CN106732688B - Composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite and preparation method thereof - Google Patents
Composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 31
- 239000010941 cobalt Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- OGFYIDCVDSATDC-UHFFFAOYSA-N silver silver Chemical compound [Ag].[Ag] OGFYIDCVDSATDC-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910002518 CoFe2O4 Inorganic materials 0.000 claims abstract description 118
- 239000011941 photocatalyst Substances 0.000 claims abstract description 86
- 239000000243 solution Substances 0.000 claims description 286
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 106
- 238000003756 stirring Methods 0.000 claims description 103
- 229910003321 CoFe Inorganic materials 0.000 claims description 100
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- 239000011859 microparticle Substances 0.000 claims description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 46
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 46
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 46
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 40
- 229910002651 NO3 Inorganic materials 0.000 claims description 37
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 36
- 239000007795 chemical reaction product Substances 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 35
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims description 35
- 230000005389 magnetism Effects 0.000 claims description 34
- 239000011259 mixed solution Substances 0.000 claims description 34
- 239000000047 product Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000012216 screening Methods 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 239000002244 precipitate Substances 0.000 claims description 22
- 239000013049 sediment Substances 0.000 claims description 22
- 229960000583 acetic acid Drugs 0.000 claims description 21
- 239000012362 glacial acetic acid Substances 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 19
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 18
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 17
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 101710134784 Agnoprotein Proteins 0.000 claims description 5
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000003546 flue gas Substances 0.000 abstract description 79
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 77
- 229910052794 bromium Inorganic materials 0.000 abstract description 19
- 229910052740 iodine Inorganic materials 0.000 abstract description 19
- 229910052801 chlorine Inorganic materials 0.000 abstract description 18
- 239000000126 substance Substances 0.000 abstract description 6
- 230000010718 Oxidation Activity Effects 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 79
- 230000000052 comparative effect Effects 0.000 description 22
- 230000008569 process Effects 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 15
- 229910052753 mercury Inorganic materials 0.000 description 14
- 238000005303 weighing Methods 0.000 description 13
- 229910052738 indium Inorganic materials 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 235000019504 cigarettes Nutrition 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000003245 coal Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000003825 pressing Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- BJINYZHIGSHXEP-UHFFFAOYSA-N bismuth;iodo hypoiodite Chemical compound [Bi].IOI BJINYZHIGSHXEP-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- -1 Hydroxyl radical free radical Chemical class 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- OLBRKKJBIBPJSE-UHFFFAOYSA-N bismuth;bromo hypobromite Chemical compound [Bi].BrOBr OLBRKKJBIBPJSE-UHFFFAOYSA-N 0.000 description 1
- 230000001925 catabolic effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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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
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
-
- 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
- B01J35/33—Electric or magnetic 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The present invention provides a kind of composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite and preparation method thereof, it provides a kind of recyclable magnetic photocatalyst Ag-AgX-BiOX-CoFe2O4(X=Cl, Br, I), the catalyst is by simple substance Ag, AgX(X=Cl, Br, I), BiOX(X=Cl, Br, I) and CoFe2O4It being combined, multiple groups part is coupled with efficiently separating conducive to photo-generate electron-hole pairs, more oxidizing species can be generated, thus enhance the oxidation activity of visible light catalyst, magnetic carrier CoFe2O4Doping can make visible light catalyst that there is sufficiently strong magnetic to recycle ability, can recycled for multiple times to reduce flue gas demercuration cost improve the environmental-protecting performance of visible light catalyst.
Description
Technical field:
The invention belongs to environmental pollution prevention and control technical fields, and in particular to a kind of composite magnetic visible light catalyst silver-halogen
Change silver-BiOX-cobalt ferrite and preparation method thereof.
Background technique:
Mercury is strong to ecological environment and the mankind due to its hypertoxicity, persistence, biological accumulation and the remote transfer ability of atmosphere
Health causes great harm.Coal combustion is considered as the main source of mercury in atmosphere.Since the energy production structure in China is main
Based on coal, coal in China total quantity consumed in 2014 is about 3,500,000,000 tons of standard coals, and coal is in non-renewable energy consumption structure
Ratio maintains 60% or so, although mercury average content only has 0.22mg/kg in coal in China, since coal consumption amount is huge,
Influence of the mercury discharged in coal-fired flue-gas to ecological environment and human health can not be ignored.This national environmental protection portion is promulgated real
The discharge of mercury in flue gas and its compound of " fossil-fuel power plant atmospheric pollutant emission standard GB13223-2011 " clear stipulaties for applying
Standard.
Mercury In Coal Combustion Flue Gas mainly exists in the form of three kinds: Elemental Mercury (Hg0), oxidation state bivalent mercury (Hg2+) and particulate form
Mercury (Hgp).Wherein oxidation state mercury (Hg2+) soluble easily in water, it can be effectively removed by existing wet flue gas desulfurizer；Particulate form
Mercury (Hgp) be easy to effectively remove by existing electrostatic dust collection equipment；And Elemental Mercury (Hg0) since fusing point is low, volatile and indissoluble
Yu Shui is difficult to remove by existing flue gas pollutant control method.Therefore, Elemental Mercury (Hg0) it is effective removing be to fire now
The a great problem in flue-gas pollutant catabolic gene field is also the research hotspot that atmosphere pollution administers field.
Currently, to remove the Elemental Mercury (Hg in flue gas0), usually first by Elemental Mercury (Hg0) it is oxidized to bivalent mercury (Hg2+),
Then it is removed again by existing wet flue gas desulfurizer.When by elemental mercury oxidation at bivalent mercury, what is generallyd use is light
The method of chemical catalysis makes visible light catalyst generate photo-generate electron-hole pairs using visible light or ultraviolet light catalyst
(e−+h+), photo-generate electron-hole pairs reacted with oxygen or water generate have strong oxidizing property superoxipe ion (•O2 —) or hydroxyl (•
OH), Elemental Mercury (Hg0) and superoxipe ion (•O2 —) or hydroxyl (•OH) it is oxidized to bivalent mercury (Hg2+), then by existing wet
The removing of method flue gas desulfurization device.
Existing widely applied visible light catalyst is one-component structure mostly, such as the Ag of simple substance, the AgX (X of one-component
=Cl, Br, I) or one-component BiOX (X=Cl, Br, I), the light that the visible light catalyst of one-component generates under visible light illumination
Raw electron hole pair is easy compound, causes its catalytic activity weaker, causes the light-catalyzed reaction time long, flue gas demercuration low efficiency
Under, meanwhile, the at high cost and recycling of existing visible light catalyst is difficult.
Summary of the invention:
In conclusion the present invention provides a kind of composite magnetic visible lights to urge in order to overcome the shortcomings of prior art problem
Agent silver-silver halide-BiOX-cobalt ferrite and preparation method thereof, it provides a kind of recyclable magnetic photocatalyst
Ag-AgX-BiOX-CoFe2O4(X=Cl, Br, I), the catalyst is by simple substance Ag, AgX(X=Cl, Br, I), BiOX(X=Cl, Br, I)
And CoFe2O4It is combined, multiple groups part is coupled with efficiently separating conducive to photo-generate electron-hole pairs, can generate more Strong oxdiative
Property substance, thus enhance the oxidation activity of visible light catalyst, magnetic carrier CoFe2O4Doping visible light catalyst can be made to have
Sufficiently strong magnetic recycles ability, can recycled for multiple times to reduce flue gas demercuration cost improve the ring of visible light catalyst
Guaranteed cost.
In order to solve the above technical problems, the technical scheme of the present invention is realized as follows:
A kind of composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite, in which: by Ag, AgX(X=Cl,
Br, I), BiOX(X=Cl, Br, I) and CoFe2O4Composition.
Technical solution of the present invention may also is that realization: by Ag, AgI, BiOI and CoFe2O4Composition, CoFe2O4、
The weight ratio of AgI and BiOI is CoFe2O4: AgI:BiOI=1:(1 ~ 10): the weight ratio of (1 ~ 10), Ag and AgI are 0.1% ~ 10%.
Technical solution of the present invention may also is that realization: by Ag, AgI, BiOI and CoFe2O4Composition, CoFe2O4、
The weight ratio of AgI and BiOI is CoFe2O4: the weight ratio of AgI:BiOI=1:1.5:2.5, Ag and AgI are 1 ~ 5%.
Technical solution of the present invention may also is that realization: by Ag, AgCl, BiOCl and CoFe2O4Composition,
CoFe2O4, AgCl and BiOCl weight ratio be CoFe2O4: AgCl:BiOCl=1:(1 ~ 5): the weight of (1 ~ 10), Ag and AgCl
Than being 0.1% ~ 10%.
Technical solution of the present invention may also is that realization: by Ag, AgCl, BiOCl and CoFe2O4Composition,
CoFe2O4, AgCl and BiOCl weight ratio be CoFe2O4: the weight ratio of AgCl:BiOCl=1:1:7, Ag and AgCl are 1 ~ 5%.
Technical solution of the present invention may also is that realization: by Ag, AgBr, BiOBr and CoFe2O4Composition,
CoFe2O4, AgBr and BiOBr weight ratio be CoFe2O4: AgBr:BiOBr=1:(1 ~ 10): the weight of (1 ~ 20), Ag and AgBr
Than being 0.1% ~ 10%.
Technical solution of the present invention may also is that realization: by Ag, AgBr, BiOBr and CoFe2O4Composition,
CoFe2O4, AgBr and BiOBr weight ratio be CoFe2O4: the weight ratio of AgBr:BiOBr=1:2:4, Ag and AgBr are 1 ~ 5%.
A kind of composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite preparation method, in which: including
Following processing step:
One, magnetic corpuscular CoFe is prepared2O4
(1), by a moles of Co (NO3)2·6H2O and 2a moles of Fe (NO3)3·9H2O dissolves in the deionization of 100 ~ 150mL
In water and uniform stirring, the mixed solution A of cobalt nitrate and ferric nitrate is obtained；
(2), 8a moles of sodium hydroxide is dissolved in the deionized water of 100 ~ 150mL and obtains solution B；
(3), by solution B be added slowly in solution A adjust solution A pH value, make solution ph maintain 12 ~ 14 it
Between, it is added while stirring in adding procedure, continues stirring after addition 2 ~ 3 hours, obtained solution C；
(4), solution C is heated, chemically reacts solution C, it is after completion of the reaction, reaction products therefrom is natural
It is cooled to room temperature, is then washed 3 ~ 5 times, it is small that hydro-thermal reaction product is finally placed in vacuum drying 24 ~ 48 in 60 ~ 80 °C of baking oven
When, the product after drying is ground, magnetism CoFe is made after screening2O4Microparticle；
Two, AgX-BiOX-CoFe is prepared2O4(X=Cl, Br, I) magnetic suspension solution
(1), a certain amount of AgX-BiOX-CoFe is conversed by weight2O4The mole of Ag in (X=Cl, Br, I) catalyst
With the mole of Bi, by the mole of Ag and the mole of Bi respectively multiplied by AgNO3With Bi (NO3)3·5H2The molecular weight of O obtains
Required AgNO3With Bi (NO3)3·5H2The weight of O, and weigh the AgNO of corresponding weight3With Bi (NO3)3·5H2O；
(2), by weighed AgNO3With Bi (NO3)3·5H2O dissolves in the glacial acetic acid aqueous solution of 100 ~ 800mL, and uniformly
Stirring, obtains the mixed solution D of silver nitrate and bismuth nitrate under acid condition；
It (3), will be by weight the magnetic CoFe prepared in weighed step 12O4Microparticle is added in solution D, and is mixed
Close stirring 30 ~ 60 minutes, obtained solution E；
(4), the mole of calculated Ag in above-mentioned steps (1) is added with the mole of Bi, obtain required KX(X=
Cl, Br, I) mole, according to KX(X=Cl, Br, I) molar amount calculate needed for KX(X=Cl, Br, I) weight；Root
KX(X=Cl, Br, I are weighed according to the weight), it is dissolved in the water of 20 ~ 200mL, the KX solution is then added drop-wise to solution E
In, it is added dropwise while stirring during being added dropwise, and continuously stirred after being added dropwise 2 ~ 3 hours, stands at least 12 hours again later, made
Obtain aaerosol solution F；
Three, magnetic photocatalyst Ag-AgX-BiOX-CoFe is prepared2O4(X=Cl, Br, I)
(1), aaerosol solution F obtained in step 2 is placed under the ultraviolet lamp of 10 ~ 100W and is irradiated and to stir 1 ~ 10 small
When；
(2), the aaerosol solution F after irradiation is stood, then the sediment in solid-liquid separation aaerosol solution F；
(3), with washing precipitate 3 ~ 5 times repeatedly of the mixed solution of ethyl alcohol and water, 60 ~ 80 °C are put the precipitate in later
It is dried in vacuo in baking oven 12 ~ 24 hours, finally by sediment grinding, the screening after drying, magnetic photocatalyst Ag- is made
AgX-BiOX-CoFe2O4(X=Cl, Br, I).
Technical solution of the present invention may also is that realization: solution C being put into hydrothermal reaction kettle in step 1 (4)
In, then hydrothermal reaction kettle is put into baking oven and is heated, oven temperature is 150 ~ 200 °C, and heating time is 8 ~ 16 hours.
Technical solution of the present invention may also is that realization: in step 2 (1), in the aqueous solution of the glacial acetic acid
The volume fraction of glacial acetic acid is 10% ~ 50%.
The invention has the benefit that
The present invention provides a kind of recyclable magnetic photocatalyst Ag-AgX-BiOX- CoFe2O4(X=Cl, Br, I),
The catalyst is by simple substance Ag, AgX, BiOX and CoFe2O4It is combined, utilizes Ag, AgX, BiOX and CoFe2O4Between four compared with
Good energy band mating structure, is conducive to efficiently separating for photo-generate electron-hole pairs, the electronics in photo-generate electron-hole pairs and sky
Oxygen in gas generate a large amount of super oxygen root free radical (•O2 —), the hole of raw electron hole centering can generate a large amount of hydroxyls with water
Base free radical (•OH)；Hydroxyl radical free radical (•OH), super oxygen root free radical (•O2 —) and hole (h+) there is very strong oxidability, energy
Enough efficiently by Elemental Mercury Hg0It is oxidized to bivalent mercury Hg2+, and magnetic material CoFe2O4Addition, possess visible light catalyst
Stronger magnetic recycles ability, reusable, significantly reduces the use cost of catalyst.Can recycled for multiple times, from
And flue gas demercuration cost is reduced, the environmental-protecting performance of visible light catalyst is improved, what it is due to introducing is visible light, so the demercuration skill
Art is not only clean but also energy conservation and environmental protection, is conducive to large-scale use.
Detailed description of the invention:
Fig. 1 is the embodiment of the present invention one, embodiment two, embodiment three, comparative example one, comparative example two and right
Than three or four kinds of catalyst demercuration efficiency comparison diagrams of embodiment；
Fig. 2 is the embodiment of the present invention four, embodiment five, embodiment six, comparative example one, comparative example four and right
Than embodiment the May 4th kind catalyst demercuration efficiency comparison diagram；
Fig. 3 is the embodiment of the present invention seven, embodiment eight, embodiment nine, comparative example one, comparative example six and right
Than seven or four kinds of catalyst demercuration efficiency comparison diagrams of embodiment.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and embodiments.
Embodiment one
A kind of composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite, by Ag, AgCl, BiOCl and
CoFe2O4Composition, CoFe2O4, AgCl and BiOCl weight ratio are as follows:
CoFe2O4: the weight ratio of AgCl:BiOCl=1:1:1, Ag and AgCl are 0.1% ~ 2%.
Above-mentioned composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite preparation method, in which: including
Following processing step:
One, magnetic corpuscular CoFe is prepared2O4
(1), by the Co(NO of 0.042 mol3)2·6H2The Fe(NO of O and 0.084mol3)3·9H2O dissolves in going for 100mL
In ionized water and uniform stirring, the mixed solution A of cobalt nitrate and ferric nitrate is obtained；
(2), the sodium hydroxide of 0.34 mol is dissolved in the deionized water of 100mL and obtains solution B；
(3), by solution B be added slowly in solution A adjust solution A pH value, make solution ph maintain 12 ~ 14 it
Between, it is added while stirring in adding procedure, continues stirring 2 hours, obtained solution C after addition；
(4), solution C is put into hydrothermal reaction kettle then hydrothermal reaction kettle is put into baking oven and is heated, oven temperature is
180 °C, heating time is 8 hours, after completion of the reaction, reaction products therefrom is naturally cooled to room temperature, is then washed 3 ~ 5 times,
Finally hydro-thermal reaction product is placed in 80 °C of baking oven and is dried in vacuo 24 hours, the product after drying is ground, is made after screening
Obtain magnetic CoFe2O4Microparticle.
Two, AgCl-BiOCl-CoFe is prepared2O4Magnetic suspension solution
(1), by the weight ratio of 1:1:1, the magnetic CoFe of 1g is chosen2O4The BiOCl of microparticle, the AgCl of 1g and 1g is carried out
It calculates, according to the weight of the AgCl of selection divided by the molecular weight of AgCl, the mole for obtaining AgCl is 0.00697mol, then Ag moles
Amount is 0.00697mol；Molecular weight is obtained divided by BiOCl according to the weight of the BiOCl of selection, the mole for obtaining BiOCl is
0.00384mol, then the mole of Bi is 0.00384mol, is then calculated according to the mole 0.00697mol of Ag required
AgNO3Weight be 1.184 grams, required Bi (NO is calculated according to the mole 0.00384mol of Bi3)3·5H2The weight of O
It is 1.863 grams；
Weigh the 1 gram of magnetism CoFe prepared in step 12O4Microparticle weighs 1.184 grams of AgNO3With 1.863 grams of Bi
(NO3)3·5H2O；
(2), by weighed AgNO3With Bi (NO3)3·5H2O dissolves in the glacial acetic acid aqueous solution that the volume ratio of 200mL is 20%
In, and uniform stirring, obtain the mixed solution D of silver nitrate and bismuth nitrate under acid condition；
(3), by 1 gram prepared in weighed step 1 magnetism CoFe2O4Microparticle is added in solution D, and is mixed
30 ~ 60 minutes, obtained solution E；
(4), by the mole 0.00384mol of the mole 0.00697mol and Bi of calculated Ag in above-mentioned steps (1)
It is added, show that the mole of required KCl is 0.01081mol, the weight of the KCl needed for calculating according to the molar amount of KCl is
0.548g；
The KCl for weighing 0.548 gram, is dissolved in the water of 20mL, and then the KCl solution is added drop-wise in solution E, drop
It is added dropwise, and is continuously stirred after being added dropwise 2 hours while stirring during adding, stand 12 hours again later, aaerosol solution is made
F。
Three, magnetic photocatalyst Ag-AgCl-BiOCl-CoFe is prepared2O4
(1), aaerosol solution F is placed under the ultraviolet lamp of 36W and irradiates and stir 2 hour；
(2), the aaerosol solution F after irradiation is stood, then the sediment in solid-liquid separation aaerosol solution F；
(3), with ethanol solution washing precipitate 3 ~ 5 times repeatedly, it is dry that vacuum in 80 °C of baking oven is put the precipitate in later
Dry 24 hours, finally by sediment grinding, the screening after drying, magnetic photocatalyst Ag-AgCl-BiOCl- is made
CoFe2O4.Ag in the magnetic photocatalyst decomposes in light gained by AgCl, and the weight ratio with AgCl is 0.1% ~ 2%.
Embodiment two
A kind of composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite, by Ag, AgCl, BiOCl and
CoFe2O4Composition, CoFe2O4, AgCl and BiOCl weight ratio are as follows:
CoFe2O4: the weight ratio of AgCl:BiOCl=1:5:10, Ag and AgCl are 2% ~ 5%.
Above-mentioned composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite preparation method, in which: including
Following processing step:
One, magnetic corpuscular CoFe is prepared2O4
(1), by the Co (NO of 0.042 mol3)2·6H2Fe (the NO of O and 0.084 mol3)3·9H2O dissolves in going for 100mL
In ionized water and uniform stirring, the mixed solution A of cobalt nitrate and ferric nitrate is obtained；
(2), the sodium hydroxide of 0.34 mol is dissolved in the deionized water of 100mL and obtains solution B；
(3), by solution B be added slowly in solution A adjust solution A pH value, make solution ph maintain 12 ~ 14 it
Between, it is added while stirring in adding procedure, continues stirring 2 hours, obtained solution C after addition；
(4), solution C is put into hydrothermal reaction kettle then hydrothermal reaction kettle is put into baking oven and is heated, oven temperature is
180 °C, heating time is 8 ~ 16 hours, after completion of the reaction, reaction products therefrom is naturally cooled to room temperature, then washes 3 ~ 5
It is secondary, finally hydro-thermal reaction product is placed in 80 °C of baking oven and is dried in vacuo 24 hours, the product after drying ground, after screening
Magnetism CoFe is made2O4Microparticle.
Two, AgCl-BiOCl-CoFe is prepared2O4Magnetic suspension solution
(1), by the weight ratio of 1:5:10, the magnetic CoFe of 1g is chosen2O4The BiOCl of microparticle, the AgCl of 5g and 10g into
Row calculates, and according to the weight of the AgCl of selection divided by the molecular weight of AgCl, the mole for obtaining AgCl is 0.03484mol, then Ag rubs
Your amount is 0.03484mol；Molecular weight is obtained divided by BiOCl according to the weight of the BiOCl of selection, the mole for obtaining BiOCl is
0.03839mol, then the mole of Bi is 0.03839mol, is then calculated according to the mole 0.03484mol of Ag required
AgNO3Weight be 5.918 grams, required Bi (NO is calculated according to the mole 0.03839mol of Bi3)3·5H2The weight of O
It is 18.622 grams；
Weigh the 1 gram of magnetism CoFe prepared in step 12O4Microparticle weighs 5.918 grams of AgNO3With 18.622 grams of Bi
(NO3)3·5H2O；
(2), by weighed AgNO3With Bi (NO3)3·5H2O dissolves in the glacial acetic acid aqueous solution that the volume ratio of 200mL is 20%
In, and uniform stirring, obtain the mixed solution D of silver nitrate and bismuth nitrate under acid condition；
(3), by 1 gram prepared in weighed step 1 magnetism CoFe2O4Microparticle is added in solution D, and is mixed
30 ~ 60 minutes, obtained solution E；
(4), by the mole 0.03839mol of the mole 0.03484mol and Bi of calculated Ag in above-mentioned steps (1)
It is added, show that the mole of required KCl is 0.07323mol, the weight of the KCl needed for calculating according to the molar amount of KCl is
5.459g；
The KCl for weighing 5.459 grams, is dissolved in the water of 50mL, and then the KCl solution is added drop-wise in solution E, drop
It is added dropwise, and is continuously stirred after being added dropwise 2 hours while stirring during adding, stand 12 hours again later, aaerosol solution is made
F。
Three, magnetic photocatalyst Ag-AgCl-BiOCl-CoFe is prepared2O4
(1), aaerosol solution F is placed under the ultraviolet lamp of 40W and irradiates and stir 5 hour；
(2), the aaerosol solution F after irradiation is stood, then the sediment in solid-liquid separation aaerosol solution F；
(3), with ethanol solution washing precipitate 3 ~ 5 times repeatedly, it is dry that vacuum in 80 °C of baking oven is put the precipitate in later
Dry 24 hours, finally by sediment grinding, the screening after drying, magnetic photocatalyst Ag-AgCl-BiOCl- is made
CoFe2O4.Ag in the magnetic photocatalyst decomposes in light gained by AgCl, and the weight ratio with AgCl is 2% ~ 5%.
Embodiment three
A kind of composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite, by Ag, AgCl, BiOCl and
CoFe2O4Composition, CoFe2O4, AgCl and BiOCl weight ratio are as follows:
CoFe2O4: the weight ratio of AgCl:BiOCl=1:1:7, Ag and AgCl are 2% ~ 3%.
Above-mentioned composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite preparation method, in which: including
Following processing step:
One, magnetic corpuscular CoFe is prepared2O4
(1), by the Co(NO of 0.042 mol3)2·6H2O and 0.084mol Fe(NO3)3·9H2O dissolve in 100mL go from
In sub- water and uniform stirring, the mixed solution A of cobalt nitrate and ferric nitrate is obtained；
(2), the sodium hydroxide of 0.34 mol is dissolved in the deionized water of 100mL and obtains solution B；
(3), by solution B be added slowly in solution A adjust solution A pH value, make solution ph maintain 12 ~ 14 it
Between, it is added while stirring in adding procedure, continues stirring 2 hours, obtained solution C after addition；
(4), solution C is put into hydrothermal reaction kettle then hydrothermal reaction kettle is put into baking oven and is heated, oven temperature is
180 °C, heating time is 8 ~ 16 hours, after completion of the reaction, reaction products therefrom is naturally cooled to room temperature, then washes 3 ~ 5
It is secondary, finally hydro-thermal reaction product is placed in 80 °C of baking oven and is dried in vacuo 24 hours, the product after drying ground, after screening
Magnetism CoFe is made2O4Microparticle.
Two, AgCl-BiOCl-CoFe is prepared2O4Magnetic suspension solution
(1), by the weight ratio of 1:1:7, the magnetic CoFe of 1g is chosen2O4The BiOCl of microparticle, the AgCl of 1g and 7g is carried out
It calculates, according to the weight of the AgCl of selection divided by the molecular weight of AgCl, the mole for obtaining AgCl is 0.00697mol, then Ag moles
Amount is 0.00697mol；Molecular weight is obtained divided by BiOCl according to the weight of the BiOCl of selection, the mole for obtaining BiOCl is
0.02687mol, then the mole of Bi is 0.02687mol, is then calculated according to the mole 0.00697mol of Ag required
AgNO3Weight be 1.184 grams, required Bi (NO is calculated according to the mole 0.02687mol of Bi3)3·5H2The weight of O
It is 13.034 grams；
Weigh the 1 gram of magnetism CoFe prepared in step 12O4Microparticle weighs 1.184 grams of AgNO3With 13.034 grams of Bi
(NO3)3·5H2O；
(2), by weighed AgNO3With Bi (NO3)3·5H2O dissolves in the glacial acetic acid aqueous solution that the volume ratio of 200mL is 20%
In, and uniform stirring, obtain the mixed solution D of silver nitrate and bismuth nitrate under acid condition；
(3), by 1 gram prepared in weighed step 1 magnetism CoFe2O4Microparticle is added in solution D, and is mixed
30 ~ 60 minutes, obtained solution E；
(4), by the mole 0.02687mol of the mole 0.00697mol and Bi of calculated Ag in above-mentioned steps (1)
It is added, show that the mole of required KCl is 0.03384mol, the weight of the KCl needed for calculating according to the molar amount of KCl is
2.523g；
The KCl for weighing 2.523 grams, is dissolved in the water of 40mL, and then the KCl solution is added drop-wise in solution E, drop
It is added dropwise, and is continuously stirred after being added dropwise 2 hours while stirring during adding, stand 12 hours again later, aaerosol solution is made
F。
Three, magnetic photocatalyst Ag-AgCl-BiOCl-CoFe is prepared2O4
(1), aaerosol solution F is placed under the ultraviolet lamp of 36W and irradiates and stir 8 hour；
(2), the aaerosol solution F after irradiation is stood, then the sediment in solid-liquid separation aaerosol solution F；
(3), with ethanol solution washing precipitate 3 ~ 5 times repeatedly, it is dry that vacuum in 80 °C of baking oven is put the precipitate in later
Dry 24 hours, finally by sediment grinding, the screening after drying, magnetic photocatalyst Ag-AgCl-BiOCl- is made
CoFe2O4.Ag in the magnetic photocatalyst decomposes in light gained by AgCl, and the weight ratio with AgCl is 2% ~ 3%.
Comparative example one
CoFe is used in the present embodiment2O4For visible light catalyst, it is specific the preparation method is as follows:
(1), by the Co (NO of 0.042 mol3)2·6H2Fe (the NO of O and 0.084 mol3)3·9H2O dissolves in going for 100mL
In ionized water and uniform stirring, the mixed solution A of cobalt nitrate and ferric nitrate is obtained；
(2), the sodium hydroxide of 0.34 mol is dissolved in the deionized water of 100mL and obtains solution B；
(3), by solution B be added slowly in solution A adjust solution A pH value, make solution ph maintain 12 ~ 14 it
Between, it is added while stirring in adding procedure, continues stirring 2 hours, obtained solution C after addition；
(4), solution C is put into hydrothermal reaction kettle and carries out hydro-thermal reaction, hydrothermal temperature is 180 °C, hydro-thermal reaction
Time is 8 ~ 16 hours, after hydro-thermal reaction, and reaction products therefrom is naturally cooled to room temperature, then washing 3 ~ 5 times, finally
Hydro-thermal reaction product is placed in 80 °C of baking oven and is dried in vacuo 24 hours, the product after drying is ground, magnetic is made after screening
Property CoFe2O4Microparticle.
Comparative example two
BiOCl-CoFe is used in the present embodiment2O4For visible light catalyst, CoFe2O4Weight ratio with BiOCl is 1:4,
It is specific the preparation method is as follows:
Step 1: preparation CoFe2O4
(1), by the Co (NO of 0.042mol3)2·6H2Fe (the NO of O and 0.084mol3)3·9H2O dissolve in 100mL go from
In sub- water and uniform stirring, the mixed solution A of cobalt nitrate and ferric nitrate is obtained；
(2), the sodium hydroxide of 0.34mol is dissolved in the deionized water of 100mL and obtains solution B；
(3), by solution B be added slowly in solution A adjust solution A pH value, make solution ph maintain 12 ~ 14 it
Between, it is added while stirring in adding procedure, continues stirring 2 hours, obtained solution C after addition；
(4), solution C is put into hydrothermal reaction kettle and carries out hydro-thermal reaction, hydrothermal temperature is 180 °C, hydro-thermal reaction
Time is 8 ~ 16 hours, after hydro-thermal reaction, and reaction products therefrom is naturally cooled to room temperature, then washing 3 ~ 5 times, finally
Hydro-thermal reaction product is placed in 80 °C of baking oven and is dried in vacuo 24 hours, the product after drying is ground, magnetic is made after screening
Property CoFe2O4Microparticle.
Step 2: preparation BiOCl-CoFe2O4
(1), by 7.276 grams of Bi (NO3)3·5H2O is added in 200 mL and aqueous solution containing 40 mL glacial acetic acid uniformly
Stirring, obtains bismuth nitrate solution under acid condition, this solution is denoted as solution D；
(2), by 1 gram of CoFe prepared in step 12O4Magnetic corpuscular is added in solution D, and in mechanical electric mixing
It mixes and is continuously stirred under device 30 minutes, this solution is denoted as solution E；
(3), the KCl for weighing 1.118 grams, is dissolved in the water of 40mL, and the KCl solution is then added drop-wise to solution E
In, it is added dropwise while stirring during being added dropwise, and continuously stirred after being added dropwise 2 hours, stands 12 hours again later, be made and suspend
Solution F.
(4), the mixed liquor of product F deionized water and ethyl alcohol is washed 3 ~ 5 times, the baking oven for being placed on 80 °C in it is dry
24 hours, the product after drying ground, sieves up to two cobalt ferrite BiOCl- CoFe of-four oxygen of bismuth oxyiodide2O4Magnetic visible light
Catalyst.
Comparative example three
AgCl-BiOCl-CoFe is used in the present embodiment2O4For visible light catalyst, CoFe2O4, AgCl and BiOCl weight
Amount than being 1:4:7, it is specific the preparation method is as follows:
One, magnetic corpuscular CoFe is prepared2O4
(1), by the Co (NO of 0.042 mol3)2·6H2Fe (the NO of O and 0.084mol3)3·9H2O dissolves in going for 100mL
In ionized water and uniform stirring, the mixed solution A of cobalt nitrate and ferric nitrate is obtained；
(2), the sodium hydroxide of 0.34 mol is dissolved in the deionized water of 100mL and obtains solution B；
(3), by solution B be added slowly in solution A adjust solution A pH value, make solution ph maintain 12 ~ 14 it
Between, it is added while stirring in adding procedure, continues stirring 2 hours, obtained solution C after addition；
(4), solution C is put into hydrothermal reaction kettle and carries out hydro-thermal reaction, hydrothermal temperature is 180 °C, hydro-thermal reaction
Time is 8 ~ 16 hours, after hydro-thermal reaction, and reaction products therefrom is naturally cooled to room temperature, then washing 3 ~ 5 times, finally
Hydro-thermal reaction product is placed in 80 °C of baking oven and is dried in vacuo 24 hours, the product after drying is ground, magnetic is made after screening
Property CoFe2O4Microparticle.
Two, magnetic photocatalyst AgCl-BiOCl-CoFe is prepared2O4
(1) weight ratio for pressing 1:4:7, chooses the magnetic CoFe of 1g2O4The BiOCl of microparticle, the AgCl of 4g and 7g is counted
It calculates, according to the weight of the AgCl of selection divided by the molecular weight of AgCl, the mole for obtaining AgCl is 0.02787mol, then Ag mole
For 0.02787mol；Molecular weight is obtained divided by BiOCl according to the weight of the BiOCl of selection, the mole for obtaining BiOCl is
0.02687mol, then the mole of Bi is 0.02687mol, is then calculated according to the mole 0.02787mol of Ag required
AgNO3Weight be 4.734 grams, required Bi (NO is calculated according to the mole 0.02687mol of Bi3)3·5H2The weight of O
It is 13.034 grams；
Weigh the 1 gram of magnetism CoFe prepared in step 12O4Microparticle weighs 4.734 grams of AgNO3With 13.034 grams of Bi
(NO3)3·5H2O；
(2) by weighed AgNO3With Bi (NO3)3·5H2O dissolves in the glacial acetic acid aqueous solution that the volume ratio of 600mL is 20%
In, and uniform stirring, obtain the mixed solution D of silver nitrate and bismuth nitrate under acid condition；
(3), by prepared in step 11 gram of magnetism CoFe2O4Microparticle is added in solution D, and is mixed 30 points
Clock, obtained solution E；
(4), by the mole 0.02687mol of the mole 0.02787mol and Bi of calculated Ag in above-mentioned steps (1)
It is added, show that the mole of required KCl is 0.05474mol, the weight of the KCl needed for calculating according to the molar amount of KCl is
4.08g；
The KCl for weighing 4.08 grams, is dissolved in the water of 40mL, and then the KCl solution is added drop-wise in solution E, drop
It is added dropwise, and is continuously stirred after being added dropwise 2 hours while stirring during adding, stand 12 hours again later, aaerosol solution is made
F。
(5), the mixed liquor of aaerosol solution F deionized water and ethyl alcohol is washed 3 ~ 5 times, the baking oven for being placed on 80 °C in
24 hours dry, the product after drying grinds, sieves up to AgCl-BiOCl-CoFe2O4Magnetic photocatalyst.
As shown in Figure 1, removing the Elemental Mercury in flue gas using wet process using the magnetic photocatalyst in embodiment one
Hg0, flue gas main component is N2、O2、CO2, Elemental Mercury Hg in flue gas0Concentration be 50 μ g/m3Under, magnetic photocatalyst
Dosage be 0.1 g/L, reaction temperature be 45 °C under the conditions of, through counting, the magnetic photocatalyst in embodiment one is to cigarette
The removal efficiency of Elemental Mercury is about 85% in gas.
As shown in Figure 1, removing the Elemental Mercury in flue gas using wet process using the magnetic photocatalyst in embodiment two
Hg0, flue gas main component is N2、O2、CO2, Elemental Mercury Hg in flue gas0Concentration be 50 μ g/m3Under, magnetic photocatalyst
Dosage be 0.1 g/L, reaction temperature be 45 °C under the conditions of, through counting, the magnetic photocatalyst in embodiment two is to cigarette
The removal efficiency of Elemental Mercury is about 88% in gas.
As shown in Figure 1, removing the Elemental Mercury in flue gas using wet process using the magnetic photocatalyst in embodiment three
Hg0, flue gas main component is N2、O2、CO2, Elemental Mercury Hg in flue gas0Concentration be 50 μ g/m3Under, magnetic photocatalyst
Dosage be 0.1 g/L, reaction temperature be 45 °C under the conditions of, through counting, the magnetic photocatalyst in embodiment three is to cigarette
The removal efficiency of Elemental Mercury is about 92% in gas.
As shown in Figure 1, using the visible light catalyst CoFe in comparative example one2O4, removed in flue gas using wet process
Elemental Mercury Hg0, flue gas main component is N2、O2、CO2, Elemental Mercury Hg in flue gas0Concentration be 50 μ g/m3Under, magnetic visible light
The dosage of catalyst is 0.1 g/L, under the conditions of reaction temperature is 45 °C, through counting, it is seen that photochemical catalyst CoFe2O4To in flue gas
The removal efficiency of Elemental Mercury is about 5%.
As shown in Figure 1, using the magnetic photocatalyst BiOCl-CoFe in comparative example two2O4, removed using wet process
Remove the Elemental Mercury Hg in flue gas0, flue gas main component is N2、O2、CO2, Elemental Mercury Hg in flue gas0Concentration be 50 μ g/m3Under,
The dosage of magnetic photocatalyst is 0.1 g/L, under the conditions of reaction temperature is 45 °C, through counting, and magnetic photocatalyst
BiOCl-CoFe2O4Removal efficiency to Elemental Mercury in flue gas is about 35%.
As shown in Figure 1, using the magnetic photocatalyst AgCl-BiOCl- CoFe in comparative example three2O4, utilize
Wet process removes the Elemental Mercury Hg in flue gas0, flue gas main component is N2、O2、CO2, Elemental Mercury Hg in flue gas0Concentration be 50 μ g/
m3Under, the dosage of magnetic photocatalyst is 0.1 g/L, under the conditions of reaction temperature is 45 °C, through counting, and magnetic visible light
Catalyst AgCl-BiOCl-CoFe2O4Removal efficiency to Elemental Mercury in flue gas is about 65%.
In conclusion magnetic photocatalyst Ag-AgCl-BiOCl-CoFe of the invention2O4Flue gas can be greatly improved
In Elemental Mercury removal efficiency.
Example IV
A kind of composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite, by Ag, AgBr, BiOBr and
CoFe2O4Composition, CoFe2O4, AgBr and BiOBr weight ratio are as follows:
CoFe2O4: the weight ratio of AgBr:BiOBr=1:1:1, Ag and AgBr are 1% ~ 2%.
Above-mentioned composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite preparation method, in which: including
Following processing step:
One, magnetic corpuscular CoFe is prepared2O4
(1), by the Co (NO of 0.042 mol3)2·6H2Fe (the NO of O and 0.084 mol3)3·9H2O dissolves in going for 100mL
In ionized water and uniform stirring, the mixed solution A of cobalt nitrate and ferric nitrate is obtained；
(2), the sodium hydroxide of 0.34 mol is dissolved in the deionized water of 100mL and obtains solution B；
(3), by solution B be added slowly in solution A adjust solution A pH value, make solution ph maintain 12 ~ 14 it
Between, it is added while stirring in adding procedure, continues stirring 2 hours, obtained solution C after addition；
(4), solution C is put into hydrothermal reaction kettle then hydrothermal reaction kettle is put into baking oven and is heated, oven temperature is
180 °C, heating time is 8 ~ 16 hours, after completion of the reaction, reaction products therefrom is naturally cooled to room temperature, then washes 3 ~ 5
It is secondary, finally hydro-thermal reaction product is placed in 80 °C of baking oven and is dried in vacuo 24 hours, the product after drying ground, after screening
Magnetism CoFe is made2O4Microparticle.
Two, AgBr-BiOBr-CoFe is prepared2O4Magnetic suspension solution
(1) weight ratio for pressing 1:1:1, chooses the magnetic CoFe of 1g2O4The BiOBr of microparticle, the AgBr of 1g and 1g is counted
It calculates, according to the weight of the AgBr of selection divided by the molecular weight of AgBr, the mole for obtaining AgBr is 0.00535mol, then Ag mole
For 0.00535mol；Molecular weight is obtained divided by BiOBr according to the weight of the BiOBr of selection, the mole for obtaining BiOBr is
0.00329mol, then the mole of Bi is 0.00329mol, is then calculated according to the mole 0.00535mol of Ag required
AgNO3Weight be 0.9088 gram, required Bi (NO is calculated according to the mole 0.00329mol of Bi3)3·5H2The weight of O
It is 1.5959 grams；
Weigh the 1 gram of magnetism CoFe prepared in step 12O4Microparticle weighs 0.9088 gram of AgNO3With 1.5959 grams of Bi
(NO3)3·5H2O；
(2), by weighed AgNO3With Bi (NO3)3·5H2O dissolves in the glacial acetic acid aqueous solution that the volume ratio of 200mL is 20%
In, and uniform stirring, obtain the mixed solution D of silver nitrate and bismuth nitrate under acid condition；
(3), by 1 gram prepared in weighed step 1 magnetism CoFe2O4Microparticle is added in solution D, and is mixed
30 ~ 60 minutes, obtained solution E；
(4), by the mole 0.00329mol of the mole 0.00535mol and Bi of calculated Ag in above-mentioned steps (1)
It is added, show that the mole of required KBr is 0.00864mol, the weight of the KBr needed for calculating according to the molar amount of KBr is
1.0282g；
The KBr for weighing 1.0282 grams, is dissolved in the water of 30mL, and then the KBr solution is added drop-wise in solution E,
It is added dropwise, and is continuously stirred after being added dropwise 2 hours while stirring during being added dropwise, stand 12 hours again later, it is molten that suspension is made
Liquid F.
Three, magnetic photocatalyst Ag-AgBr-BiOBr-CoFe is prepared2O4
(1), aaerosol solution F is placed under the ultraviolet lamp of 36W and irradiates and stir 2.5 hour；
(2), the aaerosol solution F after irradiation is stood, then the sediment in solid-liquid separation aaerosol solution F；
(3), with ethanol solution washing precipitate 3 ~ 5 times repeatedly, it is dry that vacuum in 80 °C of baking oven is put the precipitate in later
Dry 24 hours, finally by sediment grinding, the screening after drying, magnetic photocatalyst Ag-AgBr-BiOBr- is made
CoFe2O4.Ag in the magnetic photocatalyst decomposes in light gained by AgBr, and the weight ratio with AgBr is 1% ~ 2%.
Embodiment five
A kind of composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite, by Ag, AgBr, BiOBr and
CoFe2O4Composition, CoFe2O4, AgBr and BiOBr weight ratio are as follows:
CoFe2O4: the weight ratio of AgBr:BiOBr=1:10:20, Ag and AgBr are 2% ~ 5%.
Above-mentioned composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite preparation method, in which: including
Following processing step:
One, magnetic corpuscular CoFe is prepared2O4
(1), by the Co (NO of 0.042mol3)2·6H2Fe (the NO of O and 0.084mol3)3·9H2O dissolve in 100mL go from
In sub- water and uniform stirring, the mixed solution A of cobalt nitrate and ferric nitrate is obtained；
(2), the sodium hydroxide of 0.34mol is dissolved in the deionized water of 100mL and obtains solution B；
(3), by solution B be added slowly in solution A adjust solution A pH value, make solution ph maintain 12 ~ 14 it
Between, it is added while stirring in adding procedure, continues stirring 2 hours, obtained solution C after addition；
(4), solution C is put into hydrothermal reaction kettle then hydrothermal reaction kettle is put into baking oven and is heated, oven temperature is
180 °C, heating time is 8 ~ 16 hours, after completion of the reaction, reaction products therefrom is naturally cooled to room temperature, then washes 3 ~ 5
It is secondary, finally hydro-thermal reaction product is placed in 80 °C of baking oven and is dried in vacuo 24 hours, the product after drying ground, after screening
Magnetism CoFe is made2O4Microparticle.
Two, AgBr-BiOBr-CoFe is prepared2O4Magnetic suspension solution
(1) weight ratio for pressing 1:10:20, chooses the magnetic CoFe of 1g2O4The BiOBr of microparticle, the AgBr of 10g and 20g into
Row calculates, and according to the weight of the AgBr of selection divided by the molecular weight of AgBr, the mole for obtaining AgBr is 0.05347mol, then Ag rubs
Your amount is 0.05347mol；Molecular weight is obtained divided by BiOBr according to the weight of the BiOBr of selection, the mole for obtaining BiOBr is
0.06579mol, then the mole of Bi is 0.06579mol, is then calculated according to the mole 0.05347mol of Ag required
AgNO3Weight be 9.0829 grams, required Bi (NO is calculated according to the mole 0.06579mol of Bi3)3·5H2The weight of O
It is 31.9128 grams；
Weigh the 1 gram of magnetism CoFe prepared in step 12O4Microparticle weighs 9.0829 grams of AgNO3With 31.9128 grams of Bi
(NO3)3·5H2O；
(2), by weighed AgNO3With Bi (NO3)3·5H2O dissolves in the glacial acetic acid aqueous solution that the volume ratio of 200mL is 20%
In, and uniform stirring, obtain the mixed solution D of silver nitrate and bismuth nitrate under acid condition；
(3), by 1 gram prepared in weighed step 1 magnetism CoFe2O4Microparticle is added in solution D, and is mixed
30 ~ 60 minutes, obtained solution E；
(4), by the mole 0.06579mol of the mole 0.05347mol and Bi of calculated Ag in above-mentioned steps (1)
It is added, show that the mole of required KBr is 0.11926mol, the weight of the KBr needed for calculating according to the molar amount of KBr is
14.192g；
The KBr for weighing 14.192 grams, is dissolved in the water of 100mL, and then the KBr solution is added drop-wise in solution E,
It is added dropwise, and is continuously stirred after being added dropwise 2 hours while stirring during being added dropwise, stand 12 hours again later, it is molten that suspension is made
Liquid F.
Three, magnetic photocatalyst Ag-AgBr-BiOBr-CoFe is prepared2O4
(1), aaerosol solution F is placed under the ultraviolet lamp of 40W and irradiates and stir 4 hour；
(2), the aaerosol solution F after irradiation is stood, then the sediment in solid-liquid separation aaerosol solution F；
(3), with ethanol solution washing precipitate 3 ~ 5 times repeatedly, it is dry that vacuum in 80 °C of baking oven is put the precipitate in later
Dry 24 hours, finally by sediment grinding, the screening after drying, magnetic photocatalyst Ag-AgBr-BiOBr- is made
CoFe2O4.Ag in the magnetic photocatalyst decomposes in light gained by AgBr, and the weight ratio with AgBr is 2% ~ 5%.
Embodiment six
A kind of composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite, by Ag, AgBr, BiOBr and
CoFe2O4Composition, CoFe2O4, AgBr and BiOBr weight ratio are as follows:
CoFe2O4: the weight ratio of AgBr:BiOBr=1:2:4, Ag and AgBr are 2% ~ 3%.
Above-mentioned composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite preparation method, in which: including
Following processing step:
One, magnetic corpuscular CoFe is prepared2O4
(1), by the Co (NO of 0.042mol3)2·6H2Fe (the NO of O and 0.084mol3)3·9H2O dissolve in 100mL go from
In sub- water and uniform stirring, the mixed solution A of cobalt nitrate and ferric nitrate is obtained；
(2), the sodium hydroxide of 0.34mol is dissolved in the deionized water of 100mL and obtains solution B；
(3), by solution B be added slowly in solution A adjust solution A pH value, make solution ph maintain 12 ~ 14 it
Between, it is added while stirring in adding procedure, continues stirring 2 hours, obtained solution C after addition；
(4), solution C is put into hydrothermal reaction kettle then hydrothermal reaction kettle is put into baking oven and is heated, oven temperature is
180 °C, heating time is 8 ~ 16 hours, after completion of the reaction, reaction products therefrom is naturally cooled to room temperature, then washes 3 ~ 5
It is secondary, finally hydro-thermal reaction product is placed in 80 °C of baking oven and is dried in vacuo 24 hours, the product after drying ground, after screening
Magnetism CoFe is made2O4Microparticle.
Two, AgBr-BiOBr-CoFe is prepared2O4Magnetic suspension solution
(1) weight ratio for pressing 1:2:4, chooses the magnetic CoFe of 1g2O4The BiOBr of microparticle, the AgBr of 2g and 4g is counted
It calculates, according to the weight of the AgBr of selection divided by the molecular weight of AgBr, the mole for obtaining AgBr is 0.01069mol, then Ag mole
For 0.01069mol；Molecular weight is obtained divided by BiOBr according to the weight of the BiOBr of selection, the mole for obtaining BiOBr is
0.01316mol, then the mole of Bi is 0.01316mol, is then calculated according to the mole 0.01069mol of Ag required
AgNO3Weight be 1.8159 grams, required Bi (NO is calculated according to the mole 0.01316mol of Bi3)3·5H2The weight of O
It is 6.3835 grams；
Weigh the 1 gram of magnetism CoFe prepared in step 12O4Microparticle weighs 1.8159 grams of AgNO3With 6.3835 grams of Bi
(NO3)3·5H2O；
(2), by weighed AgNO3With Bi (NO3)3·5H2O dissolves in the glacial acetic acid aqueous solution that the volume ratio of 200mL is 20%
In, and uniform stirring, obtain the mixed solution D of silver nitrate and bismuth nitrate under acid condition；
(3), by 1 gram prepared in weighed step 1 magnetism CoFe2O4Microparticle is added in solution D, and is mixed
30 ~ 60 minutes, obtained solution E；
(4), by the mole 0.01316mol of the mole 0.01069mol and Bi of calculated Ag in above-mentioned steps (1)
It is added, show that the mole of required KBr is 0.02385mol, the weight of the KBr needed for calculating according to the molar amount of KBr is
2.838g；
The KBr for weighing 2.838 grams, is dissolved in the water of 50mL, and then the KBr solution is added drop-wise in solution E, drop
It is added dropwise, and is continuously stirred after being added dropwise 2 hours while stirring during adding, stand 12 hours again later, aaerosol solution is made
F。
Three, magnetic photocatalyst Ag-AgBr-BiOBr-CoFe is prepared2O4
(1), aaerosol solution F is placed under the ultraviolet lamp of 36W and irradiates and stir 3 hour；
(2), the aaerosol solution F after irradiation is stood, then the sediment in solid-liquid separation aaerosol solution F；
(3), with ethanol solution washing precipitate 3 ~ 5 times repeatedly, it is dry that vacuum in 80 °C of baking oven is put the precipitate in later
Dry 24 hours, finally by sediment grinding, the screening after drying, magnetic photocatalyst Ag-AgBr-BiOBr- is made
CoFe2O4.Ag in the magnetic photocatalyst decomposes in light gained by AgBr, and the weight ratio with AgBr is 2% ~ 3%.
Comparative example four
BiOBr-CoFe is used in the present embodiment2O4For visible light catalyst, CoFe2O4Weight ratio with BiOBr is 1:4,
It is specific the preparation method is as follows:
Step 1: preparation CoFe2O4
(1), by the Co (NO of 0.042mol3)2·6H2Fe (the NO of O and 0.084mol3)3·9H2O dissolve in 100mL go from
In sub- water and uniform stirring, the mixed solution A of cobalt nitrate and ferric nitrate is obtained；
(2), the sodium hydroxide of 0.34mol is dissolved in the deionized water of 100mL and obtains solution B；
(3), by solution B be added slowly in solution A adjust solution A pH value, make solution ph maintain 12 ~ 14 it
Between, it is added while stirring in adding procedure, continues stirring 2 hours, obtained solution C after addition；
(4), solution C is put into hydrothermal reaction kettle and carries out hydro-thermal reaction, hydrothermal temperature is 180 °C, hydro-thermal reaction
Time is 8 ~ 16 hours, after hydro-thermal reaction, and reaction products therefrom is naturally cooled to room temperature, then washing 3 ~ 5 times, finally
Hydro-thermal reaction product is placed in 80 °C of baking oven and is dried in vacuo 24 hours, the product after drying is ground, magnetic is made after screening
Property CoFe2O4Microparticle.
Step 2: preparation BiOBr-CoFe2O4
(1), by 0.013mol Bi (NO3)3·5H2O is added in 200mL and aqueous solution containing 35 mL glacial acetic acid
Even stirring obtains bismuth nitrate solution under acid condition, this solution is denoted as solution D；
(2), by 0.043mol CoFe prepared in step2O4Magnetic corpuscular is added in solution A, and in mechanical electric
It is continuously stirred 30 minutes under dynamic blender, this solution is denoted as solution E；
(3), 0.013mol KBr is added dropwise into solution E under mechanical electric stirring quiet again after continuously stirring 2 hours
It sets 12 hours, products therefrom is denoted as F；
(4), the mixed liquor of product C deionized water and ethyl alcohol is washed 3 ~ 5 times, the baking oven for being placed on 70 °C in it is dry
24 hours, the product after drying ground, sieves up to two cobalt ferrite BiOBr-CoFe of-four oxygen of bismuth oxybromide2O4Magnetic visible light is urged
Agent.
Comparative example five
AgBr-BiOBr-CoFe is used in the present embodiment2O4For visible light catalyst, wherein CoFe2O4, AgBr and BiOBr
Weight ratio be 1:3:11, it is specific the preparation method is as follows:
One, magnetic corpuscular CoFe is prepared2O4
(1), by the Co (NO of 0.042 mol3)2·6H2Fe (the NO of O and 0.084mol3)3·9H2O dissolves in going for 100mL
In ionized water and uniform stirring, the mixed solution A of cobalt nitrate and ferric nitrate is obtained；
(2), the sodium hydroxide of 0.34 mol is dissolved in the deionized water of 100mL and obtains solution B；
(3), by solution B be added slowly in solution A adjust solution A pH value, make solution ph maintain 12 ~ 14 it
Between, it is added while stirring in adding procedure, continues stirring 2 hours, obtained solution C after addition；
(4), solution C is put into hydrothermal reaction kettle and carries out hydro-thermal reaction, hydrothermal temperature is 180 °C, hydro-thermal reaction
Time is 8 ~ 16 hours, after hydro-thermal reaction, and reaction products therefrom is naturally cooled to room temperature, then washing 3 ~ 5 times, finally
Hydro-thermal reaction product is placed in 80 °C of baking oven and is dried in vacuo 24 hours, the product after drying is ground, magnetic is made after screening
Property CoFe2O4Microparticle.
Two, magnetic photocatalyst AgBr-BiOBr-CoFe is prepared2O4
(1) weight ratio for pressing 1:3:11, chooses the magnetic CoFe of 1g2O4The BiOBr of microparticle, the AgBr of 3g and 11g is carried out
It calculates, according to the weight of the AgBr of selection divided by the molecular weight of AgBr, the mole for obtaining AgBr is 0.01604mol, then Ag moles
Amount is 0.01604mol；Molecular weight is obtained divided by BiOBr according to the weight of the BiOBr of selection, the mole for obtaining BiOBr is
0.03618mol, then the mole of Bi is 0.03618mol, is then calculated according to the mole 0.01604mol of Ag required
AgNO3Weight be 2.7247 grams, required Bi (NO is calculated according to the mole 0.03618mol of Bi3)3·5H2The weight of O
It is 17.5498 grams；
Weigh the 1 gram of magnetism CoFe prepared in step 12O4Microparticle weighs 2.7247 grams of AgNO3With 17.5498 grams of Bi
(NO3)3·5H2O；
(2), by weighed AgNO3With Bi (NO3)3·5H2O dissolves in the glacial acetic acid aqueous solution that the volume ratio of 200mL is 20%
In, and uniform stirring, obtain the mixed solution D of silver nitrate and bismuth nitrate under acid condition；
(3), by 1 gram prepared in weighed step 1 magnetism CoFe2O4Microparticle is added in solution D, and is mixed
30 ~ 60 minutes, obtained solution E；
(4), by the mole 0.03618mol of the mole 0.01604mol and Bi of calculated Ag in above-mentioned steps (1)
It is added, show that the mole of required KBr is 0.05222mol, the weight of the KBr needed for calculating according to the molar amount of KBr is
6.214g；
The KBr for weighing 6.214 grams, is dissolved in the water of 80mL, and then the KBr solution is added drop-wise in solution E, drop
It is added dropwise, and is continuously stirred after being added dropwise 2 hours while stirring during adding, stand 12 hours again later, aaerosol solution is made
F。
(5), the mixed liquor of aaerosol solution F deionized water and ethyl alcohol is washed 3 ~ 5 times, the baking oven for being placed on 80 °C in
24 hours dry, the product after drying grinds, sieves up to AgBr-BiOBr-CoFe2O4Magnetic photocatalyst.
As shown in Fig. 2, removing the Elemental Mercury in flue gas using wet process using the magnetic photocatalyst in example IV
Hg0, flue gas main component is N2、O2、CO2, Elemental Mercury Hg in flue gas0Concentration be 50 μ g/m3Under, magnetic photocatalyst
Dosage be 0.1 g/L, reaction temperature be 45 °C under the conditions of, through counting, the magnetic photocatalyst in example IV is to cigarette
The removal efficiency of Elemental Mercury is about 86% in gas.
As shown in Fig. 2, removing the Elemental Mercury in flue gas using wet process using the magnetic photocatalyst in embodiment five
Hg0, flue gas main component is N2、O2、CO2, Elemental Mercury Hg in flue gas0Concentration be 50 μ g/m3Under, magnetic photocatalyst
Dosage be 0.1 g/L, reaction temperature be 45 °C under the conditions of, through counting, the magnetic photocatalyst in embodiment five is to cigarette
The removal efficiency of Elemental Mercury is about 90% in gas.
As shown in Fig. 2, removing the Elemental Mercury in flue gas using wet process using the magnetic photocatalyst in embodiment six
Hg0, flue gas main component is N2、O2、CO2, Elemental Mercury Hg in flue gas0Concentration be 50 μ g/m3Under, magnetic photocatalyst
Dosage be 0.1 g/L, reaction temperature be 45 °C under the conditions of, through counting, the magnetic photocatalyst in embodiment six is to cigarette
The removal efficiency of Elemental Mercury is about 95% in gas.
As shown in Fig. 2, using the visible light catalyst CoFe in comparative example one2O4, removed in flue gas using wet process
Elemental Mercury Hg0, flue gas main component is N2、O2、CO2, Elemental Mercury Hg in flue gas0Concentration be 50 μ g/m3Under, magnetic visible light
The dosage of catalyst is 0.1 g/L, under the conditions of reaction temperature is 45 °C, through counting, it is seen that photochemical catalyst CoFe2O4To in flue gas
The removal efficiency of Elemental Mercury is about 5%.
As shown in Fig. 2, using the magnetic photocatalyst BiOBr-CoFe in comparative example four2O4, removed using wet process
Remove the Elemental Mercury Hg in flue gas0, flue gas main component is N2、O2、CO2, Elemental Mercury Hg in flue gas0Concentration be 50 μ g/m3Under,
The dosage of magnetic photocatalyst is 0.1 g/L, under the conditions of reaction temperature is 45 °C, through counting, and magnetic photocatalyst
BiOBr-CoFe2O4Removal efficiency to Elemental Mercury in flue gas is about 40%.
As shown in Fig. 2, using the magnetic photocatalyst AgBr-BiOBr-CoFe in comparative example five2O4, utilize
Wet process removes the Elemental Mercury Hg in flue gas0, flue gas main component is N2、O2、CO2, Elemental Mercury Hg in flue gas0Concentration be 50 μ g/
m3Under, the dosage of magnetic photocatalyst is 0.1 g/L, under the conditions of reaction temperature is 45 °C, through counting, and magnetic visible light
Catalyst AgBr-BiOBr-CoFe2O4Removal efficiency to Elemental Mercury in flue gas is about 75%.
In conclusion magnetic photocatalyst Ag-AgBr-BiOBr-CoFe of the invention2O4Flue gas can be greatly improved
In Elemental Mercury removal efficiency.
Embodiment seven
A kind of composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite, in which: by Ag, AgI, BiOI
And CoFe2O4Composition, CoFe2O4, AgI and BiOI weight ratio are as follows:
CoFe2O4: the weight ratio of AgI:BiOI=1:1:1, Ag and AgI are 0.1% ~ 2%.
Above-mentioned composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite preparation method, in which: including
Following processing step:
One, magnetic corpuscular CoFe is prepared2O4
(1), by the Co (NO of 0.042mol3)2·6H2Fe (the NO of O and 0.084mol3)3·9H2O dissolve in 100mL go from
In sub- water and uniform stirring, the mixed solution A of cobalt nitrate and ferric nitrate is obtained；
(2), the sodium hydroxide of 0.34mol is dissolved in the deionized water of 100mL and obtains solution B；
(3), by solution B be added slowly in solution A adjust solution A pH value, make solution ph maintain 12 ~ 14 it
Between, it is added while stirring in adding procedure, continues stirring 2 hours, obtained solution C after addition；
(4), solution C is put into hydrothermal reaction kettle then hydrothermal reaction kettle is put into baking oven and is heated, oven temperature is
180 °C, heating time is 8 ~ 16 hours, after completion of the reaction, reaction products therefrom is naturally cooled to room temperature, then washes 3 ~ 5
It is secondary, finally hydro-thermal reaction product is placed in 80 °C of baking oven and is dried in vacuo 24 hours, the product after drying ground, after screening
Magnetism CoFe is made2O4Microparticle.
Two, AgI-BiOI-CoFe is prepared2O4Magnetic suspension solution
(1), by the weight ratio of 1:1:1, the magnetic CoFe of 1g is chosen2O4The BiOI of microparticle, the AgI of 1g and 1g is counted
It calculates, according to the weight of the AgI of selection divided by the molecular weight of AgI, the mole for obtaining AgI is 0.00426mol, then Ag mole is
0.00426mol obtains molecular weight divided by BiOI according to the weight of the BiOI of selection, and the mole for obtaining BiOI is 0.00284mol, then
The mole of Bi is 0.00284mol, then calculates required AgNO according to the mole 0.00426mol mol of Ag3Weight
Amount is 0.7236 gram, and required Bi (NO is calculated according to the mole 0.00284mol of Bi3)3·5H2The weight of O is 1.3776
Gram；
Weigh the 1 gram of magnetism CoFe prepared in step 12O4Microparticle weighs 0.7236 gram of AgNO3With 1.3776 grams of Bi
(NO3)3·5H2O；
(2), by weighed AgNO3With Bi (NO3)3·5H2O dissolves in the glacial acetic acid aqueous solution that the volume ratio of 200mL is 20%
In, and uniform stirring, obtain the mixed solution D of silver nitrate and bismuth nitrate under acid condition；
(3), by 1 gram prepared in weighed step 1 magnetism CoFe2O4Microparticle is added in solution D, and is mixed
30 ~ 60 minutes, obtained solution E；
(4), by the mole 0.00284mol of the mole 0.00426mol and Bi of calculated Ag in above-mentioned steps (1)
It is added, show that the mole of required KI is 0.0074mol, the weight of the KI needed for calculating according to the molar amount of KI is
1.1786g；
The KI for weighing 1.1786 grams, is dissolved in the water of 20mL, and then the KI solution is added drop-wise in solution E, drop
It is added dropwise, and is continuously stirred after being added dropwise 2 hours while stirring during adding, stand 12 hours again later, aaerosol solution is made
F。
Three, magnetic photocatalyst Ag-AgI-BiOI-CoFe is prepared2O4
(1), aaerosol solution F is placed under the ultraviolet lamp of 36W and irradiates and stir 2 hour；
(2), the aaerosol solution F after irradiation is stood, then the sediment in solid-liquid separation aaerosol solution F；
(3), with ethanol solution washing precipitate 3 ~ 5 times repeatedly, it is dry that vacuum in 80 °C of baking oven is put the precipitate in later
Dry 24 hours, finally by sediment grinding, the screening after drying, magnetic photocatalyst Ag-AgI-BiOI- is made
CoFe2O4.Ag in the magnetic photocatalyst decomposes in light gained by AgI, and the weight ratio with AgI is 0.1% ~ 2%.
Embodiment eight
A kind of composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite, in which: by Ag, AgI, BiOI
And CoFe2O4Composition, CoFe2O4, AgI and BiOI weight ratio are as follows:
CoFe2O4: the weight ratio of AgI:BiOI=1:10:10, Ag and AgI are 2% ~ 4%.
Above-mentioned composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite preparation method, in which: including
Following processing step:
One, magnetic corpuscular CoFe is prepared2O4
(1), by the Co (NO of 0.042mol3)2·6H2Fe (the NO of O and 0.084mol3)3·9H2O dissolve in 100mL go from
In sub- water and uniform stirring, the mixed solution A of cobalt nitrate and ferric nitrate is obtained；
(2), the sodium hydroxide of 0.34 mol is dissolved in the deionized water of 100mL and obtains solution B；
(3), by solution B be added slowly in solution A adjust solution A pH value, make solution ph maintain 12 ~ 14 it
Between, it is added while stirring in adding procedure, continues stirring 2 hours, obtained solution C after addition；
(4), solution C is put into hydrothermal reaction kettle then hydrothermal reaction kettle is put into baking oven and is heated, oven temperature is
180 °C, heating time is 8 ~ 16 hours, after completion of the reaction, reaction products therefrom is naturally cooled to room temperature, then washes 3 ~ 5
It is secondary, finally hydro-thermal reaction product is placed in 80 °C of baking oven and is dried in vacuo 24 hours, the product after drying ground, after screening
Magnetism CoFe is made2O4Microparticle.
Two, AgI-BiOI-CoFe is prepared2O4Magnetic suspension solution
(1), by the weight ratio of 1:10:10, the magnetic CoFe of 1g is chosen2O4The BiOI of microparticle, the AgI of 10g and 10g into
Row calculates, and according to the weight of the AgI of selection divided by the molecular weight of AgI, the mole for obtaining AgI is 0.04259mol, then and Ag moles
Amount obtains molecular weight divided by BiOI according to the weight of the BiOI of selection for 0.04259mol, and the mole for obtaining BiOI is
0.02842mol, then the mole of Bi is 0.02842mol, then calculates institute according to the mole 0.04259mol mol of Ag
The AgNO needed3Weight be 7.235 grams, required Bi (NO is calculated according to the mole 0.02842mol of Bi3)3·5H2O's
Weight is 13.786 grams；
Weigh the 1 gram of magnetism CoFe prepared in step 12O4Microparticle weighs 7.235 grams of AgNO3With 13.786 grams of Bi
(NO3)3·5H2O；
(2), by weighed AgNO3With Bi (NO3)3·5H2O dissolves in the glacial acetic acid aqueous solution that the volume ratio of 200mL is 20%
In, and uniform stirring, obtain the mixed solution D of silver nitrate and bismuth nitrate under acid condition；
(3), by 1 gram prepared in weighed step 1 magnetism CoFe2O4Microparticle is added in solution D, and is mixed
30 ~ 60 minutes, obtained solution E；
(4), by the mole 0.02842mol of the mole 0.04259mol and Bi of calculated Ag in above-mentioned steps (1)
It is added, show that the mole of required KI is 0.07101mol, the weight of the KI needed for calculating according to the molar amount of KI is
11.787g；
The KI for weighing 11.787 grams, is dissolved in the water of 100mL, and then the KI solution is added drop-wise in solution E, drop
It is added dropwise, and is continuously stirred after being added dropwise 2 hours while stirring during adding, stand 12 hours again later, aaerosol solution is made
F。
Three, magnetic photocatalyst Ag-AgI-BiOI-CoFe is prepared2O4
(1), aaerosol solution F is placed under the ultraviolet lamp of 40W and irradiates and stir 4 hour；
(2), the aaerosol solution F after irradiation is stood, then the sediment in solid-liquid separation aaerosol solution F；
(3), with ethanol solution washing precipitate 3 ~ 5 times repeatedly, it is dry that vacuum in 80 °C of baking oven is put the precipitate in later
Dry 24 hours, finally by sediment grinding, the screening after drying, magnetic photocatalyst Ag-AgI-BiOI- is made
CoFe2O4.Ag in the magnetic photocatalyst decomposes in light gained by AgI, and the weight ratio with AgI is 2% ~ 4%.
Embodiment nine
A kind of composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite, by Ag, AgI, BiOI and
CoFe2O4Composition, CoFe2O4, AgI and BiOI weight ratio are as follows:
CoFe2O4: the weight ratio of AgI:BiOI=1:1.5:2.5, Ag and AgI are 2 ~ 3%.
Above-mentioned composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite preparation method, in which: including
Following processing step:
One, magnetic corpuscular CoFe is prepared2O4
(1), by the Co (NO of 0.042 mol3)2·6H2Fe (the NO of O and 0.084mol3)3·9H2O dissolves in going for 100mL
In ionized water and uniform stirring, the mixed solution A of cobalt nitrate and ferric nitrate is obtained；
(2), the sodium hydroxide of 0.34 mol is dissolved in the deionized water of 100mL and obtains solution B；
(3), by solution B be added slowly in solution A adjust solution A pH value, make solution ph maintain 12 ~ 14 it
Between, it is added while stirring in adding procedure, continues stirring 2 hours, obtained solution C after addition；
(4), solution C is put into hydrothermal reaction kettle then hydrothermal reaction kettle is put into baking oven and is heated, oven temperature is
180 °C, heating time is 8 ~ 16 hours, after completion of the reaction, reaction products therefrom is naturally cooled to room temperature, then washes 3 ~ 5
It is secondary, finally hydro-thermal reaction product is placed in 80 °C of baking oven and is dried in vacuo 24 hours, the product after drying ground, after screening
Magnetism CoFe is made2O4Microparticle.
Two, AgI-BiOI-CoFe is prepared2O4Magnetic suspension solution
(1), by the weight ratio of 1:1.5:2.5, the magnetic CoFe of 1g is chosen2O4Microparticle, the AgI of 1.5g and 2.5g
BiOI is calculated, and according to the weight of the AgI of selection divided by the molecular weight of AgI, the mole for obtaining AgI is 0.00639mol, then
Ag mole obtains molecular weight divided by BiOI according to the weight of the BiOI of selection for 0.00639mol, and the mole for obtaining BiOI is
0.0071mol, then the mole of Bi is 0.0071mol, is then calculated according to the mole 0.00639mol of Ag required
AgNO3Weight be 1.0855 grams, required Bi (NO is calculated according to the mole 0.0071mol of Bi3)3·5H2The weight of O
It is 3.4439 grams；
Weigh the 1 gram of magnetism CoFe prepared in step 12O4Microparticle weighs 1.0855 grams of AgNO3With 3.4439 grams of Bi
(NO3)3·5H2O；
(2), by weighed AgNO3With Bi (NO3)3·5H2O dissolves in the glacial acetic acid aqueous solution that the volume ratio of 200mL is 20%
In, and uniform stirring, obtain the mixed solution D of silver nitrate and bismuth nitrate under acid condition；
(3), by 1 gram prepared in weighed step 1 magnetism CoFe2O4Microparticle is added in solution D, and is mixed
30 ~ 60 minutes, obtained solution E；
(4), by the mole 0.0071mol of the mole 0.00639mol and Bi of calculated Ag in above-mentioned steps (1)
It is added, show that the mole of required KI is 0.01349mol, the weight of the KI needed for calculating according to the molar amount of KI is
2.239g；
The KI for weighing 2.239 grams, is dissolved in the water of 100mL, and then the KI solution is added drop-wise in solution E, drop
It is added dropwise, and is continuously stirred after being added dropwise 2 hours while stirring during adding, stand 12 hours again later, aaerosol solution is made
F。
Three, magnetic photocatalyst Ag-AgI-BiOI-CoFe is prepared2O4
(1), aaerosol solution F is placed under the ultraviolet lamp of 36W and irradiates and stir 3 hour；
(2), the aaerosol solution F after irradiation is stood, then the sediment in solid-liquid separation aaerosol solution F；
(3), with ethanol solution washing precipitate 3 ~ 5 times repeatedly, it is dry that vacuum in 80 °C of baking oven is put the precipitate in later
Dry 24 hours, finally by sediment grinding, the screening after drying, magnetic photocatalyst Ag-AgI-BiOI- is made
CoFe2O4.Ag in the magnetic photocatalyst decomposes in light gained by AgI, and the weight ratio with AgI is 2% ~ 3%.
Comparative example six:
The present embodiment kind uses BiOI-CoFe2O4For visible light catalyst, wherein CoFe2O4Weight ratio with BiOI is 1:
4, it is specific the preparation method is as follows:
Step 1: preparation CoFe2O4
(1), by the Co (NO of 0.042mol3)2·6H2Fe (the NO of O and 0.084mol3)3·9H2O dissolve in 100mL go from
In sub- water and uniform stirring, the mixed solution A of cobalt nitrate and ferric nitrate is obtained；
(2), the sodium hydroxide of 0.34mol is dissolved in the deionized water of 100mL and obtains solution B；
(3), by solution B be added slowly in solution A adjust solution A pH value, make solution ph maintain 12 ~ 14 it
Between, it is added while stirring in adding procedure, continues stirring 2 hours, obtained solution C after addition；
(4), solution C is put into hydrothermal reaction kettle and carries out hydro-thermal reaction, hydrothermal temperature is 180 °C, hydro-thermal reaction
Time is 8 ~ 16 hours, after hydro-thermal reaction, and reaction products therefrom is naturally cooled to room temperature, then washing 3 ~ 5 times, finally
Hydro-thermal reaction product is placed in 80 °C of baking oven and is dried in vacuo 24 hours, the product after drying is ground, magnetic is made after screening
Property CoFe2O4Microparticle.
Step 2: preparation BiOI-CoFe2O4
(1), by 0.0114mol Bi (NO3)3·5H2O is added in 200 mL and aqueous solution containing 40 mL glacial acetic acid
Uniform stirring obtains bismuth nitrate solution under acid condition, this solution is denoted as solution D；
(2), by 0.0043mol CoFe prepared in step 12O4Magnetic corpuscular is added in solution D, and in machine
It is continuously stirred under tool electric mixer 30 minutes, this solution is denoted as solution E；
(3), 0.0114 mol KI is added dropwise into solution E under mechanical electric stirring quiet again after continuously stirring 2 hours
It sets 12 hours, products therefrom is denoted as F；
(4), the mixed liquor of product F deionized water and ethyl alcohol is washed 3 ~ 5 times, the baking oven for being placed on 80 °C in it is dry
24 hours, the product after drying ground, sieves up to two cobalt ferrite BiOI- CoFe of-four oxygen of bismuth oxyiodide2O4Magnetic visible light is urged
Agent.
Comparative example seven:
The present embodiment kind uses AgI-BiOI-CoFe2O4For magnetic photocatalyst, wherein CoFe2O4, AgI and BiOI
Weight ratio be 1:2:8, it is specific the preparation method is as follows:
One, magnetic corpuscular CoFe is prepared2O4
(1), by the Co (NO of 0.042mol3)2·6H2Fe (the NO of O and 0.084mol3)3·9H2O dissolve in 100mL go from
In sub- water and uniform stirring, the mixed solution A of cobalt nitrate and ferric nitrate is obtained；
(2), the sodium hydroxide of 0.34mol is dissolved in the deionized water of 100mL and obtains solution B；
(3), by solution B be added slowly in solution A adjust solution A pH value, make solution ph maintain 12 ~ 14 it
Between, it is added while stirring in adding procedure, continues stirring 2 hours, obtained solution C after addition；
(4), solution C is put into hydrothermal reaction kettle and carries out hydro-thermal reaction, hydrothermal temperature is 180 °C, hydro-thermal reaction
Time is 8 ~ 16 hours, after hydro-thermal reaction, and reaction products therefrom is naturally cooled to room temperature, then washing 3 ~ 5 times, finally
Hydro-thermal reaction product is placed in 80 °C of baking oven and is dried in vacuo 24 hours, the product after drying is ground, magnetic is made after screening
Property CoFe2O4Microparticle.
Two, magnetic photocatalyst AgI-BiOI- CoFe is prepared2O4
(1), by the weight ratio of 1:2:8, the magnetic CoFe of 1g is chosen2O4The BiOI of microparticle, the AgI of 2g and 8g is counted
It calculates, according to the weight of the AgI of selection divided by the molecular weight of AgI, the mole for obtaining AgI is 0.00852mol, then Ag mole is
0.00852mol obtains molecular weight divided by BiOI according to the weight of the BiOI of selection, and the mole for obtaining BiOI is 0.02274mol, then
The mole of Bi is 0.02274mol, then calculates required AgNO according to the mole 0.00852mol of Ag3Weight be
1.4473 grams, required Bi (NO is calculated according to the mole 0.02274mol of Bi3)3·5H2The weight of O is 11.0305 grams；
Weigh the 1 gram of magnetism CoFe prepared in step 12O4Microparticle weighs 1.4473 grams of AgNO3With 11.0305 grams of Bi
(NO3)3·5H2O；
(2), by weighed AgNO3With Bi (NO3)3·5H2O dissolves in the glacial acetic acid aqueous solution that the volume ratio of 200mL is 20%
In, and uniform stirring, obtain the mixed solution D of silver nitrate and bismuth nitrate under acid condition；
(3), by 1 gram prepared in weighed step 1 magnetism CoFe2O4Microparticle is added in solution D, and is mixed
30 ~ 60 minutes, obtained solution E；
(4), by the mole 0.02274mol of the mole 0.00852mol and Bi of calculated Ag in above-mentioned steps (1)
It is added, show that the mole of required KI is 0.03126mol, KI needed for the mole of KI is calculated multiplied by the Molecular weights of KI
Weight be 5.189g；
The KI for weighing 5.189 grams, is dissolved in the water of 100mL, and then the KI solution is added drop-wise in solution E, drop
It is added dropwise, and is continuously stirred after being added dropwise 2 hours while stirring during adding, stand 12 hours again later, aaerosol solution is made
F。
(5), the mixed liquor of aaerosol solution F deionized water and ethyl alcohol is washed 3 ~ 5 times, the baking oven for being placed on 80 °C in
24 hours dry, the product after drying grinds, sieves up to AgI-BiOI-CoFe2O4Magnetic photocatalyst.
As shown in figure 3, removing the Elemental Mercury in flue gas using wet process using the magnetic photocatalyst in embodiment seven
Hg0, flue gas main component is N2、O2、CO2, Elemental Mercury Hg in flue gas0Concentration be 50 μ g/m3Under, magnetic photocatalyst
Dosage be 0.1 g/L, reaction temperature be 45 °C under the conditions of, through counting, the magnetic photocatalyst in embodiment seven is to cigarette
The removal efficiency of Elemental Mercury is about 93% in gas.
As shown in figure 3, removing the Elemental Mercury in flue gas using wet process using the magnetic photocatalyst in embodiment seven
Hg0, flue gas main component is N2、O2、CO2, Elemental Mercury Hg in flue gas0Concentration be 50 μ g/m3Under, magnetic photocatalyst
Dosage be 0.1 g/L, reaction temperature be 45 °C under the conditions of, through counting, the magnetic photocatalyst in embodiment eight is to cigarette
The removal efficiency of Elemental Mercury is about 96% in gas.
As shown in figure 3, removing the Elemental Mercury in flue gas using wet process using the magnetic photocatalyst in embodiment seven
Hg0, flue gas main component is N2、O2、CO2, Elemental Mercury Hg in flue gas0Concentration be 50 μ g/m3Under, magnetic photocatalyst
Dosage be 0.1 g/L, reaction temperature be 45 °C under the conditions of, through counting, the magnetic photocatalyst in embodiment nine is to cigarette
The removal efficiency of Elemental Mercury is about 99% in gas.
As shown in figure 3, using the visible light catalyst CoFe in comparative example one2O4, removed in flue gas using wet process
Elemental Mercury Hg0, flue gas main component is N2、O2、CO2, Elemental Mercury Hg in flue gas0Concentration be 50 μ g/m3Under, magnetic visible light
The dosage of catalyst is 0.1 g/L, under the conditions of reaction temperature is 45 °C, through counting, it is seen that photochemical catalyst CoFe2O4To in flue gas
The removal efficiency of Elemental Mercury is about 5%.
As shown in figure 3, using the magnetic photocatalyst BiOI-CoFe in comparative example six2O4, removed using wet process
Remove the Elemental Mercury Hg in flue gas0, flue gas main component is N2、O2、CO2, Elemental Mercury Hg in flue gas0Concentration be 50 μ g/m3Under,
The dosage of magnetic photocatalyst is 0.1 g/L, under the conditions of reaction temperature is 45 °C, through counting, and magnetic photocatalyst
BiOI-CoFe2O4Removal efficiency to Elemental Mercury in flue gas is about 60%.
As shown in figure 3, using the magnetic photocatalyst AgI-BiOI-CoFe in comparative example seven2O4, utilization is wet
Method removes the Elemental Mercury Hg in flue gas0, flue gas main component is N2、O2、CO2, Elemental Mercury Hg in flue gas0Concentration be 50 μ g/m3
Under, the dosage of magnetic photocatalyst is 0.1 g/L, and under the conditions of reaction temperature is 45 °C, through counting, magnetic visible light is urged
Agent AgI-BiOI-CoFe2O4Removal efficiency to Elemental Mercury in flue gas is about 88%.
In conclusion magnetic photocatalyst Ag-AgI-BiOI-CoFe of the invention2O4It can greatly improve in flue gas
Elemental Mercury removal efficiency.
It is noted that embodiment described above is the affiliated technology neck to the illustrative and not limiting of technical solution of the present invention
The equivalent replacement of domain those of ordinary skill or the other modifications made according to the prior art, as long as not exceeding the technology of the present invention side
The thinking and range of case, should be included within interest field of the presently claimed invention.
Claims (2)
1. a kind of composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite preparation method, it is characterised in that:
The composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite is by Ag, AgX, BiOX and CoFe2O4Group
At, as X=Cl, CoFe2O4, AgCl and BiOCl weight ratio be CoFe2O4: AgCl:BiOCl=1:(1~5): (1~10),
The weight ratio of Ag and AgCl is 0.1%~10%；As X=Br, CoFe2O4, AgBr and BiOBr weight ratio be CoFe2O4:
AgBr:BiOBr=1:(1~10): the weight ratio of (1~20), Ag and AgBr are 0.1%~10%；
The preparation method comprises the technical steps that:
One, magnetic corpuscular CoFe is prepared2O4
(1) by a moles of Co (NO3)2·6H2O and b moles of Fe (NO3)3·9H2O dissolves in the deionized water of 100~150mL simultaneously
Uniform stirring, obtains the mixed solution A of cobalt nitrate and ferric nitrate, and the molar ratio of a and b are 1:2；
(2) c moles of sodium hydroxide is dissolved in the deionized water of 100~150mL and obtains solution B, the molar ratio of a and c are
1:8；
(3) solution B is added slowly to adjust the pH value of solution A in solution A, maintains solution ph between 12~14, adds
It is added while stirring during adding, continues stirring after addition 2~3 hours, obtained solution C；
(4) solution C is heated, makes solution C that hydro-thermal reaction occur, after completion of the reaction, products therefrom natural cooling will be reacted
It to room temperature, then washes 3~5 times, it is small that hydro-thermal reaction product is finally placed in vacuum drying 24~48 in 60~80 DEG C of baking oven
When, the product after drying is ground, magnetism CoFe is made after screening2O4Microparticle；
Two, AgX-BiOX-CoFe is prepared2O4Magnetic suspension solution
(1) a certain amount of AgX-BiOX-CoFe is conversed by weight2O4The mole of the mole of Ag and Bi in catalyst, by Ag
Mole and Bi mole respectively multiplied by AgNO3With Bi (NO3)3·5H2The molecular weight of O obtains required AgNO3And Bi
(NO3)3·5H2The weight of O, and weigh the AgNO of corresponding weight3With Bi (NO3)3·5H2O；
(2) by weighed AgNO3With Bi (NO3)3·5H2O dissolves in the glacial acetic acid aqueous solution of 100~800mL, and uniform stirring,
Obtain the mixed solution D of silver nitrate and bismuth nitrate under acid condition；The volume fraction of glacial acetic acid is 10% in the aqueous solution of glacial acetic acid
~50%；
It (3) will be by weight the magnetic CoFe prepared in weighed step 12O4Microparticle is added in solution D, and is mixed
30~60 minutes, obtained solution E；
(4) mole of calculated Ag in step (1) is added with the mole of Bi, obtains the mole of required KX, root
The weight of KX needed for being calculated according to the molar amount of KX；KX is weighed according to the weight, is dissolved in the water of 20~200mL,
Then the KX solution is added drop-wise in solution E, is added dropwise while stirring during being added dropwise, and it is small to continuously stir 2~3 after being added dropwise
When, it stands at least 12 hours again later, aaerosol solution F is made；
Three, magnetic photocatalyst Ag-AgX-BiOX-CoFe is prepared2O4,
(1) aaerosol solution F obtained in step 2 is placed under the ultraviolet lamp of 10~100W and irradiates and stir 1~10 hour；
(2) the aaerosol solution F after irradiation is stood, then the sediment in solid-liquid separation aaerosol solution F；
(3) mixed solution washing precipitate 3~5 times repeatedly for using ethyl alcohol and water, put the precipitate in 60~80 DEG C of baking later
It is dried in vacuo in case 12~24 hours, finally by sediment grinding, the screening after drying, magnetic photocatalyst Ag- is made
AgX-BiOX-CoFe2O4。
2. composite magnetic visible light catalyst silver-silver halide-BiOX-cobalt ferrite preparation according to claim 1
Method, it is characterised in that: solution C is put into hydrothermal reaction kettle in (4) of step 1, hydrothermal reaction kettle is then put into baking oven
Interior heating, oven temperature are 150~200 DEG C, and heating time is 8~16 hours.
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| CN108620097A (en) * | 2018-04-01 | 2018-10-09 | 云南大学 | A kind of preparation method and purposes of silver iodide/bismuth oxybromide heterojunction photocatalyst |
| CN108620099B (en) * | 2018-05-11 | 2021-02-12 | 陕西科技大学 | Double-cavity magnetic Fe3O4@mSiO2@ BiOCl-Ag/AgBr composite material and preparation method thereof |
| CN108975396B (en) * | 2018-07-25 | 2020-07-17 | 黑龙江大学 | Method for in-situ synthesis of silver/tin oxide/bismuth oxybromide photoelectric material |
| CN109603861B (en) * | 2018-11-14 | 2022-05-13 | 西南石油大学 | Ag-AgICl/Bi3O4Br0.5Cl0.5Composite photocatalyst and preparation method and application thereof |
| CN111672524B (en) * | 2019-06-13 | 2023-03-10 | 河南理工大学 | Preparation method of cerium dioxide-zinc oxide-bismuth oxyhalide-cobalt ferrite magnetic visible-light-driven photocatalyst |
| CN111686808A (en) * | 2019-06-13 | 2020-09-22 | 河南理工大学 | Preparation method of silver-silver iodide-polyaniline-bismuth oxyhalide-zinc ferrite photocatalyst |
| CN111701604A (en) * | 2020-06-10 | 2020-09-25 | 河南理工大学 | Preparation method of silver iodide-silver oxide-bismuth oxyhalide-cobalt ferrite magnetic visible-light-driven photocatalyst |
| CN113842929A (en) * | 2020-06-28 | 2021-12-28 | 华东理工大学 | Preparation method of plasma resonance effect ternary nano sunlight catalytic material |
| CN116078409B (en) * | 2023-03-14 | 2024-06-11 | 昆明理工大学 | Iron-bismuth composite photocatalyst with visible light response and preparation method and application thereof |
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