CN106732638A - A kind of photochemical catalyst Fe2O3‑WO3And preparation method thereof - Google Patents
A kind of photochemical catalyst Fe2O3‑WO3And preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 32
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 18
- 239000010937 tungsten Substances 0.000 claims abstract description 18
- 238000006731 degradation reaction Methods 0.000 claims abstract description 17
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 14
- 230000015556 catabolic process Effects 0.000 claims abstract description 13
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims abstract description 11
- 229940012189 methyl orange Drugs 0.000 claims abstract description 11
- 230000005855 radiation Effects 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 23
- 230000001699 photocatalysis Effects 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 238000001228 spectrum Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 238000007146 photocatalysis Methods 0.000 claims description 11
- -1 artificial schellite Chemical compound 0.000 claims description 10
- 238000002329 infrared spectrum Methods 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 6
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 244000248349 Citrus limon Species 0.000 claims description 3
- 235000005979 Citrus limon Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 229910001867 inorganic solvent Inorganic materials 0.000 claims description 2
- 239000003049 inorganic solvent Substances 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 150000007522 mineralic acids Chemical group 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- OQFRENMCLHGPRB-UHFFFAOYSA-N copper;dioxido(dioxo)tungsten Chemical compound [Cu+2].[O-][W]([O-])(=O)=O OQFRENMCLHGPRB-UHFFFAOYSA-N 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 81
- 230000000694 effects Effects 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 27
- 238000006555 catalytic reaction Methods 0.000 description 18
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000010453 quartz Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000005286 illumination Methods 0.000 description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 10
- 239000002131 composite material Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 238000000103 photoluminescence spectrum Methods 0.000 description 8
- 239000003708 ampul Substances 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002516 radical scavenger Substances 0.000 description 7
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 6
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 6
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 5
- 235000015165 citric acid Nutrition 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229940005561 1,4-benzoquinone Drugs 0.000 description 3
- 102000016938 Catalase Human genes 0.000 description 3
- 108010053835 Catalase Proteins 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000003292 diminished effect Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910004333 CaFe2O4 Inorganic materials 0.000 description 1
- 229910016874 Fe(NO3) Inorganic materials 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005264 electron capture Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of photochemical catalyst Fe2O3‑WO3The photochemical catalyst is after radiation of visible light 1h, degradation rate to methyl orange reaches more than 70%, present invention also offers a kind of method for preparing above-mentioned photochemical catalyst, the method is to prepare tungsten oxide with tungsten source, and iron oxide is prepared in its surface in situ, tungsten oxide is set to be combined with iron oxide by high temperature again, the method preparation method is simple, environmental protection, preparation efficiency is high.
Description
Technical field
The present invention relates to photocatalysis field, more particularly to a kind of inorganic photochemical catalyst and preparation method thereof.
Background technology
At present with regard to the world today from the point of view of, photocatalysis is undoubtedly most one of a special kind of skill of broad prospect of application.It to
We show solar energy source in very many applications, such as photocatalytic water obtains hydrogen energy source, such as can very efficient solution
The problem of certainly existing sewage disposal in the industry.
In recent years, people are in TiO2Improvement on and development possess suitable energy gap novel photocatalysis material aspect
Many effort, WO are spent3Nanostructured quickly grows due to possessing smaller energy gap.But, pure WO3Light
Catalysis activity is very low, it is impossible to reduce O by single electronic method2。
Some composite catalysts such as Pt and CuO have been used for improving WO3Catalysis activity, be by promoting polyelectron
Reduction O2Realize, but the former high cost and the complicated post processing of the latter limit their applications in practice.
In recent years, two kinds of composite quilts of semiconductor of different energy gaps are used to suppress the combination and understanding in electronics and hole
The directionality transfer of photo-generated carrier.Although some composite catalysts such as TiO2/WO3、CaFe2O4/WO3Increase to a certain extent
WO3Catalysis activity, but the synthesis step of these composite catalysts is always too complicated and can not be extended and be applied to reality
In.
It would therefore be highly desirable to develop a kind of preparation method is simple, photocatalysis efficiency it is high with WO3The compound photocatalysis of component
Agent.
The content of the invention
In order to solve the above problems, present inventor has performed studying with keen determination, as a result find：Tungsten oxide is prepared with tungsten source,
Its surface in situ prepares iron oxide, then tungsten oxide is combined with iron oxide by high temperature, is obtained with tungsten oxide as core, oxidation
Iron is the composite photo-catalyst of clad, and after radiation of visible light 1h, the degradation rate to methyl orange reaches 70% to the photochemical catalyst
More than, so as to complete the present invention.
It is an object of the invention to provide following aspect：
In a first aspect, the present invention provides a kind of photochemical catalyst Fe2O3-WO3, it is characterised in that the photochemical catalyst Fe2O3-
WO3In, the gross weight based on photochemical catalyst, in terms of the weight of wherein iron oxide, the weight fraction of iron oxide is 10%~55%；
According to its XRD difraction spectrum, the photochemical catalyst is 2 θ=22.7 °, 31.7 °, 32.8 °, 40.2 °, 48.4 °, 54.5 °
Place is respectively present diffraction maximum, and these diffraction maximums correspond respectively to (012), (104), (110), (113), and (024) and (116) is brilliant
Face；
It is 980cm in wave number according to its infrared spectrum-1Nearby there is more obvious absworption peak；
After radiation of visible light 1h, the degradation rate to methyl orange reaches more than 70% for it.
Second aspect, the present invention also provides a kind of method for preparing above-mentioned photochemical catalyst, it is characterised in that methods described bag
Include following steps：
Step 1, tungsten source is mixed with surface-active, to addition acid, insulation reaction after intensification, in removing system in system
Solvent, calcining；
Step 2, product obtained in step 1 is scattered in dispersant, to source of iron is added in system, is mixed, and removes solvent
Afterwards, solid content is calcined.
The third aspect, the present invention also provides above-mentioned photochemical catalyst for the application in terms of catalytic degradation dye wastewater.
Brief description of the drawings
Fig. 1 shows the XRD spectra of sample；
Fig. 2 shows the infrared spectrogram of sample；
Fig. 3 shows the photoluminescence spectra of sample；
Fig. 4 show comparative example 1 be obtained sample under visible light illumination Photocatalytic Degradation On Methyl Orange Solution UV-Vis spectrum with
The variation diagram of time；
Fig. 5 show comparative example 2 be obtained sample under visible light illumination Photocatalytic Degradation On Methyl Orange Solution UV-Vis spectrum with
The variation diagram of time；
Fig. 6 show embodiment 1 be obtained sample under visible light illumination Photocatalytic Degradation On Methyl Orange Solution UV-Vis spectrum with
The variation diagram of time；
Fig. 7 shows the UV-Vis DRS spectrum of sample；
Fig. 8 shows the visible light catalysis activity of sample；
Fig. 9 shows influence of the scavenger to sample photocatalytic activity；
Figure 10 shows the photocatalysis principle of the photochemical catalyst of present invention offer.
Specific embodiment
Below by the present invention is described in detail, the features and advantages of the invention will become more with these explanations
For clear, clear and definite.
The present invention described below.
In a first aspect, the present invention provides a kind of photochemical catalyst Fe2O3-WO3, it is characterised in that the photochemical catalyst Fe2O3-
WO3In, the gross weight based on photochemical catalyst, in terms of the weight of wherein iron oxide, the weight fraction of iron oxide is 10%~55%；
According to its XRD difraction spectrum, the photochemical catalyst is 2 θ=22.7 °, 31.7 °, 32.8 °, 40.2 °, 48.4 °, 54.5 °
Place is respectively present diffraction maximum, and these diffraction maximums correspond respectively to (012), (104), (110), (113), and (024) and (116) is brilliant
Face；
It is 980cm in wave number according to its infrared spectrum-1Nearby there is more obvious absworption peak；
After radiation of visible light 1h, the degradation rate to methyl orange reaches more than 70% for it.
Second aspect, the present invention also provides a kind of method for preparing above-mentioned photochemical catalyst, it is characterised in that methods described bag
Include following steps：
Step 1, tungsten source is mixed with surface-active, to addition acid, insulation reaction after intensification, in removing system in system
Solvent, calcining.
In the present invention, the tungsten source is tungstates, is preferably selected from sodium tungstate, ammonium tungstate, bismuth tungstate, artificial schellite, wolframic acid
Copper, wolframic acid silver etc., are more preferably selected from sodium tungstate, ammonium tungstate, artificial schellite, most preferably sodium tungstate.
In the present invention, the surfactant is lemon acids, preferably citric acid ester type surfactant, lemon
Acid, citrate salt APA, citric acid list lauryl alcohol ester etc., preferably citric acid.
In the present invention, the salt is inorganic acid, preferably hydrochloric acid, sulfuric acid, nitric acid etc., more preferably hydrochloric acid, further
Preferably concentration is the hydrochloric acid of (0.5~3) mol/L.
The inventors discovered that, after the tungsten source and the acid reaction, the wolframic acid for manifesting colloidal state can be generated, it is scattered in
In preparation system.
The inventors discovered that, when using citric acid as surfactant, tungsten source can be fully dispersed in system, and
And, when it is reacted with acid, the wolframic acid of generation also can be fully dispersed in system, and avoids reuniting.
In the present invention, tungsten source and the weight ratio of surfactant are 1:(0.8~1.5), preferably 1:(1.0~1.3),
Most preferably 1:1.2.
The inventors discovered that, when tungsten source is mixed with surfactant according to above-mentioned weight ratio, tungsten source and be obtained
Wolframic acid can be fully dispersed in system, meanwhile, excessive levels of impurities will not be introduced in system again.
In the present invention, the weight in tungsten source and the volume ratio of acid are 1g:(8~20) mL, preferably 1g:(10~15) mL,
Such as 1g:12.3mL.
The inventors discovered that, when the weight in tungsten source is 1g with the volume ratio of acid:During (8~20) mL, reaction system manifests acid
Property, tungsten source therein can with acid reaction generate wolframic acid, and generate wolframic acid can in system stable existence.
The inventors discovered that, the generation of wolframic acid needs certain reaction time, and with the rising of reaction temperature, reaction
Speed is accelerated, therefore, after present invention selection adds acid in system, intensification system temperature, it is preferable that raise system temperature
To 100 DEG C~150 DEG C, preferably 110 DEG C~140 DEG C, such as 120 DEG C, the inventors discovered that, when system temperature to said temperature
When, the generating rate of wolframic acid is moderate, can quickly generate wolframic acid, while also avoiding wrapping impurity.
In the present invention, soaking time is 12~36 hours, preferably 20~30 hours, such as 24 hours.
The inventors discovered that, when soaking time is the above-mentioned time, the tungsten source in reaction system can fully react with salt,
Generation wolframic acid.
In the present invention, after wolframic acid is fully generated, reaction, the solvent in removing system are stopped.
In the present invention, the method to solvent in removing system is not specially limited, it is possible to use any in the prior art
A kind of method for removing liquid phase solvent, such as normal pressure heating, heating under diminished pressure, preferably normal heating method, when using normal pressure
When heating removes solvent, the temperature of system is 60 DEG C~120 DEG C, preferably 70 DEG C~100 DEG C, such as 80 DEG C.
In the present invention, dried wolframic acid is calcined, dehydration generation WO3。
In the present invention, calcining prepares WO3Temperature be 300 DEG C~500 DEG C, preferably 350 DEG C~450 DEG C, most preferably
It is 400 DEG C.
In the present invention, calcining prepares WO3Time be 2~6 hours, preferably 3~5 hours, most preferably 5 hours.
Step 2, product obtained in step 1 is scattered in dispersant, to source of iron is added in system, is mixed, and removes solvent
Afterwards, solid content is calcined.
In the present invention, the source of iron is water-soluble molysite, such as ferric nitrate or its hydrate, iron chloride or its hydration
Thing etc., preferably Fe(NO3)39H2O.
In the present invention, the dispersant is WO3Poor solvent, makes WO obtained in step 13It is small with solid in dispersant
The form of particle is present, and source of iron can be then dissolved in dispersant, so that source of iron can be coated on WO with the rank of molecule3
Surface.
In the present invention, the dispersant is inorganic solvent, preferably water.
In the present invention is a kind of preferred embodiment, source of iron is to add system in its aqueous solution form, it is preferable that base
In the cumulative volume of iron nitrate solution, in terms of the weight of wherein ferric nitrate, the concentration of iron nitrate solution is 1.0g/L~30g/L, excellent
Elect 2.0g/L~25g/L as.
In step 2 of the present invention, tungsten oxide obtained in step 1 is 0.45g with the weight ratio of source of iron:(0.1~3g).
In the present invention, mixed system is made to heat up, and the insulation reaction under the high-temperature temperature, the inventors discovered that,
Insulation reaction can accelerate reaction rate at high temperature, promote reaction to carry out, i.e. promote source of iron to decompose, in the life of tungsten oxide surface
Into iron oxide, form uniform iron oxide coated layer.
In the present invention, tungsten oxide and the reaction temperature of source of iron are 30 DEG C~80 DEG C, preferably 40 DEG C~70 DEG C, such as 50
℃。
In the present invention, tungsten oxide and the reaction time of source of iron are 0.5~4 hour, preferably 1~3 hour, such as 2 hours.
In the present invention, the method for solvent is not specially limited in removing system, it is possible to use any one in the prior art
The method for planting solvent in removing system, such as normal pressure heating, heating under diminished pressure, normal temperature and pressure filtration method, centrifugation, preferably
It is centrifugation.
In the present invention, the system removed after solvent is dried, the present invention is not specially limited to dry mode,
The dry method of any one solid phase, such as normal pressure heating, heating under diminished pressure, preferably normal pressure in the prior art can be used
Heating.
In the present invention is a kind of preferred embodiment, when being dried using normal heating method, body when removing solvent
The temperature of system is 60~120 DEG C, preferably 70~100 DEG C, such as 80 DEG C.
In the present invention, optionally, before the drying, washed product system, it is preferable that washed with water, removes body
Water-solubility impurity in system.
In the present invention, dried solid phase is calcined, it is preferable that the temperature of calcining is 300 DEG C~500 DEG C, excellent
Elect 350 DEG C~450 DEG C as, such as 400 DEG C.
In the present invention, the time of calcining is 2~6 hours, preferably 3~5 hours, such as 4 hours.
The inventors discovered that, to calcine at the temperature disclosed above, tungsten oxide can be combined with the iron oxide on its surface, oxidation
Iron forms the compound of stabilization with tungsten oxide.
In the present invention, optionally, product is lowered the temperature after firing, it is preferable that be reduced to room temperature, and crush.
According to the third aspect of the invention we, application of the above-mentioned photochemical catalyst in terms of catalytic degradation dye wastewater is also provided,
Wherein, the dyestuff particularly relates to organic dyestuff, such as methyl orange.
According to the photochemical catalyst F that the present invention is provided2O3-WO3And preparation method thereof, have the advantages that：
(1) the photochemical catalyst photocatalysis efficiency is high, and after radiation of visible light 1h, the degradation rate to methyl orange reaches 70% for it
More than；
(2) photochemical catalyst photocatalysis performance stabilization, reusable；
(3) this prepares the method simplicity of photochemical catalyst, environmental protection, non-environmental-pollution；
(4) the method prepares the efficiency high of photochemical catalyst.
Embodiment
Embodiment 1
Accurately weigh 1.000g Disodium tungstate (Na2WO4) dihydrates and 1.200g citric acids are added in clean beaker, measured with graduated cylinder
60mL deionized waters are added in beaker, and then beaker is placed on magnetic stirring apparatus, add a small magneton regulation stirring speed
Degree, persistently stirs half an hour to ensure solute all fully dissolvings, after the time arrives, is added in above-mentioned solution and prepared in advance
12.3mL hydrochloric acid solution (concentration is 1mol/L), then carry out mixing 10min.Final resulting solution is transferred to high pressure
In sterilizer, put it into electric heating air blast thermostatic drying chamber, set oven temperature (120 DEG C), taken out after one day.It is to be heated
Time, to rear closing switch, after autoclave is cooled to room temperature, sample solution suction filtration is separated, distillation washing several times or so,
(80 DEG C) dryings whole night, are finally calcined 4h at 400 DEG C during the sample that suction filtration is obtained is placed into baking oven.Arrive the WO of yellow3
Sample.
Weigh the above-mentioned WO of 0.450g3Sample, is added in the beaker for filling 500mL distilled water, then with vigorous stirring
Addition mass concentration is 3.00gL-1The 11.7wt%Fe of 100mL2O3/WO3(i.e. Fe2O3In Fe2O3/WO3In quality percentage
Number), beaker is placed in temperature and is set in heating on 50 DEG C of magnetic stirring apparatus, stir 2h.By products therefrom centrifugation, washing
Several that product is put into 80 DEG C of dryings in an oven whole night after, each sample is put into Muffle furnace by the time again after, and (temperature is 400
DEG C) middle burning 4h, what is finally given is obtained composite photo-catalyst finished product.
Embodiment 2~4
Embodiment 2~3 is similar to the method therefor of embodiment 1, differs only in the Fe for using2O3/WO3Concentration is respectively
6.00g·L-120.9wt% (embodiment 2), 12.00gL-134.6wt% (embodiment 3) and 24.00gL-1's
51.4wt% (embodiment 4).
Comparative example
Comparative example 1
This comparative example specimen in use is obtained WO in the step 1 of embodiment 13。
Comparative example 2
This comparative example specimen in use is the F used in embodiment 12O3。
Experimental example
The XRD analysis of the sample of experimental example 1
This experimental example specimen in use is that embodiment 1~4 and comparative example 1~2 are obtained.
Using BrukerD8Advance types X-ray diffractometer (XRD), copper target (CuK α (λ=0.154nm)) ray, Ni filters
Mating plate, operating voltage 40kV, electric current 40mA, 2 θ of sweep limits=10-60 ° analyze the crystal phase structure of sample, as a result such as Fig. 1 institutes
Show, wherein,
Curve a represents that comparative example 2 is obtained the XRD spectrums of sample；
Curve b represents that embodiment 1 is obtained the XRD spectrums of sample；
Curve c represents that embodiment 2 is obtained the XRD spectrums of sample；
Curve d represents that embodiment 3 is obtained the XRD spectrums of sample；
Curve e represents that embodiment 4 is obtained the XRD spectrums of sample；
Curve f represents that embodiment 5 is obtained the XRD spectrums of sample；
Curve g represents that comparative example 1 is obtained the XRD spectrums of sample；
As shown in Figure 1, Fig. 1 is shown as 2 θ=22.7 °, 31.7 °, 32.8 °, 40.2 °, 48.4 °, 54.5 ° of diffraction maximum point
Dui Yingyu not (012), (104), (110), (113), (024) and (116) crystal face.
In Fig. 1 shown diffraction maximum out substantially with rhombohedral Fe2O3Standard value (JCPDS33-664) phase
Meet, although still have other impurities peak, but mainly Fe2O3It is in the majority, Fe in addition2O3Diffractive features peak with apicule, explanation is forged
Fe after burning2O3There is preferable crystallization situation.
In Fig. 1, WO after calcining3Diffraction maximum be consistent with the diffraction maximum of monoclinic crystal WO3.The WO that Fig. 1 shows3Spread out
θ=21.3 ° of peak 2 are penetrated, 21.8 °, 22.8 °, 32.6 °, 48.4 ° correspond respectively to (001), (002), (200), (202), (140)
Crystal face.Understand that (202) crystal face is probably the temperature of calcining because temperature control is not accurate enough in experimentation with reference to pertinent literature
Degree rising can produce (202) crystal face, other peaks to be substantially WO3Diffraction maximum produced by monoclinic system, this and this experiment institute
It is required that the WO for obtaining3Structure is consistent, i.e. product WO3Substantially it is qualified.
In addition, from Fig. 1 knowable to curve d, b, e, f and c, the diffraction maximum of (012) crystal face corresponding during 2 θ=22.7 ° is most
By force, and, in catalyst sample obtained in embodiment, with Fe2O3The increase of mass percent ground, its diffraction peak intensity is gradually
Enhancing, works as Fe2O3Diffraction peak intensity is most strong when mass percent is 20.9wt%, then, with Fe2O3Mass percent ground increases
Greatly, Fe2O3Diffraction peak intensity gradually weaken, i.e. during 2 θ=22.7 °, diffraction peak intensity order be 1d>1b>1e>1c, from diffraction
For peak intensity and catalyst activity corresponding relation, work as Fe2O3When mass percent is 20.9wt%, the catalysis activity of catalyst
Highest, this Fe measured with other experiments2O3/WO3Photocatalytic activity order is consistent.
The infrared spectrum analysis of the sample of experimental example 2
This experimental example specimen in use is that embodiment 1~4 and comparative example 1~2 are obtained.
A small amount of above-mentioned photochemical catalyst sample is taken, (ratio of sample and KBr amounts is about 1 a little to be separately added into KBr:50),
Mixture is fully ground, be made after compressing tablet (attention must assure that transparent) start with FTIS to urging
Agent carries out infrared spectrum characterization, as a result as shown in Fig. 2 wherein,
Curve a represents that comparative example 2 is obtained the infrared spectrum of sample；
Curve b represents that embodiment 1 is obtained the infrared spectrum of sample；
Curve c represents that comparative example 1 is obtained the infrared spectrum of sample；
Curve d represents that embodiment 2 is obtained the infrared spectrum of sample；
Curve e represents that embodiment 3 is obtained the infrared spectrum of sample；
Curve f represents that embodiment 4 is obtained the infrared spectrum of sample；
Curve g represents that embodiment 5 is obtained the infrared spectrum of sample.
In fig. 2, curve a is illustrated that Fe2O3Infrared spectrogram, as can be seen from the figure pure sample Fe2O3In wave number section
1633cm-1, 1400cm-1, 553cm-1There is absworption peak in vicinity, learns Fe-O's according to existing knowledge and access standard diagram
Flexural vibrations peak appears in 1400cm-1Near wave number section, its stretching vibration absworption peak probably appears in 553cm-1Wave number section is attached
Closely, the absworption peak for being produced at other wave number sections is probably to be doped with impurity.
In fig. 2, curve c is illustrated that WO3Infrared spectrogram, according to existing knowledge and consult standard diagram learn WO3
In W=O double bonds stretching vibration peak probably in 980cm-1Vicinity occurs that W-O and W-O-W stretching vibration summits are 630
~750cm-1The absworption peak occurred in this section of wave number section region.
In fig. 2, curve b, d, e and f shows that embodiment 1~4 is obtained the infrared spectrogram of catalyst.
As shown in Figure 2, different Fe2O3With WO3The photochemical catalyst of proportioning has certain absorption near characteristic peak, especially in fact
Catalyst obtained in example 2 is applied in 980cm-1Nearby there is more obvious absworption peak, thus the obtained catalysis of deducibility embodiment 2
Agent has highest catalytic performance in four kinds of photochemical catalysts prepared by embodiment.
The photoluminescence spectra analysis of the sample of experimental example 3
Photoluminescence spectra can draw the information of the separative efficiency of photo-generate electron-hole pair, and the catalysis of photochemical catalyst is lived
Property height it is relevant with the separation probability of photo-generated carrier (electron-hole pair).
It is, in general, that the peak-to-peak signal intensity on photoluminescence spectra figure is weaker, then the separation probability of its photo-generated carrier
It is higher, it follows that its photocatalytic activity is stronger.
This experimental example specimen in use is that embodiment 1,2,4 and comparative example 1 are obtained.
The optical filter that a small amount of above-mentioned photochemical catalyst sample is put into 400nm is taken, with slide sample is pressed fine and close as far as possible, profit
With the photoluminescence performance of XRF test sample, the solid phase fluorescent spectrogram excited in the case where excitation wavelength is 360nm.Knot
Fruit as shown in figure 3, wherein,
Curve 1 represents that comparative example 1 is obtained the photoluminescence spectra of sample；
Curve 2 represents that embodiment 1 is obtained the photoluminescence spectra of sample；
Curve 3 represents that embodiment 2 is obtained the photoluminescence spectra of sample；
Curve 4 represents that embodiment 4 is obtained the photoluminescence spectra of sample.
From the figure 3, it may be seen that it can be seen that photocatalytic activity order is obtained sample for embodiment 2>Embodiment 1 is obtained sample
>Embodiment 4 is obtained sample, and this is consistent with other measuring catalyst activities.
The liquid phase ultraviolet-visible light analysis of spectrum of the sample of experimental example 4
This experimental example specimen in use is that embodiment 2 and comparative example 1 and 2 are obtained.
Each 0.0500g of above-mentioned sample is accurately weighed with assay balance in quartz ampoule, numbering is 1,2,3, then at each
Small magneton of the same size is put into quartz ampoule, it is 5.000mgL finally to measure 40mL concentration with graduated cylinder-1Methyl orange solution
Pour into respectively in three quartz ampoules.Open light reaction instrument door and be sequentially placed into three quartz ampoules, timing half an hour, after the time arrives, take
Sample carries out next step experiment, then carries out photo-irradiation treatment to surplus solution, is sampled after half an hour, and previous step takes three altogether successively
Secondary sample, liquid phase ultraviolet spectra is done finally by pertinent instruments (wavelength parameter is set into 200-700nm) respectively, as a result such as Fig. 4
Shown in~Fig. 6, wherein,
Fig. 4 show comparative example 1 be obtained sample under visible light illumination Photocatalytic Degradation On Methyl Orange Solution UV-Vis spectrum with
The variation diagram of time；
Fig. 5 show comparative example 2 be obtained sample under visible light illumination Photocatalytic Degradation On Methyl Orange Solution UV-Vis spectrum with
The variation diagram of time；
Fig. 6 show embodiment 1 be obtained sample under visible light illumination Photocatalytic Degradation On Methyl Orange Solution UV-Vis spectrum with
The variation diagram of time.
From Fig. 4~Fig. 6, under the treatment of experiment condition identical, i.e. catalytic degradation methyl orange under visible light illumination,
In different catalyst systems, in identical time interval, the degree difference of absorption values reduction, i.e. different
The photocatalytic activity of photochemical catalyst difference, wherein the palliating degradation degree of composite photocatalyst substantially compares obtained in embodiment 2
Simple Fe obtained in comparative example2O3Or simple WO3It is big.
Due to occurring without new peak, it is not bound by any theory, inventors believe that, the reduction of absorption values is main
Because photocatalytic degradation reacts.
The UV-Vis DRS spectrum analysis of the sample of experimental example 5
Show the power of visible absorption degree the active size of catalyst indirectly according to catalyst.
This experimental example specimen in use is that embodiment 1~3 and comparative example 1~2 are obtained.
A small amount of above-mentioned photochemical catalyst sample is taken, table is carried out to each catalyst sample using UV-Vis DRS spectrometer
Levy, test wavelength 200-800nm, as a result as shown in fig. 7, wherein,
Curve a represents that embodiment 2 is obtained the UV-Vis DRS spectrum of sample；
Curve b represents that embodiment 1 is obtained the UV-Vis DRS spectrum of sample；
Curve c represents that embodiment 3 is obtained the UV-Vis DRS spectrum of sample；
Curve d represents that comparative example 2 is obtained the UV-Vis DRS spectrum of sample；
Curve e represents that comparative example 1 is obtained the UV-Vis DRS spectrum of sample.
As can be seen from Figure 7, photochemical catalyst can absorb ultraviolet light and visible ray obtained in embodiment 1~3, and simple
Fe2O3Or WO3Ultraviolet light and visible ray can also be absorbed.Appropriate Fe2O3The addition of load capacity can strengthen catalyst to visible ray
Absorption, and increase excessive Fe2O3Load capacity, on the contrary weakens absorption of the composite photo-catalyst to visible ray.
Also known from Fig. 7, photochemical catalyst obtained in embodiment 1~3 is to the absorbability order of visible ray：Embodiment 2
The absorption that sample is obtained is most strong, and embodiment 1 is obtained sample and embodiment 3 is obtained sample and absorbs and takes second place, and comparative example 2 is obtained sample suction
Receive poor, it is worst that comparative example 1 is obtained absorption of the sample to visible ray.
The visible light catalysis activity analysis of the sample of experimental example 6
This experimental example specimen in use is that embodiment 1~3 and comparative example 1~2 are obtained.
Accurate deserving to be called is stated each 0.050g of photochemical catalyst sample and is respectively placed in six quartz ampoules, and it is 40mL that volume is added according to this
Mass concentration is 5.00mgL-1Methyl orange solution, and in each quartz ampoule add a magneton of the same size.By stone
English pipe is put into photochemical reaction instrument, is all opened except not opening light source other switches, and solution carries out dark reaction 30min, time
To the rear different sample solution 6mL or so that draw in centrifuge tube, mark is carried out to it, sets centrifugation time, treat solvent with it is molten
Again in face of the supernatant liquor in the light suction pipe a small amount of centrifuge tube of absorption in the cuvette of rinse after matter separation completely, then
Its corresponding absorption values, record data is surveyed respectively.For the surplus solution in quartz ampoule, we open light source and it are carried out
Illumination reaction 15 minutes, after the time arrives, treatment during to the treatment of solution with dark reaction, light reaction operates take twice altogether
Sample, complete in order to reach precipitation, solution can again extend two or three minutes without muddiness, centrifugation time, suction pipe draw supernatant liquor in
In the cuvette of rinse, cuvette is put into absorption values, record data are surveyed in corresponding instrument.According to the gained extinction number of degrees
Value calculates degradation rate, then draws out the visible light activity figure of different catalysts sample, as a result as shown in figure 8, wherein,
Curve a represents the visible light catalysis activity result for being added without any photochemical catalyst；
Curve b represents that comparative example 2 is obtained sample visible light catalysis activity result；
Curve c represents that comparative example 1 is obtained sample visible light catalysis activity result；
Curve d represents that embodiment 1 is obtained sample visible light catalysis activity result；
Curve e represents that embodiment 2 is obtained sample visible light catalysis activity result；
Curve f represents that embodiment 3 is obtained sample visible light catalysis activity result；
Curve g represents that embodiment 4 is obtained sample visible light catalysis activity result；
Curve h represents that embodiment 5 is obtained sample visible light catalysis activity result；
Light off represent cloudy, turbid phase in Fig. 8；
Visible light on represent the visible light catalytic stage of reaction.
As shown in Figure 8, in four kinds of catalyst prepared by embodiment, with Fe2O3Content increase, photocatalytic activity
Increase therewith, but as the excessive Fe of addition2O3Photocatalytic activity can be caused on the contrary to be reduced.
Also known by Fig. 8, embodiment 2 is obtained the visible light catalysis activity highest of sample, embodiment 1 is obtained sample and takes second place,
Followed by embodiment 3 is obtained sample, the visible light catalysis activity that embodiment 4 is obtained sample is worst.
Fig. 8 shows that Photocatalytic activity order is:g>f>e>d>c>b>A, this light for having fully demonstrated after being combined is urged
The superiority of agent, and further demonstrate the conclusion of above-mentioned spectral characterization.
Influence of the scavenger of experimental example 7 to sample photocatalytic activity
This experimental example specimen in use is obtained for embodiment 2.
It is accurate to weigh the above-mentioned photocatalyst powders of 0.050g in quartz ampoule, numbering 1,2,3,4,5,6, in each quartz ampoule
In all add mass concentration (5mg/L) identical methyl orange solution.
Any scavenger is added without in the pipe that numbering is 1,5.000 μ L isopropanols are added in the pipe that numbering is 2, compiled
Number for 3 pipe in add 0.004g ammonium oxalate, numbering be 4 pipe in add 0.004g 1,4-benzoquinone, numbering be 5 Guan Zhongjia
Enter 3.800 μ L catalases, 0.005g natrium nitrosums are added in the pipe that numbering is 6.
Each Guan Zhongjun adds a magneton, and quartz ampoule is put into photochemical reaction instrument, in addition to not opening light source other
Switch is opened, and solution carries out dark treatment 30min, and after the time arrives, at the same time sampling centrifugation 20min opens light source to quartz
Surplus solution carries out illumination reaction one hour in pipe, supernatant liquor is drawn after the centrifugation time of dark reaction solution is arrived and surveys absorbance
Numerical value, record data.After light application time is arrived, associated process steps are with processing dark reaction.Can be counted according to absorbance
Calculate degradation rate, draw influence of each scavenger of addition to catalyst activity, drafting pattern, as a result as shown in figure 9,
Wherein,
Noscavenger represents and is not added with scavenger,
AO represents addition ammonium oxalate, plays h in inhibition system degradation process+The effect of generation；
BQ represents addition 1,4-benzoquinone, plays O in inhibition system degradation process2 -The effect of generation；
CAT represents addition catalase, plays H in inhibition system degradation process2O2The effect of generation；
IPA represents addition isopropanol, and OH is produced in playing a part of inhibition system degradation process；
NaNO3Represent and add sodium nitrate, play removing e-Effect.
This experiment, by introducing various free radical scavengers, is studied obtained in embodiment 2 with methyl orange as model compound
The photocatalysis mechanism of photochemical catalyst.
As seen from Figure 9, in the case where other conditions are constant, (1) adds clear compared with without scavenger
After agent, the activity of catalyst decreases；(2)NaNO3, catalase addition it is visible to catalyst activity influence
It is relatively minimal, can ignore, illustrate e during photo-catalytic degradation of methyl-orange under visible light illumination-、H2O2It is not main
Active specy；(3) in the case of other conditions identical, the influence of the addition activity visible to catalyst of isopropanol is maximum, says
OH is topmost active specy during bright photo-catalytic degradation of methyl-orange under visible light illumination；(4) isopropanol is added
(IPA), after ammonium oxalate (AO) and 1,4-benzoquinone (BQ), the activity of catalyst has a more obvious reduction, isopropanol (IPA) plus
Enter so that the activity of catalyst drops minimum.That is, OH, h+And O2 -Substantially work is played in Photocatalytic Degradation Process
With especially OH serves main in photocatalytic process.
It is not bound by any theory, inventors believe that photocatalysis principle such as Figure 10 institutes of the photochemical catalyst that the present invention is provided
Show, be specially enclosed in WO3Periphery is electron capture agent Fe2O3, it can rapidly catch electronics and prevent electronics from returning to conduction band
On, coming so as to electron-hole be efficiently separated, electronics and hole can generate active material with a series of substance reactions in addition
Hydroxyl radical free radical, superoxipe ion, then hydroxyl radical free radical, superoxipe ion and hole h+Degraded methyl is participated in jointly
The reaction of orange.
The present invention has been described in detail above in association with specific embodiment and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
Various equivalencings, modification can be carried out to technical solution of the present invention and embodiments thereof or is improved, these each fall within the present invention
In the range of.Protection scope of the present invention is determined by the appended claims.
Claims (10)
1. a kind of photochemical catalyst Fe2O3-WO3, it is characterised in that photochemical catalyst Fe described in the photochemical catalyst2O3-WO3In, based on light
The gross weight of catalyst, in terms of the weight of wherein iron oxide, the weight fraction of iron oxide is 10%~55%；And/or
According to its XRD difraction spectrum, the photochemical catalyst is in 2 θ=22.7 °, 31.7 °, 32.8 °, 40.2 °, 48.4 °, 54.5 ° of punishment
Not there is diffraction maximum, these diffraction maximums correspond respectively to (012), (104), (110), (113), (024) and (116) crystal face；With/
Or
It is the presence of more obvious absworption peak near 980cm-1 in wave number according to its infrared spectrum；And/or
After radiation of visible light 1h, the degradation rate to methyl orange reaches more than 70% for it.
2. a kind of method for preparing photochemical catalyst according to claim 1, it is characterised in that methods described includes following step
Suddenly：
Step 1, tungsten source is mixed with surface-active, and to acid is added in system, insulation reaction after intensification is molten in removing system
Agent, calcining；
Step 2, product obtained in step 1 is scattered in dispersant, to source of iron is added in system, is mixed, and after removing solvent, is forged
Burn solid content.
3. method according to claim 2, it is characterised in that
The tungsten source is tungstates, is preferably selected from sodium tungstate, ammonium tungstate, bismuth tungstate, artificial schellite, copper tungstate, wolframic acid silver etc., more excellent
Choosing is selected from sodium tungstate, ammonium tungstate, artificial schellite, most preferably sodium tungstate；And/or
The surfactant is lemon acids, citric acid ester type surfactant, preferably citric acid, citrate salt APA,
Citric acid list lauryl alcohol ester etc., preferably citric acid；And/or
The salt is inorganic acid, preferably hydrochloric acid, sulfuric acid, nitric acid etc., more preferably hydrochloric acid, and more preferably concentration is (0.5
The hydrochloric acid of~3) mol/L.
4. according to the method in claim 2 or 3, it is characterised in that in step 1,
Tungsten source is 1 with the weight ratio of surfactant:(0.8~1.5), preferably 1:(1.0~1.3), most preferably 1:1.2；
And/or
The weight in tungsten source is 1g with the volume ratio of acid:(8~20) mL, preferably 1g:(10~15) mL, such as 1g:12.3mL.
5. according to the method that one of claim 2~4 is described, it is characterised in that in step 1,
System temperature is increased to 100 DEG C~150 DEG C, preferably 110 DEG C~140 DEG C, such as 120 DEG C；And/or
Soaking time is 12~36 hours, preferably 20~30 hours, such as 24 hours.
6. according to the method that one of claim 2~5 is described, it is characterised in that in step 1,
Calcining prepares WO3Temperature be 300 DEG C~500 DEG C, preferably 350 DEG C~450 DEG C, most preferably 400 DEG C；And/or
Calcining prepares WO3Time be 2~6 hours, preferably 3~5 hours, most preferably 5 hours.
7. according to the method that one of claim 2~6 is described, it is characterised in that in step 2,
The dispersant is inorganic solvent, preferably water；And/or
The source of iron is water-soluble molysite, such as ferric nitrate or its hydrate, preferably iron chloride or its hydrate etc., nine water
Close ferric nitrate；And/or
Source of iron adds system in its aqueous solution form, it is preferable that the cumulative volume based on iron nitrate solution, with the weight of wherein ferric nitrate
Gauge, the concentration of iron nitrate solution is 1.0g/L~30g/L, preferably 2.0g/L~25g/L；And/or
Tungsten oxide obtained in step 1 is 0.45g with the weight ratio of source of iron:(0.1~3g).
8. according to the method that one of claim 2~7 is described, it is characterised in that in step 2,
Tungsten oxide is 30 DEG C~80 DEG C, preferably 40 DEG C~70 DEG C, such as 50 DEG C with the reaction temperature of source of iron；And/or
Tungsten oxide is 0.5~4 hour, preferably 1~3 hour, such as 2 hours with the reaction time of source of iron.
9. according to the method that one of claim 2~8 is described, it is characterised in that in step 2,
The temperature of calcining is 300 DEG C~500 DEG C, preferably 350 DEG C~450 DEG C, such as 400 DEG C；And/or
The time of calcining is 2~6 hours, preferably 3~5 hours, such as 4 hours.
10. photochemical catalyst according to claim 1 or the photocatalysis according to obtained in one of claim 2~9 methods described
Agent is used for the application in terms of catalytic degradation dye wastewater.
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| CN109174113A (en) * | 2018-09-28 | 2019-01-11 | 常州大学 | A kind of preparation method of ten poly- wolframic acid complex iron oxide photochemical catalysts |
| CN115245831A (en) * | 2021-04-26 | 2022-10-28 | 纳米及先进材料研发院有限公司 | Photocatalyst and method for producing same |
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| US6093676A (en) * | 1993-10-26 | 2000-07-25 | E. Heller & Company | Photocatalyst-binder compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109174113A (en) * | 2018-09-28 | 2019-01-11 | 常州大学 | A kind of preparation method of ten poly- wolframic acid complex iron oxide photochemical catalysts |
| CN115245831A (en) * | 2021-04-26 | 2022-10-28 | 纳米及先进材料研发院有限公司 | Photocatalyst and method for producing same |
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