CN109174114B - Method for preparing composite nano magnetic photocatalyst by using waste alkaline batteries - Google Patents
Method for preparing composite nano magnetic photocatalyst by using waste alkaline batteries Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000002699 waste material Substances 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 239000011701 zinc Substances 0.000 claims abstract description 80
- 239000000463 material Substances 0.000 claims abstract description 75
- 239000007788 liquid Substances 0.000 claims abstract description 59
- 239000000843 powder Substances 0.000 claims abstract description 56
- 238000002386 leaching Methods 0.000 claims abstract description 55
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000000975 co-precipitation Methods 0.000 claims abstract description 11
- 239000011572 manganese Substances 0.000 claims description 90
- 239000000243 solution Substances 0.000 claims description 84
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 72
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 42
- 229910001437 manganese ion Inorganic materials 0.000 claims description 42
- 239000011259 mixed solution Substances 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 238000010438 heat treatment Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 27
- 239000012153 distilled water Substances 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 229910052742 iron Inorganic materials 0.000 claims description 22
- 150000002500 ions Chemical class 0.000 claims description 21
- -1 iron ions Chemical class 0.000 claims description 21
- 241000605272 Acidithiobacillus thiooxidans Species 0.000 claims description 19
- 238000012258 culturing Methods 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 16
- 241000605222 Acidithiobacillus ferrooxidans Species 0.000 claims description 15
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 44
- 239000011787 zinc oxide Substances 0.000 abstract description 22
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- 230000003197 catalytic effect Effects 0.000 description 9
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 8
- 229960000907 methylthioninium chloride Drugs 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
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- SZKTYYIADWRVSA-UHFFFAOYSA-N zinc manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Zn++] SZKTYYIADWRVSA-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
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- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 description 4
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- 239000003054 catalyst Substances 0.000 description 4
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- 238000010276 construction Methods 0.000 description 3
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- 229910052725 zinc Inorganic materials 0.000 description 3
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- 239000000203 mixture Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
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- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
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- 230000031700 light absorption Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 238000013112 stability test Methods 0.000 description 1
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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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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
The invention discloses a method for preparing a composite nano magnetic photocatalyst by using waste alkaline batteries, which comprises the following steps: crushing the disassembled negative electrode material and positive electrode material of the waste alkaline battery, carrying out microbial leaching on the negative electrode material to obtain a preparation liquid A for preparing ferrite, and carrying out hydrothermal synthesis reaction on the preparation liquid A to obtain MnxZn1‑xFe2O4Ferrite solid powder precursor D, chemically leaching the anode electrode material to obtain manganese-doped zinc oxide material precursor E, and adding MnxZn1‑xFe2O4Carrying out coprecipitation reaction on a ferrite solid powder precursor D and a manganese-doped zinc oxide material precursor E to obtain MnxZn1‑xFe2O4@Zn0.9Mn0.1O nanometer magnetic photocatalyst. The method is simple, efficient, green and environment-friendly, and realizes high value-added resource utilization of the waste batteries.
Description
Technical Field
The invention belongs to the technical field of preparation methods of photocatalyst materials, and particularly relates to a method for preparing a composite nano magnetic photocatalyst by using waste alkaline batteries.
Background
The semiconductor nano-particles can catalyze and degrade organic pollutants under ultraviolet or sunlight, wherein ZnO has wide band gap (3.4eV), good biocompatibility and easy preparation, and is widely concerned, but the problems of low visible light utilization efficiency, fast recombination of pure-phase ZnO electron hole pairs, difficult recovery and the like exist, and the use of the ZnO is limited. Researches show that spinel ferrite has a narrower band gap than ZnO, is about 2eV or even lower, is a potential visible light photocatalytic magnetic material, has poor photocatalytic conversion efficiency and is directly used for photocatalysis due to less pure phases. Other metal elements are properly doped in the ZnO crystal lattice, so that the ZnO crystal lattice is suitable for visible light absorption, compared with a pure phase, the composite heterojunction can effectively inhibit recombination of photogenerated electrons and holes, the photocatalysis efficiency is improved, more modulation and modification possibilities are provided, and the establishment of the novel ferrite/zinc oxide nano composite structure is an effective way for endowing materials with new characteristics and improving the catalytic activity of the materials. The waste alkaline batteries contain a large amount of Zn, Mn and Fe, and can be used as preparation raw materials to prepare nano photocatalytic materials.
Disclosure of Invention
The invention aims to provide a method for preparing a composite nano magnetic photocatalyst by using waste alkaline batteries, which has the characteristics of high visible light utilization efficiency and easiness in magnetic separation and recovery.
The technical scheme adopted by the invention is that a method for preparing a composite nano magnetic photocatalyst by using waste alkaline batteries is implemented according to the following steps:
step 1, splitting anode and cathode battery materials of waste alkaline batteries, respectively mechanically crushing the anode and cathode battery materials, and screening to obtain anode electrode powder and cathode electrode powder;
step 2, preparing a biological leaching culture solution and carrying out strain culture;
and 3, adding the negative electrode powder obtained in the step 1 into the biological leaching culture solution treated in the step 2 for biological leaching, periodically sampling to monitor the concentrations of manganese ions, zinc ions and iron ions in the biological leaching solution, and after leaching is finished, adding one or more of zinc ions, manganese ions or iron ions into the biological leaching solution according to the monitored concentrations for ion concentration adjustment to obtain the prepared MnxZn1-xFe2O4The preparation liquid A of (1);
step 4, preparing Mn from the obtained Mn in step 3xZn1-xFe2O4Heating the preparation solution A to 45-55 ℃ at the heating rate of 10 ℃/min, and adding NaOH solution to adjust the pH value to obtain a mixed solution B;
and 6, adding the anode electrode powder obtained in the step 1 into hydrochloric acid for chemical leaching, periodically monitoring the concentrations of zinc ions and manganese ions, and adding the zinc ions or the manganese ions into the leaching solution for ion concentration adjustment according to the monitored concentrations to obtain Zn0.9Mn0.1O liquid precursor E;
step 7, weighing a certain amount of Mn obtained in step 5xZn1-xFe2O4Putting the solid powder precursor D into a container, adding a plurality of distilled water, putting the container into an ultrasonic instrument for ultrasonic treatment to obtain dispersion liquid F, and dropwise adding Zn obtained in the step 6 into the dispersion liquid F0.9Mn0.1O liquid precursor E is stirred to obtain a mixed solution G, ammonia water is added into the mixed solution G drop by drop to adjust the pH value of the mixed solution G, the mixed solution G is stirred to carry out coprecipitation reaction, the mixed solution G is kept stand to obtain black precipitate, the black precipitate is subjected to centrifugation and washing treatment in sequence and then is placed in an oven to be dried to obtain MnxZn1-xFe2O4@Zn0.9Mn0.1O nanometer magnetic photocatalyst.
The present invention is also characterized in that,
the particle diameters of the anode electrode powder and the cathode electrode powder in the step 1 are less than 200 mu m.
The specific steps of the step 2 are as follows: the solvent is distilled water, and the solute is: 2.0 g/L-4.0 g/L (NH)4)2SO4、2.0g/L～3.0g/LK2HPO4、1.0g/L～3.0g/LMgSO4·7H2O、0.3g/L～0.5g/LCaCl2、1.0g/L～3.0g/LKCl、30g/L～50g/LFeSO4·7H2Adding mixed bacteria of thiobacillus thiooxidans and thiobacillus ferrooxidans into O and 10-20 g/LS to prepare a biological leaching solution, controlling the temperature of the leaching solution to be 25-35 ℃ by using a heating rod, continuously aerating and aerating by using an air pump, culturing for 3-5 days, supplementing evaporated water in the culturing process, monitoring the pH value and the strain density of the leaching solution, and when the pH value is reduced to 1.0-E2.0 and the strain density reaches 2 multiplied by 108 2X 10 per mL10At one/mL, the culture was terminated.
The volume ratio of thiobacillus thiooxidans to thiobacillus ferrooxidans is 1:1, and the volume ratio of the mixed bacteria liquid to distilled water is 1: 9.
In the step 3, the solid-to-liquid ratio of the negative electrode powder to the biological extraction culture solution is 5-10%, the extraction days are 3-5 days, the total ion concentration of the adjusted zinc ions, manganese ions and iron ions is 2-3 mol/L, and Mn isxZn1- xFe2O4Wherein x is 0.3 to 0.7.
In the step 4, the adding speed of the NaOH solution is 10mL/min to 20mL/min, the mass concentration is 10 percent to 20 percent, and the pH value is 11 to 13.
In the step 5, the temperature of the heating treatment is 70-100 ℃, the heating rate is 10-20 ℃/min, and the stirring speed is 120-150 r/min; the temperature of the hot water synthesis reaction is 180-200 ℃, the reaction time is 8-10 h, the washing times are 5 times, and the drying temperature is 80 ℃.
In the step 6, the solid-to-liquid ratio of the anode electrode powder to the hydrochloric acid is 20-30%, and the concentration of the hydrochloric acid is 5-8 mol/L; the concentration ratio of the adjusted zinc ions to manganese ions is 0.9: 0.1, and the total concentration is 1 mol/L-2 mol/L.
Mn in step 7xZn1-xFe2O4The mass ratio of the ferrite solid powder precursor D to distilled water is 1:5, the ultrasonic time is 10-30 min, the pH value is 8-10, the coprecipitation reaction time is 20-30 min, the washing times are 3-5 times, and the drying temperature is 80 ℃.
Mn in step 7xZn1-xFe2O4And Zn0.9Mn0.1The mass doping ratio of O is 0-100%.
The invention has the beneficial effects that:
(1) according to the method for preparing the composite nano magnetic photocatalyst by using the waste alkaline batteries, the manganese, zinc and iron metal raw materials required by the preparation material are obtained by using the waste alkaline batteries which are easy to obtain and a safe and environment-friendly microbial leaching method, so that the method is simple and efficient, and the resource utilization of the waste batteries is realized;
(2) the invention relates to a method for preparing a composite nano magnetic photocatalyst by using waste alkaline batteries, which is characterized in that a composite nano magnetic photocatalyst easy for magnetic separation and recovery is obtained by carrying out microbial leaching, chemical leaching, hydrothermal synthesis and coprecipitation on positive and negative electrode materials of the waste alkaline batteries, the visible light utilization efficiency of the material is obviously improved, and the material can be applied to photocatalytic degradation of organic pollutants in wastewater;
drawings
FIG. 1 shows a series of Mn prepared by the process of the present inventionxZn1-xFe2O4@Zn0.9Mn0.1X-ray diffraction spectrogram of the O nano magnetic photocatalyst;
FIG. 2 shows a series of Mn prepared by the process of the present inventionxZn1-xFe2O4@Zn0.9Mn0.1Calculating a band gap of the O nano magnetic photocatalyst;
FIG. 3 shows Mn prepared by the process of the present inventionxZn1-xFe2O4@50％-Zn0.9Mn0.1A graph of the change of photocatalytic degradation efficiency with time when visible light irradiation is carried out on methylene blue in wastewater by an O nano magnetic photocatalyst;
FIG. 4 shows a series of Mn prepared by the process of the present inventionxZn1-xFe2O4@Zn0.9Mn0.1And (3) a magnetic hysteresis chart of the O nano magnetic photocatalyst.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a method for preparing a composite nano magnetic photocatalyst by using waste alkaline batteries, which is implemented by the following steps:
step 1, splitting anode and cathode battery materials of waste alkaline batteries, respectively mechanically crushing the anode and cathode battery materials, and screening to obtain anode electrode powder and cathode electrode powder with particle sizes less than 200 mu m;
step 2, preparing a biological leaching solution, and culturing strains;
distilled water as solvent and 2.0-4.0 g/L (NH) as solute4)2SO4、2.0g/L～3.0g/LK2HPO4、1.0g/L～3.0g/LMgSO4·7H2O、0.3g/L～0.5g/LCaCl2、1.0g/L～3.0g/LKCl、30g/L～50g/LFeSO4·7H2Adding mixed bacteria liquid of thiobacillus thiooxidans (Acidithiobacillus thiooxidans, A.t.) and thiobacillus ferrooxidans (A.f.) into 10 g/L-20 g/LS to prepare a bioleaching solution, wherein the volume ratio of the thiobacillus thiooxidans to the thiobacillus ferrooxidans is 1:1, the volume ratio of the mixed bacteria liquid to distilled water is 1:9, controlling the temperature of the bioleaching solution to be 25-35 ℃ by using a heating rod, continuously aerating and aerating by using an air pump, culturing for 3-5 days, supplementing evaporated water in the culturing process, monitoring the pH value and the strain density of the leaching solution, and when the pH value is reduced to 1.0-2.0 and the strain density reaches 2 x 108 2X 10 per mL10When the strain is one/mL, finishing the culture;
and 3, adding the negative electrode powder obtained in the step 1 into the bioleaching culture solution treated in the step 2 according to a solid-to-liquid ratio (w/V) of 5-10% for bioleaching, sampling every 12 hours to monitor the concentrations of manganese ions, zinc ions and iron ions in the bioleaching solution, and after the bioleaching is finished for 3-5 days, adding one or more of zinc ions, manganese ions or iron ions into the bioleaching solution according to the monitored concentrations to adjust the ion concentrations so that the total ion concentrations of the adjusted zinc ions, manganese ions and iron ions are 2-3 mol/L, thereby obtaining the ferrite material (Mn/L)xZn1-xFe2O4) The preparation solution A of (1), wherein x is 0.3-0.7;
step 4, preparing Mn from the obtained Mn in step 3xZn1-xFe2O4The temperature of the preparation liquid A is increased to 45-55 ℃ at the heating rate of 10 ℃/min, and NaOH solution with the mass concentration of 10-20% is added at the rate of 10-20 mL/min to adjust the pH value to 11-13, so as to obtain mixed liquid B;
and 6, adding the anode electrode powder obtained in the step 1 into hydrochloric acid with the concentration of 5-8 mol/L according to a solid-to-liquid ratio (w/V) of 20-30% for chemical leaching for 2 hours, monitoring the concentrations of zinc ions and manganese ions after leaching is finished, and adding zinc ions or manganese ions into the leaching solution for ion concentration adjustment according to the monitored concentrations, so that the concentration ratio of the adjusted zinc ions to the adjusted manganese ions is 0.9: 0.1, the total concentration is 1 mol/L-2 mol/L to obtain the manganese-doped zinc oxide material (Zn)0.9Mn0.1O) a liquid precursor E;
step 7, weighing a certain amount of Mn obtained in step 5xZn1-xFe2O4Placing ferrite solid powder precursor D in a container, and adding a plurality of distilled water, wherein MnxZn1-xFe2O4The mass ratio of the ferrite solid powder precursor D to the distilled water is 1:5, the ferrite solid powder precursor D and the distilled water are placed into an ultrasonic instrument for ultrasonic treatment for 10-30 min to obtain dispersion liquid F, and Zn obtained in the step 6 is dropwise added into the dispersion liquid F0.9Mn0.1O liquid precursor E, and control of MnxZn1-xFe2O4And Zn0.9Mn0.1The mass doping ratio of O is 0% -100%, stirring is carried out to obtain a mixed solution G, ammonia water is added into the mixed solution G dropwise to adjust the pH value of the mixed solution G to be 8-10, stirring is carried out again to carry out coprecipitation reaction for 20-30 min, standing is carried out to obtain a black precipitate, the black precipitate is centrifuged and washed for 3-5 times in sequence, and then is placed in an oven to be dried at the temperature of 80 ℃ to obtain MnxZn1-xFe2O4@Zn0.9Mn0.1O (MZFO @ ZMO) nanomagnetic photocatalyst.
Example 1
Step 1, splitting anode and cathode battery materials of waste alkaline batteries, respectively mechanically crushing the anode and cathode battery materials, and screening to obtain anode electrode powder and cathode electrode powder with particle sizes less than 200 mu m;
step 2, preparing a biological leaching culture solution, and culturing strains;
the solvent is distilled water, and the solute is: 2.0g/L (NH)4)2SO4、2.0g/LK2HPO4、1.0g/LMgSO4·7H2O、0.3g/LCaCl2、1.0g/LKCl、30g/LFeSO4·7H2Adding a mixed bacteria solution of thiobacillus thiooxidans (Acidithiobacillus thiooxidans, A.t.) and thiobacillus ferrooxidans (A.f.) into O and 10g/LS, wherein the volume ratio of the thiobacillus thiooxidans to the thiobacillus ferrooxidans is 1:1, the volume ratio of the mixed bacteria solution to distilled water is 1:9, controlling the temperature of a bioleaching solution to be 25 ℃ by using a heating rod, continuously aerating and aerating by using an air pump, culturing for 3 days, supplementing evaporated water in the culturing process, monitoring the pH value and the strain density of the leaching solution, and when the pH value is reduced to 1.0 and the strain density reaches 2 multiplied by 108When the strain is one/mL, finishing the culture;
and 3, adding the negative electrode powder obtained in the step 1 into the bioleaching culture solution treated in the step 2 according to a solid-to-liquid ratio (w/V) of 5% for bioleaching, sampling every 12 hours to monitor the concentrations of manganese ions, zinc ions and iron ions in the bioleaching solution, adding one or more of zinc ions, manganese ions or iron ions into the bioleaching solution according to the monitored concentrations to adjust the ion concentrations after 3 days of leaching is finished, so that the total ion concentration of the adjusted zinc ions, manganese ions and iron ions is 2mol/L, wherein x is 0.5, and thus obtaining the ferrite material (Mn/V)0.5Zn0.5Fe2O4) The preparation liquid A of (1);
step 4, preparing Mn from the obtained Mn in step 30.5Zn0.5Fe2O4The temperature of the preparation liquid A is raised to the temperature of 10 ℃/minAdding 10% NaOH solution at the mass concentration of 10mL/min at the temperature of 45 ℃ to adjust the pH value to 11, and obtaining mixed solution B;
As shown in FIG. 1, in the XRD pattern of MZFO photocatalyst obtained by the preparation method of the present invention, characteristic peaks appear at 2 theta of 29.9 degrees, 35.3 degrees, 42.8 degrees, 53.1 degrees, 56.6 degrees, 62.2 degrees, 73.5 degrees, etc., which is similar to the standard pattern PDF #22-1012 (ZnFe)2O4) Or PDF #22-1012 (MnFe)2O4) The crystal faces of (220), (311), (400), (422), (511), (440) and (533) are consistent, the substance is manganese zinc ferrite, and the test of the molar composition of the EDX elements also proves that the prepared material is pure-phase sample Mn0.5Zn0.5Fe2O4；
As shown in fig. 2, the band gap of the MZFO material prepared by UV-Vis spectroscopy measurement and calculation is 1.7eV, which is much lower than that of pure phase ZnO, and relatively speaking, the material has small band gap, higher catalytic activity and higher utilization efficiency of visible light, but the electron-hole pair is relatively easy to recombine;
as shown in fig. 3, under the irradiation of visible light for 90min, the MZFO material realizes 80% degradation of methylene blue dye; meanwhile, as shown in FIG. 4, the prepared MZFO material has excellent magnetic performance, the saturation magnetic strength Ms is as high as 62.1emu/g, and the magnetic separation operation of the material is easy to realize after the material is used.
Example 2
Step 1, splitting anode and cathode battery materials of waste alkaline batteries, respectively mechanically crushing the anode and cathode battery materials, and screening to obtain anode electrode powder and cathode electrode powder with particle sizes less than 200 mu m;
step 2, preparing a biological leaching culture solution, and culturing strains;
the solvent is distilled water, and the solute is: 3.0g/L (NH)4)2SO4、2.5g/LK2HPO4、1.5g/LMgSO4·7H2O、0.4g/LCaCl2、2.0g/LKCl、40g/LFeSO4·7H2Adding mixed bacteria liquid of thiobacillus thiooxidans (Acidithiobacillus thiooxidans, A.t.) and thiobacillus ferrooxidans (A.f.) into O and 15g/LS to prepare a biological leaching solution, wherein the volume ratio of the thiobacillus thiooxidans to the thiobacillus ferrooxidans is 1:1, the volume ratio of the mixed bacteria liquid to distilled water is 1:9, the temperature of the leaching solution is controlled to be 30 ℃ by a heating rod, then an air pump is used for continuously aerating and aerating for culturing for 4 days, the evaporated water is supplemented in the culturing process, the pH value and the strain density of the leaching solution are monitored, and when the pH value is reduced to 1.5 and the strain density reaches 2 multiplied by 10, the pH value and the strain density are monitored9When the strain is one/mL, finishing the culture;
and 3, adding the negative electrode powder obtained in the step 1 into the bioleaching culture solution treated in the step 2 according to a solid-to-liquid ratio (w/V) of 8% for bioleaching, sampling every 12 hours to monitor the concentrations of manganese ions, zinc ions and iron ions in the bioleaching solution, adding one or more of zinc ions, manganese ions or iron ions into the bioleaching solution according to the monitored concentrations to adjust the ion concentrations after 4 days of leaching is finished, so that the total ion concentration of the adjusted zinc ions, manganese ions and iron ions is 2.5mol/L, wherein x is 0.3, and thus obtaining the prepared ferrite material (Mn/V)0.3Zn0.7Fe2O4) The preparation solution A of (1);
step 4, preparing Mn from the obtained Mn in step 30.3Zn0.7Fe2O4Heating the preparation solution A to 50 ℃ at the heating rate of 10 ℃/min, and adding a NaOH solution with the mass concentration of 15% at the rate of 15mL/min to adjust the pH value to 12 to obtain a mixed solution B;
and 6, adding the anode electrode powder obtained in the step 1 into hydrochloric acid with the concentration of 5mol/L according to a solid-to-liquid ratio (w/V) of 20% for chemical leaching for 2 hours, monitoring the concentrations of zinc ions and manganese ions after leaching is finished, and adding zinc ions or manganese ions into the leaching solution according to the monitored concentrations for ion concentration adjustment to enable the concentration ratio of the adjusted zinc ions to the adjusted manganese ions to be 0.9: 0.1, the total concentration is 1mol/L to obtain the manganese-doped zinc oxide material (Zn)0.9Mn0.1O) a liquid precursor E;
step 7, weighing 10g of Mn obtained in step 50.3Zn0.7Fe2O4Placing ferrite solid powder precursor D in a container, adding 50ml (50g) of distilled water, placing in an ultrasonic instrument for ultrasonic treatment for 10min to obtain dispersion liquid F, and dropwise adding Zn obtained in the step 6 into the dispersion liquid F0.9Mn0.1O liquid precursor E, and control of Mn0.3Zn0.7Fe2O4And Zn0.9Mn0.1The mass doping ratio of O is 25 percent, namely the mass doping ratio of MZFO and ZMO is 25 percent, stirring is carried out to obtain a mixed solution G, ammonia water is dropwise added into the mixed solution G to adjust the pH value of the mixed solution G to be 8, stirring is carried out again to carry out coprecipitation reaction for 20min, standing is carried out to obtain a black precipitate, the black precipitate is sequentially centrifuged and washed for 3 times, and then placed in an oven to be dried at the temperature of 80 ℃ to obtain Mn0.3Zn0.7Fe2O4@25％-Zn0.9Mn0.1O (MZFO @ 25% -ZMO) nanomagnetic photocatalyst.
As shown in figure 1, in the XRD pattern of MZFO @ 25% -ZMO material obtained by the preparation method of the invention, characteristic peaks appear at 2 theta of 29.9 degrees, 35.3 degrees, 42.8 degrees, 53.1 degrees, 56.6 degrees, 62.2 degrees, 73.5 degrees and the like, which is similar to the standard pattern PDF #22-1012 (ZnFe)2O4) Or PDF #22-1012 (MnFe)2O4) The crystal planes of (220), (311), (400), (422), (511), (440), and (533) are consistent, which indicates that the material contains manganese-zinc ferrite, and characteristic peaks also appear at 2 θ of 31.8 °, 34.4 °, 36.3 °, 47.5 °, 56.6 °, 67.9 °, 69.1 °, and 76.9 °, which are consistent with the crystal planes of (100), (002), (101), (102), (103), (112), (201), and (202) of the standard spectrum PDF #36-1451(ZnO), and indicates that the material also contains zinc-manganese oxide mainly containing ZnO; MZFO @ 25% -ZMO keeps the characteristic peaks of two samples and realizes the construction of a heterojunction composite photocatalyst;
as shown in FIG. 2, the band gap of the prepared MZFO @ 25% -ZMO material is 1.9eV and is lower than that of pure phase ZnO by 3.4eV which is measured and calculated by a UV-Vis spectrum, and the catalytic activity of the material is higher and the utilization efficiency of visible light is higher;
as shown in FIG. 3, the MZFO @ 25% -ZMO material achieved 88% degradation of the methylene blue dye under 90min visible light exposure. Meanwhile, as shown in FIG. 4, the prepared MZFO @ 25% -ZMO material still keeps certain magnetic properties, the saturation magnetic strength Ms is 27.3emu/g, and the magnetic separation operation of the material is easy to realize after the material is used.
Example 3
Step 1, splitting anode and cathode battery materials of waste alkaline batteries, respectively mechanically crushing the anode and cathode battery materials, and screening to obtain anode electrode powder and cathode electrode powder with particle sizes less than 200 mu m;
step 2, preparing a biological leaching culture solution, and culturing strains;
the solvent is distilled water, and the solute is: 4g/L (NH)4)2SO4、3.0g/LK2HPO4、3g/LMgSO4·7H2O、0.5g/LCaCl2、3.0g/LKCl、50g/LFeSO4·7H2Adding a mixed bacterium solution of thiobacillus thiooxidans (Acidithiobacillus thiooxidans, A.t.) and thiobacillus ferrooxidans (Acidithiobacillus ferrooxidans, A.f.) into O and 20g/LS to prepare a biological leaching solution, wherein the volume ratio of the thiobacillus thiooxidans to the thiobacillus ferrooxidans is1:1, the volume ratio of the mixed bacteria liquid to distilled water is 1:9, the temperature of the bioleaching solution is controlled to be 35 ℃ by a heating rod, then an air pump is used for continuously aerating and aerating, the bioleaching solution is cultivated for 5 days, evaporated water is supplemented in the cultivating process, the pH value and the strain density of the leaching solution are monitored, and when the pH value is reduced to 2.0 and the strain density reaches 2 multiplied by 1010When the strain is one/mL, finishing the culture;
and 3, adding the negative electrode powder obtained in the step 1 into the bioleaching culture solution treated in the step 2 according to a solid-to-liquid ratio (w/V) of 10% for bioleaching, sampling every 12 hours to monitor the concentrations of manganese ions, zinc ions and iron ions in the bioleaching solution, adding one or more of zinc ions, manganese ions or iron ions into the bioleaching solution according to the monitored concentrations to adjust the ion concentrations after 5 days of leaching is finished, so that the total ion concentration of the adjusted zinc ions, manganese ions and iron ions is 3mol/L, wherein x is 0.5, and thus obtaining the ferrite material (Mn/V)0.5Zn0.5Fe2O4) The preparation solution A of (1);
step 4, preparing Mn from the obtained Mn in step 30.5Zn0.5Fe2O4The temperature of the preparation liquid A is raised to 55 ℃ at the heating rate of 10 ℃/min, and NaOH solution with the mass concentration of 10% is added at the rate of 20mL/min to adjust the pH value to 13, so as to obtain mixed liquid B;
step 6, adding the anode electrode powder obtained in the step 1 into hydrochloric acid with the concentration of 6.5mol/L according to the solid-to-liquid ratio (w/V) of 25% for chemical leaching for 2 hours, monitoring the concentrations of zinc ions and manganese ions after the leaching is finished, and adding zinc ions or manganese ions into the leaching solution according to the monitored concentrationsIon concentration adjustment is performed on the ions, so that the concentration ratio of the adjusted zinc ions to manganese ions is 0.9: 0.1, the total concentration is 1.5mol/L to obtain the manganese-doped zinc oxide material (Zn)0.9Mn0.1O) a liquid precursor E;
step 7, weighing 20g of Mn obtained in step 5xZn1-xFe2O4Placing ferrite solid powder precursor D in a container, adding 100ml (100g) of distilled water, placing in an ultrasonic instrument for ultrasonic treatment for 20min to obtain dispersion liquid F, and dropwise adding Zn obtained in the step 6 into the dispersion liquid F0.9Mn0.1O liquid precursor E, and control of Mn0.5Zn0.5Fe2O4And Zn0.9Mn0.1The mass doping ratio of O is 50 percent, namely the mass doping ratio of MZFO and ZMO is 50 percent, stirring is carried out to obtain a mixed solution G, ammonia water is dropwise added into the mixed solution G to adjust the pH value of the mixed solution G to be 9, stirring is carried out again to carry out coprecipitation reaction for 25min, standing is carried out to obtain a black precipitate, the black precipitate is sequentially centrifuged and washed for 4 times, and then placed in an oven to be dried at the temperature of 80 ℃ to obtain Mn0.5Zn0.5Fe2O4@50％-Zn0.9Mn0.1O (MZFO @ 50% -ZMO) nanomagnetic photocatalyst.
As shown in FIG. 1, the XRD pattern of the MZFO @ 50% -ZMO material obtained by the preparation method of the invention substantially maintains PDF #22-1012 (ZnFe)2O4) Or PDF #22-1012 (MnFe)2O4) And PDF #36-1451(ZnO) and other substances, and the intensity of the peaks is different, which shows that the substance contains manganese-zinc ferrite and zinc-manganese oxide, namely the construction of the heterojunction composite photocatalyst is realized, and the color of the nano composite material is changed into light black along with the increase of the amount of the added zinc-manganese oxide;
as shown in FIG. 2, the band gap of the MZFO @ 50% -ZMO material prepared by UV-Vis spectral measurement and calculation is 2.1eV, and the catalytic activity of the material is high, and the utilization efficiency of visible light is high;
as shown in FIG. 3, under the irradiation of visible light for 90min, the degradation rate of the MZFO @ 25% -ZMO material to methylene blue dye is as high as 98%. Meanwhile, as shown in FIG. 4, the prepared MZFO @ 50% -ZMO material also has certain magnetic properties, the saturation magnetic strength Ms of the material is still kept at 13.7mu/g, and the magnetic separation operation of the material can be realized after the material is used.
Example 4
Step 1, splitting anode and cathode battery materials of waste alkaline batteries, respectively mechanically crushing the anode and cathode battery materials, and screening to obtain anode electrode powder and cathode electrode powder with particle sizes less than 200 mu m;
step 2, preparing a biological leaching culture solution, and culturing strains;
the solvent is distilled water, and the solute is: 2.5g/L (NH)4)2SO4、2.5g/LK2HPO4、1.5g/LMgSO4·7H2O、0.35g/LCaCl2、1.5g/LKCl、40g/LFeSO4·7H2Adding a mixed bacterial solution of thiobacillus thiooxidans (Acidithiobacillus thiooxidans, A.t.) and thiobacillus ferrooxidans (A.f.) into O and 20g/LS to prepare a bioleaching solution, wherein the volume ratio of the thiobacillus thiooxidans to the thiobacillus ferrooxidans is 1:1, the volume ratio of the mixed bacterial solution to distilled water is 1:9, controlling the temperature of the bioleaching solution to be 35 ℃ by using a heating rod, continuously aerating and aerating by using an air pump for culturing for 4 days, supplementing evaporated water in the culturing process, monitoring the pH value and strain density of the leaching solution, and when the pH value is reduced to 1.5 and the strain density reaches 2 multiplied by 109When the strain is one/mL, finishing the culture;
and 3, adding the negative electrode powder obtained in the step 1 into the bioleaching culture solution treated in the step 2 according to a solid-to-liquid ratio (w/V) of 8% for bioleaching, sampling every 12 hours to monitor the concentrations of manganese ions, zinc ions and iron ions in the bioleaching solution, adding one or more of zinc ions, manganese ions or iron ions into the bioleaching solution according to the monitored concentrations to adjust the ion concentrations after 5 days of leaching is finished, so that the total ion concentration of the adjusted zinc ions, manganese ions and iron ions is 2.5mol/L, wherein x is 0.7, and thus obtaining the prepared ferrite material (Mn/V)0.7Zn0.3Fe2O4) Is/are as followsPreparing a solution A;
step 4, preparing Mn from the obtained Mn in step 30.7Zn0.3Fe2O4The temperature of the preparation solution A is increased to 45 ℃ at the heating rate of 10 ℃/min, and NaOH solution with the mass concentration of 20% is added at the rate of 20mL/min to adjust the pH value to 12, so as to obtain mixed solution B;
and 6, adding the anode electrode powder obtained in the step 1 into hydrochloric acid with the concentration of 8mol/L according to a solid-to-liquid ratio (w/V) of 30% for chemical leaching for 2 hours, monitoring the concentrations of zinc ions and manganese ions after leaching is finished, and adding zinc ions or manganese ions into the leaching solution according to the monitored concentrations for ion concentration adjustment to enable the concentration ratio of the adjusted zinc ions to the adjusted manganese ions to be 0.9: 0.1, the total concentration is 2mol/L, and the manganese-doped zinc oxide material (Zn) is obtained0.9Mn0.1O) a liquid precursor E;
step 7, weighing 20g of Mn obtained in step 50.7Zn0.3Fe2O4Placing ferrite solid powder precursor D in a container, adding 100ml (100g) of distilled water, placing in an ultrasonic instrument for ultrasonic treatment for 30min to obtain dispersion liquid F, and dropwise adding Zn obtained in the step 6 into the dispersion liquid F0.9Mn0.1O liquid precursor E, and control of Mn0.7Zn0.3Fe2O4And Zn0.9Mn0.1The mass doping ratio of O is 75 percent, namely the mass doping ratio of MZFO and ZMO is 75 percent, stirring is carried out to obtain a mixed solution G, ammonia water is dropwise added into the mixed solution G to adjust the pH value of the mixed solution G to be 9, stirring is carried out again to carry out coprecipitation reaction for 30min, standing is carried out to obtain a black precipitate, the black precipitate is sequentially centrifuged and washed for 5 times, and then the black precipitate is obtainedDrying in an oven at 80 deg.C to obtain Mn0.7Zn0.3Fe2O4@75％-Zn0.9Mn0.1O (MZFO @ 75% -ZMO) nanomagnetic photocatalyst.
As shown in FIG. 1, the XRD pattern of the MZFO @ 75% -ZMO material obtained by the preparation method of the invention substantially maintains PDF #22-1012 (ZnFe)2O4) Or PDF #22-1012 (MnFe)2O4) And PDF #36-1451(ZnO) and other substances, and the intensity of the peaks is different, which shows that the substance contains manganese-zinc ferrite and zinc-manganese oxide, namely the construction of the heterojunction composite photocatalyst is realized, and the color of the nano composite material is changed into light black along with the increase of the amount of the added zinc-manganese oxide;
as shown in fig. 2, the band gap of the MZFO @ 50% -ZMO material prepared by UV-Vis spectroscopy measurement and calculation is 2.2eV, and it can be seen that the band gap of the material is gradually increased along with the increase of the doping amount of the zinc-manganese oxide, and the high catalytic activity and the utilization efficiency of visible light can be still maintained;
as shown in FIG. 3, under the irradiation of visible light for 90min, the degradation rate of the MZFO @ 75% -ZMO material to methylene blue dye is still as high as 90%. Meanwhile, as shown in FIG. 4, as the content of the ZMO is increased and the magnetism is gradually weakened, the prepared MZFO @ 75% -ZMO material also has certain magnetic properties, the saturation magnetic strength Ms is 5.5meu/g, and the magnetic separation operation of the material can be realized after the material is used.
Example 5
Step 1, splitting anode and cathode battery materials of waste alkaline batteries, respectively mechanically crushing the anode and cathode battery materials, and screening to obtain anode electrode powder and cathode electrode powder with particle sizes less than 200 mu m;
and 2, adding the anode electrode powder obtained in the step 1 into hydrochloric acid with the concentration of 8mol/L according to a solid-to-liquid ratio (w/V) of 30% for chemical leaching for 2 hours, monitoring the concentrations of zinc ions and manganese ions after leaching is finished, and adding zinc ions or manganese ions into the leaching solution according to the monitored concentrations for ion concentration adjustment to enable the concentration ratio of the adjusted zinc ions to the adjusted manganese ions to be 0.9: 0.1, the total concentration is 2mol/L to obtain the manganese-doped oxygenZincized materials (Zn)0.9Mn0.1O) a liquid precursor E;
step 3, Zn obtained in the step 20.9Mn0.1Dropwise adding ammonia water into the O liquid precursor E to adjust the pH value of the mixed solution G to 10, stirring for coprecipitation reaction for 30min, standing to obtain a black precipitate, centrifuging and washing the black precipitate for 4 times in sequence, and then placing the black precipitate into an oven to be dried at the temperature of 80 ℃ to obtain Zn0.9Mn0.1O (ZMO) nano-magnetic photocatalyst.
As shown in fig. 1, in the XRD pattern of the ZMO material obtained by the preparation method of the present invention, characteristic peaks are also present at 2 θ ═ 31.8 °, 34.4 °, 36.3 °, 47.5 °, 56.6 °, 67.9 °, 69.1 °, 76.9 °, which are consistent with the crystal planes (100), (002), (101), (102), (103), (112), (201), and (202) of the standard spectrum PDF #36-1451(ZnO), and thus, it is described that ZnO-based zinc-manganese oxide is further contained; in addition, the EDX element molar composition test proves that the prepared material is pure-phase sample Zn0.9Mn0.1O；
As shown in FIG. 2, the band gap of the prepared ZMO material is 3.2eV which is measured and calculated by a UV-Vis spectrum and is lower than 3.4eV of pure-phase ZnO, and the visible manganese doping can improve the catalytic activity of the pure-phase material and increase the utilization efficiency of visible light;
as shown in FIG. 3, the ZMO material also achieves 70% degradation rate of methylene blue dye under the irradiation of visible light for 90 min.
In addition, the MZFO @ 50% -ZMO nano composite photocatalyst material prepared by the method is subjected to a catalyst stability test:
preparing 20mg/L methylene blue as simulated wastewater, adding 0.1g/L MZFO @ 50% -ZMO catalyst, placing the wastewater in a dark room for stirring to adsorb the catalyst for 1h, measuring the equilibrium concentration (initial concentration) after adsorption-desorption equilibrium, then performing catalytic degradation under sunlight for 90min (11: 00-13: 00 per day), continuously keeping aeration stirring during the period, sampling every 10min to measure the concentration change, after the photocatalytic degradation experiment is finished, magnetically separating and recovering the catalyst, performing repeated photocatalytic experiments for many times, and simultaneously calculating the catalytic degradation rate of the material to the methylene blue, namely D (%) (C (%)0-Ct)/C0X is 100%; wherein, C0Is the initial concentration of the solution, mg/L; ctThe concentration of the solution at time t is mg/L. After nine times of repeated photocatalytic experiments, the MZFO @ 50% -ZMO still has high catalytic activity, the photocatalytic degradation efficiency is kept above 90%, and good magnetic separation characteristics are kept, so that the application prospect is wide.
Claims (9)
1. A method for preparing a composite nano magnetic photocatalyst by using waste alkaline batteries is characterized by comprising the following steps:
step 1, splitting anode and cathode battery materials of waste alkaline batteries, respectively mechanically crushing the anode and cathode battery materials, and screening to obtain anode electrode powder and cathode electrode powder;
step 2, preparing a biological leaching solution, and culturing strains;
the solvent is distilled water, and the solute is: 2.0 g/L-4.0 g/L (NH)4)2SO4、2.0g/L～3.0g/LK2HPO4、1.0g/L～3.0g/LMgSO4·7H2O、0.3g/L～0.5g/LCaCl2、1.0g/L～3.0g/LKCl、30g/L～50g/LFeSO4·7H2Adding a mixed bacterial solution of thiobacillus thiooxidans and thiobacillus ferrooxidans into 10 g/L-20 g/LS to prepare a bioleaching solution, controlling the temperature of the bioleaching solution to be 25-35 ℃ by using a heating rod, continuously aerating and aerating by using an air pump, culturing for 3-5 days, supplementing evaporated water in the culturing process, monitoring the pH value and the strain density of the leaching solution, and when the pH value is reduced to 1.0-2.0 and the strain density reaches 2 multiplied by 1082X 10 per mL10When the strain is one/mL, finishing the culture;
step 3, adding the negative electrode powder obtained in the step 1 into the bioleaching culture solution treated in the step 2 for bioleaching, sampling every 12 hours to monitor the concentration of manganese ions, zinc ions and iron ions in the bioleaching solution, and adding one or more of zinc ions, manganese ions or iron ions into the bioleaching solution according to the monitored concentration after leaching is finishedSeveral ion concentration regulation are carried out to obtain the prepared MnxZn1-xFe2O4The preparation liquid A of (1);
step 4, preparing Mn from the obtained Mn in step 3xZn1-xFe2O4Heating the preparation solution A to 45-55 ℃ at the heating rate of 10 ℃/min, and adding NaOH solution to adjust the pH value to obtain a mixed solution B;
and 5, heating the mixed liquid B obtained in the step 4, continuously stirring, stopping stirring when the mixed liquid B is black thick paste, transferring the mixed liquid B into a hydrothermal high-pressure kettle for hot water synthesis reaction to obtain semi-finished liquid C, and sequentially centrifuging, washing, drying and grinding the semi-finished liquid C to obtain MnxZn1-xFe2O4Ferrite solid powder precursor D;
step 6, adding the anode electrode powder obtained in the step 1 into hydrochloric acid for chemical leaching for 2 hours, monitoring the concentration of zinc ions and manganese ions after leaching is finished, and adding zinc ions or manganese ions into the leaching solution for ion concentration adjustment according to the monitored concentration to obtain Zn0.9Mn0.1O liquid precursor E;
step 7, weighing a certain amount of Mn obtained in step 5xZn1-xFe2O4Placing the ferrite solid powder precursor D into a container, adding a plurality of distilled water, placing the container into an ultrasonic instrument for ultrasonic treatment to obtain dispersion liquid F, and dropwise adding Zn obtained in the step 6 into the dispersion liquid F0.9Mn0.1O liquid precursor E is stirred to obtain a mixed solution G, ammonia water is added into the mixed solution G drop by drop to adjust the pH value of the mixed solution G, the mixed solution G is stirred to carry out coprecipitation reaction, the mixed solution G is kept stand to obtain black precipitate, the black precipitate is subjected to centrifugation and washing treatment in sequence and then is placed in an oven to be dried to obtain MnxZn1-xFe2O4@Zn0.9Mn0.1O nanometer magnetic photocatalyst.
2. The method for preparing a composite nano magnetic photocatalyst by using waste alkaline batteries as claimed in claim 1, wherein the particle size of the anode electrode powder and the cathode electrode powder in step 1 is less than 200 μm.
3. The method for preparing the composite nano magnetic photocatalyst by using the waste alkaline batteries as claimed in claim 1, wherein the volume ratio of thiobacillus thiooxidans to thiobacillus ferrooxidans is 1:1, and the volume ratio of the mixed bacterial liquid to distilled water is 1: 9.
4. The method for preparing composite nano magnetic photocatalyst by using waste alkaline batteries as claimed in claim 1, wherein the solid-to-liquid ratio of the negative electrode powder to the bioleaching culture solution in the step 3 is 5-10%, the leaching days are 3-5 days, the total ion concentration of the adjusted zinc ions, manganese ions and iron ions is 2-3 mol/L, and Mn is 2-3 mol/LxZn1-xFe2O4Wherein x is 0.3 to 0.7.
5. The method for preparing the composite nano magnetic photocatalyst by using the waste alkaline batteries as claimed in claim 1, wherein the adding rate of the NaOH solution in the step 4 is 10mL/min to 20mL/min, the mass concentration is 10% to 20%, and the pH value is 11 to 13.
6. The method for preparing the composite nano magnetic photocatalyst by utilizing the waste alkaline batteries as claimed in claim 1, wherein the heating treatment temperature in the step 5 is 70-100 ℃, the heating rate is 10-20 ℃/min, and the stirring speed is 120-150 r/min; the temperature of the hot water synthesis reaction is 180-200 ℃, the reaction time is 8-10 h, the washing times are 5 times, and the drying temperature is 80 ℃.
7. The method for preparing the composite nano magnetic photocatalyst by using the waste alkaline batteries as claimed in claim 1, wherein the solid-to-liquid ratio of the anode electrode powder to the hydrochloric acid in the step 6 is 20-30%, and the concentration of the hydrochloric acid is 5-8 mol/L; the concentration ratio of the adjusted zinc ions to manganese ions is 0.9: 0.1, and the total concentration is 1 mol/L-2 mol/L.
8. The method for preparing composite nano magnetic photocatalyst by using waste alkaline batteries as claimed in claim 1, wherein Mn in the step 7xZn1-xFe2O4The mass ratio of the ferrite solid powder precursor D to distilled water is 1:5, the ultrasonic time is 10-30 min, the pH value is 8-10, the coprecipitation reaction time is 20-30 min, the washing times are 3-5 times, and the drying temperature is 80 ℃.
9. The method for preparing composite nano magnetic photocatalyst by using waste alkaline batteries as claimed in claim 1, wherein Mn in the step 7xZn1-xFe2O4And Zn0.9Mn0.1The mass doping ratio of O is 25-75%.
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