CN107200377B - Utilize ferriporphyrin/bismuth tungstate composite photocatalyst material processing methyl orange method - Google Patents
Utilize ferriporphyrin/bismuth tungstate composite photocatalyst material processing methyl orange method Download PDFInfo
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- CN107200377B CN107200377B CN201710485872.5A CN201710485872A CN107200377B CN 107200377 B CN107200377 B CN 107200377B CN 201710485872 A CN201710485872 A CN 201710485872A CN 107200377 B CN107200377 B CN 107200377B
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- ferriporphyrin
- bismuth tungstate
- methyl orange
- bismuth
- solution
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 221
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 220
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 213
- 239000000463 material Substances 0.000 title claims abstract description 134
- 239000002131 composite material Substances 0.000 title claims abstract description 113
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 113
- 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
- 238000012545 processing Methods 0.000 title claims abstract description 12
- 230000015556 catabolic process Effects 0.000 claims abstract description 52
- 238000006731 degradation reaction Methods 0.000 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 62
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 57
- 239000011259 mixed solution Substances 0.000 claims description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 40
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 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
- 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 23
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 22
- 230000000593 degrading effect Effects 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 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 12
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 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
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive 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
- 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
- 230000008859 change Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 description 23
- 230000001699 photocatalysis Effects 0.000 description 16
- 238000007146 photocatalysis Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000004064 recycling Methods 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
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 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
- 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 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
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 208000011117 substance-related disease Diseases 0.000 description 3
- 238000009303 advanced oxidation process reaction Methods 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
- -1 hydroxyl radical free radical Chemical class 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 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
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 230000021615 conjugation 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
- 238000005516 engineering process Methods 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
- 239000000411 inducer Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000008204 material by function Substances 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
- 150000003248 quinolines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000003786 synthesis reaction 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
-
- B01J35/19—
-
- B01J35/39—
-
- 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
Abstract
Ferriporphyrin/bismuth tungstate composite photocatalyst material processing methyl orange method is utilized the invention discloses a kind of, 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 method of the present invention has many advantages, such as that easy to operate, the period is short, easily recycles and reuses, degradation efficiency is high, can not only quickly and efficiently degrade methyl orange under acid and solutions of weak acidity, it simultaneously under strongly alkaline conditions also being capable of fast degradation methyl orange, effective fast degradation to methyl orange is realized, is had a good application prospect in the processing of practical Methyl Orange in Wastewater.
Description
Technical field
The invention belongs to the advanced oxidation process field of dyestuff, it is related to a kind of urging using bionical substance/semiconductors coupling light
Change the method for material processing methyl orange, and in particular to a kind of to handle methyl orange using ferriporphyrin/bismuth tungstate composite photocatalyst material
Method.
Background technique
Methyl orange has 10%~20% to be discharged into water environment as a kind of common dyes in its use process, and contains
The wastewater toxicity of methyl orange dye is high, contains carcinogenic, mutagenesis, teratogen；Coloration is high, inhibits the light of plant in aquatic system
Cooperation is used；COD value is high, will lead to water eutrophication.Based on above-mentioned harm, waste water containing methyl orange dye is current water treatment technology
On face need processing problem.Common processing method has absorption method, membrane separation process, common oxidizing process, bioanalysis etc., but
It is that these methods have the shortcomings that process flow is complicated, equipment requirement is high, at high cost, destruction microenvironment.Photocatalytic degradation method is
A kind of advanced oxidation processes, can effectively degrade methyl orange under the irradiation of sunlight, 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 usually in alkalinity, and pH value variation is greatly.In
In existing light catalytic treatment method, most of catalysis material could only degrade in acid condition 90% or more methyl
Orange.Therefore, exploitation pH is adaptable and has the novel photocatalysis material of efficient degradation effect by vast scientific research work methyl orange
The concern of author is of great significance using catalysis material processing methyl orange.
Summary of the invention
The technical problem to be solved in the invention be overcome the deficiencies of the prior art and provide it is a kind of it is easy to operate, the period is short,
It easily recycles and reuses, the high method for handling methyl orange using ferriporphyrin/bismuth tungstate composite photocatalyst material of degradation efficiency, it should
Method has good degradation effect to methyl orange, is a kind of method that can be widely applied to processing methyl orange.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A method of methyl orange being handled using ferriporphyrin/bismuth tungstate composite photocatalyst material, using ferriporphyrin/bismuth tungstate
Composite photocatalyst material and hydrogen peroxide handle 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 the following steps are included: by ferriporphyrin/bismuth tungstate composite photocatalyst material and methyl
Orange solution mixing carries out dark treatment, adjusts gained methyl orange and ferriporphyrin/bismuth tungstate composite photocatalyst material after reaching adsorption saturation
The pH value of the mixed solution of material is added hydrogen peroxide and carries out illumination degrading, completes the degradation 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 ferriporphyrin/bismuth tungstate composite photocatalyst material partial size is 1 μm~3 μm.Into
One step is preferred, and the mass ratio of ferriporphyrin and the bismuth tungstate described in the ferriporphyrin/bismuth tungstate composite photocatalyst material is
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
It is rapid:
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 the mixed solution of S3, the adjusting bismuth tungstate and ferriporphyrin, stands, it is compound to obtain ferriporphyrin/bismuth tungstate
Catalysis material.
In above-mentioned method, it is preferred that the step S1, specifically:
S1-1, acetonitrile is mixed with dimethyl sulfoxide, obtains 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 is mixed with the acetonitrile with the mixed solution of dimethyl sulfoxide, revolving speed be 400r/min~
5min~30min is stirred under the conditions of 1500r/min, ultrasonic 5min~30min obtains ferriporphyrin solution.
In above-mentioned method, it is preferred that the step S2, specifically: bismuth tungstate is mixed with the ferriporphyrin solution, In
Revolving speed stirs 5min~30min under conditions of being 600r/min~1200r/min, and ultrasonic 10min~30min 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 the following steps are included:
(1) sodium tungstate solution is mixed with bismuth nitrate solution, is stirred under conditions of revolving speed is 400r/min~1500r/min
10min~30min is mixed, ultrasonic 10min~30min obtains the mixed solution of sodium tungstate and bismuth nitrate；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 reaction kettle, in the case where temperature is 120 DEG C~180 DEG C
Hydro-thermal reaction 15h~25h is carried out, it is washed, 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 additive amount of the hydrogen peroxide be the methyl orange solution total volume 0.1 ‰~
0.5‰。
In above-mentioned method, it is preferred that adjust the 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 the illumination condition of 300nm~800nm；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
The molar ratio of Bi and W is 2: 1 in the mixed solution of sour bismuth.
Compared with the prior art, the advantages of the present invention are as follows:
1, the present invention provides a kind of using ferriporphyrin/bismuth tungstate composite photocatalyst material processing methyl orange method, adopts
Methyl orange is handled with ferriporphyrin/bismuth tungstate composite photocatalyst material and hydrogen peroxide, wherein ferriporphyrin/bismuth tungstate is compound
Catalysis material includes that bionical substance ferriporphyrin (Hemin-Fe (III)) and semiconductor bismuth tungstate, ferriporphyrin are 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, In
Class light Fenton's reaction occurs under the induction of a small amount of hydrogen peroxide, first generates intermediate Hemin-Fe (III) H2O2, the intermediate is not
Stablize, further reaction generates the iron of a variety of valence states, the Fe (IV) including Fe (II), Fe (III) and with oxidisability, and tool
There are the free radical of strong oxidation, such as OH, OOH (such as formula (1), (2), (3)), wherein 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 item
Generate photo-generate electron-hole pair under part, ferriporphyrin as good electronic conductor by the light induced electron fast transfer of bismuth tungstate,
And the hole with strong oxidizing property then remains on bismuth tungstate, direct oxidation degradation methyl orange.In the present invention, pass through iron porphin
The synergy of quinoline class light Fenton's reaction and bismuth tungstate photochemical catalytic oxidation effectively increases ferriporphyrin/bismuth tungstate composite photocatalyst
The photocatalysis performance of material, photocatalytic activity are remarkably reinforced, and have good degradation effect to methyl orange.In addition to this, this hair
Bright ferriporphyrin/bismuth tungstate composite photocatalyst material surface can be reacted with dissolved oxygen generate have 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
It is bright to handle the method for methyl orange with easy to operate, the period is short, easy recycling weight using ferriporphyrin/bismuth tungstate composite photocatalyst material
It is multiple utilize, the advantages that degradation efficiency is high, can not only quickly and efficiently degrade methyl orange under acid and solutions of weak acidity, at the same
Under strong alkaline condition also can fast degradation methyl orange, realize effective fast degradation to methyl orange, it is useless in practical methyl orange
It is had a 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)
2, ferriporphyrin/bismuth tungstate composite photocatalyst material for using of the present invention, including ferriporphyrin and bismuth tungstate, wherein iron porphin
It mainly include Van der Waals force, hydrophobic interaction power and ionic bond by non-covalent bond stable bond between quinoline and bismuth tungstate.
In the present invention, ferriporphyrin is a kind of nontoxic natural material, will not cause secondary pollution to environment in practical applications, and
Due to its metallic iron (Fe (III)) and the big pi-electron structure of conjugation with variable valence, good electronic conductivity is shown, it will
It, which 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 then remains on bismuth tungstate, solves the problems, such as that bismuth tungstate photo-generate electron-hole is high to recombination rate,
And then improve ferriporphyrin/bismuth tungstate composite photocatalyst material photocatalytic activity.On the other hand, bismuth tungstate can be as carrier
Ferriporphyrin, which provides good microenvironment, enhances the recyclable recycling property of ferriporphyrin to weaken the self-polymeric reaction 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 dispersibility is shown, guarantee comes into full contact with reaction solution.Ferriporphyrin/bismuth tungstate of the invention simultaneously is multiple
Light combination catalysis material can be separated by simple centrifugal process with reaction solution, convenient for recycling and reusing.Iron porphin of the 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 widely applied environmentally friendly composite photocatalyst material with excellent photocatalysis performance.
3, ferriporphyrin is only used as coating material to load in ferriporphyrin/bismuth tungstate composite photocatalyst material that the present invention uses
On bismuth tungstate crystal, this maintains the crystalline structure that bismuth tungstate is self-assembled into class bouquet by nanometer sheet, have large specific surface area,
The advantages that contact with organic pollutant is wide is conducive to organic pollutant (such as methyl in degradation water phase in practical applications
Orange).Compared to bismuth tungstate monomer catalysis material, ferriporphyrin of the present invention/bismuth tungstate composite photocatalyst material electron-hole is compound
Rate reduces, and shows better photocatalysis performance.
4, ferriporphyrin/bismuth tungstate composite photocatalyst material that the present invention uses passes through settled process using bismuth tungstate as carrier
One step is prepared.Ferriporphyrin of the present invention/bismuth tungstate composite photocatalyst material preparation method reaction condition is mild, under greenhouse
It can react, without harsh reaction condition, while this method does not need special equipment yet, and this method will not be to bismuth tungstate
Crystal form has an impact, and can guarantee that the property of synthetic material does not change, have reaction condition is mild, process flow is simple,
The advantage of environmental protection presents good development circumstances and wide application prospect in synthesis field of functional materials.
Detailed description of the invention
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, the technical scheme in the embodiment of the invention is clearly and completely described.
Fig. 1 is ferriporphyrin/bismuth tungstate composite photocatalyst material SEM figure prepared by the embodiment of the present invention 1.
Fig. 2 is ferriporphyrin/bismuth tungstate composite photocatalyst material TEM figure prepared by the embodiment of the present invention 1.
Fig. 3 is ferriporphyrin/bismuth tungstate composite photocatalyst material energy spectrum diagram prepared by the embodiment of the present invention 1.
Fig. 4 is that bismuth tungstate, the ferriporphyrin/bismuth tungstate composite photocatalyst material prepared in the embodiment of the present invention 1 is not being shared the same light
According under the conditions of degradation time to the degradation effect figure of methyl orange.
Fig. 5 is ferriporphyrin/bismuth tungstate composite photocatalyst materials different in the embodiment of the present invention 2 to the degradation effect of methyl orange
Figure.
Fig. 6 is for ferriporphyrin/bismuth tungstate composite photocatalyst material in the embodiment of the present invention 3 to methyl orange under condition of different pH
Degradation effect figure.
Fig. 7 is ferriporphyrin/bismuth tungstate composite photocatalyst material in the embodiment of the present invention 4 in different hydrogen peroxide additive amount items
To the degradation effect figure of methyl orange under part.
Specific embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
It limits the scope of the invention.
Material employed in following embodiment and instrument be it is commercially available, raw material be analyze it is pure.In following embodiment, if nothing
It illustrates, the data obtained is the average value for repeating test more than three times.
Embodiment 1
A method of methyl orange is handled using ferriporphyrin/bismuth tungstate composite photocatalyst material, comprising 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, after reaching the adsorption equilibrium to methyl orange, adjust 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 total volume, by hydrogen peroxide
It is added in methyl orange solution, carries out illumination under the illumination condition that wavelength is 300nm~800nm in the case where revolving speed is 800r/min
Degrade 60min, is separated by solid-liquid separation after the reaction was completed, completes the degradation to methyl orange, and recycle 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.
Ferriporphyrin/bismuth tungstate composite photocatalyst material that the mass ratio of above-mentioned ferriporphyrin and bismuth tungstate is 1: 10, including iron
Porphyrin and bismuth tungstate, wherein ferriporphyrin is supported on bismuth tungstate.The ferriporphyrin/bismuth tungstate composite photocatalyst material partial size is 1 μ
M~3 μm.The ferriporphyrin/bismuth tungstate composite photocatalyst material is the structure that class bouquet is self-assembled by nanometer sheet.The ferriporphyrin/
The preparation of bismuth tungstate composite photocatalyst material, comprising the following steps:
(1) Bi (NO is weighed3)3·5H2O and Na2WO4·2H2O is dissolved in the nitric acid solution and sodium hydroxide of 1mol/L respectively
In solution, bismuth nitrate solution and sodium tungstate solution are respectively obtained, wherein Bi (NO in bismuth nitrate solution3)3·5H2The concentration of O is
0.05mol/L, Na in sodium tungstate solution2WO4·2H2The concentration of O is 0.025mol/L；According to Bi: W=2: 1 molar ratio by nitre
Sour bismuth solution and sodium tungstate solution mixing, magnetic agitation 20min, ultrasonic 20min obtain tungsten under the conditions of revolving speed is 800r/min
The mixed solution of sour sodium and bismuth nitrate；The mixed solution of sodium tungstate and bismuth nitrate is transferred in reaction kettle, the hydro-thermal at 140 DEG C
Reaction 24 hours, is cooled to room temperature, is washed repeatedly with deionized water and ethyl alcohol, dried at 120 DEG C, obtain bismuth tungstate powder.
(2) it takes 20mL acetonitrile to mix with 20mL dimethyl sulfoxide, obtains the mixed solution of acetonitrile and dimethyl sulfoxide；By ferriporphyrin
It is added in the mixed solution of acetonitrile and dimethyl sulfoxide, stirs 10min, ultrasonic 15min under the conditions of revolving speed is 800r/min, mix
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, quickly stirs 30min under the conditions of revolving speed is 800r/min, ultrasonic 20min makes bismuth tungstate and iron porphin
Quinoline is uniformly 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 for 24 hours, make it
Sufficiently reaction.
(5) reaction product in step (4) is separated by solid-liquid separation, obtained solid substance uses deionized water and ethyl alcohol repeatedly
Washes clean, drying, is ground to uniform powder, obtains ferriporphyrin/bismuth tungstate composite photocatalyst material.
Fig. 1 is ferriporphyrin/bismuth tungstate composite photocatalyst material SEM figure in the embodiment of the present invention 1.It can from Fig. 1
Out, ferriporphyrin prepared by the present invention/bismuth tungstate composite photocatalyst material granular size is 1 μm~3 μm, and bismuth tungstate is integrally in colored
Spherical, ferriporphyrin loads on the surface.
Fig. 2 is ferriporphyrin/bismuth tungstate composite photocatalyst material TEM figure in the embodiment of the present invention 1.It can from Fig. 2
Out, the crystal form of bismuth tungstate is complete, is in lamellar structure, load has ferriporphyrin substance in lamellar structure.
Fig. 3 is ferriporphyrin/bismuth tungstate composite photocatalyst material power spectrum (EDS) figure in the embodiment of the present invention 1.From Fig. 3
As can be seen that ferriporphyrin prepared by the present invention/bismuth tungstate composite photocatalyst material contains C, Fe, Cl, Bi, W, O, it was demonstrated that the present invention
A kind of ferriporphyrin/bismuth tungstate composite photocatalyst material is successfully prepared in method.
Comparative example 1
It is 10: 1 by the mass ratio of methyl orange in bismuth tungstate and methyl orange solution, bismuth tungstate obtained adds in Example 1
It is added in the methyl orange solution that initial concentration is 10mg/L and carries out dark treatment 30min, after reaching the adsorption equilibrium to methyl orange, adjust
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 total volume, by peroxidating
Hydrogen is added in methyl orange solution, and light is carried out under the illumination condition that wavelength is 300nm~800nm in the case where revolving speed is 800r/min
It according to degradation 60min, is separated by solid-liquid separation after the reaction was completed, completes the degradation to methyl orange.
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 that bismuth tungstate, the ferriporphyrin/bismuth tungstate composite photocatalyst material prepared in the embodiment of the present invention 1 is not being shared the same light
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 prepared by the present invention/bismuth tungstate composite photocatalyst material (H-
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 degradation has
Machine object.
Embodiment 2
A method of methyl orange is handled using ferriporphyrin/bismuth tungstate composite photocatalyst material, comprising the following steps:
Mass ratio by methyl orange in ferriporphyrin/bismuth tungstate composite photocatalyst material and methyl orange solution is 10: 1, takes iron
Ferriporphyrin/bismuth tungstate composite photocatalyst material that the mass ratio of porphyrin and bismuth tungstate is 0.1: 10,1: 10,2: 10 is respectively added to
Initial concentration is that dark treatment 30min is carried out in the methyl orange solution of 10mg/L, after reaching the adsorption equilibrium to methyl orange, adjusts institute
The pH value for obtaining each group methyl orange and ferriporphyrin/bismuth tungstate composite photocatalyst material mixed solution is 6, total according to methyl orange solution
Hydrogen peroxide is added in each group methyl orange solution by the 0.5 ‰ of volume, in the case where revolving speed is 800r/min in wavelength be 300nm
Illumination degrading 60min is carried out under the illumination condition of~800nm, is separated by solid-liquid separation after the reaction was completed, and the drop to methyl orange is completed
Solution, and recycle ferriporphyrin/bismuth tungstate composite photocatalyst material.
Ferriporphyrin/bismuth tungstate composite photocatalyst material that the mass ratio of above-mentioned ferriporphyrin and bismuth tungstate is 0.1: 10, including
Ferriporphyrin and bismuth tungstate, wherein ferriporphyrin is supported on bismuth tungstate.The ferriporphyrin/bismuth tungstate composite photocatalyst material partial size is
1 μm~3 μm.The ferriporphyrin/bismuth tungstate composite photocatalyst material is the structure that class bouquet is self-assembled by nanometer sheet.The iron porphin
The preparation of quinoline/bismuth tungstate composite photocatalyst material, comprising the following steps:
(1) Bi (NO is weighed3)3·5H2O and Na2WO4·2H2O is dissolved in the nitric acid solution and sodium hydroxide of 1mol/L respectively
In solution, bismuth nitrate solution and sodium tungstate solution are respectively obtained, wherein Bi (NO in bismuth nitrate solution3)3·5H2The concentration of O is
0.05mol/L, Na in sodium tungstate solution2WO4·2H2The concentration of O is 0.025mol/L；According to Bi: W=2: 1 molar ratio by nitre
Sour bismuth solution and sodium tungstate solution mixing, magnetic agitation 20min, ultrasonic 20min obtain tungsten under the conditions of revolving speed is 800r/min
The mixed solution of sour sodium and bismuth nitrate；The mixed solution of sodium tungstate and bismuth nitrate is transferred in reaction kettle, the hydro-thermal at 140 DEG C
Reaction 24 hours, is cooled to room temperature, is washed repeatedly with deionized water and ethyl alcohol, dried at 120 DEG C, obtain bismuth tungstate powder.
(2) it takes 20mL acetonitrile to mix with 20mL dimethyl sulfoxide, obtains the mixed solution of acetonitrile and dimethyl sulfoxide；By ferriporphyrin
It is added in the mixed solution of acetonitrile and dimethyl sulfoxide, stirs 10min, ultrasonic 15min under the conditions of revolving speed is 800r/min, mix
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, quickly stirs 30min under the conditions of revolving speed is 800r/min, ultrasonic 20min makes bismuth tungstate and iron
Porphyrin is uniformly 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 for 24 hours, make it
Sufficiently reaction.
(5) reaction product in step (4) is separated by solid-liquid separation, obtained solid substance uses deionized water and ethyl alcohol 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.
Ferriporphyrin/bismuth tungstate composite photocatalyst material that the mass ratio of above-mentioned ferriporphyrin and bismuth tungstate is 2: 10, including iron
Porphyrin and bismuth tungstate, wherein ferriporphyrin is supported on bismuth tungstate.The ferriporphyrin/bismuth tungstate composite photocatalyst material partial size is 1 μ
M~3 μm.The ferriporphyrin/bismuth tungstate composite photocatalyst material is the structure that class bouquet is self-assembled by nanometer sheet.The ferriporphyrin/
The preparation of bismuth tungstate composite photocatalyst material, comprising the following steps:
(1) Bi (NO is weighed3)3·5H2O and Na2WO4·2H2O is dissolved in the nitric acid solution and sodium hydroxide of 1mol/L respectively
In solution, bismuth nitrate solution and sodium tungstate solution are respectively obtained, wherein Bi (NO in bismuth nitrate solution3)3·5H2The concentration of O is
0.05mol/L, Na in sodium tungstate solution2WO4·2H2The concentration of O is 0.025mol/L；According to Bi: W=2: 1 molar ratio by nitre
Sour bismuth solution and sodium tungstate solution mixing, magnetic agitation 20min, ultrasonic 20min obtain tungsten under the conditions of revolving speed is 800r/min
The mixed solution of sour sodium and bismuth nitrate；The mixed solution of sodium tungstate and bismuth nitrate is transferred in reaction kettle, the hydro-thermal at 140 DEG C
Reaction 24 hours, is cooled to room temperature, is washed repeatedly with deionized water and ethyl alcohol, dried at 120 DEG C, obtain bismuth tungstate powder.
(2) it takes 20mL acetonitrile to mix with 20mL dimethyl sulfoxide, obtains the mixed solution of acetonitrile and dimethyl sulfoxide；By ferriporphyrin
It is added in the mixed solution of acetonitrile and dimethyl sulfoxide, stirs 10min, ultrasonic 15min under the conditions of revolving speed is 800r/min, mix
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, quickly stirs 30min under the conditions of revolving speed is 800r/min, ultrasonic 20min makes bismuth tungstate and iron porphin
Quinoline is uniformly 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 for 24 hours, make it
Sufficiently reaction.
(5) reaction product in step (4) is separated by solid-liquid separation, obtained solid substance uses deionized water and ethyl alcohol 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 ferriporphyrin/bismuth tungstate composite photocatalyst materials different in the embodiment of the present invention 2 to the degradation effect of methyl orange
Figure.From figure 5 it can be seen that ferriporphyrin/bismuth tungstate composite photocatalyst material that the mass ratio of ferriporphyrin and bismuth tungstate is 1: 10
It is best to the photocatalysis effect of methyl orange；Ferriporphyrin/bismuth tungstate complex light that the mass ratio of ferriporphyrin and bismuth tungstate is 0.1: 10
Catalysis material is since the amount of ferriporphyrin is few, and caused class light Fenton's reaction effect is lower, and the conduction to bismuth tungstate light induced electron
Ferriporphyrin/bismuth tungstate composite photocatalyst material that efficiency does not have the mass ratio of ferriporphyrin and bismuth tungstate to be 1: 10 is good, so iron porphin
Quinoline and ferriporphyrin/bismuth tungstate composite photocatalyst material that the mass ratio of bismuth tungstate is 0.1: 10 are opposite to the degradation effect of methyl orange
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 more, the most surface-active site of bismuth tungstate has been covered, has reduced the amount of bismuth tungstate light induced electron, affects electron-hole
Pair generation, to influence to the rate of photocatalytic oxidation of 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
A method of methyl orange is handled using ferriporphyrin/bismuth tungstate composite photocatalyst material, comprising the following steps:
Mass ratio by methyl orange in ferriporphyrin/bismuth tungstate composite photocatalyst material and methyl orange solution is 10: 1, takes five
Ferriporphyrin/bismuth tungstate composite photocatalyst material point that the mass ratio of the ferriporphyrin and bismuth tungstate that prepare in group embodiment 1 is 1: 10
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 adjust gained each group methyl orange and ferriporphyrin/bismuth tungstate composite photocatalyst material mixed solution pH value be 3,6,
8,9,12, then according to the 0.5 ‰ of methyl orange solution total volume, hydrogen peroxide is added in each group methyl orange solution, is being turned
Speed be under 800r/min under the illumination condition that wavelength is 300nm~800nm carry out illumination degrading 60min, after the reaction was completed into
Row is separated by solid-liquid separation, and completes the degradation to methyl orange, and recycle 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
It influences, as a result as shown in Figure 6.
Fig. 6 is for ferriporphyrin/bismuth tungstate composite photocatalyst material in the embodiment of the present invention 3 to methyl orange under condition of different pH
Degradation effect figure.From fig. 6 it can be seen that ferriporphyrin/bismuth tungstate composite photocatalyst material is to first when adjusting pH value is 8 and 9
The photocatalysis performance of base orange is not high；When adjusting 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.The test data for being 6,8 and 9 by pH value compares it is found that in weak base
Under the conditions of property, OH-There is high inhibition effect to ferriporphyrin/bismuth tungstate composite photocatalyst material photocatalysis performance.In addition, from Fig. 6
In as can be seen that adjust pH value be 3 when, ferriporphyrin/bismuth tungstate composite photocatalyst material photocatalysis performance, which also has, significantly to be mentioned
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, this is because H+Only inducer, induction ferriporphyrin occur Fenton's reaction, enhance ferriporphyrin/wolframic acid
The oxidation susceptibility of bismuth composite photocatalyst material, while the conductive performance of bismuth tungstate light induced electron is improved, reduce electron-hole pair
Recombination rate, to improve ferriporphyrin/bismuth tungstate composite photocatalyst material photocatalysis performance, it was demonstrated that in acid condition (such as pH value
Be 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% can be reached in 60min to the degradation rate of methyl orange, reaction rate constant k > 0.038min-1.It should be noted that
In the case where adjusting pH value is 12, ferriporphyrin/bismuth tungstate composite photocatalyst material photocatalysis performance is changed, and is just opened
The degradation rate of beginning is suppressed, but the degradation rate in later period quickly improves, this is because under strong alkali solution, hydrogen peroxide
Do not exist with molecular forms, with the OH in solution-Reaction becomes HO2 -, and HO2 -Decomposing hydrogen dioxide solution can be induced and generate trip
From free radical, to improve to the degradation rate of methyl orange, effectively degradation methyl orange.Ferriporphyrin/bismuth tungstate i.e. of the present invention is multiple
Light combination 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% in 60min, reaction rate constant k > 0.015min-1.As it can be seen that the present invention can not only be in acid
Quickly and efficiently degrade 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, is had a good application prospect in the processing of practical Methyl Orange in Wastewater.
Embodiment 4
A method of methyl orange is handled using ferriporphyrin/bismuth tungstate composite photocatalyst material, comprising the following steps:
Mass ratio by methyl orange in ferriporphyrin/bismuth tungstate composite photocatalyst material and methyl orange solution is 10: 1, takes five
Ferriporphyrin/bismuth tungstate composite photocatalyst material point that the mass ratio of the ferriporphyrin and bismuth tungstate that prepare in group embodiment 1 is 1: 10
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 for adjusting gained each group methyl orange and ferriporphyrin/bismuth tungstate composite photocatalyst material mixed solution is 6, according to first
Hydrogen peroxide is added to each group methyl orange solution by 0.1 ‰, 0.2 ‰, 0.3 ‰, 0.4 ‰ and the 0.5 ‰ of base orange overall solution volume
In, illumination degrading 60min is carried out under the illumination condition that wavelength is 300nm~800nm in the case where revolving speed is 800r/min, has been reacted
It is separated by solid-liquid separation after, completes the degradation to methyl orange, and recycle 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 additive amount 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 additive amount items
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 additive amount of hydrogen peroxide is the 0.5 ‰ of methyl orange solution total 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 conclusion the present invention has behaviour using ferriporphyrin/bismuth tungstate composite photocatalyst material processing methyl orange method
Make that simple, the period is short, easily separated recycling, the advantages that degradation efficiency is high, can be realized and methyl orange is effectively removed.
The above is only the present invention to be disclosed with preferred embodiment, and however, it is not intended to limit the invention.It is any to be familiar with this field
Technical staff, many possible variations all are made to technical solution of the present invention using the methods and technical content of the disclosure above
And modification.Therefore, anything that does not depart from the technical scheme of the invention, according to the technical essence of the invention to above embodiments institute
Any simple modification is made, all of which are still within the scope of protection of the technical scheme of the invention.
Claims (10)
1. a kind of utilize ferriporphyrin/bismuth tungstate composite photocatalyst material processing methyl orange method, which is characterized in that use iron porphin
Quinoline/bismuth tungstate composite photocatalyst material and hydrogen peroxide handle methyl orange；The ferriporphyrin/bismuth tungstate composite photocatalyst
Material includes ferriporphyrin and bismuth tungstate, and the ferriporphyrin is supported on the bismuth tungstate；The ferriporphyrin and the bismuth tungstate
Mass ratio is 1~1.5: 10.
2. the method according to claim 1, wherein the following steps are included: ferriporphyrin/bismuth tungstate complex light is urged
Change material and mix progress dark treatment with methyl orange solution, adjusts gained methyl orange and ferriporphyrin/bismuth tungstate after reaching adsorption saturation
The pH value of the mixed solution of composite photocatalyst material is added hydrogen peroxide and carries out illumination degrading, completes the degradation to methyl orange.
3. according to the method described in claim 2, it is characterized in that, the ferriporphyrin/bismuth tungstate composite photocatalyst material grain
Diameter is 1 μm~3 μm.
4. according to the method described in claim 3, it is characterized in that, the ferriporphyrin/bismuth tungstate composite photocatalyst material system
It is standby the following steps are included:
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 the mixed solution of S3, the adjusting bismuth tungstate and ferriporphyrin, stands, obtains ferriporphyrin/bismuth tungstate complex light and urge
Change material.
5. according to the method described in claim 4, it is characterized in that, the step S1, specifically:
S1-1, acetonitrile is mixed with dimethyl sulfoxide, obtains 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 is mixed with the acetonitrile with the mixed solution of dimethyl sulfoxide, is 400r/min~1500r/ in revolving speed
5min~30min is stirred under the conditions of min, ultrasonic 5min~30min obtains ferriporphyrin solution.
6. according to the method described in claim 4, it is characterized in that, the step S2, specifically: by bismuth tungstate and the iron porphin
Quinoline solution mixing, revolving 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；The standing
Time be 15h~25h.
7. according to the method described in claim 4, it is characterized in that, the preparation of the bismuth tungstate the following steps are included:
(1) sodium tungstate solution is mixed with bismuth nitrate solution, is stirred under conditions of revolving 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 bismuth nitrate to be prepared；
(2) mixed solution of the sodium tungstate and bismuth nitrate is placed in reaction kettle, is carried out at being 120 DEG C~180 DEG C in temperature
Hydro-thermal reaction 15h~25h, washed, drying obtain bismuth tungstate.
8. the method according to any one of claim 2~7, which is characterized in that the ferriporphyrin/bismuth tungstate complex light is urged
The mass ratio for changing methyl orange in material and the methyl orange solution is 10: 0.5~3；The additive amount of the hydrogen peroxide is described
The 0.1 ‰ of methyl orange solution total volume~0.5 ‰.
9. the method according to any one of claim 2~7, which is characterized in that adjust the 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, which is characterized 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 the illumination condition of 300nm~800nm；During the illumination degrading
Mixing speed be 300r/min~900r/min；The time of the illumination degrading is 30 min~120min.
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| Enhanced photocatalytic performance of Hemin (chloro(protoporhyinato) iron(III)) anchored TiO2 photocatalyst for methyl orange degradation: A surface modification method;L. Gomathi Devi et al.,;《Applied Surface Science》;20130327;第521-528页 * |
| Mixed α-Fe2O3/Bi2WO6 oxides for photoassisted hetero-Fenton degradation of Methyl Orange and Phenol;C. Jaramillo-Páez et al.,;《Journal of Photochemistry and Photobiology A: Chemistry》;20161001;第521-533页 * |
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