CN108686683B - Preparation method of graphene/bismuth oxychloride/cobalt modified strontium ferrite composite photocatalyst - Google Patents
Preparation method of graphene/bismuth oxychloride/cobalt modified strontium ferrite composite photocatalyst Download PDFInfo
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 30
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 26
- 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
- -1 cobalt modified strontium Chemical class 0.000 title claims abstract description 19
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- 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
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- 229910002402 SrFe12O19 Inorganic materials 0.000 description 7
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- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 2
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C01B32/00—Carbon; Compounds thereof
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Abstract
A preparation method of a graphene/bismuth oxychloride/cobalt modified strontium ferrite composite photocatalyst belongs to the field of inorganic catalytic materials. The invention firstly uses an improved Hummers method to prepare graphene oxide GO and a hydrothermal method to prepare a hard magnetic material cobalt modified strontium ferrite SrFe12‑xCoxO19And preparing the graphene/bismuth oxychloride/cobalt modified strontium ferrite composite photocatalyst rGO/BiOCl/SrFe by a hydrothermal method12‑xCoxO19. The method has the advantages of simple preparation process, less used equipment cost, less energy consumption and low cost. Prepared rGO/BiOCl/SrFe12‑xCoxO19The magnetic property is stable, the photocatalytic activity is high, under the irradiation of a simulated sunlight xenon lamp, 100mL of 10mg/L rhodamine B solution is degraded by using 0.1g of prepared composite magnetic photocatalyst, the degradation rate of rhodamine B after illumination for 80min reaches 94.2%, the degradation rate of rhodamine B after repeated use for 3 times is 85.4%, and the average recovery rate is 73.2%. The product prepared by the invention can be widely used in the field of photocatalytic degradation of organic pollutants.
Description
Technical Field
The invention relates to a graphene/bismuth oxychloride/cobalt modified strontium ferrite composite photocatalyst rGO/BiOCl/SrFe12-xCoxO19Belonging to the technical field of inorganic catalytic materials.
Background art:
in the development of novel photocatalysts, BiOCl is a typical ultraviolet photosensitive catalyst and has a unique layered structure characteristic, wherein [ Bi ] is2O2]2+Two of the layer is covered with [ Cl ]2]2-Sandwiched by layers due to difference in electronegativity with [ Bi ]2O2]2+And [ Cl2]2-The vertical direction of the layer 001 is more likely to cause the separation of photo-generated electron-hole pairs, and is more conducive to obtaining good photocatalytic activity. However, the forbidden band width of BiOCl is about 3.46eV, and the absorption capacity of BiOCl to visible light is weak, so that the practical application of BiOCl in the field of photocatalysis is restricted; in addition, the difficult recovery of BiOCl itself causes secondary pollution to the environment. Therefore, the preparation of a BiOCl series photocatalytic material with strong light induction and high recovery stability becomes one of the research focuses in the field of photocatalysis.
The magnetic separation technology has wide application prospect in the field of photocatalysis, and the reported BiOCl composite magnetic photocatalyst has BiOCl/Fe3O4、BiOCl/CoFe2O4And BiOCl/SrFe12O19And the like. Under the condition of an external magnetic field, the separation and the reutilization of the catalytic material and the liquid are realized, but the photocatalytic activity of the composite magnetic catalytic material is limited and still further improved. The light absorption material with smaller composite forbidden band width becomes a feasible scheme for improving the magnetic photocatalytic material, for example, graphene is attached to the surface of the magnetic photocatalyst, so that the absorption rate of the magnetic photocatalyst to light can be increased, the transmission speed of electron-hole pairs can be increased, and the catalytic efficiency of the catalytic material is further enhanced.
Catalysts in which BiOCl is complexed with a Magnetic substance, such as "Dalton Transactions" in 2014 43 at page 2211-2220 "Magnetic composite BiOCl-SrFe12O19A novel p-n type heterojunction with enhanced photocatalytic activity (comparison document 1), the disclosed method is as follows: the SrFe is prepared by a two-step roasting method through roasting firstly12O19Then impregnating and roasting to prepare BiOCl/SrFe12O19A composite magnetic photocatalytic material. The main disadvantages of this method are: (1) magnetic matrix SrFe prepared by roasting method12O19Large particle size and small specific surface area, which is not favorable for SrFe12O19And BiOThe Cl is fully combined, so that the stability of combination cannot be ensured; (2) the composite magnetic photocatalyst prepared by the roasting method has small specific surface area, and is not beneficial to the full contact and reaction between the catalyst and organic pollutants in the photocatalytic degradation process; (3) SrFe12O19Has small coercive force and limited magnetic retention capacity, and is not beneficial to BiOCl-SrFe12O19The recovery rate of the sample is not measured in the text, and the magnetic property stability and the recovery rate of the composite sample cannot be judged; (4) after 2 times of roasting, the energy consumption is large.
The existing report on the preparation method of graphene composite magnetic photocatalyst, such as Chinese patent CN201510954121.4 (reference 2), discloses the preparation of Mn by a roasting method-oxidation reduction method1-xZnxFe2O4/BiVO4RGO, Mn is prepared by a roasting method1-xZnxFe2O4/BiVO4The complex is prepared by oxidation-reduction of RGO with Mn1-xZnxFe2O4/BiVO4Preparing Mn compositely1-xZnxFe2O4/BiVO4and/RGO. The method mainly has the following defects: (1) mn1-xZnxFe2O4The material is a soft magnetic material, has coercivity close to 0, does not have good magnetic retention capacity, and is not beneficial to recycling of the composite catalyst; (2) preparation of Mn1-xZnxFe2O4/BiVO4In the last step of/RGO, only the graphene is reduced, and the reduction of the graphene and Mn cannot be guaranteed1-xZnxFe2O4/BiVO4Good bonding and good repetition stability; (3) only the samples were tested for their rate of repeated degradation and not for their recovery. Cobalt modified strontium ferrite SrFe12-xCoxO19With Mn1-xZnxFe2O4Compared with the prior art, the magnetic material has the characteristics of high saturation magnetization (Ms), high coercivity (Oe), high magnetic conductivity and the like, and has the advantages of high production efficiency, low cost, stable product performance and the like; cobalt modified strontium ferrite SrFe12-xCoxO19Specific ratio of SrFe12O19Has higher coercive force. Thus, cobalt modified strontium ferrite SrFe12-xCoxO19The magnetic photocatalyst of the synthetic rGO is prepared for the magnetic matrix, not only has stable magnetism and high catalytic activity, but also is more convenient to separate and recycle.
Disclosure of Invention
The invention aims to provide a preparation method for synthesizing a graphene/bismuth oxychloride/cobalt modified strontium ferrite composite photocatalyst aiming at the problems of difficult recovery and low degradation rate of BiOCl, the preparation process is simple, the production cost is low, the period is short, the catalytic activity is high, the separation and recovery from a liquid phase suspension system through an external magnetic field are facilitated, the recovered catalyst still has high catalytic activity, the resource recycling is simply and efficiently realized, and the possible secondary pollution caused by the catalyst is avoided.
The graphene/bismuth oxychloride/cobalt modified strontium ferrite composite photocatalyst rGO/BiOCl/SrFe12- xCoxO19The preparation method comprises the following steps:
(1) preparation of GO
The preparation method of the graphene oxide GO is an improved Hummers method, and comprises the following specific steps: 1) a500 mL flask was charged with 75mL of concentrated H2SO4Respectively and slowly adding 1g of graphite powder and 0.5g of NaNO3, and carrying out water bath for 30 min; 2) using a spoon to mix 15g of KMnO4Slowly adding the mixture into a flask (the potassium permanganate is not added too fast, otherwise, the mixed solution is in a deep black state), and magnetically stirring the flask in ice bath for 12 hours; 3) continuing to magnetically stir in the water bath at 60 ℃ for 15 hours, and then turning the mixed solution in the flask into brown; 4) then 150mL of H with the mass fraction of 5 percent is slowly added2SO4The solution is stirred for 2 hours by magnetic force; 5) while stirring in a water bath at 60 ℃, 25mL of H was slowly added2O2And stirring for 2 hours to allow the reaction to be complete; 6) fully filling distilled water into a flask, uniformly stirring, standing for 12 hours, allowing a mixed solution in the flask to be vertically layered, and pouring out a supernatant; 7) centrifuging the lower layer mixture, washing with distilled water, repeating the operation for 3 times, and concentrating with 150mLAnd (3) ultrasonically dissolving the centrifugate by using HCl with the degree of 1mol/L, repeatedly centrifuging and washing, and finally centrifuging to obtain Graphene Oxide (GO).
(2)SrFe12-xCoxO19Preparation of
When x is 0.3, n (Sr) is expressed in terms of the molar ratio of the metal elements2+):n(Fe3+):n(Co2+) Weighing SrCl with corresponding mass respectively according to the weight ratio of 1:7-x: x2·6H2O、FeCl3·6H2O and CoCl2·6H2Dissolving O in 40mL of distilled water, adding 2mL of ethylene glycol, and carrying out ultrasonic dissolution for 30 minutes and stirring for 10 minutes to fully and uniformly dissolve the O to obtain a mixed solution A; weighing NaOH with corresponding mass according to the total molar mass of the metal elements and the condition that the pH value is 12, dissolving the NaOH in 20mL of distilled water, and carrying out ultrasonic treatment for 30 minutes to obtain a NaOH solution B; under magnetic stirring, dropwise adding the solution B into the mixed solution A by using a rubber head dropper, and after dropwise adding is finished, continuously stirring for 20 minutes to obtain brown milky mixed solution C; transferring the mixed solution C into a 100mL reaction kettle liner, sealing the reaction kettle, keeping the temperature in an oven at 200 ℃ for 20h, taking out, cooling at room temperature, performing suction filtration, washing with distilled water for multiple times, drying at 80 ℃ for 12h, and grinding to obtain SrFe12-xCoxO19。
(3)rGO/BiOCl/SrFe12-xCoxO19Preparation of
In a molar ratio of n (Bi (NO)3)3·5H2O): n (KCl) ═ 1:1, and 4.85g of Bi (NO) was weighed out separately3)3·5H2Dissolving O and 0.75g of KCl in 50mL of distilled water, and ultrasonically stirring for 60 minutes to obtain a suspension A; weighing SrFe with the theoretical BiOCl mass ratio of 25:10012-xCoxO19Adding the suspension A into the suspension A, ultrasonically stirring the suspension A for 30 minutes, then dripping 2mL of glycol serving as a dispersing agent into the suspension A, and ultrasonically stirring the suspension A for 30 minutes to obtain a mixed solution B; theoretical BiOCl mass and SrFe12-xCoxO19Determining the mass of GO according to the sum of the addition amount, then measuring GO with the mass fraction of 0.5-3.0% and adding the GO into the mixed solution B, and carrying out ultrasonic stirring for 30min to obtain mixed solution C; transferring the mixed solution C to 100The mixture is put into an inner container of a mL reaction kettle and reacts for 16 hours at 180 ℃; then cooling and filtering at room temperature, washing with distilled water for multiple times, finally drying at 80 ℃ for 12h, and grinding to obtain rGO/BiOCl/SrFe12- xCoxO19And (3) sampling.
By adopting the technical scheme, the invention mainly has the following effects:
(1) the invention adopts a hydrothermal method for preparation, and has the advantages of simple preparation operation, less required equipment and low energy consumption.
(2) Prepared composite photocatalyst rGO/BiOCl/SrFe12-xCoxO19Is SrFe12-xCoxO19The graphene is used as a carrier transfer bridge as a magnetic matrix, the absorption of the graphene in a visible light region is enhanced, the absorption wavelength is 449nm, the forbidden bandwidth is 2.76eV, and the forbidden bandwidth is obviously lower than that of BiOCl (BiOCl) by 3.46 eV.
(3) Composite photocatalyst rGO/BiOCl/SrFe prepared by using method12-xCoxO19Has higher photocatalytic activity, and 0.1g of prepared rGO/BiOCl/SrFe under the irradiation of a xenon lamp (340-800 nm) simulating sunlight12-xCoxO19The composite photocatalysis is dispersed in 100mL of rhodamine B solution with the concentration of 10mg/L, the degradation rate is close to 95 percent when the solution is illuminated for 80min, and the degradation rate of BiOCl is only 76.5 percent under the same condition.
(4) Composite photocatalyst rGO/BiOCl/SrFe prepared by using method12-xCoxO19Under the action of an external magnetic field, the recovery rate after 3 times of repeated use is more than 70%, and the degradation rate of rhodamine B after 3 times of repeated use is still more than 85% and is higher than that of BiOCl.
Drawings
FIG. 1 shows BiOCl, rGO and SrFe12-xCoxO19And rGO/BiOCl/SrFe12-xCoxO19X-ray diffraction pattern of (a).
FIG. 2 shows rGO/BiOCl/SrFe12-xCoxO19XPS chart of (a).
FIG. 3 shows SrFe12-xCoxO19And rGO/BiOCl/SrFe12-xCoxO19Hysteresis regression line graph of (1).
FIG. 4 shows BiOCl, BiOCl/SrFe12-xCoxO19And rGO/BiOCl/SrFe12-xCoxO19Graph of RhB photocatalytic degradation rate.
Detailed Description
The present invention will be further described with reference to the following specific embodiments.
Example 1
The preparation method of the graphene/bismuth oxychloride/cobalt modified strontium ferrite composite photocatalyst comprises the following specific steps:
(1) preparation of GO
The preparation process of GO is as follows: 1) a500 mL flask was charged with 75mL of concentrated H2SO4Then respectively slowly adding 1g of graphite powder and 0.5g of NaNO3Water bath for 30 min; 2) using a spoon to mix 15g of KMnO4Slowly adding the mixture into a flask (the potassium permanganate is not added too fast, otherwise, the mixed solution is in a deep black state), and magnetically stirring the flask in ice bath for 12 hours; 3) continuing to magnetically stir in the water bath at 60 ℃ for 15 hours, and then turning the mixed solution in the flask into brown; 4) then 150mL of H with the mass fraction of 5 percent is slowly added2SO4The solution is stirred for 2 hours by magnetic force; 5) while stirring in a water bath at 60 ℃, 25mL of H was slowly added2O2And stirring for 2 hours to allow the reaction to be complete; 6) fully filling distilled water into a flask, uniformly stirring, standing for 12 hours, allowing a mixed solution in the flask to be vertically layered, and pouring out a supernatant; 7) centrifuging the lower-layer mixed solution, washing with distilled water after centrifuging, repeating the operation for 3 times, performing ultrasonic dissolution on the centrifugate with 150mL of HCl with the concentration of 1mol/L, then repeatedly centrifuging and washing with water, and finally centrifuging to obtain Graphene Oxide (GO).
(2)SrFe12-xCoxO19Preparation of
When x is 0.3, n (Sr) is expressed in terms of the molar ratio of the metal elements2+):n(Fe3+):n(Co2+) Weighing SrCl with corresponding mass respectively according to the weight ratio of 1:7-x: x2·6H2O、FeCl3·6H2O and CoCl2·6H2Dissolving O in 40mL of distilled water, adding 2mL of ethylene glycol, and carrying out ultrasonic dissolution for 30 minutes and stirring for 10 minutes to fully and uniformly dissolve the O to obtain a mixed solution A; weighing NaOH with corresponding mass according to the total molar mass of the metal elements and the condition that the pH value is 12, dissolving the NaOH in 20mL of distilled water, and carrying out ultrasonic treatment for 30 minutes to obtain a NaOH solution B; under magnetic stirring, dropwise adding the solution B into the mixed solution A by using a rubber head dropper, and after dropwise adding is finished, continuously stirring for 20 minutes to obtain brown milky mixed solution C; transferring the mixed solution C into a 100mL reaction kettle liner, sealing the reaction kettle, keeping the temperature in an oven at 200 ℃ for 20h, taking out, cooling at room temperature, performing suction filtration, washing with distilled water for multiple times, drying at 80 ℃ for 12h, and grinding to obtain SrFe12-xCoxO19。
(3)rGO/BiOCl/SrFe12-xCoxO19Preparation of
In a molar ratio of n (Bi (NO)3)3·5H2O): n (KCl) ═ 1:1, and 4.85g of Bi (NO) was weighed out separately3)3·5H2Dissolving O and 0.75g of KCl in 50mL of distilled water, and ultrasonically stirring for 60 minutes to obtain a suspension A; weighing SrFe with the theoretical BiOCl mass ratio of 25:10012-xCoxO19Adding the suspension A into the suspension A, ultrasonically stirring the suspension A for 30 minutes, then dripping 2mL of glycol serving as a dispersing agent into the suspension A, and ultrasonically stirring the suspension A for 30 minutes to obtain a mixed solution B; theoretical BiOCl mass and SrFe12-xCoxO19Determining the mass of GO according to the sum of the addition amount, measuring GO with the mass fraction of 0.5%, adding the GO into the mixed solution B, and performing ultrasonic stirring for 30min to obtain mixed solution C; transferring the mixed solution C into a 100mL reaction kettle liner, and reacting for 16h at 180 ℃; then cooling and filtering at room temperature, washing with distilled water for multiple times, finally drying at 80 ℃ for 12h, and grinding to obtain rGO/BiOCl/SrFe12- xCoxO19And (3) sampling.
Example 2
The preparation method of the graphene/bismuth oxychloride/cobalt modified strontium ferrite composite photocatalyst comprises the following specific steps:
(1) same as in step (1) of example 1.
(2) Same as in step (2) of example 1.
(3)rGO/BiOCl/SrFe12-xCoxO19Preparation of
In a molar ratio of n (Bi (NO)3)3·5H2O): n (KCl) ═ 1:1, and 4.85g of Bi (NO) was weighed out separately3)3·5H2Dissolving O and 0.75g of KCl in 50mL of distilled water, and ultrasonically stirring for 60 minutes to obtain a suspension A; weighing SrFe with the theoretical BiOCl mass ratio of 25:10012-xCoxO19Adding the suspension A into the suspension A, ultrasonically stirring the suspension A for 30 minutes, then dripping 2mL of glycol serving as a dispersing agent into the suspension A, and ultrasonically stirring the suspension A for 30 minutes to obtain a mixed solution B; theoretical BiOCl mass and SrFe12-xCoxO19Determining the mass of GO according to the sum of the addition amount, measuring 1.0 mass percent of GO, adding into the mixed solution B, and ultrasonically stirring for 30min to obtain mixed solution C; transferring the mixed solution C into a 100mL reaction kettle liner, and reacting for 16h at 180 ℃; then cooling and filtering at room temperature, washing with distilled water for multiple times, finally drying at 80 ℃ for 12h, and grinding to obtain rGO/BiOCl/SrFe12- xCoxO19And (3) sampling.
Example 3
The preparation method of the graphene/bismuth oxychloride/cobalt modified strontium ferrite composite photocatalyst comprises the following specific steps:
(1) same as in step (1) of example 1.
(2) Same as in step (2) of example 1.
(3)rGO/BiOCl/SrFe12-xCoxO19Preparation of
In a molar ratio of n (Bi (NO)3)3·5H2O): n (KCl) ═ 1:1, and 4.85g of Bi (NO) was weighed out separately3)3·5H2Dissolving O and 0.75g of KCl in 50mL of distilled water, and ultrasonically stirring for 60 minutes to obtain a suspension A; weighing SrFe with the theoretical BiOCl mass ratio of 25:10012-xCoxO19Adding the suspension A into the suspension A, ultrasonically stirring the suspension A for 30 minutes, then dripping 2mL of glycol serving as a dispersing agent into the suspension A, and ultrasonically stirring the suspension A for 30 minutes to obtain a mixed solution B; push buttonTheoretical amount of BiOCl and SrFe12-xCoxO19Determining the mass of GO according to the sum of the addition amount, measuring 2.0 mass percent of GO, adding into the mixed solution B, and ultrasonically stirring for 30min to obtain mixed solution C; transferring the mixed solution C into a 100mL reaction kettle liner, and reacting for 16h at 180 ℃; then cooling and filtering at room temperature, washing with distilled water for multiple times, finally drying at 80 ℃ for 12h, and grinding to obtain rGO/BiOCl/SrFe12- xCoxO19And (3) sampling.
Example 4
The preparation method of the graphene/bismuth oxychloride/cobalt modified strontium ferrite composite photocatalyst comprises the following specific steps:
(1) same as in step (1) of example 1.
(2) Same as in step (2) of example 1.
(3)rGO/BiOCl/SrFe12-xCoxO19Preparation of
In a molar ratio of n (Bi (NO)3)3·5H2O): n (KCl) ═ 1:1, and 4.85g of Bi (NO) was weighed out separately3)3·5H2Dissolving O and 0.75g of KCl in 50mL of distilled water, and ultrasonically stirring for 60 minutes to obtain a suspension A; weighing SrFe with the theoretical BiOCl mass ratio of 25:10012-xCoxO19Adding the suspension A into the suspension A, ultrasonically stirring the suspension A for 30 minutes, then dripping 2mL of glycol serving as a dispersing agent into the suspension A, and ultrasonically stirring the suspension A for 30 minutes to obtain a mixed solution B; theoretical BiOCl mass and SrFe12-xCoxO19Determining the mass of GO according to the sum of the addition amount, measuring 3.0 mass percent of GO, adding into the mixed solution B, and ultrasonically stirring for 30min to obtain mixed solution C; transferring the mixed solution C into a 100mL reaction kettle liner, and reacting for 16h at 180 ℃; then cooling and filtering at room temperature, washing with distilled water for multiple times, finally drying at 80 ℃ for 12h, and grinding to obtain rGO/BiOCl/SrFe12- xCoxO19And (3) sampling.
Results of the experiment
Example 2 preparation of rGO/BiOCl/SrFe12-xCoxO19The catalytic degradation activity is optimal. To be made toFor comparison, rGO, BiOCl samples and BiOCl/SrFe were prepared12-xCoxO19The preparation method of rGO is that NO Bi (NO) is added in the step (3) of the example 23)3·5H2O, KCl and SrFe12-xCoxO19The BiOCl preparation method is that in the step (3) of the example 2, SrFe is not added12- xCoxO19And GO, BiOCl/SrFe12-xCoxO19The preparation method is that no GO is added in the step (3) of the example 2.
The XRD of BiOCl is shown in FIG. 1, and each diffraction peak corresponds to a pure BiOCl characteristic peak (JCPDS #06-0249) which has characteristic reflection peaks including {001}, {002}, {101}, {110}, {102} and {003}, etc., thus proving that the sample is a pure tetragonal crystal structure BiOCl with the degradation rate shown in FIG. 4 and 76.5% of 100mL rhodamine B with concentration of 10mg/L under 80 minutes illumination.
SrFe12-xCoxO19The XRD of (A) is shown in FIG. 1, which shows not only hexagonal M-phase ferrite (SrFe)12O19) And also shows CoFe2O4Characteristic peak {311} (JCPDS #22-1086) of (B), indicating the existence of Co element, SrFe12-xCoxO19The hysteresis regression line is shown in FIG. 3, and the maximum saturation magnetization is 55.5emu/g, and the coercivity is 1532.0 Oe.
BiOCl/SrFe12-xCoxO19The XRD of (1) is shown in figure, and the characteristic peaks of XRD diffraction comprise BiOCl and SrFe12- xCoxO19The peak of (a), illustrates the effectiveness of the recombination; the maximum saturation magnetization is 9.2emu/g, and the coercive force is 1712.4 Oe; the catalytic activity diagram is shown in figure 4, BiOCl/SrFe12-xCoxO19The degradation rate of 100mL of 10mg/L rhodamine B under 80-minute illumination is 88.7 percent, and the degradation rate after 3 times of repeated use is 79.7 percent.
rGO/BiOCl/SrFe12-xCoxO19The XRD of the graphene oxide is shown in figure 1, and no characteristic peak of GO exists in the XRD, which indicates that Graphene Oxide (GO) is converted into reduced graphene (rGO), namely, the prepared product isrGO/BiOCl/SrFe12-xCoxO19。rGO/BiOCl/SrFe12-xCoxO19The XPS map of (A) is shown in FIG. 2, in rGO/BiOCl/SrFe12-xCoxO19The XPS spectrum of the crystal has X-ray spectrum diffraction peaks of Co 2p, Fe 2p, O1 s, C1 s, Cl 2p, Bi 4f and Sr3d, which respectively indicate that Co is contained2+、Fe3+、O2+、C＝C、-OCl、Bi3+And Sr2+The absence of other element impurities in addition indicates the effectiveness of the elements contained in the sample prepared in example 2. rGO/BiOCl/SrFe12-xCoxO19The maximum saturation magnetization and coercive force of the resultant hysteresis regression line (D) are 9.7emu/g and 1638.3Oe, respectively, as shown in FIG. 3. After 3 times of repeated use, rGO/BiOCl/SrFe12-xCoxO19The maximum saturation magnetization and the coercive force are respectively 9.8emu/g and 1610.2Oe, which indicates that rGO/BiOCl/SrFe12-xCoxO19The magnetic property of (2) has higher stability. The catalytic activity of the compound is shown in figure 4, the degradation rate of rhodamine B under 80min illumination is 94.2%, the degradation rate after 3 times of recycling is 85.4%, the catalytic activity is still higher than that of pure BiOCl, and the compound has higher photocatalytic stability.
The photocatalysis experiment shows that when rGO/BiOCl/SrFe12-xCoxO19When the mass fraction of the medium rGO is 1%, degrading 100mL of 10mg/L rhodamine B solution by using 0.1g of prepared composite magnetic photocatalyst under the irradiation of a sunlight-simulated xenon lamp, wherein the degradation rate of rhodamine B in 80min after illumination reaches 94.2%, and the degradation rate after 3-time recycling is 85.4%; tests show that the average recovery rate of the third recovery is 73.2%, which indicates that the graphene/bismuth oxychloride/cobalt modified strontium ferrite composite photocatalyst rGO/BiOCl/SrFe prepared by the method12-xCoxO19Has high photocatalytic activity and stability.
Claims (1)
1. A preparation method of a graphene/bismuth oxychloride/cobalt modified strontium ferrite composite photocatalyst is characterized by comprising the following steps: preparing graphene oxide GO by adopting an improved Hummers methodHydrothermal method for preparing cobalt modified strontium ferrite SrFe12-xCoxO19(ii) a Separately, 4.85g of Bi (NO) was weighed3)3·5H2Dissolving O and 0.75g of KCl in 50mL of distilled water, and ultrasonically stirring for 60 minutes to obtain a suspension A; weighing SrFe with the theoretical BiOCl mass ratio of 25:10012-xCoxO19Adding the suspension A into the suspension A, dripping 2mL of glycol as a dispersing agent, and ultrasonically stirring for 30 minutes respectively to obtain a mixed solution B; theoretical BiOCl mass and SrFe12-xCoxO19Determining the mass of GO according to the sum of the addition amount, then measuring GO with the mass fraction of 0.5-3.0% and adding the GO into the mixed solution B, and carrying out ultrasonic stirring for 30min to obtain mixed solution C; transferring the mixed solution C into a 100mL reaction kettle liner, and reacting for 16h at 180 ℃; then cooling and filtering at room temperature, washing with distilled water for multiple times, drying at 80 ℃ for 12h, and grinding to obtain the graphene/bismuth oxychloride/cobalt modified strontium ferrite composite photocatalyst rGO/BiOCl/SrFe12-xCoxO19。
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