth tungstate composite photocatalyst material handles methyl orange, should
Method has good degradation effect to methyl orange, is a kind of method that can be widely applied to handle methyl orange.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
The method that a kind of utilization ferriporphyrin/bismuth tungstate composite photocatalyst material handles methyl orange, using ferriporphyrin/bismuth tungstate
Composite photocatalyst material and hydrogen peroxide are handled methyl orange；The ferriporphyrin/bismuth tungstate composite photocatalyst material includes
Ferriporphyrin and bismuth tungstate, the ferriporphyrin are supported on the bismuth tungstate.
In above-mentioned method, it is preferred that comprise the following steps：By ferriporphyrin/bismuth tungstate composite photocatalyst material and methyl
Orange solution mixing carries out dark treatment, reaches regulation gained methyl orange and ferriporphyrin/bismuth tungstate composite photocatalyst material after adsorption saturation
The pH value of the mixed solution of material, adds hydrogen peroxide and carries out illumination degrading, complete the degraded to methyl orange.
In above-mentioned method, it is preferred that ferriporphyrin described in the ferriporphyrin/bismuth tungstate composite photocatalyst material with it is described
The mass ratio of bismuth tungstate is 0.05~3: 10；The particle diameter of the ferriporphyrin/bismuth tungstate composite photocatalyst material is 1 μm~3 μm.Enter
One step is preferred, and the mass ratio of ferriporphyrin and the bismuth tungstate is described in the ferriporphyrin/bismuth tungstate composite photocatalyst material
0.2~1.5: 10.
In above-mentioned method, it is preferred that the preparation of the ferriporphyrin/bismuth tungstate composite photocatalyst material includes following step
Suddenly：
S1, ferriporphyrin is dissolved in the mixed solution of acetonitrile and dimethyl sulfoxide, obtains ferriporphyrin solution；
S2, bismuth tungstate is dissolved in the ferriporphyrin solution, obtains the mixed solution of bismuth tungstate and ferriporphyrin；
The pH value of S3, the regulation bismuth tungstate and ferriporphyrin mixed solution, stands, and obtains ferriporphyrin/bismuth tungstate and is combined
Catalysis material.
In above-mentioned method, it is preferred that the step S1, it is specially：
S1-1, acetonitrile mixed with dimethyl sulfoxide, obtain the mixed solution of acetonitrile and dimethyl sulfoxide；The acetonitrile with it is described
The volume ratio of dimethyl sulfoxide is 1: 1~2；
S1-2, ferriporphyrin mixed with the acetonitrile with the mixed solution of dimethyl sulfoxide, rotating speed be 400r/min~
5min~30min, ultrasonic 5min~30min are stirred under the conditions of 1500r/min, ferriporphyrin solution is obtained.
In above-mentioned method, it is preferred that the step S2, it is specially：Bismuth tungstate is mixed with the ferriporphyrin solution,
Rotating speed is stirring 5min~30min, ultrasonic 10min~30min under conditions of 600r/min~1200r/min, obtains bismuth tungstate
With the mixed solution of ferriporphyrin；
And/or, in the step S3, the pH value for adjusting the mixed solution of the bismuth tungstate and ferriporphyrin is 3~5；It is described
The time of standing is 15h~25h.
In above-mentioned method, it is preferred that the preparation of the bismuth tungstate comprises the following steps：
(1) sodium tungstate solution is mixed with bismuth nitrate solution, stirred under conditions of rotating speed is 400r/min~1500r/min
10min~30min, ultrasonic 10min~30min are mixed, the mixed solution of sodium tungstate and bismuth nitrate is obtained；The sodium tungstate solution by
Sodium tungstate, which is dissolved in alkaline solution, to be prepared；The bismuth nitrate solution is dissolved in acid solution by sodium nitrate to be prepared；
(2) mixed solution of the sodium tungstate and bismuth nitrate is placed in reactor, in the case where temperature is 120 DEG C~180 DEG C
Hydro-thermal reaction 15h~25h is carried out, it is scrubbed, dry, obtain bismuth tungstate.
In above-mentioned method, it is preferred that in the ferriporphyrin/bismuth tungstate composite photocatalyst material and the methyl orange solution
The mass ratio of methyl orange is 10: 0.5~3；The addition of the hydrogen peroxide for the methyl orange solution cumulative volume 0.1 ‰~
0.5‰。
In above-mentioned method, it is preferred that the regulation methyl orange and the mixing of ferriporphyrin/bismuth tungstate composite photocatalyst material
The pH value of solution is 3~12.It is further preferred that adjusting the methyl orange and ferriporphyrin/bismuth tungstate composite photocatalyst material
The pH value of mixed solution is 3~6 or 11~12.
In above-mentioned method, it is preferred that the time of the dark treatment is 20min~60min；
And/or, the illumination degrading is carried out in the case where wavelength is 300nm~800nm illumination condition；The illumination degrading mistake
Mixing speed in journey is 300r/min~900r/min；The time of the illumination degrading is 30min~120min.
In the preparation method of bismuth tungstate of the present invention, in the sodium tungstate solution concentration of sodium tungstate be 0.02mol/L~
0.025mol/L；The concentration of bismuth nitrate is 0.04mol/L~0.05mol/L in the bismuth nitrate solution；The sodium tungstate and nitre
Bi and W mol ratio is 2: 1 in the mixed solution of sour bismuth.
Compared with prior art, the advantage of the invention is that：
1st, the invention provides the method that a kind of utilization ferriporphyrin/bismuth tungstate composite photocatalyst material handles methyl orange, adopt
Methyl orange is handled with ferriporphyrin/bismuth tungstate composite photocatalyst material and hydrogen peroxide, wherein ferriporphyrin/bismuth tungstate is combined
Catalysis material includes bionical material ferriporphyrin (Hemin-Fe (III)) and semiconductor bismuth tungstate, and ferriporphyrin is supported on bismuth tungstate
On.Ferriporphyrin in ferriporphyrin of the present invention/bismuth tungstate composite photocatalyst material contains the metallic iron (Fe (III)) of variable valence,
Occur class light Fenton's reaction under the induction of a small amount of hydrogen peroxide, first produce intermediate Hemin-Fe (III) H2O2, the intermediate is not
Stable, further reaction produces the iron of a variety of valence states, including Fe (II), Fe (III) and the Fe (IV) with oxidisability, and tool
There are the free radical of strong oxidation, wherein such as OH, OOH (such as formula (1), (2), (3)), high price iron (Fe (IV)) and freedom
Base all can carry out oxidative degradation to methyl orange.Meanwhile, the bismuth tungstate in ferriporphyrin/bismuth tungstate composite photocatalyst material is in illumination bar
Under part produce photo-generate electron-hole pair, ferriporphyrin as good electronic conductor by the light induced electron fast transfer of bismuth tungstate,
And the hole with strong oxidizing property is then remained on bismuth tungstate, direct oxidation degraded methyl orange.In the present invention, pass through iron porphin
Quinoline class light Fenton's reaction and the synergy of bismuth tungstate photochemical catalytic oxidation, effectively increase ferriporphyrin/bismuth tungstate composite photocatalyst
The photocatalysis performance of material, photocatalytic activity is remarkably reinforced, and has good degradation effect to methyl orange.In addition, this hair
Bright ferriporphyrin/bismuth tungstate composite photocatalyst material surface can with dissolved oxygen react generation with strong oxidizing property hydroxyl radical free radical and
Superoxide radical (such as formula (4), (5), (6)), can also carry out oxidative degradation, and then efficient degradation methyl orange to methyl orange.This hair
The method of bright utilization ferriporphyrin/bismuth tungstate composite photocatalyst material processing methyl orange has that the simple to operate, cycle is short, easy reclaim weight
Multiple to utilize, the advantages of degradation efficiency is high, can not only quickly and efficiently degrade methyl orange under acid and solutions of weak acidity, while
Under strong alkaline condition also can fast degradation methyl orange, realize effective fast degradation to methyl orange, it is useless in actual methyl orange
There is good application prospect in water process.
Hemin-Fe(Ⅲ)+H2O2→Hemin-Fe(Ⅲ)·H2O2→Hemin-Fe(Ⅳ)+OH-+·OH (1)
Hemin-Fe(Ⅲ)+H2O2→Hemin-Fe(Ⅲ)·H2O2→Hemin-Fe(Ⅱ)+H++·OOH (2)
Hemin-Fe(Ⅱ)+H2O2→Hemin-Fe(Ⅲ)+OH-+·OH (3)
O2+e-→·O2 - (4)
·O2 -+e-+2H+→H2O2 (5)
H2O2+e-→OH-+·OH (6)
2nd, ferriporphyrin/bismuth tungstate composite photocatalyst material that the present invention is used, including ferriporphyrin and bismuth tungstate, wherein iron porphin
By non-covalent bond stable bond between quinoline and bismuth tungstate, mainly including Van der Waals force, hydrophobic interaction power and ionic bond.
In the present invention, ferriporphyrin is a kind of nontoxic natural material, will not cause secondary pollution to environment in actual applications, and
Because it has the metallic iron (Fe (III)) of variable valence and is conjugated big pi-electron structure, good electronic conductivity is shown, will
It modifies the ferriporphyrin at bismuth tungstate catalysis material surface as coating material can quickly conduct the light of bismuth tungstate generation
Raw electronics, and hole is then remained on bismuth tungstate, solves the problem of bismuth tungstate photo-generate electron-hole is high to recombination rate,
And then improve the photocatalytic activity of ferriporphyrin/bismuth tungstate composite photocatalyst material.On the other hand, bismuth tungstate can be as carrier
Ferriporphyrin provides good microenvironment, so as to weaken the self-polymeric reaction of ferriporphyrin, strengthens the recyclable recycling property of ferriporphyrin, protects
Demonstrate,prove the good electronic conductivity of ferriporphyrin.In the present invention, ferriporphyrin/bismuth tungstate composite photocatalyst material can be dispersed in molten
In liquid, preferable dispersiveness is shown, it is ensured that with fully contacting for reaction solution.Ferriporphyrin/bismuth tungstate of the present invention is multiple simultaneously
Closing light catalysis material can be separated by simple centrifugal process with reaction solution, be easy to recycle and reuse.The iron porphin of the present invention
Quinoline/bismuth tungstate composite photocatalyst material has the advantages that good dispersion, stability are strong, is easily recycled recycling, is that one kind can
With the wide variety of environmentally friendly composite photocatalyst material with excellent photocatalysis performance.
3rd, ferriporphyrin is only loaded as coating material in ferriporphyrin/bismuth tungstate composite photocatalyst material that the present invention is used
On bismuth tungstate crystal, this maintains the crystalline structure that bismuth tungstate is self-assembled into class bouquet by nanometer sheet, with specific surface area it is big,
The advantages of contact with organic pollution is wide, is conducive to organic pollution (such as methyl in degraded aqueous phase in actual applications
Orange).Compared to bismuth tungstate monomer catalysis material, the electron-hole of ferriporphyrin of the present invention/bismuth tungstate composite photocatalyst material is combined
Rate is reduced, and shows more preferable photocatalysis performance.
4th, ferriporphyrin/bismuth tungstate composite photocatalyst material that the present invention is used, using bismuth tungstate as carrier, passes through settled process
One step is prepared.The preparation method reaction condition of ferriporphyrin of the present invention/bismuth tungstate composite photocatalyst material is gentle, under greenhouse
It can react, without harsh reaction condition, while this method is also without special equipment, and this method will not be to bismuth tungstate
Crystal formation produces influence, ensure that the property of synthetic material does not change, with reaction condition is gentle, technological process simple,
The advantage of environmental protection, good development circumstances and wide application prospect are presented in complex functionality Material Field.
Brief description of the drawings
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, clear, complete description is carried out to the technical scheme in the embodiment of the present invention.
Fig. 1 is the SEM figures of ferriporphyrin/bismuth tungstate composite photocatalyst material prepared by the embodiment of the present invention 1.
Fig. 2 is the TEM figures of ferriporphyrin/bismuth tungstate composite photocatalyst material prepared by the embodiment of the present invention 1.
Fig. 3 is the energy spectrum diagram of ferriporphyrin/bismuth tungstate composite photocatalyst material prepared by the embodiment of the present invention 1.
Fig. 4 is not sharing the same light for bismuth tungstate, the ferriporphyrin/bismuth tungstate composite photocatalyst material prepared in the embodiment of the present invention 1
According under the conditions of degradation time to the degradation effect figure of methyl orange.
Fig. 5 is degradation effect of the different ferriporphyrin/bismuth tungstate composite photocatalyst materials to methyl orange in the embodiment of the present invention 2
Figure.
Fig. 6 be the embodiment of the present invention 3 in ferriporphyrin/bismuth tungstate composite photocatalyst material under condition of different pH to methyl orange
Degradation effect figure.
Fig. 7 is ferriporphyrin/bismuth tungstate composite photocatalyst material in the embodiment of the present invention 4 in different hydrogen peroxide addition bars
To the degradation effect figure of methyl orange under part.
Embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
Limit the scope of the invention.
Material and instrument employed in following examples are commercially available, and raw material is pure to analyze.In following examples, if nothing
Special instruction, the data obtained is more than the three times average values for repeating to test.
Embodiment 1
The method that a kind of utilization ferriporphyrin/bismuth tungstate composite photocatalyst material handles methyl orange, comprises the following steps：
Mass ratio by methyl orange in ferriporphyrin/bismuth tungstate composite photocatalyst material and methyl orange solution is 10: 1, takes iron
It is 10mg/L that ferriporphyrin/bismuth tungstate composite photocatalyst material that the mass ratio of porphyrin and bismuth tungstate is 1: 10, which is added to initial concentration,
Methyl orange solution in carry out dark treatment 30min, reach after the adsorption equilibrium to methyl orange, regulation methyl orange and ferriporphyrin/tungsten
The pH value of the mixed solution of sour bismuth composite photocatalyst material is 6, according to the 0.5 ‰ of methyl orange solution cumulative volume, by hydrogen peroxide
It is added in methyl orange solution, in the case where rotating speed is 800r/min in carrying out illumination under the illumination condition that wavelength is 300nm~800nm
Degraded 60min, and separation of solid and liquid is carried out after the completion of reaction, completes the degraded to methyl orange, and reclaim ferriporphyrin/bismuth tungstate complex light
Catalysis material.
When illumination degrading carries out 0min, 10min, 20min, 30min, 40min, 50min, 60min, methyl orange is surveyed in sampling
Concentration, and calculate influence of the different illumination degrading times to methyl orange degradation effect.
The mass ratio of above-mentioned ferriporphyrin and bismuth tungstate is 1: 10 ferriporphyrin/bismuth tungstate composite photocatalyst material, including iron
Porphyrin and bismuth tungstate, wherein ferriporphyrin are supported on bismuth tungstate.The particle diameter of the ferriporphyrin/bismuth tungstate composite photocatalyst material is 1 μ
M~3 μm.The ferriporphyrin/bismuth tungstate composite photocatalyst material is the structure that class bouquet is self-assembled into by nanometer sheet.The ferriporphyrin/
The preparation of bismuth tungstate composite photocatalyst material, comprises the following steps：
(1) Bi (NO are weighed3)3·5H2O and Na2WO4·2H2O, is dissolved in 1mol/L salpeter solution and sodium hydroxide respectively
In solution, bismuth nitrate solution and sodium tungstate solution are respectively obtained, Bi (NO wherein in bismuth nitrate solution3)3·5H2O concentration is
Na in 0.05mol/L, sodium tungstate solution2WO4·2H2O concentration is 0.025mol/L；According to Bi: W=2: 1 mol ratio by nitre
Sour bismuth solution and sodium tungstate solution mixing, magnetic agitation 20min, ultrasonic 20min under the conditions of rotating speed is 800r/min, obtains tungsten
The mixed solution of sour sodium and bismuth nitrate；The mixed solution of sodium tungstate and bismuth nitrate is transferred in reactor, the hydro-thermal at 140 DEG C
Reaction 24 hours, is cooled to room temperature, with deionized water and ethanol cyclic washing, is dried at 120 DEG C, obtains bismuth tungstate powder.
(2) take 20mL acetonitriles to be mixed with 20mL dimethyl sulfoxides, obtain the mixed solution of acetonitrile and dimethyl sulfoxide；By ferriporphyrin
In the mixed solution for being added to acetonitrile and dimethyl sulfoxide, 10min, ultrasonic 15min are stirred under the conditions of rotating speed is 800r/min, is mixed
After closing uniformly, ferriporphyrin solution is obtained.
(3) bismuth tungstate prepared in step (1) is added in step (2) ferriporphyrin solution so that bismuth tungstate and iron porphin
The mass ratio of quinoline is 10: 1, and quick stirring 30min, ultrasonic 20min, make bismuth tungstate and iron porphin under the conditions of rotating speed is 800r/min
Quinoline is well mixed, and obtains the mixed solution of bismuth tungstate and ferriporphyrin.
(4) it is 4 with the pH value of the mixed solution of bismuth tungstate and ferriporphyrin in nitric acid regulating step (3), stands 24h, make it
Fully reaction.
(5) reaction product in step (4) is subjected to separation of solid and liquid, gained solid matter uses deionized water and ethanol repeatedly
Washes clean, drying, is ground to uniform powder, obtains ferriporphyrin/bismuth tungstate composite photocatalyst material.
Fig. 1 is the SEM figures of ferriporphyrin/bismuth tungstate composite photocatalyst material in the embodiment of the present invention 1.Can from Fig. 1
Go out, the granular size of ferriporphyrin/bismuth tungstate composite photocatalyst material prepared by the present invention is 1 μm~3 μm, and bismuth tungstate is integrally in flower
Spherical, ferriporphyrin is loaded on the surface.
Fig. 2 is the TEM figures of ferriporphyrin/bismuth tungstate composite photocatalyst material in the embodiment of the present invention 1.Can from Fig. 2
Go out, the crystal formation of bismuth tungstate is complete, and in lamellar structure, ferriporphyrin material is loaded with lamellar structure.
Fig. 3 is power spectrum (EDS) figure of ferriporphyrin/bismuth tungstate composite photocatalyst material in the embodiment of the present invention 1.From Fig. 3
As can be seen that ferriporphyrin/bismuth tungstate composite photocatalyst material prepared by the present invention contains C, Fe, Cl, Bi, W, O, it was demonstrated that the present invention
Method successfully prepares a kind of ferriporphyrin/bismuth tungstate composite photocatalyst material.
Comparative example 1
It is that obtained bismuth tungstate adds in 10: 1, Example 1 by the mass ratio of methyl orange in bismuth tungstate and methyl orange solution
It is added in the methyl orange solution that initial concentration is 10mg/L and carries out dark treatment 30min, reach after the adsorption equilibrium to methyl orange, adjusts
The pH value of the mixed solution of section gained methyl orange and bismuth tungstate is 6, according to the 0.5 ‰ of methyl orange solution cumulative volume, by peroxidating
Hydrogen is added in methyl orange solution, in the case where rotating speed is 800r/min in carrying out light under the illumination condition that wavelength is 300nm~800nm
According to degraded 60min, separation of solid and liquid is carried out after the completion of reaction, the degraded to methyl orange is completed.
When illumination degrading carries out 0min, 10min, 20min, 30min, 40min, 50min, 60min, methyl orange is surveyed in sampling
Concentration, and calculate influence of the different illumination degrading times to methyl orange degradation effect.
Fig. 4 is not sharing the same light for bismuth tungstate, the ferriporphyrin/bismuth tungstate composite photocatalyst material prepared in the embodiment of the present invention 1
According under the conditions of degradation time to the degradation effect figure of methyl orange.In Fig. 4, ordinate be certain moment methyl orange degradation after concentration with
The ratio of its initial concentration.Figure 4, it is seen that ferriporphyrin/bismuth tungstate composite photocatalyst material (H- prepared by the present invention
Bi2WO6) than pure bismuth tungstate (Bi2WO6) there is higher photocatalysis performance, higher to the degradation rate of methyl orange, this illustrates this hair
The ferriporphyrin of bright offer/bismuth tungstate composite photocatalyst material has good visible light photocatalysis active, and can be used in degraded has
Machine thing.
Embodiment 2
The method that a kind of utilization ferriporphyrin/bismuth tungstate composite photocatalyst material handles methyl orange, comprises the following steps：
Mass ratio by methyl orange in ferriporphyrin/bismuth tungstate composite photocatalyst material and methyl orange solution is 10: 1, takes iron
The mass ratio of porphyrin and bismuth tungstate is respectively added to for 0.1: 10,1: 10,2: 10 ferriporphyrin/bismuth tungstate composite photocatalyst material
Initial concentration is reached after the adsorption equilibrium to methyl orange to carry out dark treatment 30min in 10mg/L methyl orange solution, adjusts institute
The pH value for obtaining each group methyl orange and the mixed solution of ferriporphyrin/bismuth tungstate composite photocatalyst material is 6, total according to methyl orange solution
The 0.5 ‰ of volume, hydrogen peroxide is added in each group methyl orange solution, in the case where rotating speed is 800r/min in wavelength be 300nm
Illumination degrading 60min is carried out under~800nm illumination condition, separation of solid and liquid is carried out after the completion of reaction, the drop to methyl orange is completed
Solution, and reclaim ferriporphyrin/bismuth tungstate composite photocatalyst material.
The mass ratio of above-mentioned ferriporphyrin and bismuth tungstate is 0.1: 10 ferriporphyrin/bismuth tungstate composite photocatalyst material, including
Ferriporphyrin and bismuth tungstate, wherein ferriporphyrin are supported on bismuth tungstate.The particle diameter of the ferriporphyrin/bismuth tungstate composite photocatalyst material is
1 μm~3 μm.The ferriporphyrin/bismuth tungstate composite photocatalyst material is the structure that class bouquet is self-assembled into by nanometer sheet.The iron porphin
The preparation of quinoline/bismuth tungstate composite photocatalyst material, comprises the following steps：
(1) Bi (NO are weighed3)3·5H2O and Na2WO4·2H2O, is dissolved in 1mol/L salpeter solution and sodium hydroxide respectively
In solution, bismuth nitrate solution and sodium tungstate solution are respectively obtained, Bi (NO wherein in bismuth nitrate solution3)3·5H2O concentration is
Na in 0.05mol/L, sodium tungstate solution2WO4·2H2O concentration is 0.025mol/L；According to Bi: W=2: 1 mol ratio by nitre
Sour bismuth solution and sodium tungstate solution mixing, magnetic agitation 20min, ultrasonic 20min under the conditions of rotating speed is 800r/min, obtains tungsten
The mixed solution of sour sodium and bismuth nitrate；The mixed solution of sodium tungstate and bismuth nitrate is transferred in reactor, the hydro-thermal at 140 DEG C
Reaction 24 hours, is cooled to room temperature, with deionized water and ethanol cyclic washing, is dried at 120 DEG C, obtains bismuth tungstate powder.
(2) take 20mL acetonitriles to be mixed with 20mL dimethyl sulfoxides, obtain the mixed solution of acetonitrile and dimethyl sulfoxide；By ferriporphyrin
In the mixed solution for being added to acetonitrile and dimethyl sulfoxide, 10min, ultrasonic 15min are stirred under the conditions of rotating speed is 800r/min, is mixed
After closing uniformly, ferriporphyrin solution is obtained.
(3) bismuth tungstate prepared in step (1) is added in step (2) ferriporphyrin solution so that bismuth tungstate and iron porphin
The mass ratio of quinoline is 10: 0.1, and quick stirring 30min, ultrasonic 20min, make bismuth tungstate and iron under the conditions of rotating speed is 800r/min
Porphyrin is well mixed, and obtains the mixed solution of bismuth tungstate and ferriporphyrin.
(4) it is 4 with the pH value of the mixed solution of bismuth tungstate and ferriporphyrin in nitric acid regulating step (3), stands 24h, make it
Fully reaction.
(5) reaction product in step (4) is subjected to separation of solid and liquid, gained solid matter uses deionized water and ethanol repeatedly
Washes clean, drying, is ground to uniform powder, obtains ferriporphyrin/bismuth tungstate composite photocatalyst material.
Ferriporphyrin/bismuth tungstate composite photocatalyst material that the mass ratio of above-mentioned ferriporphyrin and bismuth tungstate is 1: 10 is by embodiment
Preparation method in 1 is prepared.
The mass ratio of above-mentioned ferriporphyrin and bismuth tungstate is 2: 10 ferriporphyrin/bismuth tungstate composite photocatalyst material, including iron
Porphyrin and bismuth tungstate, wherein ferriporphyrin are supported on bismuth tungstate.The particle diameter of the ferriporphyrin/bismuth tungstate composite photocatalyst material is 1 μ
M~3 μm.The ferriporphyrin/bismuth tungstate composite photocatalyst material is the structure that class bouquet is self-assembled into by nanometer sheet.The ferriporphyrin/
The preparation of bismuth tungstate composite photocatalyst material, comprises the following steps：
(1) Bi (NO are weighed3)3·5H2O and Na2WO4·2H2O, is dissolved in 1mol/L salpeter solution and sodium hydroxide respectively
In solution, bismuth nitrate solution and sodium tungstate solution are respectively obtained, Bi (NO wherein in bismuth nitrate solution3)3·5H2O concentration is
Na in 0.05mol/L, sodium tungstate solution2WO4·2H2O concentration is 0.025mol/L；According to Bi: W=2: 1 mol ratio by nitre
Sour bismuth solution and sodium tungstate solution mixing, magnetic agitation 20min, ultrasonic 20min under the conditions of rotating speed is 800r/min, obtains tungsten
The mixed solution of sour sodium and bismuth nitrate；The mixed solution of sodium tungstate and bismuth nitrate is transferred in reactor, the hydro-thermal at 140 DEG C
Reaction 24 hours, is cooled to room temperature, with deionized water and ethanol cyclic washing, is dried at 120 DEG C, obtains bismuth tungstate powder.
(2) take 20mL acetonitriles to be mixed with 20mL dimethyl sulfoxides, obtain the mixed solution of acetonitrile and dimethyl sulfoxide；By ferriporphyrin
In the mixed solution for being added to acetonitrile and dimethyl sulfoxide, 10min, ultrasonic 15min are stirred under the conditions of rotating speed is 800r/min, is mixed
After closing uniformly, ferriporphyrin solution is obtained.
(3) bismuth tungstate prepared in step (1) is added in step (2) ferriporphyrin solution so that bismuth tungstate and iron porphin
The mass ratio of quinoline is 10: 2, and quick stirring 30min, ultrasonic 20min, make bismuth tungstate and iron porphin under the conditions of rotating speed is 800r/min
Quinoline is well mixed, and obtains the mixed solution of bismuth tungstate and ferriporphyrin.
(4) it is 4 with the pH value of the mixed solution of bismuth tungstate and ferriporphyrin in nitric acid regulating step (3), stands 24h, make it
Fully reaction.
(5) reaction product in step (4) is subjected to separation of solid and liquid, gained solid matter uses deionized water and ethanol repeatedly
Washes clean, drying, is ground to uniform powder, obtains ferriporphyrin/bismuth tungstate composite photocatalyst material.
After the completion of illumination degrading, methyl orange concentration is surveyed in sampling, and calculates different ferriporphyrins/bismuth tungstate composite photocatalyst material
Influence to methyl orange degradation effect, as a result as shown in Figure 5.
Fig. 5 is degradation effect of the different ferriporphyrin/bismuth tungstate composite photocatalyst materials to methyl orange in the embodiment of the present invention 2
Figure.From figure 5 it can be seen that the mass ratio of ferriporphyrin and bismuth tungstate is 1: 10 ferriporphyrin/bismuth tungstate composite photocatalyst material
It is best to the photocatalysis effect of methyl orange；The mass ratio of ferriporphyrin and bismuth tungstate is 0.1: 10 ferriporphyrin/bismuth tungstate complex light
Catalysis material is few due to the amount of ferriporphyrin, and caused class light Fenton's reaction effect is relatively low, and to the conduction of bismuth tungstate light induced electron
Efficiency does not have the mass ratio of ferriporphyrin and bismuth tungstate good for 1: 10 ferriporphyrin/bismuth tungstate composite photocatalyst material, so iron porphin
Quinoline is relative to the degradation effect of methyl orange for 0.1: 10 ferriporphyrin/bismuth tungstate composite photocatalyst material with the mass ratio of bismuth tungstate
It is weaker；Ferriporphyrin/bismuth tungstate composite photocatalyst material that the mass ratio of ferriporphyrin and bismuth tungstate is 2: 10 is due to ferriporphyrin mistake
It is many, the most surface-active site of bismuth tungstate has been covered, the amount of bismuth tungstate light induced electron has been reduced, have impact on electron-hole
To generation, so as to influence the rate of photocatalytic oxidation to methyl orange.In the present invention, the mass ratio of ferriporphyrin and bismuth tungstate is
0.2~1.5: 10 ferriporphyrin/bismuth tungstate composite photocatalyst material can preferably degrade methyl orange.
Embodiment 3
The method that a kind of utilization ferriporphyrin/bismuth tungstate composite photocatalyst material handles methyl orange, comprises the following steps：
Mass ratio by methyl orange in ferriporphyrin/bismuth tungstate composite photocatalyst material and methyl orange solution is 10: 1, takes five
The ferriporphyrin and the mass ratio of bismuth tungstate prepared in group embodiment 1 divides for 1: 10 ferriporphyrin/bismuth tungstate composite photocatalyst material
It is not added in the methyl orange solution that initial concentration is 10mg/L and carries out dark treatment 30min, reaches the adsorption equilibrium to methyl orange
Afterwards, successively the pH value of the mixed solution of regulation gained each group methyl orange and ferriporphyrin/bismuth tungstate composite photocatalyst material be 3,6,
8th, 9,12, then according to the 0.5 ‰ of methyl orange solution cumulative volume, hydrogen peroxide is added in each group methyl orange solution, turned
Speed is that reaction completes laggard in carrying out illumination degrading 60min under the illumination condition that wavelength is 300nm~800nm under 800r/min
Row separation of solid and liquid, completes the degraded to methyl orange, and reclaim ferriporphyrin/bismuth tungstate composite photocatalyst material.
After the completion of illumination degrading, methyl orange concentration is surveyed in sampling, and is calculated under condition of different pH to methyl orange degradation effect
Influence, as a result as shown in Figure 6.
Fig. 6 be the embodiment of the present invention 3 in ferriporphyrin/bismuth tungstate composite photocatalyst material under condition of different pH to methyl orange
Degradation effect figure.From fig. 6 it can be seen that when regulation pH value is 8 and 9, ferriporphyrin/bismuth tungstate composite photocatalyst material is to first
The photocatalysis performance of base orange is not high；When regulation pH value is 6, light of the ferriporphyrin/bismuth tungstate composite photocatalyst material to methyl orange
Catalytic efficiency has reached 93.1% after illumination degrading 60min.Contrasted from pH value for 6,8 and 9 test data, in weak base
Under the conditions of property, OH-There is high inhibition effect to the photocatalysis performance of ferriporphyrin/bismuth tungstate composite photocatalyst material.In addition, from Fig. 6
In as can be seen that regulation pH value be 3 when, the photocatalysis performance of ferriporphyrin/bismuth tungstate composite photocatalyst material, which also has, significantly to be carried
Rise, 95.3% has been reached after illumination degrading 60min to the photocatalysis efficiency of methyl orange, with pH value be 6 when degradation effect
(93.1%) difference is little, because H+Simply derivant, induction ferriporphyrin generation Fenton's reaction, strengthen ferriporphyrin/wolframic acid
The oxidation susceptibility of bismuth composite photocatalyst material, while the conductive performance of bismuth tungstate light induced electron is improved, reduction electron-hole pair
Recombination rate, so as to improve the photocatalysis performance of ferriporphyrin/bismuth tungstate composite photocatalyst material, it was demonstrated that in acid condition (such as pH value
For 3~6) under ferriporphyrin/bismuth tungstate composite photocatalyst material it is more preferable to the degradation effect of methyl orange.In acid and solutions of weak acidity
Under 90%, reaction rate constant k can be reached in 60min to the degradation rate of methyl orange>0.038min-1.It should be noted that
In the case where regulation pH value is 12, the photocatalysis performance of ferriporphyrin/bismuth tungstate composite photocatalyst material is changed, and is just opened
The degradation rate of beginning is suppressed, but the degradation rate in later stage is quickly improved, because under strong alkali solution, hydrogen peroxide
To exist with molecular forms, but with the OH in solution-Reaction becomes HO2 -, and HO2 -Decomposing hydrogen dioxide solution can be induced and produce trip
From free radical, so as to improve the degradation rate to methyl orange, methyl orange of effectively degrading.Ferriporphyrin/bismuth tungstate i.e. of the present invention is multiple
Closing light catalysis material also can effectively degrade methyl orange under strong alkaline condition (such as pH value be 11~12).It is right under strongly alkaline conditions
The degradation rate of methyl orange reaches 60%, reaction rate constant k in 60min>0.015min-1.It can be seen that, the present invention can not only be in acid
Quickly and efficiently degraded under property and solutions of weak acidity methyl orange, at the same under strongly alkaline conditions also can fast degradation methyl orange,
Effective fast degradation to methyl orange is realized, there is good application prospect in the processing of actual Methyl Orange in Wastewater.
Embodiment 4
The method that a kind of utilization ferriporphyrin/bismuth tungstate composite photocatalyst material handles methyl orange, comprises the following steps：
Mass ratio by methyl orange in ferriporphyrin/bismuth tungstate composite photocatalyst material and methyl orange solution is 10: 1, takes five
The ferriporphyrin and the mass ratio of bismuth tungstate prepared in group embodiment 1 divides for 1: 10 ferriporphyrin/bismuth tungstate composite photocatalyst material
It is not added in the methyl orange solution that initial concentration is 10mg/L and carries out dark treatment 30min, reaches the adsorption equilibrium to methyl orange
Afterwards, the pH value of the mixed solution of regulation gained each group methyl orange and ferriporphyrin/bismuth tungstate composite photocatalyst material is 6, according to first
0.1 ‰, 0.2 ‰, 0.3 ‰, 0.4 ‰ and the 0.5 ‰ of base orange overall solution volume, each group methyl orange solution is added to by hydrogen peroxide
In, in the case where rotating speed is 800r/min in carrying out illumination degrading 60min under the illumination condition that wavelength is 300nm~800nm, react
Into rear carry out separation of solid and liquid, the degraded to methyl orange is completed, and reclaim ferriporphyrin/bismuth tungstate composite photocatalyst material.
After the completion of illumination degrading, methyl orange concentration is surveyed in sampling, and calculates ferriporphyrin/bismuth tungstate composite photocatalyst material not
With the influence under the conditions of hydrogen peroxide addition to methyl orange degradation effect, as a result as shown in Figure 7.
Fig. 7 is ferriporphyrin/bismuth tungstate composite photocatalyst material in the embodiment of the present invention 4 in different hydrogen peroxide addition bars
To the degradation effect figure of methyl orange under part.As can be drawn from Figure 7, the amount of hydrogen peroxide increases, ferriporphyrin/bismuth tungstate complex light
Catalysis material is better to the degradation effect of methyl orange, when the addition of hydrogen peroxide is the 0.5 ‰ of methyl orange solution cumulative volume,
Degradation efficiency has reached 90%, illustrates under micro Hydrogen Peroxide, and ferriporphyrin/bismuth tungstate composite photocatalyst material is to first
Base orange has good Photocatalytic Degradation Property.
In summary, the method that the present invention handles methyl orange using ferriporphyrin/bismuth tungstate composite photocatalyst material, with behaviour
Make short simple, cycle, easily separated recycling, the advantages of degradation efficiency is high, effective removal to methyl orange can be realized.
It the above is only the present invention to disclose with preferred embodiment, but be not limited to the present invention.It is any to be familiar with this area
Technical staff, all using the methods and techniques content of the disclosure above technical solution of the present invention is made it is many it is possible change
And modification.Therefore, every content without departing from technical solution of the present invention, the technical spirit according to the present invention is to above example institute
Make any simple modification, still fall within technical solution of the present invention protection in the range of.
Claims (10)
1. the method that a kind of utilization ferriporphyrin/bismuth tungstate composite photocatalyst material handles methyl orange, it is characterised in that use iron porphin
Quinoline/bismuth tungstate composite photocatalyst material and hydrogen peroxide are handled methyl orange；The ferriporphyrin/bismuth tungstate composite photocatalyst
Material includes ferriporphyrin and bismuth tungstate, and the ferriporphyrin is supported on the bismuth tungstate.
2. according to the method described in claim 1, it is characterised in that comprise the following steps：Ferriporphyrin/bismuth tungstate complex light is urged
Change material and progress dark treatment is mixed with methyl orange solution, reach regulation gained methyl orange and ferriporphyrin/bismuth tungstate after adsorption saturation
The pH value of the mixed solution of composite photocatalyst material, adds hydrogen peroxide and carries out illumination degrading, complete the degraded to methyl orange.
3. method according to claim 2, it is characterised in that institute in the ferriporphyrin/bismuth tungstate composite photocatalyst material
The mass ratio for stating ferriporphyrin and the bismuth tungstate is 0.05~3: 10；The grain of the ferriporphyrin/bismuth tungstate composite photocatalyst material
Footpath is 1 μm~3 μm.
4. method according to claim 3, it is characterised in that the system of the ferriporphyrin/bismuth tungstate composite photocatalyst material
It is standby to comprise the following steps：
S1, ferriporphyrin is dissolved in the mixed solution of acetonitrile and dimethyl sulfoxide, obtains ferriporphyrin solution；
S2, bismuth tungstate is dissolved in the ferriporphyrin solution, obtains the mixed solution of bismuth tungstate and ferriporphyrin；
The pH value of S3, the regulation bismuth tungstate and ferriporphyrin mixed solution, stands, obtains ferriporphyrin/bismuth tungstate complex light and urge
Change material.
5. method according to claim 4, it is characterised in that the step S1, is specially：
S1-1, acetonitrile mixed with dimethyl sulfoxide, obtain the mixed solution of acetonitrile and dimethyl sulfoxide；The acetonitrile and the diformazan
The volume ratio of sulfoxide is 1: 1~2；
S1-2, ferriporphyrin mixed with the acetonitrile with the mixed solution of dimethyl sulfoxide, be 400r/min~1500r/ in rotating speed
5min~30min, ultrasonic 5min~30min are stirred under the conditions of min, ferriporphyrin solution is obtained.
6. method according to claim 4, it is characterised in that the step S2, is specially：By bismuth tungstate and the iron porphin
Quinoline solution mix, rotating speed be 600r/min~1200r/min under conditions of stir 5min~30min, ultrasonic 10min~
30min, obtains the mixed solution of bismuth tungstate and ferriporphyrin；
And/or, in the step S3, the pH value for adjusting the mixed solution of the bismuth tungstate and ferriporphyrin is 3~5；It is described to stand
Time be 15h~25h.
7. method according to claim 4, it is characterised in that the preparation of the bismuth tungstate comprises the following steps：
(1) sodium tungstate solution is mixed with bismuth nitrate solution, stirred under conditions of rotating speed is 400r/min~1500r/min
10min~30min, ultrasonic 10min~30min, obtain the mixed solution of sodium tungstate and bismuth nitrate；The sodium tungstate solution is by tungsten
Sour sodium, which is dissolved in alkaline solution, to be prepared；The bismuth nitrate solution is dissolved in acid solution by sodium nitrate to be prepared；
(2) mixed solution of the sodium tungstate and bismuth nitrate is placed in reactor, carried out in the case where temperature is 120 DEG C~180 DEG C
Hydro-thermal reaction 15h~25h, it is scrubbed, dry, obtain bismuth tungstate.
8. the method according to any one of claim 2~7, it is characterised in that the ferriporphyrin/bismuth tungstate complex light is urged
The mass ratio for changing material and methyl orange in the methyl orange solution is 10: 0.5~3；The addition of the hydrogen peroxide is described
The 0.1 ‰ of methyl orange solution cumulative volume~0.5 ‰.
9. the method according to any one of claim 2~7, it is characterised in that the regulation methyl orange and ferriporphyrin/tungsten
The pH value of the mixed solution of sour bismuth composite photocatalyst material is 3~12.
10. the method according to any one of claim 2~7, it is characterised in that the time of the dark treatment is 20min
~60min；
And/or, the illumination degrading is carried out in the case where wavelength is 300nm~800nm illumination condition；During the illumination degrading
Mixing speed be 300r/min~900r/min；The time of the illumination degrading is 30min~120min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126873A (en) * | 2018-08-31 | 2019-01-04 | 湖南大学 | Charcoal-ferriporphyrin composite material and preparation method and application |
| CN109292953A (en) * | 2018-10-24 | 2019-02-01 | 湖南大学 | Utilize ferriporphyrin-sheet bismuth tungstate Two-dimensional Composites processing antibiotic method |
| CN109289929A (en) * | 2018-10-24 | 2019-02-01 | 湖南大学 | Ferriporphyrin-sheet bismuth tungstate Two-dimensional Composites and preparation method thereof |
-
2017
- 2017-06-23 CN CN201710485872.5A patent/CN107200377B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| C. JARAMILLO-PÁEZ ET AL.,: "Mixed α-Fe2O3/Bi2WO6 oxides for photoassisted hetero-Fenton degradation of Methyl Orange and Phenol", 《JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A: CHEMISTRY》 * |
| L. GOMATHI DEVI ET AL.,: "Enhanced photocatalytic performance of Hemin (chloro(protoporhyinato) iron(III)) anchored TiO2 photocatalyst for methyl orange degradation: A surface modification method", 《APPLIED SURFACE SCIENCE》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126873A (en) * | 2018-08-31 | 2019-01-04 | 湖南大学 | Charcoal-ferriporphyrin composite material and preparation method and application |
| CN109292953A (en) * | 2018-10-24 | 2019-02-01 | 湖南大学 | Utilize ferriporphyrin-sheet bismuth tungstate Two-dimensional Composites processing antibiotic method |
| CN109289929A (en) * | 2018-10-24 | 2019-02-01 | 湖南大学 | Ferriporphyrin-sheet bismuth tungstate Two-dimensional Composites and preparation method thereof |
| CN109289929B (en) * | 2018-10-24 | 2020-07-10 | 湖南大学 | Ferriporphyrin-sheet bismuth tungstate two-dimensional composite material and preparation method thereof |
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