CN113526623A - Preparation method of manganese oxide nano electrode and application of manganese oxide nano electrode in tetracycline hydrochloride wastewater treatment - Google Patents
Preparation method of manganese oxide nano electrode and application of manganese oxide nano electrode in tetracycline hydrochloride wastewater treatment Download PDFInfo
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 92
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 title claims abstract description 53
- 229960004989 tetracycline hydrochloride Drugs 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004065 wastewater treatment Methods 0.000 title claims description 8
- 229910016978 MnOx Inorganic materials 0.000 claims abstract description 51
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- 238000000034 method Methods 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims description 26
- 229940071125 manganese acetate Drugs 0.000 claims description 17
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012286 potassium permanganate Substances 0.000 claims description 11
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
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- 238000009835 boiling Methods 0.000 claims description 2
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- 238000007254 oxidation reaction Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910017850 Sb—Ni Inorganic materials 0.000 description 2
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- 229920000557 Nafion® Polymers 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 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
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
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Images
Classifications
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- 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
- C02F1/46—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
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The invention discloses a preparation method of a manganese oxide nano-electrode, which comprises the steps of pretreating a titanium mesh, compounding manganese oxide and nano-graphite to prepare a composite material, and tabletting and drying the composite material to obtain the manganese oxide nano-graphite electrode. The manganese oxide cathode prepared by the method combining titanium mesh pretreatment and the MnOx/nano-G composite material has stable structural property, less raw material consumption, convenient and easily obtained reagents, high degradation rate of the composite electrode for treating tetracycline hydrochloride-containing wastewater, no secondary pollution and reusability, and can be used for degrading various antibiotics.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a preparation method of a manganese oxide nano electrode and application of the manganese oxide nano electrode in tetracycline hydrochloride wastewater treatment.
Background
The global antibiotic abuse causes the rapid increase of the concentration of various antibiotics in the water body, which directly endangers the health of human beings and the safety of ecological environment, and the traditional wastewater treatment technology is difficult to effectively remove the antibiotics in the water body, so that the rapid and economic technology for degrading the antibiotic system wastewater is an urgent problem to be solved in the field. The electrochemical advanced oxidation technology is widely applied due to the outstanding advantages of high efficiency, low cost, strong adaptability, cleanness, safety and the like, is an ideal technology for removing antibiotics in water, and the electrode is used as the core of an electrochemical system, and the development of a high-efficiency electrode is a research key.
Graphene doped Ti/SnO2The research of the Sb electrode focuses on the preparation of a high-performance electrode, the structure of the Sb electrode determines the representation of specific surface area and conductivity, compared with a bare glassy carbon electrode, the graphene modified electrode has higher electrocatalytic activity and better tetracycline hydrochloride degradation effect, and the introduction of the graphene simultaneously ensures the excellent electronic conductivity of a three-dimensional carbon conductive network, so that the electrode has higher reversible specific capacity, excellent cycle performance and good rate performance; Ti/SnO2the-Sb-Ni electrode has a better surface structure, and can indicate that graphene is doped with Ti/SnO2good-Sb electrode stability, Ti/SnO2the-Sb-Ni electrode forms SnO having a high index2Crystal face has good catalytic activity.
Therefore, how to provide a manganese oxide nano electrode and apply the manganese oxide nano electrode to tetracycline hydrochloride wastewater treatment is a problem to be solved urgently by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a manganese oxide nano electrode based on the principle of an electrochemical advanced oxidation technology, and the manganese oxide nano electrode is used for treating tetracycline hydrochloride wastewater, and simultaneously promotes the oxidation reduction of a cathode to generate hydrogen peroxide and a strong-oxidizing free radical reaction by utilizing the catalytic action of manganese, so that the oxidation efficiency of the electrode is improved, and the energy consumption is reduced.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a manganese oxide nano electrode comprises the following steps:
(1) preparing the MnOx/nano-G composite material: dissolving manganese acetate in deionized water, sequentially adding polyethylene glycol and nano-G nano-graphene under stirring for full mixing, then adding a potassium permanganate solution to obtain a mixed solution, heating the mixed solution at 80 ℃ for 30min, and then filtering, washing, drying and calcining to obtain the MnOx/nano-G composite material for preparing the electrode;
(2) preparing a MnOx/nano-G electrode: and uniformly mixing the MnOx/nano-G composite material with polytetrafluoroethylene and absolute ethyl alcohol, heating to obtain a pasty compound, compressing the compound onto a titanium mesh by using a tablet press, heating to boil for 60min, taking out and drying to obtain the MnOx/nano-G electrode.
Preferably, in the above method for preparing a manganese oxide nanoelectrode, the mass ratio of manganese acetate to deionized water in step (1) is (0.04-1) g: 1 mL; the mass ratio of manganese acetate to polyethylene glycol is 1: (83-100); the mass ratio of the manganese acetate to the nano graphene is 1: (1-5); the mass ratio of the manganese acetate to the potassium permanganate is 1: (1-5).
The beneficial effects of the above technical scheme are: when the molar ratio of manganese acetate to potassium permanganate is low, the MnOx content is low, the specific surface area is small, the reaction active sites are few, and the electrocatalytic activity is low; when the molar ratio of manganese acetate to potassium permanganate is high, although the content of MnOx is higher than that of MnOx/Nano-G, the more MnOx is, the more MnOx agglomeration easily occurs, so that the specific surface area and the reaction active sites of MnOx/Nano-G are reduced, the mass transfer on the surface of a cathode is limited, the activity of diffused oxygen molecules is reduced, and OH and O are enabled to be2-The amount of production is reduced, eventually leading to a reduction in electrocatalytic activity.
Preferably, in the above method for preparing a manganese oxide nanoelectrode, the drying temperature in step (1) is 100 ℃, and the drying time is 8h-12 h.
Preferably, in the above preparation method of the manganese oxide nano-electrode, the calcination temperature in step (1) is 300-500 ℃, and the calcination time is 1-3 h.
The beneficial effects of the above technical scheme are: the calcination temperature affects the average particle size and the shape (e.g., spherical, rod-like, etc.) of MnOx, and when the calcination temperature is too low, the average particle size of MnOx is small and the number generated is small, and the electrical conductivity of the connection with the Nano-G layer is poor; when the calcination temperature is too high, the-OH on the surface of the MnOx particles may be destroyed, resulting in growth of MnOx particles and H2O is lost, so that hard agglomeration occurs, and the high temperature can reduce the number of gaps of the Nano-G material and collapse the internal active sites, so that OH and O are caused2-、H2O2The yield of the strong oxidant is reduced, so that the degradation rate of the tetracycline hydrochloride is reduced. In addition, when the calcination time is too short, the MnOx may agglomerate, the specific surface area thereof is reduced, and the reactive sites are few; when the calcination time is too long, the diameter of MnOx increases, the specific surface area thereof significantly decreases, the number of reactive active sites decreases, and the electrochemical activity becomes poor.
Preferably, in the above method for preparing a manganese oxide nanoelectrode, the mass ratio of the MnOx/nano-G composite material to the polytetrafluoroethylene in step (2) is (1-2): 1; the mass ratio of the MnOx/nano-G composite material to the absolute ethyl alcohol is 1G: (260-265) mL.
The beneficial effects of the above technical scheme are: the mass ratio of the MnOx/nano-G composite material to the polytetrafluoroethylene affects the strength of free radicals, and when the mass ratio of the MnOx/nano-G composite material to the polytetrafluoroethylene is too low, the number of reactive sites is small, and the generation rate and efficiency of the free radicals are low; when the MnOx/nano-G composite material and polytetrafluoroethylene have higher mass, the PMS can capture excessive free radicals, the generation rate and efficiency of the free radicals are saturated, the degradation rate of tetracycline hydrochloride is almost unchanged, and the catalyst plays a role in activating an oxidant in the whole degradation system to enable the oxidant to generate free radicals with strong oxidizing property, so that the influence of the addition amount of the catalyst on a catalytic system is of great significance, meanwhile, the absolute ethyl alcohol can also influence the solubility of the MnOx/nano-G composite material, when the masses of the MnOx/nano-G composite material and the absolute ethyl alcohol are gradually increased, the solubility of the composite material is increased, and meanwhile, the degradation rate of the tetracycline hydrochloride is remarkably increased, which indicates that the absolute ethyl alcohol catalyst has high-efficiency catalytic action; when the mass ratio of the MnOx/nano-G composite material to the absolute ethyl alcohol is continuously increased, the generation rate and the efficiency of free radicals are accelerated due to the increase of active sites, the degradation rate of the tetracycline hydrochloride reaches an extreme value, and when the addition amount of the catalyst is further increased, the degradation rate of the tetracycline hydrochloride is not greatly improved due to the elimination effect of the catalyst.
Preferably, in the above method for preparing a manganese oxide nanoelectrode, the drying temperature in step (2) is 80 ℃ and the drying time is 2-3 h.
Preferably, in the above method for preparing a manganese oxide nanoelectrode, the titanium mesh is pretreated in step (2), and the pretreatment process is as follows: cutting titanium net to 0.5 mol.L-1Ultrasonic cleaning in nitric acid for 20-25min, ultrasonic removing oil with petroleum ether for 20-25min, ultrasonic cleaning with redistilled water for 20-25min, and oven drying.
The beneficial effects of the above technical scheme are: the above treatment process can remove impurities such as oxide and organic matter on the titanium mesh.
Preferably, in the above method for preparing a manganese oxide nanoelectrode, the pressure of the tablet press in step (2) is 15 MPa.
The invention also discloses application of the manganese oxide nano electrode prepared by the method in tetracycline hydrochloride wastewater treatment.
According to the technical scheme, compared with the prior art, the invention discloses a preparation method of a manganese oxide nano electrode, which has the following advantages:
(1) the invention introduces the nano graphite and the manganese oxide into an electrochemical system to realize the improvement of the catalytic performance of the electrode, explores the optimal preparation process parameters of the electrode and enriches the variety of high-performance electrochemical cathode electrodes;
(2) compared with the main cathode catalysts developed by researchers in various countries, the cathode catalyst manganese oxide adopted by the manganese oxide nano graphite composite electrode material prepared by the invention has the advantages of high catalytic performance and low cost;
(3) the manganese oxide nano graphite composite electrode material prepared by the method can improve the degradation efficiency of antibiotics, can effectively avoid secondary loss pollution caused by a catalyst, is convenient and quick to use, has stable recycling efficiency, and has good practical application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic view of an electrolytic apparatus according to an embodiment;
FIG. 2 is a scanning electron microscope (EDS) image of a MnOx/nano-G composite material;
FIG. 3 is an XRD pattern of a MnOx/nano-G composite material;
FIG. 4 is a graph showing the relationship between the absorption wavelength and the absorbance of tetracycline hydrochloride;
FIG. 5 is a standard curve of tetracycline hydrochloride concentration;
FIG. 6 is a graph of the effect of calcination temperature on tetracycline hydrochloride degradation;
FIG. 7 is a graph of the effect of calcination time on tetracycline hydrochloride degradation;
FIG. 8 is a graph of the effect of MnOx dosing on tetracycline hydrochloride degradation;
FIG. 9 is a graph of the effect of current density on tetracycline hydrochloride degradation;
FIG. 10 is a graph of the effect of plate distance on tetracycline hydrochloride degradation;
FIG. 11 is a graph of the effect of initial pH on tetracycline hydrochloride degradation.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The manganese oxide cathode prepared by the method combining titanium mesh pretreatment and the MnOx/nano-G composite material has stable structural property, less raw material consumption, convenient and easily obtained reagents, high degradation rate of the composite electrode for treating tetracycline hydrochloride-containing wastewater, no secondary pollution and reusability.
The embodiment of the invention discloses a preparation method of a manganese oxide nano electrode, which comprises the following steps:
(1) pretreatment of a titanium mesh: cutting a 20-mesh titanium net to obtain a titanium net with the concentration of 0.5 mol.L-1Ultrasonic cleaning in nitric acid for 20min, ultrasonic removing oil with petroleum ether for 20min, ultrasonic cleaning with secondary distilled water for 20min, and drying in blast drying oven for subsequent use;
(2) preparing the MnOx/nano-G composite material: dissolving 0.18G of manganese acetate in 3mL of deionized water, and sequentially adding 12mL of polyethylene glycol (PEG)400 and 0.75G of nano-G during stirring; after fully mixing, slowly adding 0.17mL of 0.1mol/L potassium permanganate solution; heating the mixed solution at the temperature of 80 ℃ for 30min, filtering, repeatedly washing the mixture by using ultrapure water and absolute ethyl alcohol, drying the mixture in a 100 ℃ drying oven until the mixture is complete, and calcining the mixture for 1 to 3 hours at the temperature of 300-500 ℃ by using a muffle furnace to obtain the MnOx/nano-G composite material for preparing the electrode;
(3) preparing a MnOx/nano-G electrode: mixing the MnOx/nano-G composite material (3.0G) with 0.75mL (1.65G) of PTFE and 10L of absolute ethyl alcohol, carrying out ultrasonic treatment for 30min, heating to form paste, cutting the dried composite, compressing the paste onto a titanium net (5cm multiplied by 5cm) by using a tablet press under 15MPa, placing the prepared composite electrode into distilled water, heating and boiling for 60min, taking out, and then placing into an oven at 80 ℃ for drying for 2h to obtain the MnOx/nano-G electrode.
Mono, MnOx/nano-G composite material optimization
The MnOx/nano-G composite material (3.0G) was mixed with 0.75mL (1.65G) of PTFE and 10L of anhydrous ethanol to prepare a MnOx/nan-G composite electrode according to step (3). The preparation conditions are optimized by observing the influence of MnOx/nano-G prepared under different conditions on the degradation effect of tetracycline hydrochloride.
(1) Influence of calcination temperature
As can be seen from FIG. 6, the degradation rate of tetracycline hydrochloride increased with the increase of the calcination temperature and then decreased. When the roasting temperature is 350, 400, 450 and 500 ℃, the degradation rates of tetracycline hydrochloride are respectively 35.8%, 45.5%, 26.92% and 14.49% at the highest. The nanometer graphite is incinerated due to the overhigh calcining temperature, the reactive sites on the surface are damaged and inactivated, the conductivity and the catalytic performance of the composite material are weakened, and the degradation effect of the tetracycline hydrochloride is influenced. When the composite material is calcined at 400 ℃, the phenol degradation effect of the cathode chamber is the best, which shows that at the temperature, the crystal form and the catalytic performance of the manganese oxide are the best, the nano graphite can keep the original chemical property at the temperature, and the catalytic action of the composite material is the strongest, so that the calcination temperature selected in the experiment is the best at 400 ℃.
(2) Calcination time
As can be seen from FIG. 7, when the calcination time is 1h, the degradation rate of tetracycline hydrochloride reaches 36.7% at the highest, and with further increase of the calcination time, the degradation rate of tetracycline hydrochloride reaches 46.5%, because with increase of the calcination time, the residual polyethylene glycol is removed from the surface of the manganese oxide, and simultaneously, the crystallinity of the manganese oxide is gradually enhanced, and the active sites are increased. However, the phenol degradation rate at 3h of calcination is reduced to 21.1% due to further increase of the calcination time, because the nano graphite in the composite material is gradually incinerated along with the increase of the calcination time, the specific surface area of the material is possibly reduced, and meanwhile, the generation of ash causes the conductivity of the material to be reduced.
(3)MnOxAmount of addition
As can be seen from FIG. 8, too high or too low manganese oxide loading is detrimental to tetracycline hydrochloride degradation. When the manganese acetate: potassium permanganate is selected from 1:1 to 1.5: 1, the degradation rate of the tetracycline hydrochloride is increased, because the increase of the manganese oxide can increase the catalytic active sites, and the catalytic activity of the material is improved. But when the manganese acetate: when the potassium permanganate is too high, the manganese oxide is a semiconductor, so that the conductivity is poor, the electron transfer rate of the material is reduced, and the cathode reaction rate is inhibited. Therefore, manganese acetate is selected: 1.5 parts of potassium permanganate: 1 is the most preferred.
Using MnOxElectro-catalytically degrading tetracycline hydrochloride in water by using/nan-G composite electrode, 150mL of 10mg/L tetracycline hydrochloride (TC), and 0.1mol/L Na electrolyte2SO4pH 5.17, I600 mA, plate distance d 10mm, effective area 20cm2Taking water samples after the electrolysis reaction at the time of 10min and 20min respectively, and detecting the tetracycline hydrochloride concentration at the position of lambda being 276.4nm by using an ultraviolet spectrophotometer. The device for degrading antibiotics has the advantages of green production process, low energy consumption, simple equipment maintenance and resource saving, organically combines the processes of catalysis, electrolysis and the like, and combines the processes into a device for comprehensively treating the antibiotic wastewater.
In conclusion, MnO was determined by comparing the degradation effects of tetracycline hydrochloride in the electrolysis systemxThe best preparation conditions of the/nano-G composite material are as follows: manganese acetate: 1.5 parts of potassium permanganate: 1, calcining for 2 hours in a muffle furnace at 400 ℃.
The influence of different electrode materials on the degradation rate of the antibiotic wastewater is analyzed, and the results are shown in table 1.
TABLE 1 Effect of different electrodes on the degradation rate of antibiotic wastewater
Secondly, the electrocatalytic degradation condition is optimized
And (3) degrading tetracycline hydrochloride in the water by changing the electrocatalytic degradation condition by using the composite cathode manufactured under the optimal composite material condition so as to determine the optimal electrocatalytic degradation condition.
The method comprises the following specific steps: adding 150mL tetracycline hydrochloride wastewater to be treated into the electrolytic cell, and adding a proper amount of Na2SO4(0.1mol/L) as electrolyte, iridium ruthenium anode and self-made MnOxThe/nano composite cathode is inserted into the electrolytic bath and connected with a power supply, and each polar plateThe effective area of the reactor is 4cm multiplied by 5cm, the electrode distance is adjusted by a small clamping groove in an electrolytic cell according to the experiment requirement, the current intensity is adjusted by a direct current power supply, reaction liquid is taken at intervals of 10min, the reaction liquid is filtered by a 0.45uL microporous filter membrane to be tested, and the influence of the initial concentration of TC is discussed.
At 0.1mol/L Na2SO4In the electrolyte, the distance d between the polar plates is 10mm, and the effective area is 20cm2Respectively taking 150mL of tetracycline hydrochloride of 10mg/L and 20mg/L, respectively, electrolyzing for 10min and 20min, respectively, taking a water sample after reaction, and detecting the concentration of the tetracycline hydrochloride at the position of lambda being 276.4nm by using an ultraviolet spectrophotometer.
Experiments show that the degradation rate of the electrode material provided by the invention on antibiotics is high, and the degradation rate can reach about 85% after 20mg/L of antibiotics and 20min of electrolysis.
The effect of different initial concentrations of TC on the degradation resistance of tetracycline hydrochloride wastewater is shown in table 2.
TABLE 2 influence of different initial TC concentrations on the degradation resistance of tetracycline hydrochloride wastewater
Third, the experimental characterization
Material characterization: the method is mainly characterized by characterization means such as XRD and EDS, and all samples are dried for characterization. X-ray diffraction (XRD) phase analysis of the samples was carried out using an X-ray diffractometer model Bruker D8 advance, see FIG. 3, showing that the manganese oxide in the composite was MnO2And Mn2O3And MnO of2Is a main component of manganese oxide; elemental analysis was performed after spraying gold on the samples using an SU3500 elemental analyzer (EDS), see fig. 2, and the data shows C, O, Mn total elements with the highest carbon content.
Fourthly, testing electrochemical performance
A three-electrode system is adopted, a MnOx/nano-G composite material or nano-G loaded glassy carbon electrode (GCE, the diameter of which is 3mm), a platinum electrode (Pt) and a Saturated Calomel Electrode (SCE) are respectively used as working electrodes, and a counter electrode and a reference electrode are used for carrying out electrochemical performance test on a CS310H electrochemical workstation. 3mg of sample powder (MnOx/nano-G composite material or nano-G composite material) was added to 1mL of 1:1 anhydrous ethanol and 15. mu.L of Nafion (perfluorosulfonic acid, 5% by weight%) solution, stirred for 36 hours to form a uniform suspension, and then 8. mu.L of the suspension was pipetted onto a glassy carbon electrode (diameter 3mm) and dried at room temperature.
Electrochemical impedance spectroscopy: 20mg/L tetracycline hydrochloride and 0.1mol/L Na electrolyte2SO4The sine wave of the mixed solution is 5mV, and the scanning sine wave frequency is 100 KHz-0.01 Hz.
Fifthly, determining the content of tetracycline hydrochloride
The 20mg/L tetracycline hydrochloride solution is quantitatively determined by an ultraviolet visible spectrophotometer at the wavelength of 276.4nm, wherein the wavelength is the maximum absorption wavelength of the tetracycline hydrochloride within the range of 200-400 nm, as shown in FIG. 4. Preparing tetracycline hydrochloride with concentration of 0, 1, 2, 4, 6, 8, 10, 20, 40, 60mg/L, measuring absorbance A of different tetracycline hydrochloride concentrations at lambda of 276.4nm with ultraviolet spectrophotometer, drawing standard curve and obtaining linear regression equation A of 0.0358cTC-0.0093, and correlation coefficient R2The concentration of tetracycline hydrochloride at different absorbances was calculated using a linear regression equation at 0.99, and the standard curve of the TC concentration is shown in fig. 5.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. For the scheme disclosed by the embodiment, the scheme corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
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 (9)
1. The preparation method of the manganese oxide nano electrode is characterized by comprising the following steps of:
(1) preparing the MnOx/nano-G composite material: dissolving manganese acetate in deionized water, sequentially adding polyethylene glycol and nano graphene under stirring for full mixing, then adding a potassium permanganate solution to obtain a mixed solution, heating the mixed solution at 80 ℃ for 30min, and then filtering, washing, drying and calcining to obtain a MnOx/nano-G composite material;
(2) preparing a MnOx/nano-G electrode: and (3) uniformly mixing the MnOx/nano-G composite material with polytetrafluoroethylene and absolute ethyl alcohol, heating to obtain a pasty compound, compressing the compound onto a titanium mesh by using a tablet press, heating and boiling for 60-90min, taking out, and drying to obtain the MnOx/nano-G electrode.
2. The method for preparing a manganese oxide nanoelectrode according to claim 1, wherein the mass volume ratio of manganese acetate to deionized water in step (1) is (0.04-1) g: 1 mL; the mass ratio of manganese acetate to polyethylene glycol is 1: (83-100); the mass ratio of the manganese acetate to the nano graphene is 1: (1-5); the mass ratio of the manganese acetate to the potassium permanganate is 1: (1-5).
3. The method for preparing a manganese oxide nano-electrode according to claim 1, wherein the drying temperature in step (1) is 100 ℃ and the drying time is 8-12 h.
4. The method as claimed in claim 1, wherein the calcination temperature in step (1) is 300-500 ℃ and the calcination time is 1-3 h.
5. The method for preparing the manganese oxide nano-electrode according to claim 1, wherein the mass ratio of the MnOx/nano-G composite material to the polytetrafluoroethylene in the step (2) is (1-2): 1; the mass-volume ratio of the MnOx/nano-G composite material to the absolute ethyl alcohol is 1G: (260-265) mL.
6. The method for preparing a manganese oxide nano-electrode according to claim 1, wherein the drying temperature in step (2) is 80 ℃ and the drying time is 2-3 h.
7. The method for preparing the manganese oxide nano-electrode according to claim 1, wherein the titanium mesh is pretreated in the step (2), and the pretreatment comprises the following steps: cutting titanium net to 0.5 mol.L-1Ultrasonic cleaning in nitric acid for 20-25min, ultrasonic removing oil with petroleum ether for 20-25min, ultrasonic cleaning with redistilled water for 20-25min, and oven drying.
8. The method for preparing a manganese oxide nanoelectrode according to claim 1, wherein the pressure of said tablet press in step (2) is 10-15 MPa.
9. An application of the manganese oxide nano-electrode prepared by the method of any one of claims 1 to 8 in tetracycline hydrochloride-containing wastewater treatment.
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