CN107497462A - A kind of bismuth stannate/silver-colored silver chlorate photocatalysis film material and preparation method thereof - Google Patents
A kind of bismuth stannate/silver-colored silver chlorate photocatalysis film material and preparation method thereof Download PDFInfo
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- CN107497462A CN107497462A CN201710440835.2A CN201710440835A CN107497462A CN 107497462 A CN107497462 A CN 107497462A CN 201710440835 A CN201710440835 A CN 201710440835A CN 107497462 A CN107497462 A CN 107497462A
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- 239000000463 material Substances 0.000 title claims abstract description 62
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 29
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 28
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 26
- 229940071182 stannate Drugs 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 title abstract 2
- 239000010408 film Substances 0.000 claims abstract description 133
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 56
- 238000004528 spin coating Methods 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 18
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000010409 thin film Substances 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000011521 glass Substances 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- ONVGIJBNBDUBCM-UHFFFAOYSA-N silver;silver Chemical compound [Ag].[Ag+] ONVGIJBNBDUBCM-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000012459 cleaning agent Substances 0.000 claims description 6
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910020462 K2SnO3 Inorganic materials 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- 239000013504 Triton X-100 Substances 0.000 claims description 5
- 229920004890 Triton X-100 Polymers 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 235000012054 meals Nutrition 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 238000007540 photo-reduction reaction Methods 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 16
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 9
- 239000000975 dye Substances 0.000 description 9
- 238000002474 experimental method 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
- 238000004458 analytical method Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 8
- 230000005855 radiation Effects 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000005357 flat glass Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
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- 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
- 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of bismuth stannate/silver-colored silver chlorate Bi2Sn2O7/ Ag AgCl photocatalysis film materials and preparation method thereof.Bismuth stannate nanometer powder is synthesized by hydro-thermal method, Bi is prepared by scattered, spin coating, sintering, deposition and photo-reduction2Sn2O7/ Ag AgCl photocatalysis film materials.The thin-film material has excellent crystallinity, dispersiveness, photoelectric properties, visible light catalysis activity and very high film strength.Bi2Sn2O7The photocatalytic activity of/Ag AgCl photocatalysis film materials is very high, and is much higher than the Bi of single-phase2Sn2O7Film.Bi2Sn2O7/ Ag AgCl photocatalysis film material specific surface areas are bigger, and the absorption to visible ray is stronger, and the separative efficiency of its electron hole is higher.
Description
Technical field
The invention belongs to photocatalysis film materials synthesis field, in particular to a kind of bismuth stannate/silver-silver chloride
Bi2Sn2O7/ Ag-AgCl photocatalysis film materials and preparation method thereof.
Background technology
Today's society, water pollution problems is more and more severeer, the health of serious threat to the mankind, influences the sustainable development of society
Exhibition.Traditional physical absorption can not effectively handle the organic pollution in water, and be chemically treated and easily cause secondary pollution.Light
Catalysis technique can have low cost, easy to operate, non-secondary pollution using the irradiation of light come the organic pollution in degradation water
The advantages of, turn into one of effective ways for solving water pollution problems.However, most of photochemical catalysts only have response to ultraviolet light,
It is low to the utilization rate of sunshine, seriously limit the application in actual industrial life.It is it is, thus, sought for visible light-responded
Photochemical catalyst.Bismuth stannate (Bi2Sn2O7) it is a kind of novel semi-conductor catalysis material, its energy gap is about 2.73eV, energy
Enough water bodys for effectively containing organic pollutants using sun light processing, have the advantages that inexpensive, nontoxic, chemical property is stable.Ag@
AgCl can absorb visible ray on a large scale, and extensive research has been caused as photochemical catalyst.The photocatalysis studied at present
Material is mostly dusty material, but dusty material can occur reunion and cause catalytic effect to reduce in actual applications, and solution
In powder be not readily separated and reclaim.Compared with dusty material, thin-film material has intensity high, is uniformly dispersed, and is easy to circulation profit
With, the advantages that facilitating is reclaimed, and the self-cleaning ability of thin-film material is strong, should with bigger reality in photocatalysis field
With value.Thin-film material, which has, to be uniformly dispersed, and specific surface area is big, the advantages that being easily recycled.
The content of the invention
The present invention is relatively low to visible light utilization efficiency for the photochemical catalyst for solving presently, there are, and fine catalyst recovery is tired
Difficulty, secondary pollution problems are easily caused, propose a kind of bismuth stannate/silver-silver chloride (Bi2Sn2O7/ Ag-AgCl) photocatalysis film
The preparation method of material, to improve feasibility of the photocatalysis in actual water treatment applications.
The present invention is achieved by the following technical solutions：
A kind of bismuth stannate/silver-silver chloride Bi2Sn2O7The preparation method of/Ag-AgCl photocatalysis film materials specifically include as
Lower step：
Step 1, nanometer Bi2Sn2O7The preparation of powder：It is 1 by mol ratio:1 bismuth nitrate and potassium stannate be mixed in from
In sub- water and continue to stir, the pH that ammoniacal liquor regulation mixed liquor is added dropwise is 12.Continue stirring 1 hour, mixed liquor is transferred to poly- four
Constant temperature thermal response is carried out in the reactor of PVF liner, obtains a nanometer Bi2Sn2O7Powder.
The cleaning of step 2, base material：The present invention uses common sheet glass as base material 15mm × 20mm, by glass
Glass substrate, which is sequentially placed into cleaning agent, ionized water and absolute ethyl alcohol, to be cleaned by ultrasonic for several times, is then dried up in air atmosphere standby.
Step 3, Bi2Sn2O7The preparation of film：Take Bi2Sn2O7Powder, Triton X-100, acetic acid and ethanol
Mixing, and it is sufficiently mixed mixed liquor.A certain amount of mixing drop is taken in the substrate of glass cleaned up, with glass bar handle
Spin coating liquid deploys, spin coating, drying, sintering, prepares Bi2Sn2O7Film.
Step 4, Bi2Sn2O7The preparation of/AgCl films：The Bi that will be prepared2Sn2O7It is molten that film is immersed in silver nitrate successively
Liquid is with hydrochloric acid, preparing Bi2Sn2O7/ AgCl films.
Step 5, Bi2Sn2O7The preparation of/Ag-AgCl films：By Bi2Sn2O7/ AgCl films, which are placed under xenon lamp, to be irradiated, system
Standby Bi2Sn2O7/ Ag-AgCl films.
Nanometer Bi described in above-mentioned steps 12Sn2O7In the preparation of powder, the mol ratio of bismuth nitrate and potassium stannate is：1:1.
The temperature of constant temperature thermal response described in above-mentioned steps 1 is 180 DEG C, reaction time 24h.
The cleaning step of base material is described in above-mentioned steps 2：Substrate of glass is put into cleaning agent first and is ultrasonically treated
30 min, then take out and be cleaned by ultrasonic 10min with deionized water again with distilled water flushing is clean, be subsequently put in absolute ethyl alcohol
It is cleaned by ultrasonic 20min.
Bi described in above-mentioned steps 32Sn2O7Bi in the preparation of film2Sn2O7Powder, Triton X-100, acetic acid
And the dosage mol ratio of ethanol is 2:1:8:13.
The finely dispersed approach of mixed liquor is set to be described in above-mentioned steps 3：Mixed liquor is placed in mortar and grinds 10 minutes so
Ultrasound 30 minutes afterwards.
The actual conditions of spin coating, drying and sintering is described in above-mentioned steps 3：1000rpm rotating speed spin coating 30 seconds, 60 DEG C
Dry 10 minutes, be then transferred in Muffle furnace in baking oven, and be warming up to 250 DEG C with 5 DEG C/min programming rate and be incubated 1 small
When.
Bi is prepared described in above-mentioned steps 42Sn2O7The step of/AgCl films is：By Bi2Sn2O7Film is immersed in silver nitrate
0.01M is placed in vacuum environment 10 minutes in solution, and the liquid of deionized water wash and remove residual is used after taking-up.Then will
It is immersed in 0.01M in hydrochloric acid, is kept for 10 minutes under vacuum environment and uses deionized water rinsing.Aforesaid operations circulation is made three times
Standby Bi2Sn2O7/ AgCl films.
Bi is prepared described in above-mentioned steps 52Sn2O7The reaction condition of/Ag-AgCl films：10 are irradiated respectively under 300W xenon lamps
Minute, 20 minutes, 30 minutes.
The present invention has distinguishing feature compared with prior art：
1st, Bi prepared by the present invention2Sn2O7/ Ag-AgCl films are uniform, and intensity is high, and stability is good, is easily recycled.
2nd, Bi prepared by the present invention2Sn2O7The catalytic degradation excellent performance of/Ag-AgCl films to organic dyestuff.
3rd, the Bi prepared2Sn2O7The preparation process of/Ag-AgCl films is green, simple to operate, actual application value
It is high.
Brief description of the drawings
Fig. 1 prepares Bi for the present invention2Sn2O7The building-up process schematic diagram of/Ag-AgCl films.
Fig. 2 is Bi2Sn2O7(BSO) film, Bi2Sn2O7/ Ag@AgCl-10 (BAA-10) film, Bi2Sn2O7/Ag@
AgCl-20 (BAA-20) films and Bi2Sn2O7The XRD spectrograms of/Ag@AgCl-30 (BAA-30) film.
Fig. 3 is Bi2Sn2O7Film and Bi2Sn2O7The scanning electron microscope (SEM) photograph of/Ag@AgCl-20 films.
Fig. 4 is glass, Bi2Sn2O7Film and three kinds of Bi2Sn2O7The UV-visible absorption spectrum of/Ag@AgCl films.
Fig. 5 is that acid red 18 (a) and the degraded figure of methyl orange (b) are catalyzed under different catalysts visible ray.
Fig. 6 is Bi2Sn2O7/ Ag@AgCl-20 films are can be by the automatical cleaning ability test result figure under light irradiation.
Fig. 7 is Bi under visible ray2Sn2O7The repeated experiment result of/Ag@AgCl-20 film catalysts acid red 18 degraded
Scheme (a)；Bi after six repetitions are tested2Sn2O7XRD spectra (b) and the SEM figure (c) of/Ag@AgCl-20 films.Wherein, contracted in figure
It is written as：BSO：Bi2Sn2O7Film, BAA-10：Bi2Sn2O7/ Ag@AgCl-10 films, BAA-20： Bi2Sn2O7/Ag@AgCl-20
Film and BAA-30：Bi2Sn2O7/ Ag@AgCl-30 films.
Fig. 8 prepares Bi to change dispersant2Sn2O7Thin-film electro subgraph.
Embodiment
Clear, complete description is carried out to the present invention with reference to embodiment, makes those skilled in the art more comprehensively geographical
The solution present invention.
The primary raw material that synthetic material of the present invention uses has：Bismuth nitrate (Bi (NO3)3·5H2O, analysis are pure), potassium stannate
(K2SnO3·3H2O, analysis it is pure), ammoniacal liquor (NH3·H2O, analysis it is pure), Triton X-100 (C8H17C6H4
(OCH2CH2)nOH (n ≈ 10), analysis it is pure), acetic acid (C2H4O2, analysis it is pure), ethanol (C2H6O, analysis are pure).
Fig. 1 prepares Bi for the present invention2Sn2O7The synthesis schematic diagram of/Ag-AgCl films, including three parts：Part I leads to
Cross hydrothermal synthesis method and prepare Bi2Sn2O7Dusty material；Part II prepares Bi on the glass substrate2Sn2O7Thin-film material；3rd
Part is to prepare Bi by deposition and photo-reduction2Sn2O7/ Ag-AgCl thin-film materials.
Embodiment 1
The present invention prepares nanometer Bi by hydrothermal synthesis method2Sn2O7Powder.Weigh 4.38g Bi (NO3)3·5H2O and
2.70 g K2SnO3·3H2Two kinds of materials are simultaneously sufficiently mixed in 90mL deionized waters by O, under magnetic stirring, by by
Ammoniacal liquor is added dropwise in drop, and the pH value of mixing liquid is adjusted into 12.Continue stirring one hour, mixture is then transferred to 200 mL's
In polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, and add deionized water to 160mL.It is warming up to 180 DEG C, keeps 24h, subsequent natural cooling,
Filter and be dried in vacuo 60 DEG C and obtain faint yellow nanometer stannic acid bismuth meal end.
The present invention use common sheet glass as base material 15mm × 20mm, due to substrate material surface easily adsorb it is miscellaneous
Matter may be to Bi2Sn2O7The performance of film has an impact, therefore substrate is cleaned before spin coating prepares film, to protect
Card prepares the film of better performances.Substrate of glass is put into cleaning agent first and is ultrasonically treated half an hour, then takes out use
Distilled water flushing is clean to be cleaned by ultrasonic 10 minutes with deionized water again, is subsequently put in absolute ethyl alcohol and is cleaned by ultrasonic 20 minutes, empty
It is standby that atmosphere encloses middle drying.
The Bi for taking 0.2g to prepare respectively2Sn2O7Powder, 0.08mL Triton X-100s, 0.06mL acetic acid and
1.0mL ethanol is ground 10 minutes in mortar.Then it is made to be sufficiently mixed and be uniformly dispersed within 30 minutes mixed liquor ultrasound.Take
A certain amount of mixing drop deploys spin coating liquid with glass bar in the substrate of glass cleaned up, makes whole surface covering full
Spin coating liquid, then with 1000rpm rotating speed spin coating 30 seconds, then the good film of spin coating is placed in 60 DEG C of baking ovens and dries 10 points
Clock, it is then transferred in Muffle furnace, and is warming up to 250 DEG C with 5 DEG C/min heating rate and is incubated 1 hour, you can obtains uniformly
Bi2Sn2O7Film.
The Bi that will be prepared2Sn2O7Film is immersed in 0.01M in silver nitrate solution and is placed in vacuum environment 10 minutes (very
Altitude can make Ag+In infiltration film as much as possible), with the liquid of deionized water wash and remove residual after taking-up.Then
0.01M in hydrochloric acid is immersed in, is kept for 10 minutes under vacuum environment and uses deionized water rinsing.Aforesaid operations circulate three times
Prepare Bi2Sn2O7/ AgCl films.Finally by Bi2Sn2O7/ AgCl films, which are placed under 300W xenon lamps, to be irradiated, and prepares Bi2Sn2O7/
Ag-AgCl films.The sample being prepared is labeled as Bi2Sn2O7/ Ag-AgCl-n, wherein " n " represents photo-reduction time difference
For 10 minutes, 20 minutes, 30 minutes.
Above is Bi in embodiment 12Sn2O7The preparation process of/Ag-AgCl films, the present invention are carried out to prepared film
A series of signs are as a result as follows.
Fig. 2 is Bi2Sn2O7Film, Bi2Sn2O7/ Ag@AgCl-10 films, Bi2Sn2O7/ Ag@AgCl-20 films and
Bi2Sn2O7The XRD spectra of/Ag@AgCl-30 films.Wherein Bi2Sn2O7The diffraction maximum of film and standard card No. 87-0284
Matching completely, that illustrate to be prepared is the Bi of cube crystalline phase2Sn2O7Crystal.Three kinds of Bi2Sn2O7/ Ag@AgCl films it is main
Diffraction maximum is apparent and sharp, with Bi2Sn2O7, cube crystalline phase AgCl (JCPDS 31-1238) and elemental silver (JCPDS
No.04-0783 standard card) matches, it was demonstrated that Bi2Sn2O7With the compound successes of Ag AgCl.It is in addition, not any in spectrogram
Impurity peaks, illustrate the photocatalysis film material free from admixture prepared.
Fig. 3 is Bi2Sn2O7Film and Bi2Sn2O7The surface sweeping electromicroscopic photograph of/Ag@AgCl-20 films.Can from Fig. 3 a and 3b
To find out Bi2Sn2O7Film is made up of a large amount of finely dispersed spheric granules, and its film surface is smooth, even particle size, grain
Footpath is about 50nm.Gap and duct between particle be present and form porous membrane structure.This loose structure can make functional material
Into wherein.Bi2Sn2O7There are the Ag@AgCl particles that diameter is about 400nm to cause film surface thick in/Ag@AgCl-20 films
Rough (Fig. 3 c and 3d).Observe Bi2Sn2O7The section SEM photograph (such as Fig. 3 e) of film is it can be seen that film thickness is about 1.3 μm.
Fig. 4 is glass, Bi2Sn2O7Film and three kinds of Bi2Sn2O7The uv-visible absorption spectra of/Ag@AgCl films.Its
Middle glass pair can not absorb light, and all film catalysts have certain absorption to visible ray.With Bi2Sn2O7Film
Compare, Bi2Sn2O7Absorption of/Ag AgCl the films to visible ray has apparent enhancing phenomenon, illustrates that it has engine dyeing in catalysis
Expect higher to the utilization rate of visible ray in degradation process.From the embedded figure in Fig. 4 as can be seen that Bi2Sn2O7/Ag@AgCl-20
Absorption of the film to visible ray is most strong, illustrates that it maximally effective can carry out catalytic reaction using visible ray.
Acid red 18 studies the visible light catalytic performance of thin-film material with methyl orange as target degradation product, and photocatalysis is real
It is photochemical catalyst that a piece of membrane material is taken in testing, and the dyestuff 5mg/L for taking 20mL is target degradation product.Light source is that 300W xenon lamps are furnished with
420nm filter plates, photocatalysis experiment are carried out at room temperature.First reaction system is placed in stir 30 minutes in dark surrounds and reached
To adsorption equilibrium, then open light source and carry out light-catalyzed reaction.1mL mixing is taken out from system within every 5 minutes in course of reaction
Liquid, detect the concentration of dyestuff using ultraviolet-visible spectrophotometer after centrifugation and its degraded situation is analyzed with this.
Fig. 5 be different catalysts visible ray under be catalyzed acid red 18 (a) and methyl orange (b) degraded situation, wherein C0It is
The initial concentration of dyestuff, C are the concentration that dyestuff passes through radiation of visible light certain time.Meanwhile we have studied do not urging
The degraded situation certainly of acid red 18 and methyl orange under radiation of visible light, as a result shows radiation of visible light 75 minutes in the presence of agent
Acid red 18 or the latter two dyestuff of 150 minutes methyl orange are all hardly degraded.In Bi2Sn2O7When film is as catalyst,
The degradation rate of acid red 18 is 41.2%, and the degradation rate of methyl orange is 30.3%.But in Bi2Sn2O7/ Ag@AgCl-10 films
Or Bi2Sn2O7When/Ag@AgCl-30 films are as catalyst, degradation rate of the acid red 18 after radiation of visible light 75 minutes
Respectively reach 68% and 86%, and methyl orange degradation rate after radiation of visible light 150 minutes reaches 68% and 88%.In addition,
Bi2Sn2O7In the presence of/Ag@AgCl-20 films, degradation rate all highests of two kinds of dyestuffs, respectively 99.8% (acid red 18) and
99.5% (methyl orange).It can be seen that Bi2Sn2O7The photocatalytic activity of/Ag@AgCl films is apparently higher than single-phase Bi2Sn2O7
Film, and Bi2Sn2O7The catalytic activity highest of/Ag@AgCl-20 films.
To investigate the automatical cleaning ability of the membrane material prepared by the present invention, take 0.1mL, 10mg/L acid red 18s drip in
Bi2Sn2O7/ Ag-AgCl-20 film surfaces, the change feelings with radiation of visible light, contrasting drop are respectively placed in dark surrounds
Condition.
Fig. 6 is Bi2Sn2O7The automatical cleaning ability test of/Ag@AgCl-20 films under visible light illumination.In experiment, take
0.1mL, 10mg/L acid red 18 are dripped in film surface (Fig. 6 a).Fig. 6 b and 6c is to put the film after drop acid red 18 respectively
In dark surrounds spontaneously dry or radiation of visible light 10 minutes under conditions of dyestuff situation of change.Contrast two figures it can be found that
The acid red 18 that film surface adheres under radiation of visible light can decompose completely, illustrate Bi2Sn2O7/ Ag@AgCl-20 film materials
Material has very strong automatical cleaning ability under visible light.This causes many aspects of the thin-film material in real life all to have very
High application value.Bi can be prepared in the glass surface of large area2Sn2O7/ Ag@AgCl films, are placed on solar irradiation
The water bottom containing organic pollution of flowing under penetrating, with the flowing of water body, film can be constantly in catalytic degradation water
Pollutant, so as to reach the purpose for removing pollutant, and thin-film material is easy to reclaim and recycled, and will not cause two
Secondary pollution.
In order to study the stability of film, the present invention is taken with a piece of Bi2Sn2O7/ Ag@AgCl-20 films, continuous 6 leachings
Enter in acid red 18 solution 20mL, 5mg/L.Survey the degraded situation of its six times catalysis acid red 18s., will after experiment terminates every time
Film reclaims, and is fully washed with deionized water, enters after being dried in vacuo under normal temperature 2 hours as catalyst in identical environment
Row next time test by photocatalytic degradation.The degraded situation of methyl orange in six experiments of analysis.
Fig. 7 is Bi under visible ray2Sn2O7The repeated experiment result of/Ag@AgCl-20 film catalysts acid red 18 degraded.
In six repetitions are tested it can be seen from Fig. 7 a, Bi2Sn2O7The catalytic activity of/Ag@AgCl-20 films does not almost reduce,
The crystal structure and pattern for repeating the rear film of experiment are tested by XRD and SEM.Observe Fig. 7 b to understand, carry out light and urge
After changing experiment, the XRD characteristic peaks of sample do not have any change, illustrate that the crystal structure of catalyst does not have in catalytic process
Any destruction.Observation SEM photograph (Fig. 7 c) is it can be found that catalyst keeps its original pattern constant, and analysis can more than
To infer, testing the film sample of preparation has excellent visible light catalysis activity and stability, and thin-film material intensity is very
Height, there is practicality.
Embodiment 2
In order to contrast, stannic acid bismuth thin film is prepared using different dispersant bismuth stannate powder.Wherein bismuth stannate powder is same
Sample is prepared by hydrothermal synthesis method.Weigh 4.38g Bi (NO3)3·5H2O and 2.70g K2SnO3·3H2O and by two kinds
Material is sufficiently mixed in 90mL deionized waters, under magnetic stirring, by the way that ammoniacal liquor is added dropwise dropwise, by the pH value of mixing liquid
It is adjusted to 12.Continue stirring one hour, then mixture is transferred in 200mL polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, and add
Deionized water is to 160mL.180 DEG C are warming up to, keeps 24h, 60 DEG C of subsequent natural cooling, suction filtration and vacuum drying obtain yellowish
Color nanometer stannic acid bismuth meal end.
Common sheet glass is used as base material 15mm × 20mm, because the easy adsorbing contaminant of substrate material surface may
To Bi2Sn2O7The performance of film has an impact, therefore substrate is cleaned before spin coating prepares film, to ensure to prepare
Go out the film of better performances.Substrate of glass is put into cleaning agent first and is ultrasonically treated half an hour, then takes out and uses distilled water
Rinse well and be cleaned by ultrasonic 10 minutes with deionized water again, be subsequently put in absolute ethyl alcohol and be cleaned by ultrasonic 20 minutes, air atmosphere
Middle drying is standby.
The Bi for taking 0.2g to prepare respectively2Sn2O7Powder, 0.08mL Triton X-100s and 1.0mL ethanol are in grinding
Ground 10 minutes in alms bowl.Then it is made to be sufficiently mixed and be uniformly dispersed within 30 minutes mixed liquor ultrasound.Take a certain amount of mixed liquor
Drip in the substrate of glass cleaned up, spin coating liquid deployed with glass bar, make the full spin coating liquid of whole surface covering, then with
1000rpm rotating speed spin coating 30 seconds, then the good film of spin coating is placed in 60 DEG C of baking ovens and dried 10 minutes, is then transferred to horse
Not in stove, and it is warming up to 250 DEG C with 5 DEG C/min heating rate and is incubated 1 hour, you can obtains Bi2Sn2O7Film.
Fig. 8 is the Bi prepared using the dispersant2Sn2O7Film photo, it is found that thin-film material surface is not uniform enough
It is smooth, there is granular sensation, be inferred to that the structure of material is uneven, and distribution of pores is irregular, be unfavorable for photocatalytically degradating organic dye
Absorption and decomposition in experiment to noxious material, therefore such a dispersant is not suitable for preparing Bi2Sn2O7Film.
Embodiment 3
In order to contrast, stannic acid bismuth thin film is prepared using different dispersant bismuth stannate powder.Wherein bismuth stannate powder is same
Sample is prepared by hydrothermal synthesis method.Weigh 4.38g Bi (NO3)3·5H2O and 2.70g K2SnO3·3H2O and by two kinds
Material is sufficiently mixed in 90mL deionized waters, under magnetic stirring, by the way that ammoniacal liquor is added dropwise dropwise, by the pH value of mixing liquid
It is adjusted to 12.Continue stirring one hour, then mixture is transferred in 200mL polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, and add
Deionized water is to 160mL.180 DEG C are warming up to, keeps 24h, 60 DEG C of subsequent natural cooling, suction filtration and vacuum drying obtain yellowish
Color nanometer stannic acid bismuth meal end.
Common sheet glass is used as base material 15mm × 20mm, because the easy adsorbing contaminant of substrate material surface may
To Bi2Sn2O7The performance of film has an impact, therefore substrate is cleaned before spin coating prepares film, to ensure to prepare
Go out the film of better performances.Substrate of glass is put into cleaning agent first and is ultrasonically treated half an hour, then takes out and uses distilled water
Rinse well and be cleaned by ultrasonic 10 minutes with deionized water again, be subsequently put in absolute ethyl alcohol and be cleaned by ultrasonic 20 minutes, air atmosphere
Middle drying is standby.
The Bi for taking 0.2g to prepare respectively2Sn2O7Powder, 1mL isopropanols are ground 10 minutes in mortar.Then by mixed liquor
Ultrasound makes it be sufficiently mixed and be uniformly dispersed in 30 minutes.A certain amount of mixing drop is taken to be used in the substrate of glass cleaned up
Glass bar deploys spin coating liquid, makes the full spin coating liquid of whole surface covering, then with 1000rpm rotating speed spin coating 30 seconds, then will
The good film of spin coating is placed in 60 DEG C of baking ovens and dried 10 minutes, is then transferred in Muffle furnace, and with 5 DEG C/min heating rate
It is warming up to 250 DEG C and is incubated 1 hour, you can obtains Bi2Sn2O7Film.
As a result the Bi prepared using the dispersant is shown2Sn2O7Film strength is very low, and it is poor to be combined with base material, immerses water
Middle film is easily destroyed, it is impossible to be used in photocatalytically degradating organic dye, therefore such a dispersant is not suitable for preparing Bi2Sn2O7
Film.
Claims (10)
1. a kind of bismuth stannate/silver-silver chloride photocatalysis film material, it is characterised in that the bismuth stannate/silver-silver chloride light is urged
Change thin-film material to be made by lower step：
Step 1, prepare nanometer Bi2Sn2O7Powder：Reaction solution is prepared, carries out constant temperature thermal response, subsequent natural cooling, suction filtration and true
Sky dries 60 DEG C and obtains faint yellow nanometer stannic acid bismuth meal end；
Step 2, cleaning glass substrate material；
Step 3, prepare Bi2Sn2O7Film：By Bi2Sn2O7Powder, Triton X-100, acetic acid and ethanol mixed preparing
Bi2Sn2O7Dispersion liquid, drip in substrate of glass, and spin coating liquid is deployed with glass bar, spin coating, drying, sintering, be made
Bi2Sn2O7Film；
Step 4, prepare Bi2Sn2O7/ AgCl films：The Bi that will be prepared2Sn2O7Film is immersed in silver nitrate solution and salt successively
In acid, Bi is prepared2Sn2O7/ AgCl films；
Step 5, prepare Bi2Sn2O7/ Ag-AgCl films：By Bi2Sn2O7/ AgCl films, which are placed under xenon lamp, to be irradiated, and is prepared
Bi2Sn2O7/ Ag-AgCl films.
A kind of 2. bismuth stannate according to claim 1/silver-silver chloride photocatalysis film material, it is characterised in that step 1
It is middle to prepare concretely comprising the following steps for reaction solution：It is 1 to take mol ratio:1 Bi (NO3)3·5H2O and K2SnO3·3H2O, and be sufficiently mixed
In deionized water, under magnetic stirring, by the way that ammoniacal liquor is added dropwise dropwise, the pH value of mixing liquid is adjusted to 12, and stir 1h.
A kind of 3. bismuth stannate according to claim 1/silver-silver chloride photocatalysis film material, it is characterised in that step 1
In, constant temperature heating reaction temperature is 180 DEG C, reaction time 24h.
A kind of 4. bismuth stannate according to claim 1/silver-silver chloride photocatalysis film material, it is characterised in that step 2
In, base material is simple glass, and size is 15 × 20mm.
A kind of 5. bismuth stannate according to claim 1/silver-silver chloride photocatalysis film material, it is characterised in that step 2
In, the cleaning method step of base material is substrate of glass to be put into cleaning agent be ultrasonically treated 30min first, then taken out
It is cleaned by ultrasonic 10min with deionized water again with distilled water flushing is clean, is subsequently put in absolute ethyl alcohol and is cleaned by ultrasonic 20min, it is empty
It is standby that atmosphere encloses middle drying.
A kind of 6. bismuth stannate according to claim 1/silver-silver chloride photocatalysis film material, it is characterised in that step 3
In, it is 2 according to mol ratio:1:8:13 ratio, takes Bi2Sn2O7Powder, Triton X-100, acetic acid and ethanol, and
It is set to be sufficiently mixed and be uniformly dispersed to form Bi2Sn2O7Dispersion liquid.
A kind of 7. bismuth stannate according to claim 1/silver-silver chloride photocatalysis film material, it is characterised in that step 3
In, the actual conditions of spin coating, drying and sintering is described in step 3：1000rpm rotating speed spin coating 30 seconds, dry in 60 DEG C of baking ovens
10 minutes, then be warming up to 250 DEG C with 5 DEG C/min programming rate and be incubated 1 hour.
A kind of 8. bismuth stannate according to claim 1/silver-silver chloride photocatalysis film material, it is characterised in that step 4
In, the concentration of silver nitrate solution and hydrochloric acid is 0.01M, and it is 10 minutes to immerse the time, and circulation is immersed three times.
A kind of 9. bismuth stannate according to claim 1/silver-silver chloride photocatalysis film material, it is characterised in that step 5
In, described preparation Bi2Sn2O7The reaction condition of/Ag-AgCl films：10-30min is irradiated respectively under 300W xenon lamps.
A kind of 10. preparation method of bismuth stannate based on described in claim 1-9/silver-silver chloride photocatalysis film material.
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| CN105618037A (en) * | 2015-12-25 | 2016-06-01 | 西北大学 | Titanium dioxide-silver composite photocatalysis film and preparing method and application thereof |
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| CN114515590A (en) * | 2022-03-11 | 2022-05-20 | 西安建筑科技大学 | Heterogeneous photocatalytic material and preparation and application thereof |
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