CN108686683A - A kind of preparation method of graphene/bismuth oxychloride/cobalt improved strontium ferrite composite photo-catalyst - Google Patents
A kind of preparation method of graphene/bismuth oxychloride/cobalt improved strontium ferrite composite photo-catalyst Download PDFInfo
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- CN108686683A CN108686683A CN201810494792.0A CN201810494792A CN108686683A CN 108686683 A CN108686683 A CN 108686683A CN 201810494792 A CN201810494792 A CN 201810494792A CN 108686683 A CN108686683 A CN 108686683A
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 25
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 23
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 19
- 239000010941 cobalt Substances 0.000 title claims abstract description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 19
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229940073609 bismuth oxychloride Drugs 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 239000012153 distilled water Substances 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 abstract description 17
- 238000006731 degradation reaction Methods 0.000 abstract description 17
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 10
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 9
- 229940043267 rhodamine b Drugs 0.000 abstract description 9
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 238000005286 illumination Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 229910052724 xenon Inorganic materials 0.000 abstract description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 239000000356 contaminant Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 11
- 238000013019 agitation Methods 0.000 description 11
- 238000004064 recycling Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 229910002402 SrFe12O19 Inorganic materials 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 229910002915 BiVO4 Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000005415 magnetization Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 3
- 229910002518 CoFe2O4 Inorganic materials 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
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- 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
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C01B32/00—Carbon; Compounds thereof
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Abstract
A kind of preparation method of graphene/bismuth oxychloride/cobalt improved strontium ferrite composite photo-catalyst, belongs to inorganic catalysis material field.The present invention is first prepared for graphene oxide GO with improved Hummers methods, hydro-thermal method is prepared for the cobalt improved strontium ferrite SrFe of retentive material12-xCoxO19, then graphene/bismuth oxychloride/cobalt improved strontium ferrite composite photo-catalyst rGO/BiOCl/SrFe prepared by hydro-thermal method12-xCoxO19.The method of the present invention preparation process is simple, few using equipment sheet, and less energy consumption is at low cost.The rGO/BiOCl/SrFe of preparation12-xCoxO19Magnetic property is stablized and photocatalytic activity is high, under the irradiation of simulated solar irradiation xenon lamp, with the rhodamine B solution of the 0.1g a concentration of 10mg/L of composite magnetic photocatalyst for degrading 100mL prepared, illumination 80min reaches 94.2% to the degradation rate of rhodamine B, it is 85.4% to the degradation rate of rhodamine B after reusing 3 times, average recovery rate 73.2%.The product that the present invention prepares can be widely used in the field of photocatalysis degradation organic contaminant.
Description
Technical field
The present invention relates to a kind of graphene/bismuth oxychloride/cobalt improved strontium ferrite composite photo-catalyst rGO/BiOCl/
SrFe12-xCoxO19Preparation method, belong to inorganic catalysis material technical field.
Background technology:
In novel photocatalyst development, BiOCl is typical UV sensitive catalyst, has unique layer structure special
Point, Qi Zhong [Bi2O2]2+Layer is by two Ge [ in crystal;Cl2]2-Layer is clipped in the middle, due to electronegativity difference, with;Bi2O2]2+With
[Cl2]2-The vertical direction { 001 } of layer is easier to cause the separation of photo-generate electron-hole pair, more contributes to obtain good light
Catalytic activity.But the energy gap of BiOCl is about 3.46eV, and it is weaker to the absorbability of visible light, it constrains BiOCl and exists
Practical application in photocatalysis field;In addition, the difficult recycling of BiOCl itself can cause the secondary pollution to environment.Therefore, it prepares
A kind of photoinduction by force and the high BiOCl series catalysis materials of recycling stability become photocatalysis field research emphasis it
One.
Magnetic separation technique has broad application prospects in photocatalysis field, and the existing BiOCl composite magnetic light reported for work is urged
Agent has BiOCl/Fe3O4,BiOCl/CoFe2O4And BiOCl/SrFe12O19Deng.Under externally-applied magnetic field, catalysis material is realized
With the separation and recycling of liquid, but the photocatalytic activity of these composite magnetic catalysis materials is limited, still has further
It improves.The compound smaller light absorbent of energy gap becomes the feasible program for improving magnetic photocatalytic material, such as graphene
It is attached to the surface of magnetic photocatalyst, not only can increase magnetic photocatalyst to the absorptivity of light but also may also speed up electricity
The transmission speed in sub- hole pair further enhances the catalytic efficiency of catalysis material.
BiOCl and the compound catalyst of magnetisable material, the of such as " Dalton Transactions " 2014 volume 43
2211-2220 pages of " Magnetic composite BiOCl-SrFe12O19:a novel p–n type
Heterojunction with enhanced photocatalytic activity " one are literary (documents 1), disclosed side
Method is:Using two one-step baking methods, first roasting prepares SrFe12O19, then impregnate-roast and prepare BiOCl/SrFe12O19Composite magnetic
Catalysis material.The major defect of this method is:(1) magnetic matrix SrFe prepared by roasting method12O19Particle size is larger, than
Surface area is smaller, is unfavorable for SrFe12O19With the abundant combination of BiOCl, it can not ensure the stability combined;(2) legal system is roasted
Standby composite magnetic photochemical catalyst specific surface area is smaller, is unfavorable for catalyst itself and organic pollution in Photocatalytic Degradation Process
Come into full contact with and react;(3)SrFe12O19Coercivity it is smaller, magnetic holding capacity is limited, is unfavorable for BiOCl-SrFe12O19
Recycling, determination of recovery rates is not carried out yet to sample in text, can not judge that the magnetic property of composite sample is stable and recycles
Rate height;(4) pass through 2 roastings, energy consumption is big.
The preparation method of existing report graphene composite magnetic photochemical catalyst, such as Chinese patent CN201510954121.4
(documents 2) disclose and prepare Mn with roasting method-redox1-xZnxFe2O4/BiVO4/ RGO, prepares first with roasting method
Go out Mn1-xZnxFe2O4/BiVO4Compound recycles oxidation-reduction method to make RGO and Mn1-xZnxFe2O4/BiVO4It is compound to prepare
Mn1-xZnxFe2O4/BiVO4/RGO.This method is primarily present following deficiency:(1)Mn1-xZnxFe2O4This as soft magnetic material,
Coercivity does not have good magnetic holding capacity, is unfavorable for the recycling of composite catalyst close to 0;(2) it prepares
Mn1-xZnxFe2O4/BiVO4Only be to reduce graphene when the last one step of/RGO, can not ensure reduced graphene with
Mn1-xZnxFe2O4/BiVO4It is abundant combination and good repetition stability;(3) it only tested only the repetition drop of sample in text
Solution rate, the not rate of recovery of test sample.Cobalt improved strontium ferrite SrFe12-xCoxO19With Mn1-xZnxFe2O4It compares, not only has
Have the features such as high saturation and magnetic intensity (Ms), high-coercive force (Oe) and high magnetic permeability, and it is high, at low cost with production efficiency and
The advantages that properties of product are stablized;Cobalt improved strontium ferrite SrFe12-xCoxO19Compare SrFe12O19With higher coercivity.Therefore,
With cobalt improved strontium ferrite SrFe12-xCoxO19The magnetic photocatalyst for closing rGO is prepared for magnetic matrix, not only magnetic stability,
Catalytic activity is high, and is more convenient for detaching and recycle.
Invention content
The purpose of the present invention is for the recycling of BiOCl difficulties and the not high problem of degradation rate, propose to synthesize a kind of graphene/chlorine
The preparation method of bismuth oxide/cobalt improved strontium ferrite composite photo-catalyst, the process of preparing is simple, and production cost is low, week
Phase is short, and catalytic activity is high, and convenient for detaching and recycling from liquid phase suspension system by externally-applied magnetic field, the catalyst after recycling is still
With higher catalytic activity, both the realization resource reutilization of simple and efficient, in turn avoided the secondary dirt that catalyst may be brought
Dye.
Graphene/bismuth oxychloride of the present invention/cobalt improved strontium ferrite composite photo-catalyst rGO/BiOCl/SrFe12- xCoxO19Preparation method it is as follows:
(1) preparation of GO
The preparation method of graphene oxide GO is improved Hummers methods, and detailed process is as follows:1) in the flask of 500mL
The middle dense H that 75mL is added2SO4, then it is respectively added slowly to 1g graphite powders and the NaNO3 of 0.5g, water-bath 30min;It 2) will with spoon
The KMnO of 15g4It is slowly added into flask (potassium permanganate should not add too fast, otherwise have the danger burst), is mixed at this time
Liquid is aterrimus, by magnetic agitation 12h in flask ice bath;3) it is mixed in flask after continuation magnetic agitation 15h in 60 DEG C of water-baths
Liquid becomes brown;4) it is slow added into the H that 150mL mass fractions are 5%2SO4Solution, and after magnetic agitation 2h;5) again at 60 DEG C
In lower stirring in water bath, it is slowly added to the H of 25mL2O2, and continue stirring 2h and make its reaction abundant;6) it will fill it up with and distill in flask
Water, and stir evenly, 12h is stood, upper lower leaf occurs in mixed liquor in flask, and supernatant liquor is outwelled;7) lower layer is mixed
Liquid is centrifuged, and after centrifugation again wash with distilled water, uses the HCl of a concentration of 1mol/L of 150mL again after 3 operations repeatedly
Ultrasonic dissolution is carried out to centrifugate, is centrifuged repeatedly and washes again later, graphene oxide (GO) is obtained after finally centrifuging.
(2)SrFe12-xCoxO19Preparation
As x=0.3, by metal elemental mole ratios n (Sr2+):n(Fe3+):n(Co2+)=1:7-x:X weighs correspondence respectively
The SrCl of quality2·6H2O,FeCl3·6H2O and CoCl2·6H2O is dissolved in 40mL distilled water, 2ml ethylene glycol is added, and surpass
Sound is dissolved 30 minutes and is stirred 10 minutes, so that it is sufficiently uniformly dissolved, is obtained mixed solution A;According to total mole of metallic element
The condition that quality and pH value are 12, the NaOH for weighing corresponding mass are dissolved in 20mL distilled water, and ultrasound 30 minutes obtains
NaOH solution B;Under magnetic stirring, solution B is added dropwise to rubber head dropper in mixed solution A, after completion of dropwise addition, continues to stir
It mixes 20 minutes, obtains brown emulsus mixed liquor C;Mixed liquor C is transferred in the reaction kettle liner of 100mL, capping kettle,
It is taken out after keeping the temperature 20h in 200 DEG C of baking oven, cooling at room temperature, suction filtration is repeatedly washed, and dried at 80 DEG C with distilled water
12h, grinding obtain SrFe12-xCoxO19。
(3)rGO/BiOCl/SrFe12-xCoxO19Preparation
N (Bi (NO in molar ratio3)3·5H2O):N (KCl)=1:1, the Bi (NO of 4.85g are weighed respectively3)3·5H2O and
The KCl of 0.75g is dissolved in 50mL distilled water, is stirred by ultrasonic 60 minutes, is obtained suspension A;It weighs and generates BiOCl with theoretical
Mass ratio is 25:100 SrFe12-xCoxO19It is added in suspension A, ultrasonic agitation instills 2mL after 30 minutes in suspension A
Ethylene glycol is stirred by ultrasonic 30 minutes as dispersant, obtains mixed liquid B;The BiOCl mass and SrFe generated by theory12- xCoxO19Additive amount summation determines the quality of GO, then measures the GO that mass fraction is 0.5%~3.0% and be added in mixed liquid B,
30min is stirred by ultrasonic, obtains mixed liquor C;Mixed liquor C is transferred in 100mL reaction kettle liners, reacts 16h at 180 DEG C;
Then it cools down, filter at room temperature, repeatedly washed with distilled water, 12h is dried at last 80 DEG C, grinding obtains rGO/BiOCl/
SrFe12-xCoxO19Sample.
The present invention uses above-mentioned technical proposal, mainly has the following effects:
(1) present invention is prepared using hydro-thermal method, and preparation manipulation is simple, and required equipment is few, and low energy consumption.
(2) the composite photo-catalyst rGO/BiOCl/SrFe prepared12-xCoxO19It is with SrFe12-xCoxO19As magnetism
Matrix, the bridge transmitted using graphene as carrier, and absorption of the enhancing to visible light region, absorbing wavelength 449nm,
Energy gap is 2.76eV, hence it is evident that is less than the energy gap 3.46eV of BiOCl.
(3) composite photo-catalyst rGO/BiOCl/SrFe prepared by the method for the present invention12-xCoxO19There is higher photocatalysis to live
Property, under the xenon lamp irradiation of simulated solar irradiation (340~800nm), the rGO/BiOCl/SrFe of 0.1g preparations12-xCoxO19It is compound
Photocatalysis is scattered in the rhodamine B solution of a concentration of 10mg/L of 100mL, and illumination 80min degradation rates are close to 95%, and identical item
The degradation rate of BiOCl is only 76.5% under part.
(4) composite photo-catalyst rGO/BiOCl/SrFe prepared by the method for the present invention12-xCoxO19Adding magnetic fields outside
Under, 3 times reuse after the rate of recovery reused at 70% or more, 3 time to the degradation rate of rhodamine B still reach 85% with
On, it is higher than the degradation rate of BiOCl.
Description of the drawings
Fig. 1 is BiOCl, rGO, SrFe12-xCoxO19And rGO/BiOCl/SrFe12-xCoxO19X ray diffracting spectrum.
Fig. 2 is rGO/BiOCl/SrFe12-xCoxO19XPS figure.
Fig. 3 is SrFe12-xCoxO19And rGO/BiOCl/SrFe12-xCoxO19Magnetic hysteresis return line chart.
Fig. 4 is BiOCl, BiOCl/SrFe12-xCoxO19And rGO/BiOCl/SrFe12-xCoxO19RhB photocatalytic activities
Figure.
Specific implementation mode
With reference to embodiment, it further illustrates the present invention.
Embodiment 1
A kind of preparation of graphene/bismuth oxychloride/cobalt improved strontium ferrite composite photo-catalyst, is as follows:
(1) preparation of GO
The preparation process of GO is as follows:1) the dense H of 75mL is added in the flask of 500mL2SO4, then it is respectively added slowly to 1g
The NaNO of graphite powder and 0.5g3, water-bath 30min;2) with spoon by the KMnO of 15g4It is slowly added into flask that (potassium permanganate is not
Should add too fast, otherwise have the danger burst), mixed liquor is aterrimus at this time, by magnetic agitation 12h in flask ice bath; 3)
Mixed liquor becomes brown in flask after continuation magnetic agitation 15h in 60 DEG C of water-baths;4) being slow added into 150mL mass fractions is
5% H2SO4Solution, and after magnetic agitation 2h;5) again at 60 DEG C in stirring in water bath, it is slowly added to the H of 25mL2O2, and continue
Stirring 2h makes its reaction abundant;6) distilled water will be filled it up in flask, and is stirred evenly, 12h is stood, and mixed liquor goes out in flask
Now upper lower leaf, supernatant liquor is outwelled;7) lower layer's mixed liquor is centrifuged, it is after centrifugation again wash with distilled water, so anti-
Ultrasonic dissolution is carried out to centrifugate again with the HCl of a concentration of 1mol/L of 150mL after multiple 3 operations, is centrifuged repeatedly again later and water
It washes, graphene oxide (GO) is obtained after finally centrifuging.
(2)SrFe12-xCoxO19Preparation
As x=0.3, by metal elemental mole ratios n (Sr2+):n(Fe3+):n(Co2+)=1:7-x:X weighs correspondence respectively
The SrCl of quality2·6H2O,FeCl3·6H2O and CoCl2·6H2O is dissolved in 40mL distilled water, 2ml ethylene glycol is added, and surpass
Sound is dissolved 30 minutes and is stirred 10 minutes, so that it is sufficiently uniformly dissolved, is obtained mixed solution A;According to total mole of metallic element
The condition that quality and pH value are 12, the NaOH for weighing corresponding mass are dissolved in 20mL distilled water, and ultrasound 30 minutes obtains
NaOH solution B;Under magnetic stirring, solution B is added dropwise to rubber head dropper in mixed solution A, after completion of dropwise addition, continues to stir
It mixes 20 minutes, obtains brown emulsus mixed liquor C;Mixed liquor C is transferred in the reaction kettle liner of 100mL, capping kettle,
It is taken out after keeping the temperature 20h in 200 DEG C of baking oven, cooling at room temperature, suction filtration is repeatedly washed, and dried at 80 DEG C with distilled water
12h, grinding obtain SrFe12-xCoxO19。
(3)rGO/BiOCl/SrFe12-xCoxO19Preparation
N (Bi (NO in molar ratio3)3·5H2O):N (KCl)=1:1, the Bi (NO of 4.85g are weighed respectively3)3·5H2O and
The KCl of 0.75g is dissolved in 50mL distilled water, is stirred by ultrasonic 60 minutes, is obtained suspension A;It weighs and generates BiOCl matter with theoretical
Amount is than being 25:100 SrFe12-xCoxO19It is added in suspension A, ultrasonic agitation instills 2mL after 30 minutes in suspension A
Ethylene glycol is stirred by ultrasonic 30 minutes as dispersant, obtains mixed liquid B;The BiOCl mass and SrFe generated by theory12- xCoxO19Additive amount summation determines the quality of GO, then measures the GO that mass fraction is 0.5% and be added in mixed liquid B, and ultrasound is stirred
30min is mixed, mixed liquor C is obtained;Mixed liquor C is transferred in 100mL reaction kettle liners, reacts 16h at 180 DEG C;Then exist
Cooling at room temperature, suction filtration, is repeatedly washed with distilled water, and 12h is dried at last 80 DEG C, and grinding obtains rGO/BiOCl/SrFe12- xCoxO19Sample.
Embodiment 2
A kind of preparation of graphene/bismuth oxychloride/cobalt improved strontium ferrite composite photo-catalyst, is as follows:
(1) with the step (1) in embodiment 1.
(2) with the step (2) in embodiment 1.
(3)rGO/BiOCl/SrFe12-xCoxO19Preparation
N (Bi (NO in molar ratio3)3·5H2O):N (KCl)=1:1, the Bi (NO of 4.85g are weighed respectively3)3·5H2O and
The KCl of 0.75g is dissolved in 50mL distilled water, is stirred by ultrasonic 60 minutes, is obtained suspension A;It weighs and generates BiOCl with theoretical
Mass ratio is 25:100 SrFe12-xCoxO19It is added in suspension A, ultrasonic agitation instills 2mL after 30 minutes in suspension A
Ethylene glycol is stirred by ultrasonic 30 minutes as dispersant, obtains mixed liquid B;The BiOCl mass and SrFe generated by theory12- xCoxO19Additive amount summation determines the quality of GO, then measures the GO that mass fraction is 1.0% and be added in mixed liquid B, and ultrasound is stirred
30min is mixed, mixed liquor C is obtained;Mixed liquor C is transferred in 100mL reaction kettle liners, reacts 16h at 180 DEG C;Then exist
Cooling at room temperature, suction filtration, is repeatedly washed with distilled water, and 12h is dried at last 80 DEG C, and grinding obtains rGO/BiOCl/SrFe12- xCoxO19Sample.
Embodiment 3
A kind of preparation of graphene/bismuth oxychloride/cobalt improved strontium ferrite composite photo-catalyst, is as follows:
(1) with the step (1) in embodiment 1.
(2) with the step (2) in embodiment 1.
(3)rGO/BiOCl/SrFe12-xCoxO19Preparation
N (Bi (NO in molar ratio3)3·5H2O):N (KCl)=1:1, the Bi (NO of 4.85g are weighed respectively3)3·5H2O and
The KCl of 0.75g is dissolved in 50mL distilled water, is stirred by ultrasonic 60 minutes, is obtained suspension A;It weighs and generates BiOCl with theoretical
Mass ratio is 25:100 SrFe12-xCoxO19It is added in suspension A, ultrasonic agitation instills 2mL after 30 minutes in suspension A
Ethylene glycol is stirred by ultrasonic 30 minutes as dispersant, obtains mixed liquid B;The BiOCl mass and SrFe generated by theory12- xCoxO19Additive amount summation determines the quality of GO, then measures the GO that mass fraction is 2.0% and be added in mixed liquid B, and ultrasound is stirred
30min is mixed, mixed liquor C is obtained;Mixed liquor C is transferred in 100mL reaction kettle liners, reacts 16h at 180 DEG C;Then exist
Cooling at room temperature, suction filtration, is repeatedly washed with distilled water, and 12h is dried at last 80 DEG C, and grinding obtains rGO/BiOCl/SrFe12- xCoxO19Sample.
Embodiment 4
A kind of preparation of graphene/bismuth oxychloride/cobalt improved strontium ferrite composite photo-catalyst, is as follows:
(1) with the step (1) in embodiment 1.
(2) with the step (2) in embodiment 1.
(3)rGO/BiOCl/SrFe12-xCoxO19Preparation
N (Bi (NO in molar ratio3)3·5H2O):N (KCl)=1:1, the Bi (NO of 4.85g are weighed respectively3)3·5H2O and
The KCl of 0.75g is dissolved in 50mL distilled water, is stirred by ultrasonic 60 minutes, is obtained suspension A;It weighs and generates BiOCl with theoretical
Mass ratio is 25:100 SrFe12-xCoxO19It is added in suspension A, ultrasonic agitation instills 2mL after 30 minutes in suspension A
Ethylene glycol is stirred by ultrasonic 30 minutes as dispersant, obtains mixed liquid B;The BiOCl mass and SrFe generated by theory12- xCoxO19Additive amount summation determines the quality of GO, then measures the GO that mass fraction is 3.0% and be added in mixed liquid B, and ultrasound is stirred
30min is mixed, mixed liquor C is obtained;Mixed liquor C is transferred in 100mL reaction kettle liners, reacts 16h at 180 DEG C;Then exist
Cooling at room temperature, suction filtration, is repeatedly washed with distilled water, and 12h is dried at last 80 DEG C, and grinding obtains rGO/BiOCl/SrFe12- xCoxO19Sample.
Experimental result
RGO/BiOCl/SrFe prepared by embodiment 212-xCoxO19Catalytic degradation activity is best.In order to facilitate comparison, prepare
RGO, BiOCl sample and BiOCl/SrFe12-xCoxO19, rGO preparation methods are to be added without Bi in 2 step of embodiment (3)
(NO3)3·5H2O, KCl and SrFe12-xCoxO19, BiOCl preparation methods are to be added without SrFe in 2 step of embodiment (3)12- xCoxO19And GO, BiOCl/SrFe12-xCoxO19Preparation method is to be added without GO in 2 step of embodiment (3).
The XRD of BiOCl as shown in Figure 1, each diffraction maximum both corresponds to pure BiOCl characteristic peaks (JCPDS#06-0249),
The feature reflection peak having includes { 001 }, { 002 }, { 101 }, { 110 }, { 102 } and { 003 } etc., this demonstrate that sample is pure four
The BiOCl of square crystal structure, degradation rate as shown in figure 4, under illumination in 80 minutes the rhodamine B for 10mg/L dense to 100mL
Degradation rate be 76.5%.
SrFe12-xCoxO19XRD as shown in Figure 1, it not only shows hexagonal crystal system M phase ferrites (SrFe12O19) one
Series of features diffraction maximum, but also show CoFe2O4Characteristic peak { 311 } (JCPDS#22-1086), illustrate Co elements
In the presence of SrFe12-xCoxO19As shown in figure 3, its maximum saturation intensity of magnetization is 55.5emu/g, coercivity is the magnetic hysteresis tropic
1532.0Oe。
BiOCl/SrFe12-xCoxO19XRD as shown in Figure 1, its XRD diffractive features peak contains BiOCl and SrFe12- xCoxO19Peak, illustrate compound validity;Its maximum saturation intensity of magnetization is 9.2emu/g, and coercivity is 1712.4 Oe;
Catalytic activity figure is as shown in figure 4, BiOCl/SrFe12-xCoxO19In sieve for 10mg/L dense to 100mL under illumination in 80 minutes
The degradation rate of red bright B is 88.7%, and the degradation rate after 3 reuses is 79.7%.
rGO/BiOCl/SrFe12-xCoxO19XRD as shown in Figure 1, the characteristic peak without GO in its XRD, illustrates graphite oxide
Alkene (GO) has been converted into reduced graphene (rGO), that is, the product prepared is rGO/BiOCl/SrFe12-xCoxO19。 rGO/
BiOCl/SrFe12-xCoxO19XPS scheme as shown in Fig. 2, in rGO/BiOCl/SrFe12-xCoxO19Xps energy spectrum in there is Co
The X-ray energy spectrum diffraction maximum of 2p, Fe 2p, O 1s, C 1s, Cl 2p, Bi 4f and Sr3d, have respectively illustrated Co2+,Fe3+,O2 +, C=C ,-OCl, Bi3+And Sr2+Presence, occur illustrating contained by the sample prepared by embodiment 2 without other elements miscellaneous peak in addition
The validity of element.rGO/BiOCl/SrFe12-xCoxO19The magnetic hysteresis tropic as shown in figure 3, its maximum saturation intensity of magnetization and
Coercivity is respectively 9.7emu/g and 1638.3Oe.After being reused at 3 times, rGO/BiOCl/SrFe12-xCoxO19Maximum
Saturation magnetization and coercivity are respectively 9.8emu/g and 1610.2Oe, illustrate rGO/BiOCl/SrFe12-xCoxO19Magnetic
Property have higher stability.Its catalytic activity as shown in figure 4, be to the degradation rate of rhodamine B under 80min illumination
94.2%, the degradation rate after being reused at 3 times is 85.4%, and the catalytic activity of still higher than pure BiOCl has higher
Photocatalysis stability.
Photocatalysis experiment display, works as rGO/BiOCl/SrFe12-xCoxO19When the mass fraction of middle rGO is 1%, simulating
Under the xenon lamp irradiation of sunlight, with the rhodamine B of the 0.1g a concentration of 10mg/L of composite magnetic photocatalyst for degrading 100mL prepared
Solution, illumination 80min reach 94.2% to the degradation rate of rhodamine B, and recycling is 85.4% using 3 degradation rates;Test table
Bright, the average recovery rate recycled three times is 73.2%, illustrates the graphene/bismuth oxychloride/cobalt improved strontium prepared using the present invention
Ferrite composite photo-catalyst rGO/BiOCl/SrFe12-xCoxO19With higher photocatalytic activity and stability.
Claims (1)
1. a kind of preparation method of graphene/bismuth oxychloride/cobalt improved strontium ferrite composite photo-catalyst, it is characterised in that including
Following steps:Graphene oxide GO is prepared using improved Hummers methods, cobalt improved strontium ferrite is prepared using hydro-thermal method
SrFe12-xCoxO19;Bi (the NO of 4.85g are weighed respectively3)3·5H2The KCl of O and 0.75g is dissolved in 50mL distilled water, ultrasound
Stirring 60 minutes, obtains suspension A;It is 25 to weigh with the theoretical BiOCl mass ratioes that generate:100 SrFe12-xCoxO19It is added outstanding
In turbid A, 2mL ethylene glycol is instilled as dispersant, is stirred by ultrasonic each 30 minutes, obtains mixed liquid B;It is generated by theory
BiOCl mass and SrFe12-xCoxO19Additive amount summation determines the quality of GO, then it is 0.5%~3.0% to measure mass fraction
GO is added in mixed liquid B, and 30min is stirred by ultrasonic, obtains mixed liquor C;Mixed liquor C is transferred in 100mL reaction kettle liners,
16h is reacted at 180 DEG C;Then it cools down, filter at room temperature, after repeatedly being washed with distilled water, dry 12h at 80 DEG C, grind
Mill, obtains graphene/bismuth oxychloride/cobalt improved strontium ferrite composite photo-catalyst rGO/BiOCl/SrFe12-xCoxO19。
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