CN108579776A - Multi-lager semiconductor visible light catalyst and the preparation method and application thereof - Google Patents
Multi-lager semiconductor visible light catalyst and the preparation method and application thereof Download PDFInfo
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- CN108579776A CN108579776A CN201711480221.3A CN201711480221A CN108579776A CN 108579776 A CN108579776 A CN 108579776A CN 201711480221 A CN201711480221 A CN 201711480221A CN 108579776 A CN108579776 A CN 108579776A
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- mixed solution
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- visible light
- distilled water
- lager semiconductor
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 239000004065 semiconductor Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000012153 distilled water Substances 0.000 claims abstract description 24
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000010452 phosphate Substances 0.000 claims abstract description 7
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 6
- 150000005309 metal halides Chemical class 0.000 claims abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 38
- 239000002351 wastewater Substances 0.000 claims description 28
- 229910052709 silver Inorganic materials 0.000 claims description 21
- 239000004332 silver Substances 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical group O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 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
- 238000005660 chlorination reaction Methods 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000000862 absorption spectrum Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 35
- 229960000907 methylthioninium chloride Drugs 0.000 description 35
- 238000000034 method Methods 0.000 description 19
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 18
- -1 silver halide Chemical class 0.000 description 17
- 230000000694 effects Effects 0.000 description 16
- 230000001699 photocatalysis Effects 0.000 description 15
- 229940019931 silver phosphate Drugs 0.000 description 15
- 229910000161 silver phosphate Inorganic materials 0.000 description 15
- 238000007146 photocatalysis Methods 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- WCXDHFDTOYPNIE-RIYZIHGNSA-N (E)-acetamiprid Chemical compound N#C/N=C(\C)N(C)CC1=CC=C(Cl)N=C1 WCXDHFDTOYPNIE-RIYZIHGNSA-N 0.000 description 1
- 239000005875 Acetamiprid Substances 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000203 mixture Substances 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
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of multi-lager semiconductor visible light catalyst, include the following steps：It takes containing Ag+Metal salt be added distilled water in, stir to obtain the first mixed solution；Ferriferous oxide is added thereto, stirs to obtain the second mixed solution；It takes soluble metal halide to be added in distilled water, stirs to obtain third mixed solution；Gained third mixed solution is added dropwise in the second mixed solution, the 4th mixed solution is stirred to obtain；It takes soluble phosphate to be added in distilled water, stirs to obtain the 5th mixed solution；5th mixed solution is added dropwise in the 4th mixed solution, the 6th mixed solution is stirred evenly to obtain；6th mixed solution is filtered, washed, is dried, multi-lager semiconductor visible light catalyst is obtained.Gained catalyst amount is few, stable in catalytic performance, absorption spectrum is wide, will not cause secondary pollution, can be widely applied to sewage disposal.
Description
Technical field
The invention belongs to sewage disposal technologies, more particularly to a kind of multi-lager semiconductor visible light catalyst and its preparation side
Method and application.
Technical background
With the continuous quickening of human society process of industrialization, the mankind are growing day by day to the consumption of natural resources, lead to ring
The discharge capacity of border pollutant also increasingly increases, and pollutant kind is various.Becoming increasingly conspicuous for environmental problem, has seriously affected
The survival and development of human society.For China, propulsion and the disconnection of pollution treatment ability and the prison of relevant department of urbanization
It is unfavorable to manage, and has resulted in quite serious environmental problem, especially water pollution problems.Water pollution has become restriction society warp
One of an important factor for Ji development.Especially strong toxicity, concentration is high, organic wastewater of difficult for biological degradation to traditional wastewater biology at
Science and engineering skill brings unprecedented challenge.In recent years, photocatalysis technology shows good foreground in environmental area, becomes one
The environmentally friendly green technique of kind.Photocatalysis technology is facilitated by semiconductor light-catalyst under conditions of illumination
Chemical reaction, can be decomposed numerous to environment and the harmful organic substance of human body and part inorganic substances using light-catalyzed reaction.
Light-catalysed advantage is that (1) can be degradable for H by the multiple pollutant in water2O and CO2；(2) can use cleaning, can be again
Raw sunlight is as light source；(3) simple, easy to operate, strong, non-secondary pollution of oxidisability of device etc..
The core of photocatalysis technology research is to develop excellent photochemical catalyst.TiO2Because having stable structure, excellent
Photochemical properties, nontoxic and lower cost the advantages that obtain extensive concern, be that current most widely used semiconductor light is urged
Change material.But TiO2Be widely used and be subject to many limitations：(1) can only sunlight (only be accounted for by the ultraviolet light of λ ＜ 400nm
4%) it is driven；(2) photoinduced electron and photo-induced hole are easy compound, it is suppressed that the photocatalytic activity of semiconductor；(3) it is not easily recycled
And recycling, cause secondary pollution.Ferriferous oxide is also a kind of efficient photochemical catalyst, compared to TiO2, ferriferous oxide it is excellent
Point is that the maximum excitation wavelength of its photoresponse is 600nm or so, compared to TiO2Ultra-violet (UV) band absorbing wavelength it is long, to sunlight
Utilization rate it is higher, account for 40% or so；Secondly ferriferous oxide is nontoxic and pollution-free, and cheap and chemical stability is good；In addition iron
Oxide hydrophilicity is good, is conducive to polar substances and is infiltrated on its surface, is greatly facilitated for improving its photocatalysis efficiency
Effect.But there is also photoinduced electrons and photo-induced hole to be easy compound, the disadvantage of inhibition conductor photocatalysis activity for ferriferous oxide.
Silver orthophosphate can absorb absorbing wavelength and be less than the light of 530nm, and ferriferous oxide photoinduced electron and photo-induced hole can effectively be inhibited to be easy
Compound problem, but silver orthophosphate has certain dissolubility, and it is also unstable under light illumination.There is no aoxidize iron at present
Object, silver orthophosphate, silver halide are used for the report of catalytic degradation organic wastewater after being organically combined.
Invention content
For the drawbacks described above of the prior art, this application provides a kind of dosages few, stable in catalytic performance, absorption spectrum
Extensively, will not cause secondary pollution, recyclable recycling multi-lager semiconductor visible light catalyst, and further provide above-mentioned urge
The preparation method and application of agent.
Technical solution：The preparation method of multi-lager semiconductor visible light catalyst described herein, includes the following steps：
(1) it takes containing Ag+Metal salt be added distilled water in, stir to obtain the first mixed solution；
(2) ferriferous oxide is added into the first mixed solution obtained by step (1), stirs to obtain the second mixed solution；
(3) it takes soluble metal halide to be added in distilled water, stirs to obtain third mixed solution；
(4) third mixed solution obtained by step (3) is added dropwise in the second mixed solution obtained by step (2), is stirred
4th mixed solution
(5) it takes soluble phosphate to be added in distilled water, stirs to obtain the 5th mixed solution；
(6) the 5th mixed solution obtained by step (5) is added dropwise in the 4th mixed solution obtained by step (4), stirring is equal
It is even to obtain the 6th mixed solution；
(7) the 6th mixed solution obtained by step (6) is filtered, washed, dried, obtain multi-lager semiconductor visible light catalytic
Agent.
It is described to contain Ag in step (1)+Metal salt be silver nitrate；It is described to contain Ag+Metal salt substance amount with
The volume ratio of distilled water is 1.5~6.5：1.
In step (2), ferriferous oxide is natural hematite powder (chemical composition is di-iron trioxide)；The ferriferous oxide of addition
Mass volume ratio with the first mixed solution obtained by step (1) is 0.2~1.5：1.
In step (2), mixing time 0.8-1.5h, stir speed (S.S.) is 50~200rpm.
In step (3), soluble metal halide is sodium chloride, potassium chloride, sodium bromide or potassium bromide；Soluble metal halogen
The amount of the substance of compound and the volume ratio of distilled water are 0.9~4：1.
In step (4), drop rate is 0.5-2 drops/sec, preferably 1 drop/sec.
In step (4), mixing time 2.5-3.5h, stir speed (S.S.) is 50~200rpm.
In step (5), soluble phosphate is sodium phosphate, disodium hydrogen phosphate or disodium hydrogen phosphate；Soluble phosphate
The amount of substance and the volume ratio of distilled water are 0.6~2.6：1.
In step (6), drop rate is 0.5-2 drops/sec, preferably 1 drop/sec.
In step (6), mixing time 2.5-3.5h, stir speed (S.S.) is 50~200rpm.
In step (7), the 6th mixed solution is crossed 0.22 μm of water system filter membrane by described be filtered into, and is washed solid for that will filter gained
Body substance is added in pure water and centrifuges again, and repeatedly, final filtration obtained solid substance is dried.
The stirring condition not being defined refers to being stirred with the stir speed (S.S.) of 50~200rpm.
It is also within the scope of the present invention that gained multi-lager semiconductor visible light catalyst is prepared according to the above method.
Application of the above-mentioned multi-lager semiconductor visible light catalyst in administering organic wastewater is also in the scope of the present invention.
Application of the above-mentioned multi-lager semiconductor visible light catalyst in administering organic wastewater, the specifically described multi-lager semiconductor
Visible light catalyst acts on the hydroxyl radical free radical that hydrogen peroxide generates strong oxidizing property, having in oxidized waste water under illumination effect
Machine object.When administering organic wastewater with the catalyst, under normal temperature condition, multilayer is added into the waste water containing organic pollution
Semiconductor visible light catalyst, it is 0.1-0.3g/L to make its solid content, and adding hydrogen peroxide makes its a concentration of 0.1~1g/L,
5~60min of light processing under 3~9 environment of pH.
Preferably, adding silver halide/silver phosphate/ferriferous oxide multi-lager semiconductor visible light catalyst makes its solid content be
0.2g/L, adding hydrogen peroxide makes its a concentration of 0.85g/L, is handled in the case where pH is 7~8 environment.
It is administered by this method, organic wastewater removal rate reaches 95% or more.In the case that condition is suitable, organic wastewater
Removal rate can reach 100%, effect highly significant.
Heretofore described mass volume ratio unit is g：ML, the amount and volume ratio unit of substance are mmol：mL.
Advantageous effect：It is compared to the prior art, the application prepares gained silver halide/silver phosphate/ferriferous oxide multilayer half
Conductor visible light catalyst has the advantage that：(1) not soluble in water, belong to non-equal in the process of photocatalytic degradation organic wastewater
Phase catalysis oxidation, this enables catalysis material after catalytic process relatively easily to separate recycling from water phase,
The catalysis material only has a small amount of digestion of metallic ion in catalytic process, will not cause to significantly affect to water quality, is a kind of environment
Friendly photochemical catalyst；(2) catalyst amount is less, can be carried out under room temperature, is not necessarily to external energy, and easy to operate, warp
It helps feasible, is suitable for the processing of organic wastewater with difficult degradation thereby；It (3) can be degradable for H by the multiple pollutant in water2O and CO2；It can
To use cleaning, reproducible sunlight as light source.
Description of the drawings
Fig. 1 be silver with the amount of ferriferous oxide substance than it is different when prepare gained silver halide/silver phosphate/ferriferous oxide multilayer
Semiconductor visible light catalyst photocatalysis methylene blue；
Fig. 2 is the picture for preparing gained silver halide/silver phosphate/ferriferous oxide multi-lager semiconductor visible light catalyst；
Fig. 3 is to prepare gained silver halide/silver phosphate/ferriferous oxide multi-lager semiconductor visible light catalyst photocatalysis treatment Asia
The effect of methyl blue waste water；
Fig. 4 is the photocatalysis treatment effect under different catalysts dosage；
Fig. 5 is the photocatalysis treatment effect under different hydrogen peroxide dosages；
Fig. 6 is the photocatalysis treatment effect under different pH；
Fig. 7 is that catalyst reuses test result.
Specific implementation mode
The application is explained in detail with reference to specific embodiment.
Embodiment 1
Prepare Ag+The silver halide/silver phosphate different from the amount ratio of ferriferous oxide substance/ferriferous oxide multi-lager semiconductor can
Light-exposed catalyst.
(1) weigh 5.3 respectively, 10.6,10.9,21.2g silver nitrates be added in 20mL distilled water, in the case where rotating speed is 100rpm
Stir process 0.5h, makes it fully dissolve；
(2) 10g Fe are weighed2O3It is added in four the first mixed solutions obtained by (1), in the case where rotating speed is 100rpm at stirring
Manage 1h；
(3) weigh 2.23 respectively, 4.46,6.69,4.460gKBr be separately added into 10mL distilled water, be in rotating speed
Stir process 0.5h under 100rpm, makes it fully dissolve；
(4) step (3) acquired solution is separately added into the second mixed solution obtained by step (2) by 1 drop/sec of rate dropwise
In, the stir process 3h in the case where rotating speed is 100rpm；
(5) weigh 4.75,9.50,14.25,19.0gNa3PO4·12H2O is added in 10mL distilled water, is in rotating speed
Stir process 0.5h under 100rpm；
(6) step (5) acquired solution is separately added by 1 drop/sec of rate in mixed solution obtained by step (4) dropwise,
The stir process 3h in the case where rotating speed is 100rpm；
(7) by the amount of silver and ferriferous oxide substance obtained by step (6) than being respectively that 0.5,1,1.5,2 four kinds of products steam
Distilled water is washed five times, filtering, and dry 6h, obtains silver halide/silver phosphate/ferriferous oxide multilayer and partly lead in 60 DEG C of air atmosphere
Body visible light catalyst.
100mL methylene blue waste water is taken to be placed in glass reactor, the initial concentration of methylene blue is 10mg/L, and pH is
8.0.Four kinds of catalyst obtained by above-mentioned preparation are added into reactor respectively, it is 0.2g/L to make its solid content, then will reaction
Device is placed on magnetic stirring apparatus, rotating speed 80rpm, and hydrogen peroxide, which is added, makes its a concentration of 0.85g/L, opens simulated solar irradiation
Source is irradiated reactor, is reacted at room temperature, timing sampling, with UV spectrophotometer measuring methylene blue residual concentration.Processing knot
Fruit such as Fig. 1, as seen from Figure 1, when the amount ratio of silver and ferriferous oxide substance is 1.5, treatment effect is best.
Embodiment 2
The amount of silver and ferriferous oxide substance is urged than the silver halide/silver phosphate for 1.5/ferriferous oxide multi-lager semiconductor visible light
The preparation method of agent, includes the following steps：
(1) 10.9gAgNO is weighed3It is added in 20mL distilled water, the stir process 0.5h in the case where rotating speed is 100rpm makes it fill
Divide dissolving；
(2) 10gFe is weighed2O3It is added in the first mixed solution obtained by (1), the stir process 1h in the case where rotating speed is 100rpm；
(3) it weighs 6.69gKBr to be added in 10mL distilled water, the stir process 0.5h in the case where rotating speed is 100rpm makes it fully
Dissolving；
(4) step (3) acquired solution is pressed to 1 drop/sec of rate dropwise to be added in the second mixed solution obtained by step (2),
The stir process 3h in the case where rotating speed is 100rpm；
(5) 14.25gNa is weighed3PO4·12H2O is added in 10mL distilled water, the stir process in the case where rotating speed is 100rpm
0.5h；
(6) step (5) acquired solution is pressed to 1 drop/sec of rate dropwise to be added in mixed solution obtained by step (4), is being turned
Speed is stir process 3h under 100rpm；
(7) step (6) products therefrom is washed with distilled water five times, is filtered, dry 6h, obtains in 60 DEG C of air atmosphere
To silver halide/silver phosphate/ferriferous oxide multi-lager semiconductor visible light catalyst.
The picture that embodiment 2 prepares gained ferriferous oxide/silica gel composite photo-catalyst is as shown in Figure 2.
Embodiment 3
Gained silver halide/silver phosphate/ferriferous oxide multi-lager semiconductor visible light catalyst light is prepared in order to verify embodiment 2
The effect of catalytic treatment methylene blue waste water has done following three groups of experiments.
Experiment I
100mL methylene blue waste water is taken to be placed in glass reactor, the initial concentration of methylene blue is 10mg/L, and pH is
8.0.Embodiment 2 is added into reactor simultaneously and prepares gained catalyst, it is 0.2g/L to make its solid content, then by reactor
It being placed on magnetic stirring apparatus, rotating speed 80rpm, hydrogen peroxide, which is added, makes its a concentration of 0.85g/L, opens simulated solar light source,
Reactor is irradiated, is reacted at room temperature, timing sampling, with UV spectrophotometer measuring methylene blue residual concentration.
Experiment II
It is added without hydrogen peroxide, other conditions are the same as experiment I.
Experiment III
It is added without silver halide/silver phosphate/ferriferous oxide multi-lager semiconductor visible light catalyst, other conditions are the same as experiment I.
Handling result such as Fig. 3, as seen from Figure 3, experiment II and experiment III fail to effectively remove methylene blue,
The removal rate of methylene blue is only respectively 2% and 5% after 35min, and in testing I, catalyst is made with hydrogen peroxide under light illumination
Treatment effect highly significant, the removal rate of methylene blue nearly reaches 100% after 35min.
Embodiment 4
Embodiment 2 prepares gained silver halide/silver phosphate/ferriferous oxide multi-lager semiconductor visible light catalyst, in catalyst
In the case of dosage difference, photocatalysis treatment methylene blue waste water.
100mL methylene blue waste water is taken to be placed in glass reactor, the initial concentration of methylene blue is 10mg/L, and pH is
8.0.Simultaneously into reactor be added embodiment 2 prepare gained catalyst, make its solid content be 0.05,0.1,0.15,0.2g/
Then reactor is placed on magnetic stirring apparatus by L, rotating speed 80rpm, and hydrogen peroxide, which is added, makes its a concentration of 0.85g/L, opens
Simulated solar light source irradiates reactor, reacts at room temperature, timing sampling, remaining with UV spectrophotometer measuring methylene blue
Concentration.
Specific handling result is shown in Fig. 4.
Fig. 4 the result shows that, catalyst amounts are bigger, and the removal effect of methylene blue is better after 35min.When catalyst is thrown
When dosage reaches 0.2g/L, Acetamiprid removal rate nearly reaches 100%.
Embodiment 5
Embodiment 2 prepares gained silver halide/silver phosphate/ferriferous oxide multi-lager semiconductor visible light catalyst, in hydrogen peroxide
In the case of dosage difference, photocatalysis treatment methylene blue waste water.
100mL methylene blue waste water is taken to be placed in glass reactor, the initial concentration of methylene blue is 10mg/L, and pH is
8.0.Embodiment 2 is added into reactor simultaneously and prepares gained catalyst, it is 0.2g/L to make its solid content, then by reactor
Be placed on magnetic stirring apparatus, rotating speed 80rpm, be added hydrogen peroxide make its a concentration of 0.58,0.67,0.77,0.85g/L, beat
Solar source is intended in die sinking, irradiates reactor, reacts at room temperature, timing sampling, surplus with UV spectrophotometer measuring methylene blue
Remaining concentration.
Specific handling result is shown in Fig. 5.
Fig. 5 the result shows that, concentration of hydrogen peroxide is within the scope of 0.58~0.85g/L, and hydrogen peroxide dosage is bigger, methylene
The removal effect of base indigo plant is better.React 35min after methylene blue removal rate from concentration of hydrogen peroxide be 0.58g/L when 83%
Increase to 100% when concentration of hydrogen peroxide is 0.3g/L.
Embodiment 6
Embodiment 2 prepares gained silver halide/silver phosphate/ferriferous oxide multi-lager semiconductor visible light catalyst, in photocatalysis
The experiment of the methylene blue waste water of the different initial pH of the lower processing of effect.
100mL methylene blue waste water is taken to be placed in glass reactor, the initial concentration of methylene blue is 10mg/L, with 1M's
NaOH and H2SO4The initial pH for adjusting separately methylene blue waste water is 3,5,7,8,9, while embodiment 2 is added into reactor and makes
Standby gained catalyst, it is 0.2g/L to make its solid content, then reactor is placed on magnetic stirring apparatus, rotating speed 80rpm adds
Entering hydrogen peroxide makes its a concentration of 0.85g/L, opens simulated solar light source, irradiates reactor, reacts at room temperature, timing sampling,
With UV spectrophotometer measuring methylene blue residual concentration.
Specific handling result is shown in Fig. 6.
Fig. 6 the result shows that, pH be 8 under conditions of methylene blue degradation effect it is best, methylene blue removal rate is several after 35min
Reach 100%, and under the conditions of remaining pH, methylene blue removal rate is 40%~60% after 35min.
Embodiment 7
Embodiment 2 prepares gained silver halide/silver phosphate/ferriferous oxide multi-lager semiconductor visible light catalyst and makees in photocatalysis
With lower processing methylene blue waste water, catalyst is reused.
100mL methylene blue waste water is taken to be placed in glass reactor, the initial concentration of methylene blue is 10mg/L, and pH is
8.0.Embodiment 2 is added into reactor simultaneously and prepares gained catalyst, it is 0.2g/L to make its solid content, then by reactor
It being placed on magnetic stirring apparatus, rotating speed 80rpm, hydrogen peroxide, which is added, makes its a concentration of 0.85g/L, opens simulated solar light source,
Reactor is irradiated, after reacting 35min at room temperature, with UV spectrophotometer measuring methylene blue residual concentration.After reaction
It takes out catalyst to be separated by solid-liquid separation, separation rear catalyst is washed with distilled water to be dried three times, is participated in above-mentioned reaction again, is repeated
Six times.
Specific handling result is shown in Fig. 7.
Fig. 7 the result shows that, catalyst is reused five times, and methylene blue removal rate is without significant change after handling 35min, the
The removal rate of methylene blue just decreased significantly when six uses, illustrate that the catalyst has good stability, service life
It is long.
Claims (9)
1. a kind of preparation method of multi-lager semiconductor visible light catalyst, which is characterized in that include the following steps：
(1) it takes containing Ag+Metal salt be added distilled water in, stir to obtain the first mixed solution；
(2) ferriferous oxide is added into the first mixed solution obtained by step (1), stirs to obtain the second mixed solution；
(3) it takes soluble metal halide to be added in distilled water, stirs to obtain third mixed solution；
(4) third mixed solution obtained by step (3) is added dropwise in the second mixed solution obtained by step (2), stir the 4th
Mixed solution；
(5) it takes soluble phosphate to be added in distilled water, stirs to obtain the 5th mixed solution；
(6) the 5th mixed solution obtained by step (5) is added dropwise in the 4th mixed solution obtained by step (4), stir the 6th
Mixed solution；
(7) the 6th mixed solution obtained by step (6) is filtered, washed, dried, obtain multi-lager semiconductor visible light catalyst.
2. preparation method according to claim 1, which is characterized in that described to contain Ag in step (1)+Metal salt be nitre
Sour silver；It is described to contain Ag+Metal salt substance amount and distilled water volume ratio be 1.5~6.5：1.
3. preparation method according to claim 1, which is characterized in that in step (2), ferriferous oxide is natural hematite
Powder；The mass volume ratio of the ferriferous oxide of addition and the first mixed solution obtained by step (1) is 0.2~1.5：1.
4. preparation method according to claim 1, which is characterized in that in step (3), soluble metal halide is chlorination
Sodium, potassium chloride, sodium bromide or potassium bromide；The amount of the substance of soluble metal halide and the volume ratio of distilled water are 0.9~4：
1。
5. preparation method according to claim 1, which is characterized in that in step (5), soluble phosphate be sodium phosphate,
Disodium hydrogen phosphate or disodium hydrogen phosphate；The amount of the substance of soluble phosphate and the volume ratio of distilled water are 0.6~2.6：1.
6. any one of claim 1-5 prepares gained multi-lager semiconductor visible light catalyst.
7. any one of claim 1-5 prepares gained multi-lager semiconductor visible light catalyst answering in administering organic wastewater
With.
8. applying according to claim 7, which is characterized in that under normal temperature condition, into the waste water containing organic pollution
Add multi-lager semiconductor visible light catalyst, make its solid content be 0.1-0.3g/L, add hydrogen peroxide make its a concentration of 0.1
~1g/L, 5~60min of light processing under 3~9 environment of pH.
9. applying according to claim 8, which is characterized in that adding multi-lager semiconductor visible light catalyst makes its solid content
For 0.2g/L, adding hydrogen peroxide makes its a concentration of 0.85g/L, is handled in the case where pH is 7~8 environment, organic wastewater removal rate reaches
To 95% or more.
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