CN107159190A - A kind of spherical bismuth tungstate load oxidation bismuth titanium oxide composite photo-catalyst and preparation method and application - Google Patents
A kind of spherical bismuth tungstate load oxidation bismuth titanium oxide composite photo-catalyst and preparation method and application Download PDFInfo
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- CN107159190A CN107159190A CN201710457562.2A CN201710457562A CN107159190A CN 107159190 A CN107159190 A CN 107159190A CN 201710457562 A CN201710457562 A CN 201710457562A CN 107159190 A CN107159190 A CN 107159190A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 16
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 16
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 230000003647 oxidation Effects 0.000 title claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 8
- JIBLGKATRGJBSB-UHFFFAOYSA-N bismuth oxygen(2-) titanium(4+) Chemical compound [Bi+3].[O-2].[Ti+4] JIBLGKATRGJBSB-UHFFFAOYSA-N 0.000 title claims abstract description 5
- 229910002115 bismuth titanate Inorganic materials 0.000 title claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 13
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 9
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 79
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 22
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000013019 agitation Methods 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 12
- 229960000583 acetic acid Drugs 0.000 claims description 11
- 239000012362 glacial acetic acid Substances 0.000 claims description 11
- 235000011187 glycerol Nutrition 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 238000004448 titration Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 238000010335 hydrothermal treatment Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000000527 sonication Methods 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 33
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 230000010718 Oxidation Activity Effects 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 125000005909 ethyl alcohol group Chemical group 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N CHCl3 Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241001634884 Cochlicopa lubricella Species 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B01J35/39—
-
- B01J35/51—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a kind of spherical bismuth tungstate load oxidation bismuth titanium oxide composite photo-catalyst and preparation method and application, the composite photo-catalyst is spherical, and using bismuth tungstate as carrier, carried with doped has the titanium oxide of bismuth oxide thereon；Bismuth tungstate, bismuth oxide, the amount ratio of the material of titanium oxide are 3 48:6:68.The composite photo-catalyst that the present invention is prepared is chondritic, with specific surface area is big, catalytic oxidation activity is high, performance is stable, reproducible, yield is high, lower-price characteristic, can be under common energy-saving lamp irradiation below catalytic degradation indoor formaldehyde to China's indoor air formaldehyde maximum permissible concentration, with significant catalytic oxidation activity.
Description
Technical field
The invention belongs to catalyst field, and in particular to a kind of spherical bismuth tungstate load oxidation bismuth-titanium oxide complex light is urged
Agent.
Background technology
Bi2WO6As a kind of new visible-light photocatalyst, energy gap is 2.7eV or so, is that one kind potentially may be used
See luminescent material.Kudo etc. utilizes Bi2WO6Catalyst photocatalytic water produces H2And O2, Zou etc. has found Bi2WO6In visible light conditions
Under being capable of effectively mineralising CHCl3And CH3The harmful substances such as CHO, and Bi2WO6Visible ray can be absorbed and its structure is closely related.
Bi2WO6It is by Bi as simplest laminated perovskite2O2 2+And WO6 2-It is alternately arranged, WO6 2-Form the class calcium of regular octahedron
Perovskite like structure, conduction band is made up of W 5d tracks, and valence band is collectively constituted by Bi 6s and O 2p tracks.Due to Bi 6s rails
The 2p orbital hybridizations of road energy and O, raise the valence band current potential of catalyst, and energy gap reduces, so as to be favorably improved catalyst
Visible light catalysis activity.
TiO2As a kind of N-type semiconductor material, because its oxidability is strong, toxicity is low, Stability Analysis of Structures and cheap,
In organic pollutant degradation, most commonly used application has been obtained in terms of self-cleaning surface and carbon dioxide reduction.But TiO2
Photochemical catalyst itself is there is also certain defect, and such as light-catalyzed reaction efficiency is low, light induced electron easily and hole-recombination, quantum yield
It is low；Band gap is relatively wide (3.0 ~ 3.2eV), can only utilize extremely least a portion of solar energy by below 400nm ultraviolet excitation
Deng.Therefore, researcher, which puts forth effort on, seeks various methods, retaining TiO2While characteristic, self shortcoming is overcome.Researcher
By to TiO2Carry out doped transition metal ionses, precious metal surface deposition, semiconductors coupling, nonmetal doping and codope etc.
Operation, improves TiO2Catalyst is to the utilization rate of visible ray, wherein due to Bi2O3Light sensitive effect thin pillar, doped with
Bi2O3TiO2Have proved to be a kind of effective ways for obtaining notable photocatalytic activity under visible light illumination.
The content of the invention
The invention aims to solve defect present in prior art to live with greater catalytic oxidation there is provided one kind
The novel photocatalyst of property.
In order to achieve the above object, the invention provides a kind of spherical bismuth tungstate (Bi2WO6) load bismuth oxide (Bi2O3)-
Titanium oxide (TiO2) composite photo-catalyst, the composite photo-catalyst is spherical, and using bismuth tungstate as carrier, carried with doped is aerobic thereon
Change the titanium oxide of bismuth；Bismuth tungstate, bismuth oxide, the amount ratio of the material of titanium oxide are 3-48:6:68, the amount ratio of preferred substance is 3-
24:6:68, the amount ratio of optimisation substance is 6:6:68.
Present invention also offers the preparation method of above-mentioned composite photo-catalyst：Absolute ethyl alcohol and glacial acetic acid are mixed, and added
Enter bismuth nitrate solid, glycerine and butyl titanate are mixed composition solution D by stirring and dissolving formation solution C, then solution C is straight
Connect and be added dropwise in solution D, stirred in titration, flower-shaped Bi is added after being added dropwise to complete2WO6Powder, through ultrasound and stewing process until
Gel is formed, then the gel is dried into grinding, and is calcined the obtained spherical Bi2WO6/Bi2O3-TiO2Composite photo-catalyst；Institute
It is 5 to state absolute ethyl alcohol, glycerine, glacial acetic acid and butyl titanate volume ratio:5:1:2, butyl titanate, bismuth nitrate and flower-shaped
Bi2WO6The amount ratio of material is 68:12:3-48, the amount ratio of preferred substance is 68:12:3-24.
Comprise the following steps that：
(1) flower-shaped Bi2WO6Preparation
Step 1：In the salpeter solution that bismuth nitrate solid is dissolved in, magnetic agitation to formation clear solution A；Again by sodium tungstate solid
It is dissolved in sodium hydroxide solution, magnetic agitation is to formation clear solution B, then solution A is slowly added dropwise into solution B, produces white
Color sediment, to form suspension, after continuing ultrasound 30min after completion of dropping, is added dropwise alkaline solution regulation pH to 6.0, and will
The suspension is transferred in stainless steel cauldron and carried out, plus distilled water is to the 80% of polytetrafluoroethylliner liner volume, and through a constant temperature
The hydro-thermal process of degree, after heat treatment terminates, flower-shaped Bi is made in natural cooling, filtering and washing, drying and grinding2WO6Powder.
Salpeter solution concentration is 4.0 mol/L in step 1, and concentration of sodium hydroxide solution is 2.0 mol/L, and the alkalescence is molten
Liquid is ammonia spirit, and concentration is 4.0 mol/L, and the amount ratio of the material of the bismuth nitrate and sodium tungstate is 2:1；Hydrothermal temperature is
160 ~ 180 DEG C, 24h insulations；Drying temperature is 80 DEG C, 6h；
(2) spherical Bi2WO6/Bi2O3-TiO2The preparation of composite photo-catalyst
Step 2：Absolute ethyl alcohol and glacial acetic acid are mixed, and add a small amount of bismuth nitrate solid, stirring and dissolving formation solution C, by third
Triol and butyl titanate mixing composition solution D, then solution C is directly instilled in solution D, stir, be added dropwise to complete in titration
After add made flower-shaped Bi in a certain amount of step 12WO6Powder, through ultrasound and stewing process until forming sol-gel, then should
Spherical Bi is made in gel drying grinding and roasting2WO6/Bi2O3-TiO2Composite photo-catalyst.
Absolute ethyl alcohol, glycerine, glacial acetic acid and butyl titanate volume ratio are 5 in step 2:5:1:2, butyl titanate,
Bismuth nitrate and flower-shaped Bi2WO6The amount ratio of material is 68:12:Bi in 3-48, i.e. gained sample2WO6/Bi2O3-TiO2Mass ratio is
0.25-4：1, preferably butyl titanate, bismuth nitrate and flower-shaped Bi2WO6The amount ratio of material is 68:12:In 3-24, i.e. gained sample
Bi2WO6/Bi2O3-TiO2Mass ratio is 0.25-2:1, butyl titanate, bismuth nitrate and flower-shaped Bi2WO6The amount ratio of material is most preferably
68:12:Bi in 6, i.e. gained sample2WO6/Bi2O3-TiO2Mass ratio is 0.5:1.Drying temperature is 80 DEG C, 6h, and calcining heat is
450~550℃、9 h。
Present invention also offers application of the above-mentioned composite photo-catalyst in degraded air in terms of organic pollution, especially exist
Application in terms of formaldehyde in indoor air of degrading.
The present invention has advantages below compared with prior art：
The composite photo-catalyst that the present invention is prepared is chondritic, with specific surface area is big, catalytic oxidation activity is high, performance
Stable, reproducible, yield is high, lower-price characteristic, can common energy-saving lamp irradiation under catalytic degradation indoor formaldehyde to I
Below state's indoor air formaldehyde maximum permissible concentration, with significant catalytic oxidation activity.Experiments verify that 0.4g catalyst exists
Under the irradiation of 36w common energy-saving lamps, reactor volume can be 0.2m by 36h3, concentration is 1.033 mg/m3Formaldehyde is down to 0.080
mg/m3Hereinafter, Indoor Air Quality standards are reached（GB/T 18883-2002）, catalytic conversion reaches 92.2%.
Brief description of the drawings
Fig. 1 is flower-shaped Bi prepared by the embodiment of the present invention 12WO6The scanning electron microscope (SEM) photograph of photochemical catalyst；
Fig. 2 is spherical Bi prepared by the embodiment of the present invention 22WO6/Bi2O3-TiO2Composite photo-catalyst scanning electron microscope (SEM) photograph；
Fig. 3 is spherical Bi prepared by the embodiment of the present invention 22WO6/Bi2O3-TiO2Composite photo-catalyst catalysis oxidation formaldehyde activity
Figure.
Embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1
Step 1：Flower-shaped Bi2WO6Preparation
The 20ml that 2.42g bismuth nitrate solids are dissolved in, 4.0mol/L HNO3In solution, magnetic agitation to formation clear solution A；
0.82g sodium tungstate solids are dissolved in 30ml, 2.0mol/L NaOH solutions again, magnetic agitation extremely forms clear solution B, then will
Solution A is slowly added dropwise into solution B, produces white depositions, to form suspension, and 30min is stirred after continuation after completion of dropping,
4.0mol/L ammoniacal liquor aqueous slkali is added dropwise and adjusts pH to 6.0, and the suspension is transferred to progress in stainless steel cauldron, plus distillation
Water is to the 80% of polytetrafluoroethylliner liner volume, and the hydro-thermal process through 160 DEG C, 24h, and after heat treatment terminates, natural cooling is taken out
Filter washing, 80 DEG C, 6h dryings, and grind obtained flower-shaped Bi2WO6Powder, its flower-shaped Bi2WO6Scanning electron microscope (SEM) photograph is as shown in Figure 1.
Step 2：Spherical Bi2WO6/Bi2O3-TiO2The preparation of composite photo-catalyst
10.0ml absolute ethyl alcohols and 2.0ml glacial acetic acid are mixed, and add 1.01g bismuth nitrate solids, stirring and dissolving formation solution
C, composition solution D is mixed by 10.0ml glycerine and 4.0ml butyl titanates, then solution C is directly instilled in solution D, side drop
Deckle is stirred, and made flower-shaped Bi in 0.36g steps 1 is added after being added dropwise to complete2WO6Powder, through ultrasound and stewing process until being formed
Sol-gel, the gel is dried through 80 DEG C, 6h, grinds to form powdery, 450 DEG C, the obtained spherical Bi of 9 h roastings2WO6/Bi2O3-TiO2
Bi in composite photo-catalyst, gained sample2WO6/Bi2O3-TiO2Mass ratio is 0.25:1.
Take the spherical Bi prepared2WO6/Bi2O3-TiO2The g of composite photo-catalyst 0.4 irradiates in 36w common energy-saving lamps
Under, reactor volume can be 0.2m by 36h3, concentration is 1.054mg/m3Formaldehyde is down to 0.182mg/m3Hereinafter, catalytic conversion
Reach 82.7%.
Embodiment 2
Step 1：Flower-shaped Bi2WO6Preparation
The 20ml that 2.42g bismuth nitrate solids are dissolved in, 4.0mol/L HNO3In solution, magnetic agitation to formation clear solution A；
0.82g sodium tungstate solids are dissolved in 30ml, 2.0mol/L NaOH solutions again, magnetic agitation extremely forms clear solution B, then will
Solution A is slowly added dropwise into solution B, produces white depositions, to form suspension, and 30min is stirred after continuation after completion of dropping,
4.0mol/L ammoniacal liquor aqueous slkali is added dropwise and adjusts pH to 6.0, and the suspension is transferred to progress in stainless steel cauldron, plus distillation
Water is to the 80% of polytetrafluoroethylliner liner volume, and the hydro-thermal process through 160 DEG C, 24h, and after heat treatment terminates, natural cooling is taken out
Filter washing, 80 DEG C, 6h dryings, and grind obtained flower-shaped Bi2WO6Powder.
Step 2：Spherical Bi2WO6/Bi2O3-TiO2The preparation of composite photo-catalyst
10.0ml absolute ethyl alcohols and 2.0ml glacial acetic acid are mixed, and add 1.01g bismuth nitrate solids, stirring and dissolving formation solution
C, composition solution D is mixed by 10.0ml glycerine and 4.0ml butyl titanates, then solution C is directly instilled in solution D, side drop
Deckle is stirred, and made flower-shaped Bi in 0.72g steps 1 is added after being added dropwise to complete2WO6Powder, through ultrasound and stewing process until being formed
Sol-gel, the gel is dried through 80 DEG C, 6h, grinds to form powdery, 450 DEG C, the obtained spherical Bi of 9 h roastings2WO6/Bi2O3-TiO2
Bi in composite photo-catalyst, gained sample2WO6/Bi2O3-TiO2Mass ratio is 0.5:1, i.e. mass ratio are 1:2, its composite catalyzing
Agent scanning electron microscope (SEM) photograph is as shown in Fig. 2 catalyst oxidation of formaldehyde activity figure is as shown in Figure 3.
Take the spherical Bi prepared2WO6/Bi2O3-TiO2The g of composite photo-catalyst 0.4 irradiates in 36w common energy-saving lamps
Under, reactor volume can be 0.2m by 36h3, concentration is 1.033 mg/m3Formaldehyde is down to 0.080 mg/m3Hereinafter, interior is reached
Air quality standard（GB/T 18883-2002）, catalytic conversion reaches 92.2%.
Embodiment 3
Step 1：Flower-shaped Bi2WO6Preparation
The 20ml that 2.42g bismuth nitrate solids are dissolved in, 4.0mol/L HNO3In solution, magnetic agitation to formation clear solution A；
0.82g sodium tungstate solids are dissolved in 30ml, 2.0mol/L NaOH solutions again, magnetic agitation extremely forms clear solution B, then will
Solution A is slowly added dropwise into solution B, produces white depositions, to form suspension, and 30min is stirred after continuation after completion of dropping,
4.0mol/L ammoniacal liquor aqueous slkali is added dropwise and adjusts pH to 6.0, and the suspension is transferred to progress in stainless steel cauldron, plus distillation
Water is to the 80% of polytetrafluoroethylliner liner volume, and the hydro-thermal process through 160 DEG C, 24h, and after heat treatment terminates, natural cooling is taken out
Filter washing, 80 DEG C, 6h dryings, and grind obtained flower-shaped Bi2WO6Powder.
Step 2：Spherical Bi2WO6/Bi2O3-TiO2The preparation of composite photo-catalyst
10.0ml absolute ethyl alcohols and 2.0ml glacial acetic acid are mixed, and add 1.01g bismuth nitrate solids, stirring and dissolving formation solution
C, composition solution D is mixed by 10.0ml glycerine and 4.0ml butyl titanates, then solution C is directly instilled in solution D, side drop
Deckle is stirred, and made flower-shaped Bi in 1.44g steps 1 is added after being added dropwise to complete2WO6Powder, through ultrasound and stewing process until being formed
Sol-gel, the gel is dried through 80 DEG C, 6h, grinds to form powdery, 550 DEG C, the obtained spherical Bi of 9 h roastings2WO6/Bi2O3-TiO2
Bi in composite photo-catalyst, gained sample2WO6/Bi2O3-TiO2Mass ratio is 1:1.
Take the spherical Bi prepared2WO6/Bi2O3-TiO2Composite photo-catalyst 0.4g 36w common energy-saving lamps irradiation under,
Reactor volume can be 0.2m by 36h3, concentration is 1.022 mg/m3Formaldehyde is down to 0.143 mg/m3Hereinafter, catalytic conversion reaches
To 86.0%.
Embodiment 4
Step 1：Flower-shaped Bi2WO6Preparation
The 20ml that 2.42g bismuth nitrate solids are dissolved in, 4.0mol/L HNO3In solution, magnetic agitation to formation clear solution A；
0.82g sodium tungstate solids are dissolved in 30ml, 2.0mol/L NaOH solutions again, magnetic agitation extremely forms clear solution B, then will
Solution A is slowly added dropwise into solution B, produces white depositions, to form suspension, and 30min is stirred after continuation after completion of dropping,
4.0mol/L ammoniacal liquor aqueous slkali is added dropwise and adjusts pH to 6.0, and the suspension is transferred to progress in stainless steel cauldron, plus distillation
Water is to the 80% of polytetrafluoroethylliner liner volume, and the hydro-thermal process through 180 DEG C, 24h, and after heat treatment terminates, natural cooling is taken out
Filter washing, 80 DEG C, 6h dryings, and grind obtained flower-shaped Bi2WO6Powder.
Step 2：Spherical Bi2WO6/Bi2O3-TiO2The preparation of composite photo-catalyst
10.0ml absolute ethyl alcohols and 2.0ml glacial acetic acid are mixed, and add 1.01g bismuth nitrate solids, stirring and dissolving formation solution
C, composition solution D is mixed by 10.0ml glycerine and 4.0ml butyl titanates, then solution C is directly instilled in solution D, side drop
Deckle is stirred, and made flower-shaped Bi in 2.88g steps 1 is added after being added dropwise to complete2WO6Powder, through ultrasound and stewing process until being formed
Sol-gel, the gel is dried through 80 DEG C, 6h, grinds to form powdery, 500 DEG C, the obtained spherical Bi of 9 h roastings2WO6/Bi2O3-TiO2
Bi in composite photo-catalyst, gained sample2WO6/Bi2O3-TiO2Mass ratio is 2:1.
Take the spherical Bi prepared2WO6/Bi2O3-TiO2The g of composite photo-catalyst 0.4 irradiates in 36w common energy-saving lamps
Under, reactor volume can be 0.2m by 36h3, concentration is 1.012 mg/m3Formaldehyde is down to 0.214 mg/m3Hereinafter, catalyzed conversion
Rate reaches 78.9%.
Embodiment 5
Step 1：Flower-shaped Bi2WO6Preparation
The 20ml that 2.42g bismuth nitrate solids are dissolved in, 4.0mol/L HNO3In solution, magnetic agitation to formation clear solution A；
0.82g sodium tungstate solids are dissolved in 30ml, 2.0mol/L NaOH solutions again, magnetic agitation extremely forms clear solution B, then will
Solution A is slowly added dropwise into solution B, produces white depositions, to form suspension, and 30min is stirred after continuation after completion of dropping,
4.0mol/L ammoniacal liquor aqueous slkali is added dropwise and adjusts pH to 6.0, and the suspension is transferred to progress in stainless steel cauldron, plus distillation
Water is to the 80% of polytetrafluoroethylliner liner volume, and the hydro-thermal process through 180 DEG C, 24h, and after heat treatment terminates, natural cooling is taken out
Filter washing, 80 DEG C, 6h dryings, and grind obtained flower-shaped Bi2WO6Powder.
Step 2：Spherical Bi2WO6/Bi2O3-TiO2The preparation of composite photo-catalyst
10.0ml absolute ethyl alcohols and 2.0ml glacial acetic acid are mixed, and add 1.01g bismuth nitrate solids, stirring and dissolving formation solution
C, composition solution D is mixed by 10.0ml glycerine and 4.0ml butyl titanates, then solution C is directly instilled in solution D, side drop
Deckle is stirred, and made flower-shaped Bi in 5.76g steps 1 is added after being added dropwise to complete2WO6Powder, through ultrasound and stewing process until being formed
Sol-gel, the gel is dried through 80 DEG C, 6h, grinds to form powdery, 500 DEG C, the obtained spherical Bi of 9 h roastings2WO6/Bi2O3-TiO2
Bi in composite photo-catalyst, gained sample2WO6/Bi2O3-TiO2Mass ratio is 4:1.
Take the spherical Bi prepared2WO6/Bi2O3-TiO2Composite photo-catalyst 0.4g 36w common energy-saving lamps irradiation under,
Reactor volume can be 0.2m by 36h3, concentration is 1.035 mg/m3Formaldehyde is down to 0.692mg/m3Hereinafter, catalytic conversion is
33.1%。
Claims (10)
1. a kind of spherical bismuth tungstate load oxidation bismuth-titanium oxide composite photo-catalyst, it is characterised in that：The composite photo-catalyst
To be spherical, using bismuth tungstate as carrier, carried with doped has the titanium oxide of bismuth oxide thereon；The bismuth tungstate, bismuth oxide, titanium oxide
The amount ratio of material is 3-48:6:68.
2. composite photo-catalyst according to claim 1, it is characterised in that：The bismuth tungstate, bismuth oxide, the thing of titanium oxide
The amount ratio of matter is 3-24:6:68.
3. composite photo-catalyst according to claim 1, it is characterised in that：The bismuth tungstate, bismuth oxide, the thing of titanium oxide
The amount ratio of matter is 3:3:34.
4. the preparation method of any composite photo-catalyst of claims 1 to 3, it is characterised in that：The preparation method includes
Following steps：Absolute ethyl alcohol and glacial acetic acid are mixed, and add bismuth nitrate solid, stirring and dissolving formation solution C, by glycerine and
Butyl titanate mixing composition solution D, then solution C is directly added dropwise in solution D, stir, add after being added dropwise to complete in titration
Enter flower-shaped Bi2WO6Powder, grinds, and be calcined obtained institute through ultrasound and stewing process up to forming gel, then by gel drying
State spherical Bi2WO6/Bi2O3-TiO2Composite photo-catalyst；The absolute ethyl alcohol, glycerine, glacial acetic acid and butyl titanate volume
Than for 5:5:1:2, butyl titanate, bismuth nitrate and flower-shaped Bi2WO6The amount ratio of material is 68:12:3-48.
5. the preparation method of composite photo-catalyst according to claim 4, it is characterised in that：The butyl titanate, nitre
Sour bismuth and flower-shaped Bi2WO6The amount ratio of material is 68:12:3-24.
6. preparation method according to claim 5, it is characterised in that：The drying temperature of the gel is 80 DEG C, during drying
Between 6h；The sintering temperature is 450 ~ 550 DEG C, and roasting time is 9 h.
7. preparation method according to claim 6, it is characterised in that：The flower-shaped Bi2WO6Powder passes through following convenient system
It is standby：In the salpeter solution that bismuth nitrate solid is dissolved in, magnetic agitation to formation clear solution A；Sodium tungstate solid is dissolved in hydrogen-oxygen
Change in sodium solution, magnetic agitation is slowly added dropwise to solution B by solution A, persistently surpassed to clear solution B is formed
Sonication, produces white depositions, to form suspension, after continuing ultrasound 30min after completion of dropping, is adjusted using alkaline solution
The suspension is transferred in stainless steel cauldron and carried out to 6.0 by pH, plus distilled water is to polytetrafluoroethylliner liner volume
80%, and hydrothermal treatment, after hydro-thermal process terminates, then through natural cooling, flower-shaped Bi is made in filtering and washing, drying and grinding2WO6Powder
End；The salpeter solution concentration is 4.0 mol/L, and concentration of sodium hydroxide solution is 2.0 mol/L；The alkaline solution is ammoniacal liquor
Solution, concentration is 4.0 mol/L；The amount ratio of the material of the bismuth nitrate and sodium tungstate is 2:1.
8. preparation method according to claim 7, it is characterised in that：The hydro-thermal process temperature is 160 ~ 180 DEG C, 24h
Insulation；The drying temperature is 80 DEG C, and drying time is 6h.
9. application of any composite photo-catalyst of claims 1 to 3 in degraded air in terms of organic pollution.
10. application according to claim 9, it is characterised in that：Composite photo-catalyst first in degraded room air
Application in terms of aldehyde.
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| CN112875751B (en) * | 2020-12-29 | 2022-09-02 | 内蒙古工业大学 | Preparation method of sulfur-doped bismuth trioxide, negative electrode material and supercapacitor |
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