CN108126713A - Photochemical catalyst based on pole narrow-band semiconductor for solid conduction channel and its preparation method and application - Google Patents
Photochemical catalyst based on pole narrow-band semiconductor for solid conduction channel and its preparation method and application Download PDFInfo
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- CN108126713A CN108126713A CN201810106907.4A CN201810106907A CN108126713A CN 108126713 A CN108126713 A CN 108126713A CN 201810106907 A CN201810106907 A CN 201810106907A CN 108126713 A CN108126713 A CN 108126713A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 239000004065 semiconductor Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000007787 solid Substances 0.000 title claims abstract description 18
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 claims abstract description 85
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 34
- 230000001699 photocatalysis Effects 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000013049 sediment Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- 229910020462 K2SnO3 Inorganic materials 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 239000011858 nanopowder Substances 0.000 claims 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 19
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 16
- 238000007146 photocatalysis Methods 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000003911 water pollution Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 210000000746 body region Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- -1 rare-earth ion Chemical class 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910020923 Sn-O Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000002864 food coloring agent Nutrition 0.000 description 1
- 235000019249 food preservative Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 208000005135 methemoglobinemia Diseases 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to based on the photochemical catalyst of pole narrow-band semiconductor for solid conduction channel and its preparation method and application.It is prepared by colloidal sol hydro-thermal and method for calcinating, in Er3+：Y3Al5O12@NiGa2O4And Bi2Sn2O7Between be inserted into a pole narrow gap semiconductor CoS2, form a novel Z-type photocatalytic system.The photocatalytic activity of the photochemical catalyst of preparation passes through the assessment that is converted to nitrite and sulphite under being irradiated in simulated solar irradiation.The result shows that prepared Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Composite material shows highly stable photocatalytic activity in nitrite and sulphite conversion process.
Description
Technical field
The invention belongs to photocatalysis fields, are specifically related to a kind of based on the light that pole narrow-band semiconductor is solid conduction channel
Catalyst Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Preparation method and in photocatalytic conversion nitrite and sulfurous
Application in hydrochlorate.
Background technology
Water is that human lives and production activity are indispensable.In the modern life, due to industrial wastewater and sanitary sewage
It flows into river and lake, water pollution is serious.Water pollution directly endangers human health, and huge negative shadow is caused to social life
It rings.Wherein, the nitrite of surface water and groundwater and sulphite staining are very serious.This urgent Pollution Crisis
Global concern is caused.Nitrite can be used as food color and preservative, essentially from food industrial wastewater.
Underground water containing high concentration nitrite can cause human body methemoglobinemia occur, cause feeblemindedness even dead
It dies.Sulphite is essentially from papermaking, process hides, pharmacy, staple fibre, the waste water of metal plating waste water discharge.Not only influence water
Matter, and with the increase of acidity, can also generate sulfur dioxide, further pollute environment.Nitrite and sulfite content
The excessively high immune system that can destroy aquatic animal, induces various diseases.The processing of nitrite and sulphite is studied for protecting
Shield and improvement environment have important practical significance.Therefore, it is necessary to containing for water nitrite and sulphite is reduced as far as possible
Amount.Various processing methods are developed to processing nitrite and sulphite, and if electronics is dialysed, reverse osmosis, ionic membrane is raw
Object degradation and photocatalysis technology etc..In all methods, photocatalysis is considered as a kind of feasible and promising water pollution
Treatment technology.
Z-type photocatalytic system can have stronger oxidisability and stronger reproducibility simultaneously through suitably modified.Two
The combination of suitable gap semiconductor and the introducing of appropriate electron channel can control the compound of photo-generate electron-hole pair and
Expand the response range of light, be very suitable for the sunlight photocatalysis conversion of nitrite and sulphite.Select suitable band gap
The semiconductor light-catalyst of structure is of great significance.NiGa2O4With wider 3.54eV band gap, high-energy can be absorbed
Sunlight, and due to relatively negative conduction band and with stronger reproducibility.Bi2Sn2O7Narrow band gap with 2.79eV can be inhaled
The sunlight of low energy is received, and there is strong oxidizing property due to the valence band of corrigendum.In NiGa2O4/Bi2Sn2O7Photocatalytic system
In, it can be seen that NiGa2O4Valence band and Bi2Sn2O7Conduction band be closer to.In addition, NiGa2O4As wide band gap semiconducter,
It could only be excited under ultraviolet light (λ≤350nm), and ultraviolet light only accounts for the sub-fraction of sunlight.Which has limited
NiGa2O4Application in nitrite and sulphite photocatalytic conversion.
Invention content
In order to accelerate electron transfer rate, present invention design synthesis is a kind of by pole narrow-band semiconductor CoS2As conductive channel
To efficiently separate the NEW TYPE OF COMPOSITE photochemical catalyst Er of light induced electron and hole3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7.This
Compound involved by invention belongs to novel Z-type semiconductor light-catalyst, is applied to while converts nitrite and sulfurous acid
Salt is simultaneously generated in ammonium sulfate fertilizer, easy to operate, pollution-free, catalyst stability is good, is easily isolated.
The technical solution adopted by the present invention is：It is described based on the photochemical catalyst that pole narrow-band semiconductor is solid conduction channel
For the photochemical catalyst of solid conduction channel be Er based on pole narrow-band semiconductor3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7。
The above-mentioned preparation method based on the photochemical catalyst that pole narrow-band semiconductor is solid conduction channel, including walking as follows
Suddenly：By appropriate Er3+:Y3Al5O12@NiGa2O4/CoS2Nanometer powder and Bi2Sn2O7Nanometer powder is added in absolute ethyl alcohol, is surpassed
Sound disperses, and the heating of gained suspension is boiled, and the constant temperature 30-40min at 100 DEG C, filtration drying, gained powder is finely ground, in Muffle
In stove, taken out after 200 DEG C of calcining 2.0h, grind, obtain Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7。
Above-mentioned preparation method, the Er3+:Y3Al5O12@NiGa2O4/CoS2Preparation method is：In Er3+:
Y3Al5O12@NiGa2O4Appropriate absolute ethyl alcohol is added in nanometer powder, ultrasonic disperse at 40-60 DEG C, is mixed with magnetic stirring apparatus
It closes uniformly, CoS is added in after stirring half an hour2Then powder is cleaned with absolute ethyl alcohol and distilled water, after centrifugal drying, be put into horse
Not in stove, taken out after roasting 2h at 500 DEG C, grind, obtain Er3+:Y3Al5O12@NiGa2O4/CoS2Nanometer powder.
Above-mentioned preparation method, the Er3+:Y3Al5O12@NiGa2O4The preparation method of nanometer powder includes following step
Suddenly：By Ga2O3Solid is added in nickel nitrate solution, and the mixed liquor of generation adjusts pH to 12, then adds in Er3+:Y3Al5O12After
Continuous stirring 20min, obtained aaerosol solution are transferred in reaction kettle, react 48h at 180 DEG C, be cooled to room temperature, obtain sediment
It is cleaned with deionized water, then dries 8h at 80 DEG C, obtain Er3+:Y3Al5O12@NiGa2O4Powder, powder is finely ground, 500
DEG C Muffle furnace in, roast 2h, it is ground to get to Er again after taking-up3+:Y3Al5O12@NiGa2O4Nanometer powder.
Above-mentioned preparation method, the CoS2Preparation method is：By appropriate CoCl2And Na2S2O3It is dissolved in deionized water
In, ultrasound 30 minutes, obtained aaerosol solution is transferred in reaction kettle, is reacted 16h at 200 DEG C, is cooled to room temperature, is precipitated
Object is cleaned with deionized water, is then dried 8 hours at 60 DEG C, is obtained CoS2Powder.
Above-mentioned preparation method, the Bi2Sn2O7Preparation method is：By appropriate Bi (NO3)3·5H2O and K2SnO3·
3H2O is mixed in deionized water, adjusts PH=12 while stirring, ultrasound 30 minutes, the reaction was complete to promote it.What is obtained is outstanding
Floating solution is transferred in reaction kettle, is reacted for 24 hours, is cooled to room temperature at 180 DEG C, is obtained sediment and is cleaned with deionized water, then
It is dried 8 hours at 60 DEG C, obtains Bi2Sn2O7Powder.
It is above-mentioned based on pole narrow-band semiconductor for solid conduction channel photochemical catalyst in photocatalytic conversion nitrite and
Application in sulphite.Method is as follows：In the aqueous solution containing nitrite and sulphite, irradiated with 500W xenon lamps,
Light application time is 4.0h.
It is above-mentioned based on pole narrow-band semiconductor be solid conduction channel photochemical catalyst Er3+:Y3Al5O12@NiGa2O4/CoS2/
Bi2Sn2O7Under simulated solar irradiation irradiation, the process analysis procedure analysis of nitrite and sulphite is converted：Due to NiGa2O4Valence band with
Bi2Sn2O7Conduction band current potential is close, Bi2Sn2O7Conduction band electron is easily transferred to NiGa2O4On valence band hole.But in order to further
Improve their transfer rate.The present invention has been selected the narrower CoS of bandwidth2As solid conduction channel.NiGa2O4In valence band
Electronics have very strong reducing power, it can make the NO with certain oxidisability2 -Reduction, generates NH respectively4 +And N2.Tool
The product of body depends on pH, and acid conditions of the pH less than 7 easily generates NH4 +Ion, alkaline condition of the pH value more than 7 easily generate
N2.Simultaneously in Bi2Sn2O7Valence band on SO3 2-It is SO by the Hole oxidation in valence band4 2-, can be with the NH of generation4 +With reference to generation
Ammonium sulfate ((NH4)2SO4).Actually in NO2 -And SO3 2-In processing procedure, ultimately generate containing ammonium sulfate ((NH4)2SO4) water
Solution can directly be used by proper treatment as chemical fertilizer.
Beneficial effects of the present invention：
Er prepared by the present invention3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Photochemical catalyst property is stablized, and high temperature resistant is resistance to
Acid and alkali corrosion, with simple Er3+:Y3Al5O12@NiGa2O4And Bi2Sn2O7It compares, catalyst of the invention is in the irradiation of sunlight
The efficiency of lower conversion nitrite and sulphite, which has, to be increased substantially.Composite photo-catalyst Er in the present invention3+:
Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Not only there is traditional photochemical catalyst, but also it is most it is worth noting that needle
To NiGa2O4And Bi2Sn2O7Bandwidth feature and conduction band and valence band location are unique, devise a kind of by CoS2It is logical as conduction
The novel photocatalyst in road.This method solve photocatalysis the problem of light induced electron and hole-recombination, is greatly improved to turn
Change the efficiency of nitrite and sulphite.
Description of the drawings
Fig. 1 is NiGa2O4, Bi2Sn2O7And Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Photoluminescence spectra
(PL) figure.
Fig. 2 a are Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7X-ray photoelectron spectroscopy (XPS) figure.
Fig. 2 b are Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Er elements XPS figure.
Fig. 2 c are Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Y element XPS figure.
Fig. 2 d are Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Al elements XPS figure.
Fig. 2 e are Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Ni elements XPS figure.
Fig. 2 f are Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Ga elements XPS figure.
Fig. 2 g are Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Bi elements XPS figure.
Fig. 2 h are Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Sn elements XPS figure.
Fig. 2 i are Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7S elements XPS figure.
Fig. 2 j are Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7O elements XPS figure.
Fig. 2 k are Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Co elements XPS figure.
Fig. 3 is Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Transmission electron microscope (TEM) figure.
Fig. 4 is Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Infrared spectrum (IR) figure.
Fig. 5 a are influence figure of the simulated solar irradiation irradiation time to the photocatalytic conversion rate of nitrite and sulphite.
Fig. 5 b are influence figure of the corresponding kinetics to the photocatalytic conversion rate of nitrite and sulphite.
Fig. 6 a are to prepare the influence figure of the photocatalytic activity of sample to the photocatalytic conversion rate of nitrite and sulphite.
Fig. 6 b are influence figure of the access times to the photocatalytic conversion rate of nitrite and sulphite.
Fig. 7 is Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Photocatalytic conversion nitrite and sulphite mechanism.
Specific embodiment
Embodiment 1Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7
(1) NiGa is prepared2O4Nanometer powder
By 0.376g Ga2O3Powder is added in 50mL 1mol/L nickel nitrate solutions, the mixture sodium hydroxide of generation
PH to 12 (stirring 30min in tune) is adjusted, obtained aaerosol solution is transferred in reaction kettle reacts 48h at 180 DEG C, is cooled to
Room temperature obtains light blue sediment and is cleaned several times with deionized water, then dries 8h at 60 DEG C, obtain NiGa2O4Powder.It will
Powder is finely ground, in 500 DEG C of Muffle furnace, roasts 2h, ground to get to NiGa again after taking-up2O4Nanometer powder.
(2) CoS is prepared2Nanometer powder
By 2.62g CoCl2With 3.16g Na2S2O3It is dissolved in 60ml deionized waters, ultrasound 30 minutes, obtained suspension
Solution is transferred in reaction kettle, is reacted 16h at 200 DEG C, is cooled to room temperature, and is obtained sediment and is cleaned several times with deionized water, so
It is dried 8 hours at 60 DEG C afterwards, obtains CoS2Powder.
(3) Bi is prepared2Sn2O7Nanometer powder
By 8.76g Bi (NO3)3·5H2O and 5.40g K2SnO3·3H2O is blended in 150ml deionized waters, side stirring
While it is transferred to PH=12 with ammonium hydroxide or potassium hydroxide.Ultrasound 30 minutes, to promote it, the reaction was complete, and obtained aaerosol solution is transferred to
It in reaction kettle, reacts for 24 hours, is cooled to room temperature at 180 DEG C, obtain sediment and cleaned several times with deionized water, dried at 60 DEG C
8 hours, obtain Bi2Sn2O7Powder.
(4) Er is prepared3+:Y3Al5O12Nanometer powder
By 0.032g Er2O3(99.99%), 5.679g Y2O3(99.99%) powder is dissolved in 100mL concentrated nitric acids
(65.00%) in and magnetic force heating stirring is until water white transparency.Then Al (NO are weighed in proportion3)3·9H2O (99.99%) is molten
Solution is stirred with glass bar and is slowly added in rare-earth ion solution in distilled water at room temperature.Using citric acid as chelating
Agent and cosolvent, according to n citric acids：N rare earth ion=3:1 weighs citric acid, and with water dissolution is distilled, in 50-60 DEG C of heating
Stirring stops when solution is in thick.In this process without precipitation generation, the glutinous colloidal solution of foaming is finally obtained.It will
Thick solution is put into 80 DEG C of heating 36h of baking oven constant temperature.In the drying process until solvent evaporated does not have sediment generation, finally
Obtain foam sol.Obtained colloidal sol heats 50min at 500 DEG C, then calcines 2h respectively at 1100 DEG C respectively.Finally, from height
The substance of sintering is taken out in warm stove and is cooled to room temperature to obtain Er in air3+:Y3Al5O12Powder.
(5) Er is prepared3+:Y3Al5O12@NiGa2O4Nanometer powder
By 0.376g Ga2O3Solid is added in 50mL 1mol/L nickel nitrate solutions, the mixed liquor 1mol/L hydrogen of generation
Sodium oxide molybdena adjusts pH to 12 (stirring 30min in tune), then adds in Er3+:Y3Al5O12Continue to stir 20min.Obtained suspension
Solution is transferred in reaction kettle, is reacted 48h at 180 DEG C, is cooled to room temperature, and is obtained sediment and is cleaned several times with deionized water, so
8h is dried at 80 DEG C afterwards, obtains Er3+:Y3Al5O12@NiGa2O4Powder.Powder is finely ground, in 500 DEG C of Muffle furnace, roasting
2h, it is ground to get to Er again after taking-up3+:Y3Al5O12@NiGa2O4Nano-particle.
(6) Er is prepared3+:Y3Al5O12@NiGa2O4/CoS2Nanometer powder
By 6g Er3+:Y3Al5O12@NiGa2O4Powder is put into addition 200mL absolute ethyl alcohols, ultrasonic disperse 30 in beaker
Min at 40~60 DEG C, is uniformly mixed with magnetic stirring apparatus, and CoS is added in after stirring half an hour2Then powder uses absolute ethyl alcohol
With distilled water cleaning for several times, it after centrifugal drying, is put into Muffle furnace after roasting 2h at 500 DEG C and takes out, grind, obtain Er3+:
Y3Al5O12@NiGa2O4/CoS2Nanometer powder.
(7) Er is prepared3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Nanometer powder
By 6g Er3+:Y3Al5O12@NiGa2O4/CoS2With 6g Bi2Sn2O7Nanometer powder is added to 200mL absolute ethyl alcohols
In, suspension heating is boiled constant temperature 30min by ultrasonic disperse 30min, is filtered after 8.0h dry at 60 DEG C, and powder is finely ground,
In Muffle furnace, taken out after 200 DEG C of calcining 2.0h, grind, obtain Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7。
(8) it detects
(1) Fig. 1 is NiGa2O4,Bi2Sn2O7And Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Photoluminescence spectra
(PL) picture analyzing.
Luminescence generated by light (PL) spectrum is to determine that photo-generate electron-hole is to compound important method in semiconductor.In general,
More low intensive signal shows that the recombination rate of electron hole pair is relatively low in PL spectrum.On the contrary, higher intensity show it is higher
Electron hole pair recombination rate.It can clearly be seen that Er from Fig. 13+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7PL intensity
Compare Er3+:Y3Al5O12@NiGa2O4And Bi2Sn2O7It is low, illustrate Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7With relatively low
Electron hole pair recombination rate.(1)NiGa2O4And Bi2Sn2O7Form Z-type photocatalytic system, Bi2Sn2O7Conduction band on photoproduction
Electronics can be with NiGa2O4Valence band on photohole recombine.(2)CoS2Conduction band and the position of valence band be located at
Bi2Sn2O7Conduction band positions and NiGa2O4Valence band between.Due to the presence of narrow-band semiconductor, become acceleration electron transfer rate
Conductive channel.
(2) Fig. 2 a- Fig. 2 k are Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7X-ray photoelectron spectroscopy (XPS) figure
Piece is analyzed.
Er is had studied with x-ray photoelectron spectroscopy (XPS)3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Chemical group
Into.Er, Y, Al are can be seen that from Fig. 2 a- Fig. 2 k, O, Ni, Ga, S, Bi, the peak of Co and Sn elements can be found.In 74.0eV
The peak and Er occurred at (Al 2p), 157.4eV (Y 3d), 173.7eV (Er 4d) and 530.5 (O 1s)3+:Y3Al5O12Group
Into consistent.The peak and NiGa presented at 530.5eV (O 1s) and 20.5eV (Ga 3d)2O4Composition closely conform to.
Bi2Sn2O7Bi (4f7/2) and Bi (4f5/2) peak is respectively 158.7 and 164.5eV, illustrate Bi2Sn2O7In there are Bi3+。 Sn
(3d5/2) and Sn (3d3/2) occur two peaks at 486.9 and 494.8eV, illustrate that there are Sn4 +.These the result shows that prediction
Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7It has been produced.
(3) Fig. 3 is Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Transmission electron microscope (TEM) picture analyzing.
It further carries out going deep into observation by transmission electron microscope shown in Fig. 3 (TEM).It can be determined from Fig. 3 (a-1)
Larger-size rule particle is Er3+:Y3Al5O12@NiGa2O4Particle.Er3+:Y3Al5O12@NiGa2O4In dark part be
Er3+:Y3Al5O12, it is wrapped NiGa2O4In.As can be seen that the smaller particle that size is 20-50nm is confirmed as Bi2Sn2O7
Particle.In addition, in Er3+:Y3Al5O12@NiGa2O4And Bi2Sn2O7Between, there are many more smaller particles, this should be CoS2It receives
Rice corpuscles.The TEM being further amplified in Fig. 3 (a-2) can be seen that their definite relationship and composition.In Fig. 3 (a-2),
0.298,0.281,0.331 with the measurement point of 0.314nm respectively with Er3+:Y3Al5O12D221Plane, NiGa2O4D220It is flat
Face, Bi2Sn2O7D311Plane and CoS2D111Plane matches.It is studied by TEM, can not only determine its structure and group
Into, and can prove the Er of prediction3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7It has been produced.
(4) Fig. 4 is Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Infrared spectrum (IR) picture analyzing.
In order to provide the Er for about the chemical information for preparing sample structure, determining preparation3+:Y3Al5O12@NiGa2O4/
CoS2/Bi2Sn2O7Infrared spectrum, it is corresponding that the results are shown in Figure 4.In Fig. 4, in 3430cm-1The peak at place is due to ν (OH)
What stretching vibration obtained.In about 789cm-1The metal oxygen vibration at place is the feature of Y-O stretching frequencies, this may be Er3+:
Y3Al5O12.In Fig. 4, infrared spectrum clearly demonstrates the presence of two strong absworption peaks.In 455cm-1The absorption peak ownership at place
The stretching vibration model of metal oxygen, about 692cm in tetrahedral site-1The peak at place belongs to Octahedral Complexes.According to the two
Absorption peak is it has been confirmed that form the Single spinel with sublattice four sides body region and octahedral body region
NiGa2O4.In 515cm-1And 634cm-1The peak at place is attributed to BiO respectively8Bi-O stretching vibrations and Bi in dodecahedron2Sn2O7
SnO6Sn-O stretching vibrations in octahedron.In Fig. 4,1116 cm are appeared in-1Peak belong to CoS2Co=O bending
Vibration mode.
Embodiment 2Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7In photocatalytic conversion nitrite and sulphite
In application
(1) photocatalysis of simulated solar irradiation irradiation time and corresponding kinetics to nitrite and sulphite
The influence of conversion ratio
Er is carried out under simulated solar irradiation irradiation3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Photochemical catalyst is to nitrous acid
The photocatalytic conversion of salt and sulphite.Before light irradiation, NO will be contained2 -And SO3 2-Solution stir 30 points in the dark
Clock, and reach absorption-desorption balance.Then, it takes out solution example within every 1.0 hours, passes through sulfate by ion chromatography nitrite
With the conversion ratio of sulphite.It can be seen that from Fig. 5 a-1 with the increase of simulated solar irradiation irradiation time, photocatalytic conversion rate
It is in rising trend.Under sunlight irradiation in 4.00 hours, for NO2 -And SO3 2-, photocatalytic conversion rate is reachable respectively
82.32% and 92.18%, NH4 +, NO3 -, N2And SO4 2-Production rate is respectively 70.83%, 10.17%, 1.32% He
90.89%.From experimental result as can be seen that NO3 -And N2Production rate well below NH4 +, this shows the Z-type Er in design3+:
Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7In photocatalytic system, the major part NO in pH=5.002 -It is converted into NH4 +.In addition,
In Fig. 5 a-1, SO3 2-Conversion ratio be slightly below SO4 2-Yield, this may be due to SO3 2-It can convert except SO4 2-Except
Other a small amount of sulfur-containing compounds.
In order to speculate the simulated solar irradiation photocatalytic conversion reaction equation of nitrite and sulphite, as shown in Fig. 5 a-2,
Kinetics is studied.As can be seen that first kernel response and all-ln (C of irradiation time (t)t/C0)(Ct:T irradiates
The instantaneous concentration of time, C0:Initial concentration) data can consider and linear relationship is substantially presented.Corresponding to NO2 -And SO3 2-Reaction
Kinetics equation is respectively-ln (Ct/C0)=0.4502t+0.0137 (R2=0.9870) and-ln (Ct/C0)=0.6739t-
0.0879(R2=0.9681).For NO2 -And SO3 2-, rate constant is respectively 0.4502min–1,0.6739min–1。
(2) compare the photocatalytic activity for preparing sample and access times to turn the photocatalysis of nitrite and sulphite
The influence of rate
Photochemical catalyst (the Er prepared at three kinds has been carried out under simulated solar irradiation irradiation3+:Y3Al5O12@NiGa2O4, Bi2Sn2O7
And Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7) in the presence of the photocatalytic conversion of nitrite and sulphite.From figure
6a can be seen that nitrite in the presence of three kinds of photochemical catalysts prepared in aqueous solution and sulphite conversion ratio is different,
Conversion ratio depends on photochemical catalyst used.For NiGa2O4For, as wide band gap semiconducter photochemical catalyst, it has more negative
Conduction band (CB), show stronger reproducibility.NO2 -NH can be converted into4 +And N2, under simulated solar irradiation irradiation,
NiGa2O4Conduction band (CB) on, NO2 -Conversion ratio is higher and NH4 +Productivity it is also higher.For Bi2Sn2O7, as narrowband
Gap semiconductor photochemical catalyst, it has more effective valence band (VB), shows stronger oxidisability, SO3 2-SO can be converted into4 2-, and
And higher conversion ratio can be obtained in valence band.Z-type photochemical catalyst Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Together
When have more negative conduction band (CB) and correct valence band (VB).Obviously, under the irradiation of simulated solar irradiation, NO2 -And SO3 2-Turn
Rate is higher than single photochemical catalyst Er3+:Y3Al5O12@NiGa2O4Or Bi2Sn2O7Conversion ratio.In addition, due to CoS2As leading
Electric channel further improves electron transfer rate.
It repeats to test by carrying out nitrite and the sulphite photocatalytic conversion under simulated solar irradiation, has evaluated Er3 +:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Stability, as shown in Figure 6 b.Clearly for Er3+:Y3Al5O12@
NiGa2O4/CoS2/Bi2Sn2O7, with the increase of number of use, the simulated solar irradiation photocatalysis of nitrite and sulphite turns
Rate is declined slightly.Simulated solar irradiation irradiation under by five times reuse after NO2 -And SO3 2-Conversion ratio respectively reach
74.23% and 85.38%.Show the Er in the case where simulated solar irradiation irradiates3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Photocatalysis
Agent can keep higher performance for a long time.
Er3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7Photocatalytic conversion nitrite and sulphite mechanism：In order to
The compound of the hole on the electronics and valence band on conduction band is effectively inhibited, by NiGa2O4And Bi2Sn2O7Combination is urged with forming Z-type light
Change system is necessary.However, electronics flow velocity can reduce the activity of Z-type photocatalytic system more slowly.Noble metal quilt is had been reported that recently
Accelerate electronics flow velocity as conductive channel.Nevertheless, still there is the defects of some are significant in practical applications.It is used
Noble metal has narrow and fixed energy level, may deviate Bi2Sn2O7Conduction band and NiGa2O4Valence band, this is unfavorable for light induced electron
Pass through the flowing of noble metal.In addition, it can also increase the range ability of light induced electron using noble metal.
The problem of being brought in order to avoid noble metal as conductive channel can select very narrow gap semiconductor CoS2Make
Accelerate electron transfer rate for solid conduction channel.Narrow-band semiconductor conduction band positions are very close to Bi2Sn2O7Conduction band positions,
The valence band location of narrow-band semiconductor is in close proximity to NiGa2O4Valence band location.Addition and Bi due to narrow-band semiconductor2Sn2O7With
NiGa2O4With reference to forming a series of smaller electron energy level of differences.Conductive channel, Bi are used as by narrow-band semiconductor2Sn2O7It leads
The light induced electron taken is easy to be transferred to NiGa2O4In valence band.Moreover, CoS2As the narrow-band semiconductor of inorganic material, with
NiGa2O4And Bi2Sn2O7With certain compatibility.They be combined with each other well, form larger contact area.By narrowband half
The resistance very little for the conductive channel that conductor is formed, this is conducive to the transmission rate for accelerating electronics.
Claims (8)
1. based on the photochemical catalyst that pole narrow-band semiconductor is solid conduction channel, it is characterised in that：It is described based on pole narrowband half
Conductor is Er for the photochemical catalyst of solid conduction channel3+:Y3Al5O12@NiGa2O4/CoS2/Bi2Sn2O7。
2. it is described in claim 1 based on preparation method of the pole narrow-band semiconductor for the photochemical catalyst of solid conduction channel, it is special
Sign is, includes the following steps：By appropriate Er3+:Y3Al5O12@NiGa2O4/CoS2Nanometer powder and Bi2Sn2O7Nanometer powder adds
Enter into absolute ethyl alcohol, ultrasonic disperse, the heating of gained suspension is boiled, the constant temperature 30-40min at 100 DEG C, filtration drying, institute
It is finely ground to obtain powder, in Muffle furnace, is taken out after 200 DEG C of calcining 2.0h, grinds, obtain Er3+:Y3Al5O12@NiGa2O4/CoS2/
Bi2Sn2O7。
3. preparation method as claimed in claim 2, it is characterised in that：The Er3+:Y3Al5O12@NiGa2O4/CoS2It prepares
Method is：In Er3+:Y3Al5O12@NiGa2O4Appropriate absolute ethyl alcohol is added in nanometer powder, ultrasonic disperse at 40-60 DEG C, is used
Magnetic stirring apparatus is uniformly mixed, and CoS is added in after stirring half an hour2Then powder is cleaned with absolute ethyl alcohol and distilled water, centrifugation is dry
It after dry, is put into Muffle furnace, is taken out after roasting 2h at 500 DEG C, grind, obtain Er3+:Y3Al5O12@NiGa2O4/CoS2Nano powder
End.
4. preparation method as claimed in claim 3, it is characterised in that：The Er3+:Y3Al5O12@NiGa2O4Nanometer powder
Preparation method includes the following steps：By Ga2O3Solid is added in nickel nitrate solution, and the mixed liquor of generation adjusts pH to 12, then
Add in Er3+:Y3Al5O12Continue to stir 20min, obtained aaerosol solution is transferred in reaction kettle, and 48h is reacted at 180 DEG C, is cooled down
It to room temperature, obtains sediment and is cleaned with deionized water, then dry 8h at 80 DEG C, obtain Er3+:Y3Al5O12@NiGa2O4Powder
Body, powder is finely ground, in 500 DEG C of Muffle furnace, 2h is roasted, it is ground to get to Er again after taking-up3+:Y3Al5O12@
NiGa2O4Nanometer powder.
5. preparation method as claimed in claim 3, it is characterised in that：The CoS2Preparation method is：By appropriate CoCl2With
Na2S2O3In deionized water, ultrasound 30 minutes, obtained aaerosol solution is transferred in reaction kettle, is reacted at 200 DEG C for dissolving
16h is cooled to room temperature, and is obtained sediment and is cleaned with deionized water, is then dried 8 hours at 60 DEG C, is obtained CoS2Powder.
6. preparation method as claimed in claim 2, it is characterised in that：The Bi2Sn2O7Preparation method is：By appropriate Bi
(NO3)3·5H2O and K2SnO3·3H2O is mixed in deionized water, adjusts PH=12 while stirring, and ultrasound 30 minutes obtains
Aaerosol solution is transferred in reaction kettle, is reacted for 24 hours, is cooled to room temperature at 180 DEG C, is obtained sediment and is cleaned with deionized water, so
It is dried 8 hours at 60 DEG C afterwards, obtains Bi2Sn2O7Powder.
7. it is described in claim 1 based on pole narrow-band semiconductor for solid conduction channel photochemical catalyst in photocatalytic conversion nitrous
Application in hydrochlorate and sulphite.
8. the use as claimed in claim 7, which is characterized in that method is as follows：In the water containing nitrite and sulphite
In solution, irradiated with 500W xenon lamps, light application time 4.0h.
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