CN107349942A - A kind of fluorine tungsten codope photocatalyst and preparation method thereof - Google Patents
A kind of fluorine tungsten codope photocatalyst and preparation method thereof Download PDFInfo
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- CN107349942A CN107349942A CN201710619787.3A CN201710619787A CN107349942A CN 107349942 A CN107349942 A CN 107349942A CN 201710619787 A CN201710619787 A CN 201710619787A CN 107349942 A CN107349942 A CN 107349942A
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- tungsten
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- photocatalyst
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- codope
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 64
- ZKIHCVGCBDREBT-UHFFFAOYSA-N [F].[W] Chemical compound [F].[W] ZKIHCVGCBDREBT-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910001868 water Inorganic materials 0.000 claims abstract description 33
- 238000012545 processing Methods 0.000 claims abstract description 30
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 19
- 238000007385 chemical modification Methods 0.000 claims abstract description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 16
- 230000020477 pH reduction Effects 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 15
- 230000008025 crystallization Effects 0.000 claims abstract description 15
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 15
- 239000010937 tungsten Substances 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 12
- 230000001376 precipitating effect Effects 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 23
- 239000010936 titanium Substances 0.000 claims description 22
- 229910052719 titanium Inorganic materials 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000002516 radical scavenger Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 239000000284 extract Substances 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 9
- 229930002875 chlorophyll Natural products 0.000 claims description 9
- 235000019804 chlorophyll Nutrition 0.000 claims description 9
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 claims description 9
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 9
- 238000005286 illumination Methods 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 7
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- MGKOSOIDPUKBRW-UHFFFAOYSA-H F[Ti](F)(F)(F)(F)F Chemical group F[Ti](F)(F)(F)(F)F MGKOSOIDPUKBRW-UHFFFAOYSA-H 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 9
- 239000011218 binary composite Substances 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 17
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 15
- 230000001699 photocatalysis Effects 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical group [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 238000007146 photocatalysis Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 9
- 229940012189 methyl orange Drugs 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 239000005357 flat glass Substances 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 210000001367 artery Anatomy 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 235000011837 pasties Nutrition 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 230000000391 smoking effect Effects 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- PEYVWSJAZONVQK-UHFFFAOYSA-N hydroperoxy(oxo)borane Chemical compound OOB=O PEYVWSJAZONVQK-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/90—Odorous compounds not provided for in groups B01D2257/00 - B01D2257/708
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Water Supply & Treatment (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a kind of fluorine tungsten codope photocatalyst and preparation method thereof, and preparation method includes step：A, first prepare tungsten titanium solution, precipitating reagent is added in tungsten titanium solution and forms colloidal solution；B, photoelectrocatalysis processing, photosensitizer processing or chemical modification is carried out to the colloidal solution to handle；C, the colloidal solution handled through step B is subjected to high-temperature calcination；D, remove the crystallization water and obtain solid fine grain, fluorine tungsten codope photocatalyst is then formed using acidification.Present invention addition tungsten source ultimately forms binary composite photo catalyst, reduces energy gap.The present invention also improves particle structure by means such as photosensitizer, photoelectrocatalysis or chemical modifications, forms micro- mesoporous particle, improves surface states on particles, strengthens trapping efficiency of the surface to photon.
Description
Technical field
The present invention relates to photocatalysis technology field, more particularly to a kind of fluorine tungsten codope photocatalyst and preparation method thereof.
Background technology
As a kind of new wastewater processing technology, it has shown that extensively in terms of the advanced treating of organic wastewater for photocatalysis
Wealthy application prospect, it is using thorough mineralising organic pollution as remarkable advantage and by the common concern of domestic and international researcher.Light
Catalyst is also widely used in construction and decoration market and indoor cart, and photocatalytic process is with the degraded to organic matter almost without selection
Property, can thorough mineralising organic pollution, the advantages of non-secondary pollution, equipment is simple, small investment, and effect is well etc. unique.Photocatalysis
Oxidation technology is that semiconductor catalyst will have by the very strong OH free radicals of sunshine or action of ultraviolet light generation oxidability
Organic pollutants are degraded to H2O and CO2.The technology has the degraded to organic matter is selectively low, cheap and easy to get, recyclable to repeat profit
With, operating cost is low the features such as.Traditional photocatalysis oxidation technique uses TiO2For catalyst, there is inexpensive, nontoxic, catalysis to live
Property it is high, oxidability is strong, stability is good, the characteristics of being easily recycled.
But due to TiO2Can band greater band gap (be about 3.2ev), it is necessary to which the higher ultraviolet light of energy can just make its valency
Electronics in band is stimulated, and shows photocatalytic activity.And in nature, ultraviolet radiation content in sunshine compared with
It is low, 6.5% or so of sunshine total illumination is only accounted for, it is relatively low to the utilization rate of sunshine.In addition, light induced electron and electron hole
It is compound also to cause quantum yield low, limit the application of the technology in practice.
Research finds that W-Sn deposits have good catalytic performance, wherein WO3Due to the advantages of it is cheap and is easy to get by
To favor, WO3Can band band gap it is narrower (2.4eV-2.8eV), can make full use of visible ray, but its redox ability compared with
It is weak, by changing WO3Structure can further improve photoresponse scope and photocatalysis performance with other metals are loaded.
Many researchs have been done for the properties modifying of photocatalyst material respectively by each research institute and major colleges and universities, improve it and flutter and catch
The efficiency of photon, suppress the compound of electron hole pair, it is important raising to improve the utilization rate that electronics transits to conduction band from valence band
The approach of photocatalytic activity.
Traditional photocatalyst is primarily present following defect：
1st, the property of particle and its size have a very important relation, small size nano-particle can the energy, environment,
Catalysis etc. shows more excellent property.Nano-particle is coordinated insufficient, particle diameter is small, specific surface area is big etc. due to surface atom
Make it that agglomeration can often occur often with having high surface-active, thus a kind of thermodynamic unstable system of conduct.
2nd, traditional dioxide photocatalyst titanium energy gap is in energy gap wide 3.2ev so that electronics is from valence band transition
Higher energy is needed to conduction band.Requirement to intensity of illumination just can only be in UV intensity.
3rd, guided for dioxide photocatalyst titanium structure, either crystal defect existing for anatase titanium dioxide or rutile-type
Photocatalysis effect all be limitation.
Therefore, prior art has yet to be improved and developed.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of fluorine tungsten codope photocatalyst and its system
Preparation Method, it is intended to solve the problems such as traditional photocatalyst material is unstable, photocatalysis effect is limited.
Technical scheme is as follows：
A kind of preparation method of fluorine tungsten codope photocatalyst, it is characterised in that including step：
A, first prepare tungsten titanium solution, precipitating reagent is added in tungsten titanium solution and forms colloidal solution；
B, photoelectrocatalysis processing, photosensitizer processing or chemical modification is carried out to the colloidal solution to handle；
C, the colloidal solution handled through step B is subjected to high-temperature calcination；
D, remove the crystallization water and obtain solid fine grain, fluorine tungsten codope photocatalyst is then formed using acidification.
Preferably, the tungsten titanium solution in the step A is prepared as follows：
A1, titanium source dissolved, then add scavenger, then heating preheating；
A2, heated again, then continue at reflux and flowed back；
A3, ammonium dihydrogen phosphate, tungsten source, nitric acid formation tungsten titanium solution are added in the solution that backflow obtains again.
Preferably, the photoelectrocatalysis processing in the step B specifically includes：
Using semiconductor oxide film as working electrode, platinum filament is that saturated calomel electrode is as reference electrode, light to electrode
It is 50W-100W according to intensity, photoelectrocatalysis action time is 30min or more.
Preferably, the photosensitizer processing in the step B specifically includes：
Colloidal solution 16-24h is soaked with chlorophyll extract solution, is then dried in vacuo.
Preferably, the chemical modification processing in the step B specifically includes：
Addition chemical reagent is modified colloidal solution, and the chemical reagent added is neopelex.
Preferably, the titanium source is ammonium hexa-fluorotitanate, and the tungsten source is isopolytungstate, phosphotungstic acid, silico-tungstic acid, miscellaneous gold more
Belong at least one of tungstates.
Preferably, in the step A, precipitating reagent is TMAH, ammoniacal liquor and CO (NH2)2At least one of.
Preferably, in the step C, high-temperature calcination temperature is between 600 DEG C -900 DEG C.
Preferably, in the step D, the pH after acidifying is between 4-5.
A kind of fluorine tungsten codope photocatalyst, wherein, it is made of the preparation method described in as above any one.
Beneficial effect：Present invention addition tungsten source ultimately forms binary composite photo catalyst, reduces energy gap.The present invention is also
Particle structure is improved by means such as photosensitizer, photoelectrocatalysis or chemical modifications, forms micro- mesoporous particle, improves particle surface
State, strengthen trapping efficiency of the surface to photon.
Embodiment
The present invention provides a kind of fluorine tungsten codope photocatalyst and preparation method thereof, to make the purpose of the present invention, technical scheme
And effect is clearer, clear and definite, the present invention is described in more detail below.It should be appreciated that specific implementation described herein
Example is not intended to limit the present invention only to explain the present invention.
The present invention provides a kind of preparation method of fluorine tungsten codope photocatalyst, and it includes step：
S1, first prepare tungsten titanium solution, precipitating reagent is added in tungsten titanium solution and forms colloidal solution；
S2, photoelectrocatalysis processing, photosensitizer processing or chemical modification processing are carried out to the colloidal solution；
S3, by the colloidal solution handled through step S2 carry out high-temperature calcination；
S4, the removal crystallization water obtain solid fine grain, then form fluorine tungsten codope photocatalyst using acidification.
Present invention addition precipitating reagent in tungsten titanium solution carries out precipitation and forms colloidal solution, then forms shape by surface treatment
Into micro- mesoporous particle, then calcined, decrystallize water, improves crystallinity, and last acidification forms fluorine tungsten codope photocatalyst,
That is fluorine tungsten codope quantum stage photocatalyst F-WO3-TiO2。
Preferably, the tungsten titanium solution in the step S1 is prepared as follows：
S11, titanium source dissolved, then add scavenger, then heating preheating；
S12, heated again, then continue at reflux and flowed back；
S13, ammonium dihydrogen phosphate, tungsten source, nitric acid formation tungsten titanium solution are added in the solution that backflow obtains again.
In step s 11, scavenger therein can be HBO3, count in mass ratio, it is excellent that the scavenger accounts for material rate
Elect 1-3% as, that is, the mass ratio for accounting for titanium source is 1-3%.The titanium source is preferably ammonium hexa-fluorotitanate.
In step s 12, the product that step S11 is obtained is transferred in Muffle furnace or micro-wave oven, carries out microwave preheating, preheating temperature
Then degree control is flowed back at 60~100 DEG C.For example with 2 backflows, wherein, the 1st return time is 20~30min,
Temperature is 40~60 DEG C；2nd 1~2h of return time, temperature are 60~100 DEG C.
In step s 13, addition ammonium dihydrogen phosphate, tungsten source, nitric acid are mixed, in the total solution and step S11 of mixing
Titanium source mass ratio be 1/2~3/4 between, so as to form the tungsten titanium solution of stable homogeneous.In ammonium dihydrogen phosphate, tungsten source, nitre
In the total solution of acid mixing, count in mass ratio, tungsten source accounting is more than 6/10, and ammonium dihydrogen phosphate accounting is 1/10~2/10, nitric acid
Accounting is 1/10~2/10.The tungsten source is at least one in isopolytungstate, phosphotungstic acid, silico-tungstic acid, miscellaneous polymetallic tungsten hydrochlorate
Kind.
In step sl, precipitating reagent is added in the foregoing tungsten titanium solution being prepared and forms colloidal solution.It is therein heavy
Shallow lake agent can be that precipitating reagent is TMAH, ammoniacal liquor and CO (NH2)2At least one of.I.e. described precipitating reagent include but
The part being not limited in above-claimed cpd.In addition, counting in mass ratio, the addition of precipitating reagent is not less than 2 times of titanium source quality.
In step s 2, it is surface-treated, can be specifically carried out using three kinds of modes：At photoelectrocatalysis processing, photosensitizer
These three modes are specifically described by reason or chemical modification processing below.
For first way, photoelectrocatalysis processing specifically includes：
Using semiconductor oxide film as working electrode, platinum filament is that saturated calomel electrode is as reference electrode, light to electrode
It is 50W-100W according to intensity, photoelectrocatalysis action time is 30min or more.
Using above-mentioned photoelectrocatalysis processing decorative material surface, (applied voltage 1V, error range are positive and negative 0.2V, illumination
Intensity is 50W~100W, more than photoelectrocatalysis action time 30min), improve photon and flutter the rate of catching.
For the second way, photosensitizer processing specifically includes：
Colloidal solution 16-24h is soaked with chlorophyll extract solution, is then dried in vacuo.Specifically can be first using grinding
Grinding agent (in mass ratio, quartz sand：Calcium carbonate：Acetone=1：1：1) greenery extraction chlorophyll formation chlorophyll extract solution is ground, then
The colloidal solution for making to be formed with step with chlorophyll extract solution, effect duration was at 16 to 24 hours.
For the third mode, chemical modification processing specifically includes：
Add chemical reagent and surface modification is carried out to colloidal solution, selected chemical reagent is preferably detergent alkylate sulphur
Sour sodium, the mass ratio of addition by formation colloidal solution 1/10th, a length of more than 24 hours during surface modification.
In the step S3, the colloidal solution handled through step S2 is transferred in Muffle furnace and carries out high-temperature calcination, high temperature
Calcining heat is preferably between 600 DEG C -900 DEG C；
In the step S4, remove the crystallization water and obtain solid fine grain.Specifically, attached water and the crystallization water are removed, is washed out,
So as to improve crystallinity.Finally carry out acidification and obtain fluorine tungsten codope photocatalyst, the pH after acidifying is between 4-5.Acidifying
Step can be：Add deionized water 500ml to be redissolved solid fine grain, then add the HCl that mass concentration is 20% and carry out
Acidification, form fluorine tungsten codope quantum stage photocatalyst F-WO3-TiO2High fine grain powder.
The present invention also provides a kind of fluorine tungsten codope photocatalyst, wherein, using the preparation method system described in as above any one
Into.
The technology contents of the present invention are described in detail with reference to specific embodiment.
Embodiment one:
Step 1：Selection titanium source ammonium hexa-fluorotitanate 50g be dissolved among 500ml beakers, to beaker among add 10mlHBO3
Scavenger, then continue in Muffle furnace, heating preheating, preheating temperature is 90 DEG C.
Step 2：Take out beaker and be put into heating (microwave power 800-1000w, that is, preheated) in micro-wave oven, then turn
Enter reflux to be flowed back, divide once backflow and secondary back.Preheating temperature is controlled at 80 DEG C, is then flowed back.Such as
Using 2 backflows, wherein, the 1st return time is 25min, and temperature is 45 DEG C；2nd return time 1.5h, temperature 80
℃。
Step 3：The solution of backflow is transferred to there-necked flask again, and inserts 10ml ammonium dihydrogen phosphates, 10ml phosphotungstic acids, 10ml nitre
Acid (being that analysis is pure), forms the tungsten titanium solution of stable homogeneous, is then persistently slowly stirred 1h in heat collecting type thermostatic mixer.
Step 4：Weigh 10ml ammoniacal liquor and CO (NH2)2(the two ratio is 1 to mixed liquor:1, that is, be 5ml) add above-mentioned stir
Mix in device, homogeneous precipitation, solution can slowly form stable colloidal solution.
Step 5：With 10ml Aqueous dispersions agent polyacrylic acid, it is slowly dropped into colloidal solution, rate of addition 1ml/s.
Step 6：Solution shifts：The mixing liquid that step 5 is obtained is transferred in tetrafluoroethene reactor.
Step 7：Photoelectrocatalysis processing：Solution in tetrafluoroethene reactor is transferred to the electrochemical reaction electricity prepared
Among magnetic, catalysis time 35min, intensity of illumination is 50w uviol lamps.Photoelectrocatalysis：Semiconductor oxide film is as work electricity
Pole, platinum filament are to form electrochemical cell as reference electrode to electrode saturated calomel electrode.Electric field can assist photocatalysis, subtract
Few light induced electron and the recombination rate in hole.
Step 8：Reactor solution after photoelectrocatalysis is transferred to Muffle furnace drying, preheats under the conditions of 90 DEG C, during preheating
Between be 20min, be transferred in high-temperature calcination stove calcine immediately, calcining heat be 500 DEG C, calcination time 2h.
Step 9：After calcining terminates, cool, washing, remove attached water (water of attachment) and the crystallization water, improve crystallinity.
Step 10：Add deionized water 500ml to be redissolved, then carrying out acidification, (adding 20ml mass concentrations is
20% HCl) acidifying after pH be 4.5.
Step 11：Ultimately form fluorine tungsten codope quantum stage photocatalyst F-WO3-TiO2High fine grain powder (can pass through vacuum
Drying mode obtains powder).
Embodiment two:
Step 1：Selection titanium source ammonium hexa-fluorotitanate 50g be dissolved among 500ml beakers, to beaker among add 10ml
HBO3Scavenger, then continue in Muffle furnace, heating preheating.Preheating temperature is 90 DEG C.
Step 2：Take out beaker and be put into heating (microwave power 800-1000w, that is, preheated) in micro-wave oven, then turn
Enter reflux to be flowed back, divide once backflow and secondary back.Preheating temperature is controlled at 60 DEG C, is then flowed back.Such as
Using 2 backflows, wherein, the 1st return time is 20min, and temperature is 60 DEG C；2nd return time 2h, temperature are 60 DEG C.
Step 3：The solution of backflow is transferred to there-necked flask again, and inserts 10ml ammonium dihydrogen phosphates, 10ml silico-tungstic acids, 10ml nitre
Acid (being that analysis is pure).The tungsten titanium solution of stable homogeneous is formed, is then persistently slowly stirred 1h in heat collecting type thermostatic mixer.
Step 4：Weigh 10g TMAHs solid to add in agitator, homogeneous precipitation, solution can be formed slowly surely
Determine colloidal solution.
Step 5：With 10ml Aqueous dispersions agent polyacrylamides, it is slowly dropped into colloidal solution, rate of addition 1ml/s.
Step 6：Solution shifts：The mixing liquid that step 5 is obtained is transferred in tetrafluoroethene reactor.
Step 7：Chemical modification is handled：Anion surfactant detergent alkylate sulphur is added in tetrafluoroethene reactor
Sour sodium.Neopelex and the mass ratio of titanium source are 1:30.Neopelex can effective dispersion product, help
In preventing from reuniting.
Step 8：Reactor solution after chemical modification is handled is transferred to Muffle furnace drying, is preheated under the conditions of 90 DEG C, in advance
The hot time is 20min, is transferred in high-temperature calcination stove calcines immediately, and calcining heat is 500 DEG C, calcination time 2h.
Step 9：After calcining terminates, rapid cooling, washing, attached water and the crystallization water are removed, improve crystallinity.
Step 10：Add deionized water 500ml to be redissolved, then carrying out acidification, (adding 20ml mass concentrations is
20% HCl) acidifying after pH be 5.
Step 11：Ultimately form fluorine tungsten codope quantum stage photocatalyst F-WO3-TiO2High fine grain powder.
Embodiment three:
Step 1：Selection titanium source ammonium hexa-fluorotitanate 50g be dissolved among 500ml beakers, to beaker among add 10ml
HBO3Scavenger, then continue in Muffle furnace, heating preheating, preheating temperature is 90 DEG C.
Step 2：Take out beaker and be put into heating (microwave power 800-1000w, that is, preheated) in micro-wave oven, then turn
Enter reflux to be flowed back, divide once backflow and secondary back.Preheating temperature is controlled at 100 DEG C, is then flowed back.Such as
Using 2 backflows, wherein, the 1st return time is 30min, and temperature is 40 DEG C；2nd return time 1h, temperature are 100 DEG C.
Step 3：The solution of backflow is transferred to there-necked flask again, and insert 10ml ammonium dihydrogen phosphates, 10ml isopolytungstates,
10ml nitric acid (being that analysis is pure), forms the tungsten titanium solution of stable homogeneous, then continues slowly to stir in heat collecting type thermostatic mixer
Mix 1h.
Step 4：Weigh 10g sodium hydrate solids to add in above-mentioned agitator, homogeneous precipitation, solution can slowly form stabilization
Colloidal solution.
Step 5：With Aqueous dispersions agent 10ml polyvinyl alcohol, it is slowly dropped into colloidal solution, rate of addition 1ml/s.
Step 6：Solution shifts：The mixing liquid that step 5 is obtained is transferred in tetrafluoroethene reactor.
Step 7：Photosensitizer processing：
The preparation of photosensitizer catalyst：The greenery that 5g is fresh are taken, are cleaned, middle arteries is removed, quick chopping, is put into mortar,
5g quartz sands, 5g calcium carbonate and 5m L acetone are added in mortar, is developed into pasty state at room temperature；It is green that rough leaf is obtained after filtering
Plain extract solution.The colloidal solution 24h in reactor is soaked with 5m L chlorophyll extract solution, then vacuum dried is that can obtain light afterwards
Titanium tungsten base crystal grain after sensitized treatment.
Step 8：Reactor solution after photosensitizer is handled is transferred to Muffle furnace drying, preheats, preheats under the conditions of 90 DEG C
Time is 20min, is transferred in high-temperature calcination stove calcines immediately, and calcining heat is 500 DEG C, calcination time 2h.
Step 9：After calcining terminates, rapid cooling, washing, attached water and the crystallization water are removed, improve crystallinity.
Step 10：Add deionized water 500ml to be redissolved, then carrying out acidification, (adding 20ml mass concentrations is
20% HCl) acidifying after pH be 4.
Step 11：Ultimately form fluorine tungsten codope quantum stage photocatalyst F-WO3-TiO2High fine grain powder.
Example IV:
Step 1：Selection titanium source ammonium hexa-fluorotitanate 50g be dissolved among 500ml beakers, to beaker among add 10mlHBO3
Scavenger, then continue in Muffle furnace, heating preheating, preheating temperature is 90 DEG C.
Step 2：Take out beaker and be put into heating (microwave power 800-1000w, that is, preheated) in micro-wave oven, then turn
Enter reflux to be flowed back, divide once backflow and secondary back.Preheating temperature is controlled at 70 DEG C, is then flowed back.Such as
Using 2 backflows, wherein, the 1st return time is 22min, and temperature is 50 DEG C；2nd return time 1.2h, temperature 90
℃。
Step 3：The solution of backflow is transferred to there-necked flask again, and inserts 10ml hexamethylenes, 10ml silico-tungstic acids, 10ml nitric acid
(being that analysis is pure), forms the tungsten titanium solution of stable homogeneous, is then persistently slowly stirred 1h in heat collecting type thermostatic mixer.
Step 4：Weigh 10ml ammoniacal liquor and CO (NH2)2(the two mass ratio is 1 to mixed liquor:1) add in above-mentioned agitator,
Homogeneous precipitation, solution can slowly form stable colloidal solution.
Step 5：With Aqueous dispersions agent 15ml polyacrylic acid, it is slowly dropped into colloidal solution, rate of addition 1ml/s.
Step 6：Solution shifts：The mixing liquid that step 5 is obtained is transferred in tetrafluoroethene reactor.
Step 7：Photoelectrocatalysis processing：Solution in tetrafluoroethene reactor is transferred to the electrochemical reaction electricity prepared
Among magnetic, catalysis time 30min, intensity of illumination is 50w uviol lamps.Photoelectrocatalysis：Semiconductor oxide film is as work electricity
Pole, platinum filament are to form electrochemical cell as reference electrode to electrode saturated calomel electrode.Electric field can assist photocatalysis, subtract
Few light induced electron and the recombination rate in hole.
Step 8：Reactor solution after photoelectrocatalysis is transferred to Muffle furnace drying, preheats under the conditions of 90 DEG C, during preheating
Between be 20min, be transferred in high-temperature calcination stove calcine immediately, calcining heat be 500 DEG C, calcination time 2h.
Step 9：After calcining terminates, rapid cooling, washing, attached water and the crystallization water are removed, improve crystallinity.
Step 10：Add deionized water 500ml to be redissolved, then carrying out acidification, (adding 20ml mass concentrations is
20% HCl) acidifying after pH be 4.2.
Step 11：Ultimately form fluorine tungsten codope quantum stage photocatalyst F-WO3-TiO2High fine grain powder.
Embodiment five:
Step 1：Selection titanium source ammonium hexa-fluorotitanate 50g be dissolved among 500ml beakers, to beaker among add 10mlHBO3
Scavenger, then continue in Muffle furnace, heating preheating, preheating temperature is 90 DEG C.
Step 2：Take out beaker and be put into heating (microwave power 800-1000w, that is, preheated) in micro-wave oven, then turn
Enter reflux to be flowed back, divide once backflow and secondary back.Preheating temperature is controlled at 90 DEG C, is then flowed back.Such as
Using 2 backflows, wherein, the 1st return time is 27min, and temperature is 42 DEG C；2nd return time 1.8h, temperature 65
℃。
Step 3：The solution of backflow is transferred to there-necked flask again, and insert the miscellaneous polymetallic tungsten hydrochlorate of 10ml hexamethylenes, 10ml,
10ml nitric acid (being that analysis is pure), forms the tungsten titanium solution of stable homogeneous, then continues slowly to stir in heat collecting type thermostatic mixer
Mix 1h.
Step 4：Weigh 10g TMAHs solid to add in agitator, homogeneous precipitation, solution can be formed slowly surely
Fixed colloidal solution.
Step 5：With 15ml Aqueous dispersions agent POLYPROPYLENE GLYCOLs, it is slowly dropped into colloidal solution, rate of addition 1ml/s..
Step 6：Solution shifts：The mixing liquid that step 5 is obtained is transferred in tetrafluoroethene reactor.
Step 7：Chemical modification is handled：Anion surfactant detergent alkylate sulphur is added in tetrafluoroethene reactor
Sour sodium.Neopelex and the mass ratio of titanium source are 1:30.Neopelex can effective dispersion product, help
In preventing from reuniting.
Step 8：Reactor solution after chemical modification is handled is transferred to Muffle furnace drying, is preheated under the conditions of 90 DEG C, in advance
The hot time is 20min, is transferred in high-temperature calcination stove calcines immediately, and calcining heat is 500 DEG C, calcination time 2h.
Step 9：After calcining terminates, rapid cooling, washing, attached water and the crystallization water are removed, improve crystallinity.
Step 10：Add deionized water 500ml to be redissolved, then carrying out acidification, (adding 20ml mass concentrations is
20% HCl) acidifying after pH be 5.
Step 11：Ultimately form fluorine tungsten codope quantum stage photocatalyst F-WO3-TiO2High fine grain powder.
Embodiment six:
Step 1：Selection titanium source ammonium hexa-fluorotitanate 50g be dissolved among 500ml beakers, to beaker among add 10mlHBO3
Scavenger, then continue in Muffle furnace, heating preheating, preheating temperature is 90 DEG C.
Step 2：Take out beaker and be put into heating (microwave power 800-1000w, that is, preheated) in micro-wave oven, then turn
Enter reflux to be flowed back, divide once backflow and secondary back.Preheating temperature is controlled at 75 DEG C, is then flowed back.Such as
Using 2 backflows, wherein, the 1st return time is 24min, and temperature is 55 DEG C；2nd return time 1.7h, temperature 70
℃。
Step 3：The solution of backflow is transferred to there-necked flask again, and inserts 10ml hexamethylenes, 10ml isopolytungstates, 10ml nitre
Acid (being that analysis is pure), forms the tungsten titanium solution of stable homogeneous, is then persistently slowly stirred 1h in heat collecting type thermostatic mixer.
Step 4：Weigh 10g sodium hydrate solids to add in above-mentioned agitator, homogeneous precipitation, solution can slowly form stabilization
Colloidal solution.
Step 5：With 15ml Aqueous dispersions agent polyvinyl alcohol, it is slowly dropped into colloidal solution, rate of addition 1ml/s.
Step 6：Solution shifts：The mixing liquid that step 5 is obtained is transferred in tetrafluoroethene reactor.
Step 7：Photosensitizer processing：
The preparation of photosensitizer catalyst：The greenery that 5g is fresh are taken, are cleaned, middle arteries is removed, quick chopping, is put into mortar,
5g quartz sands, 5g calcium carbonate and 5m L acetone are added in mortar, is developed into pasty state at room temperature；It is green that rough leaf is obtained after filtering
Plain extract solution.The colloidal solution 24h in reactor is soaked with 5m L chlorophyll extract solution, then vacuum dried is that can obtain light afterwards
Titanium tungsten base crystal grain after sensitized treatment.
Step 8：Reactor solution after photosensitizer is handled is transferred to Muffle furnace drying, preheats, preheats under the conditions of 90 DEG C
Time is 20min, is transferred in high-temperature calcination stove calcines immediately, and calcining heat is 500 DEG C, calcination time 2h.
Step 9：After calcining terminates, rapid cooling, washing, attached water and the crystallization water are removed, improve crystallinity.
Step 10：Add deionized water 500ml to be redissolved, then carrying out acidification, (adding 20ml mass concentrations is
20% HCl) acidifying after pH be 4.8.
Step 11：Ultimately form fluorine tungsten codope quantum stage photocatalyst F-WO3-TiO2High fine grain powder.
Embodiment seven:
Step 1：Selection titanium source ammonium hexa-fluorotitanate 50g be dissolved among 500ml beakers, to beaker among add 10mlHBO3
Scavenger, then continue in Muffle furnace, heating preheating, preheating temperature is 90 DEG C.
Step 2：Take out beaker and be put into heating (microwave power 800-1000w, that is, preheated) in micro-wave oven, then turn
Enter reflux to be flowed back, divide once backflow and secondary back.Preheating temperature is controlled at 85 DEG C, is then flowed back.Such as
Using 2 backflows, wherein, the 1st return time is 28min, and temperature is 55 DEG C；2nd return time 1.4h, temperature 72
℃。
Step 3：The solution of backflow is transferred to there-necked flask again, and inserts 10ml Solsperse 2000s, 10ml phosphotungstic acids, 10ml nitric acid
(being that analysis is pure), forms the tungsten titanium solution of stable homogeneous, is then persistently slowly stirred 1h in heat collecting type thermostatic mixer.
Step 4：Weigh 10ml ammoniacal liquor and CO (NH2)2Mixed liquor is added in above-mentioned agitator, and homogeneous precipitation, solution can be slowly
Form stable colloidal solution.
Step 5：With 10ml Aqueous dispersions agent alkylamines, it is slowly dropped into colloidal solution, rate of addition 1ml/s.
Step 6：Solution shifts：The mixing liquid that step 5 is obtained is transferred in tetrafluoroethene reactor.
Step 7：Photoelectrocatalysis processing：Solution in tetrafluoroethene reactor is transferred to the electrochemical reaction electricity prepared
Among magnetic, catalysis time 30min, intensity of illumination is 50w uviol lamps.Photoelectrocatalysis：Semiconductor oxide film is as work electricity
Pole, platinum filament are to form electrochemical cell as reference electrode to electrode saturated calomel electrode.Electric field can assist photocatalysis, subtract
Few light induced electron and the recombination rate in hole.
Step 8：Reactor solution after photoelectrocatalysis is transferred to Muffle furnace drying, preheats under the conditions of 90 DEG C, during preheating
Between be 20min, be transferred in high-temperature calcination stove calcine immediately, calcining heat be 500 DEG C, calcination time 2h.
Step 9：After calcining terminates, rapid cooling, washing, attached water and the crystallization water are removed, improve crystallinity.
Step 10：Add deionized water 500ml to be redissolved, then carrying out acidification, (adding 20ml mass concentrations is
20% HCl) acidifying after pH be 4.5.
Step 11：Ultimately form fluorine tungsten codope quantum stage photocatalyst F-WO3-TiO2High fine grain powder.
Embodiment eight:
Step 1：Selection titanium source ammonium hexa-fluorotitanate 50g be dissolved among 500ml beakers, to beaker among add 10mlHBO3
Scavenger, then continue in Muffle furnace, heating preheating, preheating temperature is 90 DEG C.
Step 2：Take out beaker and be put into heating (microwave power 800-1000w, that is, preheated) in micro-wave oven, then
It is transferred to reflux to be flowed back, divides once backflow and secondary back.Preheating temperature is controlled at 96 DEG C, is then flowed back.Example
Such as using 2 backflows, wherein, the 1st return time is 21min, and temperature is 54 DEG C；2nd return time 1.6h, temperature 78
℃。
Step 3：The solution of backflow is transferred to there-necked flask again, and inserts 10ml Solsperse 2000s, 10ml silico-tungstic acids, 10ml nitric acid
(being that analysis is pure), forms the tungsten titanium solution of stable homogeneous, is then persistently slowly stirred 1h in heat collecting type thermostatic mixer.
Step 4：Weigh 10g TMAHs solid to add in above-mentioned agitator, homogeneous precipitation, solution can slowly shape
Into stable colloidal solution.
Step 5：With 10ml Aqueous dispersions agent polyacrylic acid, it is slowly dropped into colloidal solution, rate of addition 1ml/s.
Step 6：Solution shifts：The mixing liquid that step 5 is obtained is transferred in tetrafluoroethene reactor.
Step 7：Chemical modification is handled：Anion surfactant detergent alkylate sulphur is added in tetrafluoroethene reactor
Sour sodium.Neopelex and the mass ratio of titanium source are 1:30.Neopelex can effective dispersion product, help
In preventing from reuniting.
Step 8：Reactor solution after chemical modification is handled is transferred to Muffle furnace drying, is preheated under the conditions of 90 DEG C, in advance
The hot time is 20min, is transferred in high-temperature calcination stove calcines immediately, and calcining heat is 500 DEG C, calcination time 2h.
Step 9：After calcining terminates, rapid cooling, washing, attached water and the crystallization water are removed, improve crystallinity.
Step 10：Add deionized water 500ml to be redissolved, then carrying out acidification, (adding 20ml mass concentrations is
20% HCl) acidifying after pH be 5.
Step 11：Ultimately form fluorine tungsten codope quantum stage photocatalyst F-WO3-TiO2High fine grain powder.
Embodiment nine:
Step 1：Selection titanium source ammonium hexa-fluorotitanate 50g be dissolved among 500ml beakers, to beaker among add 10ml
HBO3Scavenger, then continue in Muffle furnace, heating preheating.Preheating temperature is 90 DEG C.
Step 2：Take out beaker and be put into heating (microwave power 800-1000w, that is, preheated) in micro-wave oven, then
It is transferred to reflux to be flowed back, divides once backflow and secondary back.Preheating temperature is controlled at 66 DEG C, is then flowed back.Example
Such as using 2 backflows, wherein, the 1st return time is 26min, and temperature is 48 DEG C；2nd return time 1.3h, temperature 78
℃。
Step 3：The solution of backflow is transferred to there-necked flask again, and inserts 10ml Solsperse 2000s, 10ml isopolytungstates, 10ml
Nitric acid (being that analysis is pure).The tungsten titanium solution of stable homogeneous is formed, is then persistently slowly stirred 1h in heat collecting type thermostatic mixer.
Step 4：Weigh 10g sodium hydrate solids to add in agitator, homogeneous precipitation, solution can slowly form stable glue
Liquid solution.
Step 5：With 10ml Aqueous dispersions agent polyacrylamides, it is slowly dropped into colloidal solution, rate of addition 1ml/s.
Step 6：Solution shifts：The mixing liquid that step 5 is obtained is transferred in tetrafluoroethene reactor.
Step 7：Photosensitizer processing：
The preparation of photosensitizer catalyst：The greenery that 5g is fresh are taken, are cleaned, middle arteries is removed, quick chopping, is put into mortar,
5g quartz sands, 5g calcium carbonate and 5m L acetone are added in mortar, is developed into pasty state at room temperature；It is green that rough leaf is obtained after filtering
Plain extract solution.The colloidal solution 24h in reactor is soaked with 5m L chlorophyll extract solution, then vacuum dried is that can obtain light afterwards
Titanium tungsten base crystal grain after sensitized treatment.
Step 8：Reactor solution after photosensitizer is handled continues to be transferred to Muffle furnace drying, is preheated under the conditions of 90 DEG C,
Preheating time is 20min, is transferred in high-temperature calcination stove calcines immediately, and calcining heat is 500 DEG C, calcination time 2h.
Step 9：After calcining terminates, rapid cooling, washing, attached water and the crystallization water are removed, improve crystallinity.
Step 10：Add deionized water 500ml to be redissolved, then carrying out acidification, (adding 20ml mass concentrations is
20% HCl) acidifying after pH be 4.7.
Step 11：Ultimately form fluorine tungsten codope quantum stage photocatalyst F-WO3-TiO2High fine grain powder.
The present invention is tested to obtained fluorine tungsten codope photocatalyst.Test performance is included to nuisance formaldehyde point
Solution test, organic matter methylene blue methyl orange have carried out degradation efficiency test, bactericidal effect test, the test of smell smog.
Organic matter methyl blue methyl orange degradation efficiency, method of testing：
Experiment parameter：Cylindrical glass reactor 500ml, light source 50-300w, 25 ± 2 DEG C of Water Tank with Temp.-controlled water temperature, methyl orange
Dissolving ratio is 1：500ml, titanium dioxide concentration of ordinary dissolution are 1%.Methyl orange standard liquid mixed proportion is methyl orange solution：Two
Titanium oxide solution=10：1.
Description of test and experimental procedure
A, the experimental rig of photo-catalytic degradation of methyl-orange is cylindrical glass reactor, is positioned in Water Tank with Temp.-controlled, temperature
25 ± 2 DEG C are maintained at, light source is 50-300w high pressure ultraviolet lamps, is placed among cylindrical glass reactor, is continued in course of reaction
Aeration.
B, the methyl orange standard liquid prepared and photocatalyst powder are added in cylindrical glass reactor, it is lasting to expose
Gas, photocatalyst powder is set to be dispersed in methyl orange standard liquid, meanwhile, high pressure ultraviolet lamp is preheated, will circle after 30min
Cylindricality glass reactor is positioned in Water Tank with Temp.-controlled, and uviol lamp is placed among reactor；
C, sample afterwards at regular intervals.With the impermeable light processing of black, occur a number of sample after a few houres, contrast
The color of several groups of samples.
Methyl orange concentration is analyzed simultaneously
D, repeat experiment and repeatedly obtain concentration curve.
E, experimental result：Methyl orange change in concentration is as shown in Table 1：
Table one
For the decomposition efficiency of methylene blue.
Step 1,2 blocks of sheet glass are selected first, one piece of coating fluorine tungsten codope photocatalyst, another piece does not process.
Step 2, by 2 blocks of sheet glass all drip it is upper one drop methylene blue solution (solution concentration 1%).
Step 3,2 blocks of sheet glass are placed in illumination under ultraviolet light 50w.
Step 4, contrast 2 blocks of sheet glass on methylene blue change.
Step 5, record time.
Test result indicates that：Fluorine tungsten codope photocatalyst decomposes methylene blue completely, without doing under action of ultraviolet light
The methylene blue of processing can not be decomposed under action of ultraviolet light, specifically as shown in Table 2.
Table two
Adhesive force is analyzed：
Step 1,2 blocks of sheet glass are taken, uniformly coat fluorine tungsten codope photocatalyst and domestic traditional photocatalyst respectively.
The outward appearance of applicator in two step 2, observation sheet glass.
Applicator is dried after step 3,1~2h etc..
Interpretation of result：Traditional photocatalyst coats on, it may appear that white loaded article, and fluorine tungsten codope photocatalyst coats it
On, form a kind of nanometer film layer.Water flush clean is used after dried, desorption phenomenon occurs in traditional photocatalyst, so as to influence
Catalytic efficiency：And fluorine tungsten codope photocatalyst will not be affected by it, continue to play effectively stable photocatalysis property.
Decomposition efficiency of the fluorine tungsten codope photocatalyst to smog smoke
Experimental provision is single by magazine, symmetrical uviol lamp, sealed transparent glass container lid, smoking air pipe composition
To choke valve.
(1) smog
A, magazine internal symmetry UNICOM, external smoking are calmed the anger mouth (carry one-way throttle valve), install first internal magazine with
Completely the same uviol lamp.
B, spraying method is used on 1 uviol lamp, the photocatalyst of the spray even application present invention, another does not spray, and stands,
Stable curing film forming.
C, glass container lid is covered, connects external smoking air pipe, cigarette on point, is calmed the anger, is made in a short time as mist more
Overflow two containers.
D, ultraviolet violet light switch, observation smog are opened
E, result：Have side's smog dissipation speed of photocatalyst quickly tens seconds it is just basic disappear complete, and another be not coated with
The smog of photocatalyst or dense, nature dissipation is not belonged to substantially；Exchange the position of two container bottles, it is found that do not dissipate cigarette
Mist dissipates rapidly.As a result surface：The photocatalyst of the present invention has very strong dissipation role to smog.
(2) smoke
Tested with smog it is basically identical, unlike press flue gas after, isolate cross over pipe, two devices of isolation, after 1-2h
Open two containers and hear smell (sequentially for first hear the side for having photocatalyst) in two containers.
As a result show：Do not have side's smell of photocatalyst in what the no difference of common smoke, and have side's gas of photocatalyst
Taste is different, and excitant significantly reduces, and the photocatalyst of this explanation present invention has decomposed the organic matter in smog.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can
To be improved or converted according to the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect scope.
Claims (10)
1. a kind of preparation method of fluorine tungsten codope photocatalyst, it is characterised in that including step：
A, first prepare tungsten titanium solution, precipitating reagent is added in tungsten titanium solution and forms colloidal solution；
B, photoelectrocatalysis processing, photosensitizer processing or chemical modification is carried out to the colloidal solution to handle；
C, the colloidal solution handled through step B is subjected to high-temperature calcination；
D, remove the crystallization water and obtain solid fine grain, fluorine tungsten codope photocatalyst is then formed using acidification.
2. the preparation method of fluorine tungsten codope photocatalyst according to claim 1, it is characterised in that in the step A
Tungsten titanium solution is prepared as follows：
A1, titanium source dissolved, then add scavenger, then heating preheating；
A2, heated again, then continue at reflux and flowed back；
A3, ammonium dihydrogen phosphate, tungsten source, nitric acid formation tungsten titanium solution are added in the solution that backflow obtains again.
3. the preparation method of fluorine tungsten codope photocatalyst according to claim 1, it is characterised in that in the step B
Photoelectrocatalysis processing specifically includes：
Using semiconductor oxide film as working electrode, platinum filament is strong as reference electrode, illumination to electrode, saturated calomel electrode
It is 30min or more to spend for 50W-100W, photoelectrocatalysis action time.
4. the preparation method of fluorine tungsten codope photocatalyst according to claim 1, it is characterised in that in the step B
Photosensitizer processing specifically includes：
Colloidal solution 16-24h is soaked with chlorophyll extract solution, is then dried in vacuo.
5. the preparation method of fluorine tungsten codope photocatalyst according to claim 1, it is characterised in that in the step B
Chemical modification processing specifically includes：
Addition chemical reagent is modified colloidal solution, and the chemical reagent added is neopelex.
6. the preparation method of fluorine tungsten codope photocatalyst according to claim 2, it is characterised in that the titanium source is hexafluoro
Titanium acid ammonium, the tungsten source are at least one of isopolytungstate, phosphotungstic acid, silico-tungstic acid, miscellaneous polymetallic tungsten hydrochlorate.
7. the preparation method of fluorine tungsten codope photocatalyst according to claim 1, it is characterised in that in the step A, sink
Shallow lake agent is TMAH, ammoniacal liquor and CO (NH2)2At least one of.
8. the preparation method of fluorine tungsten codope photocatalyst according to claim 1, it is characterised in that high in the step C
Warm calcining heat is between 600 DEG C -900 DEG C.
9. the preparation method of fluorine tungsten codope photocatalyst according to claim 1, it is characterised in that in the step D, acid
PH after change is between 4-5.
10. a kind of fluorine tungsten codope photocatalyst, it is characterised in that using the preparation method as described in claim any one of 1-9
It is made.
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| US20080039770A1 (en) * | 2006-08-10 | 2008-02-14 | Medtronic, Inc. | Devices with Photocatalytic Surfaces and Uses Thereof |
| CN102000566A (en) * | 2010-10-15 | 2011-04-06 | 徐志兵 | Method for preparing photoactivated silver/titanium dioxide complex |
| CN102120182A (en) * | 2011-02-12 | 2011-07-13 | 武汉理工大学 | Method for preparing fluorine and tungste co-doped anatase type nano titanium dioxide composite powder |
| CN102139206A (en) * | 2011-01-20 | 2011-08-03 | 武汉理工大学 | Preparation method of composite photocatalyst containing nitrogen-doped titanium dioxide and zinc titanate |
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2017
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080039770A1 (en) * | 2006-08-10 | 2008-02-14 | Medtronic, Inc. | Devices with Photocatalytic Surfaces and Uses Thereof |
| CN102000566A (en) * | 2010-10-15 | 2011-04-06 | 徐志兵 | Method for preparing photoactivated silver/titanium dioxide complex |
| CN102139206A (en) * | 2011-01-20 | 2011-08-03 | 武汉理工大学 | Preparation method of composite photocatalyst containing nitrogen-doped titanium dioxide and zinc titanate |
| CN102120182A (en) * | 2011-02-12 | 2011-07-13 | 武汉理工大学 | Method for preparing fluorine and tungste co-doped anatase type nano titanium dioxide composite powder |
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