CN113896299B - electro-Fenton reaction cathode material of ferromanganese layered double metal hydroxide loaded biochar, and preparation method and application thereof - Google Patents
electro-Fenton reaction cathode material of ferromanganese layered double metal hydroxide loaded biochar, and preparation method and application thereof Download PDFInfo
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- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 46
- 239000010406 cathode material Substances 0.000 title claims abstract description 44
- 229910000616 Ferromanganese Inorganic materials 0.000 title claims abstract description 42
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 19
- 150000004692 metal hydroxides Chemical class 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000006260 foam Substances 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000011565 manganese chloride Substances 0.000 claims abstract description 6
- 229940099607 manganese chloride Drugs 0.000 claims abstract description 6
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000004098 Tetracycline Substances 0.000 claims description 32
- 229960002180 tetracycline Drugs 0.000 claims description 32
- 229930101283 tetracycline Natural products 0.000 claims description 32
- 235000019364 tetracycline Nutrition 0.000 claims description 32
- 150000003522 tetracyclines Chemical class 0.000 claims description 32
- 239000010865 sewage Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 229960002089 ferrous chloride Drugs 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 235000011837 pasties Nutrition 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 239000003344 environmental pollutant Substances 0.000 abstract description 7
- 231100000719 pollutant Toxicity 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 21
- 238000006731 degradation reaction Methods 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
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- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention discloses an electro-Fenton reaction cathode material of ferromanganese layered double metal hydroxide loaded biochar, and a preparation method and application thereof, and belongs to the technical field of water treatment advanced electro-Fenton oxidation. The invention takes pyrolyzed biochar as a carrier, and ferromanganese layered double hydroxide (MnFe-LDH) is loaded on the surface of the biochar. The preparation method comprises the steps of mixing and stirring ferric chloride, manganese chloride, urea, ammonium fluoride, biochar and water, performing hydrothermal reaction, washing and drying, mixing with ethanol and polytetrafluoroethylene, and coating on foam nickel to form the MnFe-LDH@BC electro-Fenton cathode material. The method has the advantages of simple process, convenient operation, low cost, high treatment efficiency, good removal effect, wide application range, high recycling rate, environment friendliness, cleanness and no pollution, can be widely used, can efficiently remove pollutants in water, and has high application value and commercial value.
Description
Technical Field
The invention belongs to the technical field of advanced oxidation of sewage treatment, and relates to a simple method for preparing an electro-Fenton reaction cathode material of ferromanganese layered double hydroxide-supported biochar. More particularly relates to a preparation method of an electro-Fenton reaction cathode material of ferromanganese layered double hydroxide supported biochar and application thereof in sewage treatment.
Background
In recent years, the removal of personal care products (PPCPs) from wastewater has attracted attention due to the potentially toxic effects of drugs and PPCPs on humans and aquatic organisms. Antibiotics are widely used in medicine and agriculture as a main category of PPCPs, but some of the unabsorbed antibiotics enter the ecosystem through medical wastewater and domestic sewage. Advanced oxidation techniques (AOPs) have a significant effect on the removal of such refractory organics, with the electro-Fenton method having received extensive attention from researchers. And (3) reducing oxygen at the cathode by an external electric field to generate hydrogen peroxide, and reacting the obtained hydrogen peroxide with Fe (II) in the solution to generate active oxygen substances to degrade pollutants. Thus, the cathode material is a major factor limiting the development of the electro-Fenton system.
Carbon materials such as graphite carbon, carbon sponge, graphite felt and reticulated vitreous carbon are currently considered to be very promising cathode materials due to their abundant reserves, excellent conductivity, good chemical stability. Biomass charcoal is a porous solid particulate matter with high aromaticity and rich carbon, which is produced by thermochemical conversion of carbon-rich waste under anaerobic or anoxic conditions. The catalyst has rich pore structure, large specific surface area and more oxygen-containing active groups on the surface, however, the active sites of the raw biochar are relatively limited, so that the performance of catalyzing degradation of refractory pollutants is poor. Therefore, it is necessary to use the proper heteroatom doping biochar to improve its catalytic performance.
Layered Double Hydroxides (LDHs) are a class of metal hydroxides consisting of two or more metal elements. The high-efficiency electrode material has been receiving a great deal of attention as an electrochemically efficient electrode material because of its extremely strong anion exchange capacity, high redox activity and specific layered structure. Wherein the metal of the LDH (e.g., fe, co, ni, mn) generally consists of +2 and +3 transition metal cations, with these transition metals being in combination with H 2 O 2 In situ reaction to form reactive oxygen species to degrade organic contaminants. In contrast, contains environment-friendly metals such as Fe 3+ And Mn of 2+ Has not been reported for electro-Fenton reaction, and Fe plays a relatively important role in electro-Fenton, not only can be used for H 2 O 2 The in-situ reaction generates active oxygen substances, and Fe circulation is formed, so that the reaction can be continued conveniently. And Mn ions have a high valence state, so that Fe interconversion can be promoted.
LDHs, however, have some aggregation, which significantly limits their catalyst activity. Thus, combining biochar and LDH increases the catalytic activity of the biochar on the one hand and the dispersibility of the LDH on the other hand. The MnFe-LDH loaded on the biochar not only enhances the physical and chemical synergistic effect of the MnFe-LDH and the biochar and promotes the transfer of electrons, but also reduces the accumulation of LDH and exposes more active sites.
Therefore, developing an electro-Fenton reaction cathode material with a simple process, easy industrialization and good characteristics for ferromanganese layered double metal hydroxide loaded biochar is a technical problem to be solved urgently by those skilled in the art.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a preparation method of an electro-Fenton reaction cathode material of manganese-iron layered double metal hydroxide loaded biochar, which is simple in process and easy for industrial production, and the material prepared by the method can treat durable organic matters in water, has high treatment efficiency, good removal effect, wide application range, high recycling rate, environment friendliness, cleanness and no pollution, is a material which can be widely used, and has high application value and commercial value.
In order to achieve the above object, the technical scheme of the present invention is as follows:
a preparation method of an electro-Fenton reaction cathode material of ferromanganese layered double metal hydroxide loaded biochar specifically comprises the following steps:
(1) Adding manganese chloride and ferrous chloride into water, stirring to dissolve completely, adding urea, ammonium fluoride and pyrolyzed biochar, and stirring to obtain uniform solution for later use;
(2) Placing the uniform solution into a reaction kettle for hydrothermal reaction, then washing the product with deionized water and absolute ethyl alcohol alternately for several times, and drying to obtain MnFe-LDH@BC powder;
(3) Mixing the MnFe-LDH@BC powder with polytetrafluoroethylene dispersion and absolute ethyl alcohol, uniformly dispersing by ultrasonic to form suspension, and heating to obtain uniform pasty substances;
(4) And paving the uniform paste substance on the pretreated foam nickel, and finally drying to obtain the electro-Fenton reaction cathode material of the ferromanganese layered double metal hydroxide loaded biochar.
Preferably, in the reaction system of the step (1), the molar ratio of manganese chloride to ferrous chloride is 3:1, the molar ratio of ferromanganese to urea to ammonium fluoride is 1:5:5, the doping amount of the biochar is 3-30% of the total mass of ferromanganese, urea and ammonium fluoride.
Preferably, the hydrothermal reaction temperature in the step (2) is 100-140 ℃ and the reaction time is 6-12 h.
Preferably, in the step (3), the solid-to-liquid ratio of the MnFe-ldh@bc powder, the polytetrafluoroethylene dispersion and the ethanol is (0.1 to 0.6) g: (0.1-0.6) mL: (1-6) mL, and the mass concentration of the polytetrafluoroethylene dispersion is 55-65%.
Preferably, in the step (4), the foamed nickel substrate coated with the uniform paste material is dried at 105 ℃ for 0.5-1.5 h.
In conclusion, the invention provides a preparation method of a ferromanganese layered double hydroxide supported biochar electro-Fenton reaction cathode material, which is environment-friendly and suitable for industrial production.
The invention also claims an electro-Fenton reaction cathode material of the ferromanganese layered double metal hydroxide supported biochar prepared by the method.
And the invention also aims to provide an application of the electro-Fenton reaction cathode material of the ferromanganese layered double metal hydroxide loaded biochar in sewage treatment, which is environment-friendly and suitable for industrial production.
Specifically, the specific steps of the electro-Fenton cathode material of the layered double hydroxide loaded biochar for treating sewage are as follows: the layered double hydroxide loaded biochar is used as an electro-Fenton reaction cathode material, an electrode pair is formed between the layered double hydroxide loaded biochar and an anode in an electrolytic cell, sewage containing tetracycline is degraded under a direct current power supply, air is aerated into the sewage, and electro-Fenton reaction is carried out, so that the sewage treatment is completed.
Further, the initial concentration of the tetracycline in the water body is less than or equal to 20mg/L; the pH value of the tetracycline water body is 3-9; the direct current power supply keeps the current density to be 5-25mA.
Compared with the prior art, the invention provides the electro-Fenton reaction cathode material of the ferromanganese layered double metal hydroxide loaded biochar, and the preparation method and the application thereof, and the electro-Fenton reaction cathode material has the following excellent effects:
firstly, the special layered structure of the layered double hydroxide and the good catalytic property of transition metal in the layered double hydroxide are utilized to load the layered double hydroxide on the biochar, and meanwhile, the biochar has good adsorption property and conductivity, and the surface of the biochar contains rich functional groups, and meanwhile, the dispersibility of the layered double hydroxide can be enhanced, so that the layered double hydroxide is used as a cathode plate of an electro-Fenton reaction, and the electron transfer in the reaction process is promoted. In the reaction process, iron ions in the material and hydrogen peroxide form active oxygen substances to degrade pollutants. On the other hand, the existence of manganese ions enables the redox cycle conversion of iron ions to be orderly carried out, and the reaction is promoted to continuously occur, so that the good pollutant removal effect is finally achieved.
Furthermore, the pH range in the solution is limited widely, and the tetracycline removal rate can achieve better removal effect when the pH is 3-7; and the invention does not need to additionally add ferrous ions, thereby saving the cost and avoiding the influence of iron mud precipitation on the electro-Fenton reaction and environmental pollution in the reaction process, and further realizing high-efficiency green catalysis.
Secondly, the preparation method of the layered double hydroxide loaded biochar is simple, low in cost and environment-friendly, the prepared electro-Fenton cathode material has good degradation capability on tetracycline, and the removal rate reaches 94.2% when the tetracycline concentration is 20 mg/L. Compared with biodegradation, membrane separation, redox and photocatalysis, the method for degrading tetracycline by using the layered double hydroxide loaded biochar as the electro-Fenton cathode material has the advantages of simple operation and high degradation efficiency.
Finally, the layered double hydroxide loaded biochar in the biochar electro-Fenton cathode material solves the problem of recycling of waste agricultural biochar, and avoids the environmental problem caused by large accumulation of agricultural waste straws.
Therefore, by combining the above, the preparation process disclosed by the invention is simple, convenient to operate, low in cost, high in treatment efficiency, good in removal effect, wide in application range, high in recycling rate, green, environment-friendly, clean and pollution-free, is a method which can be widely adopted, can efficiently remove pollutants in water, and has high application value and commercial value.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of an electro-Fenton reaction cathode material of ferromanganese layered double hydroxide supported biochar.
FIG. 2 is an X-ray diffraction pattern of an electro-Fenton reaction cathode material of ferromanganese layered double hydroxide supported biochar.
FIG. 3 is a graph showing the effect of the manganese-iron layered double hydroxide-supported biochar on the degradation of tetracycline by the electro-Fenton cathode material prepared in example 1 and the non-supported manganese-iron layered double hydroxide.
FIG. 4 is a graph showing the comparison of the degradation rates of the electro-Fenton cathode material of the ferromanganese layered double hydroxide-supported biochar prepared in example 1 to tetracycline at different pH values.
FIG. 5 is a graph showing the comparison of the degradation rates of the electro-Fenton cathode material of the ferromanganese layered double hydroxide-supported biochar prepared in example 1 to tetracycline at different current densities.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention discloses a preparation method of an electro-Fenton reaction cathode material of ferromanganese layered double hydroxide loaded biochar, which is environment-friendly, simple and convenient in process and suitable for industrial production.
The present invention will be further specifically illustrated by the following examples, which are not to be construed as limiting the invention, but rather as falling within the scope of the present invention, for some non-essential modifications and adaptations of the invention that are apparent to those skilled in the art based on the foregoing disclosure.
The technical scheme of the invention will be further described below with reference to specific embodiments.
Example 1:
(1) Adding 2.7mmol of manganese chloride and 0.9mmol of ferrous chloride into 60ml of water, stirring to dissolve completely, adding 18mmol of urea, 18mmol of ammonium fluoride and 0.5g of biochar pyrolyzed at 600 ℃, and stirring and mixing uniformly;
(2) Placing the solution obtained in the step (1) in a 100mL reaction kettle, and performing hydrothermal reaction for 6 hours at 120 ℃;
(3) Cooling the reacted product to room temperature, alternately washing with deionized water and absolute ethyl alcohol for several times, and keeping the obtained precipitate at 80 ℃ for 12 hours for drying and dehydrating to obtain MnFe-LDH@BC powder;
(4) MnFe-LDH@BC powder and polytetrafluoroethylene dispersion with the mass concentration of 60% and absolute ethyl alcohol are mixed according to 0.5g:0.5mL: mixing 5mL of the materials in proportion, performing ultrasonic dispersion for 30min to obtain uniform electrode slurry, heating the electrode slurry at the temperature of 80 ℃ to obtain pasty substances, performing ultrasonic soaking and cleaning on foam nickel for 2 times by using acetone, and then performing cleaning and drying by using deionized water to finish pretreatment;
(5) Pressing the electrode paste on a pretreated foam nickel substrate into slices with the thickness of 1mm, and finally drying the electrode at the temperature of 105 ℃ to obtain the MnFe-LDH@BC electro-Fenton reaction cathode plate.
(6) The resulting electro-Fenton cathode and Pt electrode were combined into an electrode pair and placed in 50mM Na 2 SO 4 The electrolyte was added with tetracycline at an initial concentration of 20mg/L, with 0.1mol/L NaOH and 0.1mol/L H 2 SO 4 Adjusting the pH of the solution to be 3.0, and adding an external current to be 15mA; and (5) recycling and uniformly treating the waste liquid after the electrolysis is completed.
Example 2:
the same as in example 1, except that 0.25g of biochar was mixed with the layered double hydroxide precursor.
Example 3:
the same as in example 1, except that 1g of biochar was mixed with the layered double hydroxide precursor.
The electro-Fenton cathode materials prepared in examples 1-3 and the control group (biochar only) were tested for tetracycline degradation rate in wastewater, and the results are shown in Table 1.
TABLE 1
| Numbering device | Rate of tetracycline degradation |
| Example 1 | 94.16％ |
| Example 2 | 89.94％ |
| Example 3 | 82.75％ |
| Control group | 66.96％ |
It can be seen that the doping amount of the biochar in the cathode material has a certain influence on the tetracycline degradation rate, and firstly, a control group can be seen that the pure biochar has a certain adsorption capacity on the tetracycline, which is probably due to the larger specific surface area and the pore structure. Ferromanganese layered double hydroxide by example 1The removal rate of the tetracycline can be greatly improved by taking the loaded biochar as an electrode. However, too little biochar is doped as in example 2, so that ORR active sites on the surface of the material are few, and electrons are prevented from being fully transferred, so that the tetracycline degradation rate is low; excessive biochar doping as in example 3 results in a reduced proportion of ferromanganese layered double hydroxides, reduced catalytic activity provided, and also affects O due to excessive resistance of the cathode material 2 Mass transfer at the electrode surface, thereby affecting the rate of tetracycline degradation.
Example 4:
the same as in example 1 was conducted except that the solution was adjusted to pH 3, 5 and 7, respectively, for electrolysis. The results of the degradation rate of the electro-Fenton cathode material prepared in the example on tetracycline are shown in fig. 4.
Example 5:
the procedure was as in example 1, except that electrolysis was carried out with the applied current set to 5, 15 and 25mA, respectively. The results of the degradation rate of the electro-Fenton cathode material prepared in the example on tetracycline are shown in fig. 5.
FIG. 1 is a scanning electron microscope image of the ferromanganese layered double hydroxide-loaded biochar electro-Fenton composite material prepared in example 1 of the present invention. As can be seen from fig. 1, the ferromanganese layered double hydroxide-supported biochar presents sphere-like particles, and the surface also presents a layered sheet structure.
FIG. 2 is an X-ray diffraction pattern of the ferromanganese layered double hydroxide-supported biochar electro-Fenton composite material prepared in example 1 of the present invention. As can be seen from fig. 2, the ferromanganese layered double hydroxide supported biochar electro-Fenton composite material almost retains all the main characteristic peaks (2θ=51.5°,45.1 °,41.4 °,37.5 °,31.4 ° and 24.2 °) of the ferromanganese layered double hydroxide, thus proving that the ferromanganese layered double hydroxide is successfully supported on the biochar surface.
FIG. 3 is a graph showing the effect of the manganese-iron layered double hydroxide-supported biochar on the degradation of tetracycline by the electro-Fenton cathode material prepared in example 1 and the non-supported manganese-iron layered double hydroxide. As can be seen from the graph in FIG. 3, the degradation rate of the ferromanganese-loaded layered double metal hydroxide biochar cathode to tetracycline reaches 94.16%, which is far higher than that of the pure biochar cathode, and the effect of the loaded electrode in experiments for simulating the degradation of tetracycline in sewage is obvious, and the effectiveness of the ferromanganese-loaded layered double metal hydroxide biochar as an electro-Fenton cathode to degrade the tetracycline in sewage is demonstrated.
FIG. 4 is a graph showing the comparison of the degradation rates of the electro-Fenton cathode material of the ferromanganese layered double hydroxide-supported biochar prepared in example 1 to tetracycline at different pH values. It can be seen that the degradation rate for tetracycline is maintained at a relatively high level over a wide range of pH 3-7, with a maximum of 94.16% being reached at ph=3. Therefore, compared with the traditional electro-Fenton, the material has wider pH range, can better accept and treat pollutants in water, is not easy to produce iron mud, and is green and pollution-free.
FIG. 5 is a graph showing the comparison of the degradation rates of the electro-Fenton cathode material of the ferromanganese layered double hydroxide-supported biochar prepared in example 1 to tetracycline at different current densities. It can be found that when the current is too small, the electric energy required by the electro-Fenton system cannot be provided, the oxygen reduction process is affected, when the current is increased, the electron transfer speed on the surface of the electrode is increased, and the degradation of the tetracycline is facilitated, but with the continuous increase of the current, side reactions such as cathodic hydrogen evolution or anodic oxygen evolution and the like can be accompanied, so that the current efficiency and the degradation rate of the tetracycline in the electro-Fenton are reduced.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. The preparation method of the electro-Fenton reaction cathode material of ferromanganese layered double metal hydroxide loaded biochar is characterized by comprising the following steps of:
(1) Adding manganese chloride and ferrous chloride into water, stirring to dissolve completely, adding urea, ammonium fluoride and pyrolyzed biochar, and stirring to obtain uniform solution for later use;
(2) Placing the uniform solution into a reaction kettle for hydrothermal reaction, then washing the product with deionized water and absolute ethyl alcohol alternately for several times, and drying to obtain MnFe-LDH@BC powder;
(3) Mixing the MnFe-LDH@BC powder with polytetrafluoroethylene dispersion and absolute ethyl alcohol, uniformly dispersing by ultrasonic to form suspension, and heating to obtain uniform pasty substances;
(4) Pressing the uniform paste substance onto pretreated foam nickel, and finally drying to obtain the electro-Fenton reaction cathode material of ferromanganese layered double metal hydroxide loaded biochar;
in the reaction system of the step (1), the molar ratio of manganese chloride to ferrous chloride is 3:1, the molar ratio of ferromanganese to urea to ammonium fluoride is 1:5:5, the doping amount of the biochar is 3-30% of the total mass of ferromanganese, urea and ammonium fluoride;
the electro-Fenton reaction cathode material of ferromanganese layered double metal hydroxide loaded biochar can be applied to sewage treatment, and comprises the following specific steps: taking ferromanganese layered double metal hydroxide loaded biochar as an electro-Fenton reaction cathode material, forming an electrode pair with an anode in an electrolytic cell, degrading a water body containing tetracycline under a direct current power supply, and exposing air into sewage to perform electro-Fenton reaction to finish the treatment of the sewage;
the initial concentration of the tetracycline in the water body is less than or equal to 20mg/L; the pH value of the tetracycline water body is 3-9; the direct current power supply keeps the current density to be 5-25mA.
2. The method for preparing the electro-Fenton reaction cathode material of ferromanganese layered double metal hydroxide loaded biochar according to claim 1, wherein the hydrothermal reaction temperature in the step (2) is 100-140 ℃ and the reaction time is 6-12 h.
3. The method for preparing the electro-Fenton reaction cathode material of ferromanganese layered double hydroxide supported biochar according to claim 1, wherein in the step (3), the solid-to-liquid ratio of MnFe-LDH@BC powder, polytetrafluoroethylene dispersion and absolute ethyl alcohol is (0.1-0.6) g: (0.1-0.6) mL: (1-6) mL, and the mass concentration of the polytetrafluoroethylene dispersion is 55-65%.
4. The method for preparing the electro-Fenton reaction cathode material of ferromanganese layered double metal hydroxide supported biochar according to claim 1, wherein in the step (4), a foam nickel substrate with uniform paste material is dried and kept at 105 ℃ for 0.5-1.5 h.
5. An electro-Fenton reaction cathode material of ferromanganese layered double hydroxide-supported biochar prepared by the method according to any one of claims 1 to 4.
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| CN108837803A (en) * | 2018-06-28 | 2018-11-20 | 东北农业大学 | A kind of layered double-hydroxide loads the preparation method of biological carbon composite |
| CN109234755A (en) * | 2018-10-30 | 2019-01-18 | 江苏大学 | A kind of layered double hydroxide composite construction elctro-catalyst and preparation method |
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| CN110117046A (en) * | 2019-05-15 | 2019-08-13 | 哈尔滨工业大学 | A kind of preparation method and application of the electric Fenton cathode of green |
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| CN108837803A (en) * | 2018-06-28 | 2018-11-20 | 东北农业大学 | A kind of layered double-hydroxide loads the preparation method of biological carbon composite |
| CN109234755A (en) * | 2018-10-30 | 2019-01-18 | 江苏大学 | A kind of layered double hydroxide composite construction elctro-catalyst and preparation method |
| CN109364939A (en) * | 2018-11-15 | 2019-02-22 | 湖南大学 | Utilize the method for charcoal load ferrimanganic bimetallic oxide light Fenton composite material removal antibiotic |
| CN110117046A (en) * | 2019-05-15 | 2019-08-13 | 哈尔滨工业大学 | A kind of preparation method and application of the electric Fenton cathode of green |
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