CN117602710A - Electrocatalytic composite anode and preparation method and application thereof - Google Patents
Electrocatalytic composite anode and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 74
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 63
- 229910052796 boron Inorganic materials 0.000 claims abstract description 41
- 238000000576 coating method Methods 0.000 claims abstract description 38
- 238000006731 degradation reaction Methods 0.000 claims abstract description 38
- 230000015556 catabolic process Effects 0.000 claims abstract description 37
- 239000011248 coating agent Substances 0.000 claims abstract description 36
- 239000002351 wastewater Substances 0.000 claims abstract description 23
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 12
- 239000002344 surface layer Substances 0.000 claims abstract description 11
- 238000004070 electrodeposition Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 65
- 238000000034 method Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
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- 238000001354 calcination Methods 0.000 claims description 6
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
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- 239000010405 anode material Substances 0.000 abstract description 2
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 16
- 229940012189 methyl orange Drugs 0.000 description 16
- 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 14
- 229960000907 methylthioninium chloride Drugs 0.000 description 14
- PGSADBUBUOPOJS-UHFFFAOYSA-N neutral red Chemical compound Cl.C1=C(C)C(N)=CC2=NC3=CC(N(C)C)=CC=C3N=C21 PGSADBUBUOPOJS-UHFFFAOYSA-N 0.000 description 14
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- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
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- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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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
- C02F1/46104—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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses an electrocatalytic composite anode, which comprises a titanium polar plate and SnO formed on the surface of the titanium polar plate 2 ‑Sb 2 O 5 Coating and formed on SnO by electrodeposition 2 ‑Sb 2 O 5 Boron modified PbO of coating surface 2 ‑CeO 2 An active surface layer. The electrocatalytic composite anode provided by the invention optimizes the active components of the anode material and increases SnO 2 ‑Sb 2 O 5 Intermediate partLayer, enhancement of titanium-based PbO 2 Catalytic capacity and lifetime of the coated electrode. Based on the electrocatalytic composite anode, the invention also provides a preparation method of the electrocatalytic composite anode and application of the electrocatalytic composite anode in degradation of high-concentration dye wastewater.
Description
Technical Field
The invention relates to the technical field of electrochemical oxidation, in particular to an electrocatalytic composite anode, a preparation method and application thereof.
Background
With the rapid development of modern industry, the total amount of industrial wastewater discharged is increased gradually, wherein dye wastewater occupies a larger area. The high-concentration dye wastewater has high chromaticity and high toxicity, and can cause harm to the environment and human health, so that the high-concentration dye wastewater can be discharged after being treated by adopting effective means. At present, the treatment of dye wastewater can be divided into three methods according to the principle, namely a biological method, a physical method and a chemical method. The three methods have advantages and disadvantages, and comprehensively consider the factors of convenient operation, thorough degradation, mild conditions and the like, wherein the electrochemical oxidation method has the advantages of energy conservation, environmental protection, no pollution, mild conditions, simple device, strong operability, easiness in automation and the like, and becomes one of the water treatment methods with the most application prospects.
In PbO 2 The DSA electrode (Dimensionally Stable Anode ) constructed for the main active component has the outstanding advantages of low use cost, strong corrosion resistance, small polar distance change, high catalytic activity and the like, replaces the traditional insoluble graphite anode, is largely put into industrial production and is widely applied to the fields of chemical industry, metallurgy, electroplating, water treatment, environmental protection, ocean, cathode protection and the like. But titanium-based PbO 2 In practical application, the coating of the coated electrode is easy to fall off, and the substrate is easy to generate TiO 2 The passivation film causes the problems of poor conductivity, short service life and the like of the electrode, especially when facing different types of high-concentration dye wastewater, the electrocatalytic oxidation efficiency is low, the degradation is incomplete, and the application range of the electrode is greatly limited.
In view of the above, it is necessary to provide a new electrode material that solves the above-mentioned technical problems.
Disclosure of Invention
The invention aims to provide an electrocatalytic composite anode, which is prepared by optimizing active components of anode materials and increasing SnO (zinc oxide) 2 -Sb 2 O 5 Intermediate layer for improving titanium-based PbO 2 Catalytic capacity and lifetime of the coated electrode.
The technical scheme of the invention is as follows:
an electrocatalytic composite anode comprises a titanium polar plate and SnO formed on the surface of the titanium polar plate 2 -Sb 2 O 5 Coating and formed on SnO by electrodeposition 2 -Sb 2 O 5 Boron modified PbO of coating surface 2 -CeO 2 An active surface layer.
Further, snO 2 -Sb 2 O 5 The thickness of the coating is 60-80 mu m; boron modified PbO 2 -CeO 2 The thickness of the active surface layer is 25-35 μm.
The invention also provides a preparation method of the electrocatalytic composite anode, which comprises the following steps:
step S1, preprocessing a titanium polar plate;
s2, preparing SnO on the surface of the titanium polar plate 2 -Sb 2 O 5 The coating specifically comprises the following steps:
step S21, sequentially adding SnCl by taking 1-butanol as a solvent 4 ·5H 2 O、SbCl 3 And a proper amount of concentrated HCl, and fully stirring to prepare a mixed solution A;
step S22, coating the mixed solution A on the surface of the titanium polar plate, drying and calcining for 10-30min at 450-600 ℃; specifically, the calcination temperature may be 450 ℃, 500 ℃, 550 ℃, or 600 ℃, or may be other temperature values within the range;
step S23, repeating the step S228-12 times, and preparing SnO on the titanium electrode plate 2 -Sb 2 O 5 A coating; coating times of mixed solution A and SnO 2 -Sb 2 O 5 The thickness of the coating is related and can be adjusted according to the thickness requirement in practical application;
step S3, depositing the metal oxide on the SnO by an electrodeposition mode 2 -Sb 2 O 5 Depositing the surface of the coating to obtain boron modified PbO 2 -CeO 2 The active surface layer specifically comprises the following steps:
s31, adding boron powder into acetone, magnetically stirring and dispersing uniformly, performing solvothermal reaction for 12-24 hours at 160-200 ℃, then performing ultrasonic dispersion and centrifugation, and collecting upper-layer boron alkene nanosheet dispersion liquid; specifically, the solvothermal reaction temperature can be 160 ℃, 180 ℃ or 200 ℃, or can be other temperature values within the range; the reaction time can be 12h, 16h, 20h or 24h, or other time values within the range;
step S32, pb (NO) 3 ) 2 、Ce(NO 3 ) 3 Adding a proper amount of NaF into deionized water, stirring until the NaF is fully dissolved, then adding concentrated nitric acid to adjust the pH to 2-3, preparing a solution C, and then adding a proper amount of boron alkene nanosheet dispersion liquid to obtain a solution D;
step S33, using the electrode sheet prepared in the step S2 as an anode, using a stainless steel sheet as a cathode, using the solution D as an electroplating solution, and using 10-30mA/cm at 20-40 DEG C 2 Is electrodeposited for 1-2h; specifically, the electrodeposition temperature may be 20 ℃,25 ℃, 30 ℃, 35 ℃ or 40 ℃, or may be other temperature values within the range;
step S34, taking out the electrode plate after the reaction is finished, flushing and drying at normal temperature to obtain boron modified Ti/SnO 2 -Sb 2 O 5 /PbO 2 -CeO 2 Electrocatalytic composite anodes.
Further, in step S2, snCl 4 ·5H 2 O and SbCl 3 The mass ratio of (2) is 10:1.
Further, in step S3, pb (NO 3 ) 2 The concentration is 0.3mol/L, ce (NO) 3 ) 3 The concentration is 1.5g/L, the concentration of NaF is 0.4g/L, the concentration of concentrated nitric acid is 16mol/L, and the concentration of the boron alkene nanosheet dispersion liquid is 0.8mg/mL.
Further, in step S1, the pretreatment process of the titanium electrode plate includes:
step S11, putting the titanium polar plate into NaOH solution, soaking for 20-60min at 70-100 ℃, taking out and cleaning with deionized water; specifically, the alkaline temperature may be 70 ℃, 80 ℃, 90 ℃ or 100 ℃, or may be other temperature values within the range; the soaking time can be 20min, 30min, 40min, 50min or 60min, or can be other values within the range;
step S12, placing the titanium polar plate in oxalic acid solution, etching for 2-3 hours at 80-100 ℃, and washing the titanium polar plate clean by deionized water after the reaction is finished; specifically, the etching temperature of the oxalic acid solution may be 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃, or may be other temperature values within the range.
Preferably, the concentration of the NaOH solution is 14mol/L, and the solubility of the oxalic acid solution is 1mol/L.
The invention also provides application of the electrocatalytic composite anode in degradation of high-concentration dye wastewater.
Further, the electrocatalytic composite anode is used for degrading high-concentration dye wastewater, and comprises the following steps:
step S1, respectively adding acid/alkali into the anionic/cationic dye wastewater, regulating the pH value to 1-3 or 12-14, uniformly stirring, aging for 36-72h, filtering, and removing bottom sediment to obtain supernatant;
step S2, adding sodium sulfate as electrolyte into the supernatant fluid in the step S1, taking the composite anode as an anode, taking a stainless steel plate as a cathode, and taking the stainless steel plate as a cathode at a concentration of 10-30mA/cm 2 And performing electrochemical oxidation treatment for 1-3h in a constant-current mode to obtain degraded dye wastewater.
Further, in step S2, the concentration of sodium sulfate was 0.012mol/L.
Compared with the prior art, the electrocatalytic composite anode and the preparation method and application thereof provided by the invention have the beneficial effects that:
1. the invention provides an electrocatalytic composite anode, which sequentially forms SnO on the surface of a titanium polar plate 2 -Sb 2 O 5 Coating and boron modified PbO 2 -CeO 2 Active surface layer, enhancement of titanium-based PbO by optimization of electrode surface active layer composition, and addition of an intermediate protective layer 2 The catalytic capability and the service life of the coating electrode are improved, so that the degradation capability of the electrode to high-concentration dye wastewater is improved effectively. Wherein SnO 2 -Sb 2 O 5 The coating is used as an intermediate layer, so that the titanium polar plate in the electrocatalytic process is effectively protected and prevented from being converted into non-conductive TiO 2 Increase the system cell voltage and for maintaining boron modified PbO 2 -CeO 2 The compact structure of the active surface layer keeps the high capacitance of the composite electrode to have obvious promotion effect, thereby realizing high-efficiency electrocatalytic degradation. Through tests, the electrocatalytic composite anode can effectively electrocatalytic degradation of multi-type dye solutions with the concentration of up to 1g/L, realizes remarkable fading of the solutions in a short time, reduces TOC by 80%, and has obvious degradation effect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an optical photograph of a titanium plate during various treatments;
FIG. 2 is an XRD pattern of a titanium plate during various treatments;
FIG. 3 is an SEM of a titanium plate during various treatments;
FIG. 4 is an optical photograph and TEM photograph of a boron alkene nanoplatelet dispersion;
FIG. 5 is a graph of electrochemical LSV for different coated electrodes;
FIG. 6 is a photograph of a process for electrocatalytically degrading methyl orange dye solution with a composite titanium plate;
FIG. 7 is a graph of ultraviolet absorbance spectra before and after electrocatalytic degradation of methyl orange dye solution;
FIG. 8 is a photograph of a process for electrocatalytically degrading methylene blue dye solution of a composite titanium plate;
FIG. 9 is a graph of ultraviolet absorbance spectra before and after electrocatalytic degradation of methylene blue dye solutions;
FIG. 10 is a photograph of a process for electrocatalytically degrading neutral red dye solution by a composite titanium plate;
FIG. 11 is a graph of ultraviolet absorption spectra before and after electrocatalytic degradation of a neutral red dye solution;
FIG. 12 is a photograph of the electrocatalytic anode of comparative example 1 used for electrocatalytic degradation of methyl orange, methylene blue, neutral red dye solutions.
Detailed Description
In order to better understand the technical solution in the embodiments of the present invention and make the above objects, features and advantages of the present invention more obvious and understandable, the following detailed description of the present invention will be further described.
The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1
The preparation method of the electrocatalytic composite anode comprises the following steps:
step S1, preprocessing a titanium polar plate, wherein the steps are as follows:
weighing 280g of NaOH, adding the weighed 280g of NaOH into 220mL of deionized water, uniformly stirring, and fully dissolving to obtain a NaOH solution;
polishing a titanium polar plate with the thickness of 50 multiplied by 1mm by sand paper, and flushing with deionized water to remove a surface oxide film; then placing the mixture into NaOH solution, heating the mixture to 80 ℃ for reaction for 30min, and cleaning surface alkali liquor with deionized water after the reaction is finished;
the titanium plate was then vertically placed into 20% H 2 C 2 O 4 The solution (m%) is etched for 2-3h under boiling condition, and is thoroughly washed by deionized water again, and then is stored in absolute ethyl alcohol for standby.
S2, preparing SnO on the surface of the titanium polar plate 2 -Sb 2 O 5 The coating specifically comprises the following steps:
step S21, sequentially adding SnCl by taking 1-butanol as a solvent 4 ·5H 2 O、SbCl 3 And a proper amount of concentrated HCl, and fully stirring to prepare a mixed solution A; specific:
weigh 20g SnCl 4 ·5H 2 O、2gSbCl 3 Adding into 95mL of 1-butanol, adding 5mL of concentrated HCl, stirring uniformly, and dissolving completely to obtain solution A.
Step S22, coating the mixed solution A on the surface of a titanium polar plate, drying the surface at the temperature of 110 ℃ in an oven, then transferring to the other surface for coating, transferring to a muffle furnace after drying, heating to 500 ℃ at 5 DEG/min, and calcining for 10min;
step S23, repeating the operation process of step S22 for 9 times after cooling, and finally annealing and calcining in a muffle furnace for 60min to prepare SnO on the titanium electrode plate 2 -Sb 2 O 5 A coating layer with a thickness of 70 μm;
step S3, depositing the metal oxide on the SnO by an electrodeposition mode 2 -Sb 2 O 5 Depositing the surface of the coating to obtain boron modified PbO 2 -CeO 2 The active surface layer specifically comprises the following steps:
step S31, adding 100mg boron powder (AR, sigma-aldrich) to 100mL CH 3 COCH 3 Magnetic stirring and dispersing uniformly, transferring the dispersion liquid into a polytetrafluoroethylene lining reaction kettle, performing solvothermal reaction at 200 ℃ for 24 hours, then performing ultrasonic dispersion for 2 hours by a probe under the condition of 225W, centrifuging at 6000-8000 rpm for 15 minutes, and collecting upper-layer boron alkene nanosheet dispersion liquid;
step S32, 29.8gPb (NO 3 ) 2 、0.5gCe(NO 3 ) 3 Adding 270mL of deionized water into 0.2g of NaF, stirring uniformly, dissolving completely, and adding 1mL of concentrated HNO 3 Regulating the pH value to 2 to obtain a solution C; then adding the boron alkene nanosheet dispersion liquid to make the concentration of the boron alkene nanosheet dispersion liquid be 0.8mg/mL, and uniformly mixing to obtain a solution D;
step S33, taking the titanium polar plate prepared in the step S2 as an anode, taking a stainless steel sheet with the thickness of 50 multiplied by 1mm as a cathode, taking the solution D as electroplating solution, connecting a constant current power supply externally at the polar plate spacing of 2cm and at the temperature of 25 ℃ to 20mA/cm 2 Electrodepositing for 1h;
step S34, after the electro-deposition is finished, washing residual substances on the surface of the titanium polar plateAir-drying at 25deg.C to obtain boron modified Ti/SnO 2 -Sb 2 O 5 /PbO 2 -CeO 2 Electrocatalytic composite anode, boron modified PbO 2 -CeO 2 The thickness of the active skin layer was 30. Mu.m.
Referring to FIG. 1, an optical photograph of a titanium plate during different treatments is shown in FIG. 1a, and FIG. 1b shows the pretreated titanium plate, and SnO is introduced 2 -Sb 2 O 5 Coated titanium electrode plate fig. 1c shows a boron modified composite titanium electrode plate. As can be seen from fig. 1, the surface of the pretreated titanium polar plate presents a rough state, and the specific surface area is increased; while SnO is introduced into 2 -Sb 2 O 5 After the intermediate layer (figure 1 b) and the modified active layer (figure 1 c), the surfaces of the pole pieces respectively show compact coatings with different colors, and the fact that both types of coatings are tightly combined with the Ti substrate is confirmed.
Please refer to fig. 2, which shows the XRD patterns of the titanium electrode plate during different treatments. As can be seen from FIG. 2, snO 2 -Sb 2 O 5 Diffraction peaks of the intermediate layer XRD pattern confirm SnO 2 -Sb 2 O 5 Successfully introduced, the diffraction peak of the XRD pattern of the boron modified active layer corresponds to beta-PbO with good crystallinity 2 Boron alkene and CeO 2 No obvious characteristic diffraction peak appears under the influence of the crystallinity and doping amount of the product.
Referring to FIG. 3, SEM pictures of titanium plates during various treatments are shown, wherein FIG. 3a shows the introduction of SnO 2 -Sb 2 O 5 Coated titanium plates fig. 3b shows a boron modified composite titanium plate. As can be seen from fig. 3, the surface compactness of the boron modified composite titanium polar plate is better, the crystal size is uniform, the problems of coating falling, titanium matrix oxidation and the like are not easy to occur in the electrocatalytic process, the electrocatalytic efficiency of the polar plate is improved, and the service life is prolonged.
Referring to fig. 4, an optical photograph and a TEM photograph of the borane nano-sheet dispersion are shown, wherein fig. 4a shows the optical photograph and fig. 4b shows the TEM photograph. As can be seen from FIG. 4, the borane nanosheet dispersion showed a significant Tyndall effect (FIG. 4 a), demonstrating the colloidal nature of the dispersion, and TEM photograph (FIG. 4 b) confirmed that the product prepared by the liquid phase exfoliation method was two-dimensional sheet-like, boraneThe nano-sheet has good conductivity and electron-deficient property, so that when the nano-sheet is used as a dopant, pbO deposited at an anode and an electro-deposition 2 -CeO 2 The coating is tightly combined, which is beneficial to improving the oxygen evolution potential of the electrode, thereby improving the catalytic efficiency of the electrode. Referring to FIG. 5, which is an electrochemical LSV graph of different coated electrodes, FIG. 5 shows that the oxygen evolution potential of the boron modified composite titanium electrode is higher than that of Ti/SnO 2 -Sb 2 O 5 And Ti/SnO 2 -Sb 2 O 5 /PbO 2 An electrode, which is beneficial to reducing anode O in the electrolytic process 2 And improves the service life of the electrode and the catalytic efficiency.
Example 2
Boron modified Ti/SnO of example 1 2 -Sb 2 O 5 /PbO 2 -CeO 2 The electrocatalytic composite anode is applied to degradation of high-concentration dye wastewater, and the specific method comprises the following steps:
weighing 0.5g of methyl orange, adding into 500mL of deionized water, fully stirring, adding 1mL of concentrated HCl to adjust pH=2 after complete dissolution, stirring for 60min, standing for 48h, and filtering to obtain 300mL of supernatant;
to the obtained supernatant, 0.5g of sodium sulfate was added as an electrolyte, and the mixture was stirred well and dissolved well.
The composite electrode prepared in example 1 was used as an anode, a stainless steel plate was used as a cathode, the distance between the two electrodes was 2cm, and the electrode was placed vertically in a solution at 30mA/cm under the condition of externally connecting a DC power supply 2 And (3) performing electrochemical oxidation treatment for 30min in a constant-current mode, closing a power supply after the reaction is finished, and collecting the treated solution.
Referring to fig. 6 and 7 in combination, fig. 6 is a photograph showing a process of electrocatalytically degrading a methyl orange dye solution by a composite titanium plate, wherein fig. 6a shows an initial methyl orange dye solution, fig. 6b shows a methyl orange dye solution after aging for 48 hours, and fig. 6c shows a methyl orange dye solution after electrocatalytically degrading; FIG. 7 is a graph showing the ultraviolet absorption spectra of methyl orange dye solutions before and after electrocatalytic degradation. FIG. 6 shows that the solution precipitates after aging, the supernatant has no obvious change in color, and the color of the supernatant is basically faded to be colorless after electrocatalytic degradation; this is also confirmed by the ultraviolet spectral results of the solution before and after electrolysis in FIG. 7.
Example 3
Boron modified Ti/SnO of example 1 2 -Sb 2 O 5 /PbO 2 -CeO 2 The electrocatalytic composite anode is applied to degradation of high-concentration dye wastewater, and the specific method comprises the following steps:
the procedure of example 2 was followed except that methyl orange was changed to an equivalent amount of methylene blue, and 2.5ml of 12mol/LNaOH was added to the prepared dye solution to adjust ph=13, and the same procedure as in example 1 was followed to obtain a corresponding degraded solution.
Referring to fig. 8 and 9 in combination, fig. 8 is a photograph showing a process of electrocatalytically degrading a methylene blue dye solution by a composite titanium plate, fig. 8a shows an initial methylene blue dye solution, fig. 8b shows a methylene blue dye solution after aging for 48 hours, and fig. 8c shows a methylene blue dye solution after electrocatalytically degrading; FIG. 9 is a graph of ultraviolet absorbance spectra before and after electrocatalytic degradation of methylene blue dye solutions. FIG. 8 shows that the solution precipitates after aging, the supernatant liquid has no obvious change in color, the color of the supernatant liquid fades to be colorless after electrocatalytic degradation, and the ultraviolet spectrum results of the solution before and after electrolysis in FIG. 9 also prove that.
Example 4
Boron modified Ti/SnO of example 1 2 -Sb 2 O 5 /PbO 2 -CeO 2 The electrocatalytic composite anode is applied to degradation of high-concentration dye wastewater, and the specific method comprises the following steps:
the methyl orange of example 2 was changed to an equivalent neutral red, and 2.5ml of 12mol/LNaOH was added to the prepared dye solution to adjust ph=13, and the other steps were the same as in example 1 to obtain a corresponding degraded solution.
Referring to fig. 10 and 11 in combination, fig. 10 is a photograph showing a process of electrocatalytically degrading a neutral red dye solution by a composite titanium plate, wherein fig. 10a shows an initial neutral red dye solution, fig. 10b shows a neutral red dye solution after aging for 48 hours, and fig. 10c shows a neutral red dye solution after electrocatalytically degrading; FIG. 11 is a graph of ultraviolet absorbance spectra before and after electrocatalytic degradation of a neutral red dye solution. FIG. 10 shows that the solution precipitates after aging, the supernatant liquid has no obvious change in color, the color of the supernatant liquid fades to be colorless after electrocatalytic degradation, and the ultraviolet spectrum results of the solution before and after electrolysis of FIG. 11 also prove that.
The TOC change values before and after electrocatalytic degradation of different types of dyes for the anode of example 1 are shown in table 1:
table 1: TOC change values (in mg/L) before and after electrocatalytic degradation of different types of dyes
As can be seen from the data in Table 1, the composite electrode provided by the invention is adopted to perform electrocatalytic degradation on high-concentration methyl orange, methylene blue and neutral red dye wastewater, and the TOC value is obviously reduced, so that the composite electrode has obvious degradation effects on different types of high-concentration dye wastewater.
Comparative example 1
On the basis of example 1, the preparation of SnO on the surface of a titanium polar plate is eliminated 2 -Sb 2 O 5 And (3) coating, wherein in the preparation process of the active surface layer, the step of adding the boron alkene nanosheet dispersion liquid into the solution C is omitted. The obtained electrocatalytic anode comprises a titanium electrode and PbO formed on the surface of the titanium electrode 2 -CeO 2 An active skin layer, and the active skin layer is not modified with boron.
The electrocatalytic anode of comparative example 1 was used for degradation of dye wastewater of high concentration methyl orange, methylene blue, neutral red, etc., in the same manner as in examples 2 to 4.
Referring to fig. 12, there is a photograph of an electrode of comparative example 1 for electrocatalytic degradation of methyl orange, methylene blue, neutral red dye solutions, wherein the first group represents electrocatalytic degradation of methyl orange dye, the second group represents electrocatalytic degradation of methylene blue dye, and the third group represents electrocatalytic degradation of neutral red dye. From the electrocatalytic anode of comparative example 1 (pure titanium-based PbO 2 Pole piece) shows that the three high-concentration dye wastewater degradation process photographs show that the electrocatalytic degradation effect is poor, which is related to factors such as the deficiency of the middle layer and the insufficient density of the active layer, and further illustrates the boron modified Ti/SnO of the invention 2 -Sb 2 O 5 /PbO 2 -CeO 2 The electrocatalytic composite anode has better catalytic effect when facing different types of high-concentration dye wastewater.
The TOC change values before and after electrocatalytic degradation of different types of dyes for the anode of comparative example 1 are shown in table 2:
table 2: TOC change values (in mg/L) before and after electrocatalytic degradation of different types of dyes
As can be seen from the data in table 2, when electrocatalytic degradation is performed on the high concentration methyl orange, methylene blue and neutral red dye wastewater by using the electrode of comparative example 1, the TOC value after catalysis is significantly reduced compared with the composite electrode of example 1, which shows that the electrocatalytic efficiency of the electrode without boron modification is lower while reducing the intermediate layer, which is consistent with the results of the previous figures.
Comparative example 2
In the preparation process of example 1, practice shows that SnO 2 -Sb 2 O 5 The brush coating times and the concentration of the boron alkene nano sheet dispersion liquid in the modification process have obvious influence on the properties of the composite electrode sheet. The rest steps are kept unchanged, the coating brushing times are sequentially changed by adopting a single-factor variable control thought, and the concentration of the boron alkene nanosheet dispersion liquid is used for obtaining the titanium pole piece prepared under different technological parameters.
Experiments show that when the brushing times are less than 8 times, the thickness of the middle coating of the electrode is thinner, the situation of rapid rise of the cell voltage can occur in the electrolysis process, and the situation is related to oxidation of the titanium polar plate, so that effective protection is formed; if the amount of the coating is more than 15 times, the partial coating area becomes white and breaks during the calcination process, so that a complete coating cannot be formed, and the Ti polar plate cannot be effectively protected.
For the modified boron alkene nanosheet dispersion liquid, when the concentration exceeds 1.5mg/mL, the local concentration is too high, so that the boron alkene nanosheets are settled, an electrode coating cannot be effectively modified, and the preparation cost is high. On the other hand, when the concentration is less than 0.5mg/mL, the dispersion is limited by the concentration, the potential is low, and effective doping cannot be formed at the anode.
The pole piece prepared by the process is comprehensively evaluated in morphology and electrochemical degradation effect, the brushing times are selected to be 9 times, the concentration of the boron alkene nanosheet dispersion liquid is 0.8mg/mL, and the prepared composite anode has optimal electrocatalytic degradation effect.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention.
Claims (10)
1. An electrocatalytic composite anode is characterized by comprising a titanium polar plate and SnO formed on the surface of the titanium polar plate 2 -Sb 2 O 5 Coating and formed on SnO by electrodeposition 2 -Sb 2 O 5 Boron modified PbO of coating surface 2 -CeO 2 An active surface layer.
2. The electrocatalytic composite anode of claim 1, wherein SnO 2 -Sb 2 O 5 The thickness of the coating is 60-80 mu m; boron modified PbO 2 -CeO 2 The thickness of the active surface layer is 25-35 μm.
3. A method of preparing the electrocatalytic composite anode of claim 1, comprising the steps of:
step S1, preprocessing a titanium polar plate;
s2, preparing SnO on the surface of the titanium polar plate 2 -Sb 2 O 5 The coating specifically comprises the following steps:
step S21, sequentially adding SnCl by taking 1-butanol as a solvent 4 ·5H 2 O、SbCl 3 And a proper amount of concentrated HCl, and fully stirring to prepare a mixed solution A;
step S22, coating the mixed solution A on the surface of the titanium polar plate, drying and calcining for 10-30min at 450-600 ℃;
step S23, repeating the step S228-12 times, and preparing SnO on the titanium electrode plate 2 -Sb 2 O 5 A coating;
step S3, depositing the metal oxide on the SnO by an electrodeposition mode 2 -Sb 2 O 5 Depositing the surface of the coating to obtain boron modified PbO 2 -CeO 2 The active surface layer specifically comprises the following steps:
s31, adding boron powder into acetone, magnetically stirring and dispersing uniformly, performing solvothermal reaction for 12-24 hours at 160-200 ℃, then performing ultrasonic dispersion and centrifugation, and collecting upper-layer boron alkene nanosheet dispersion liquid;
step S32, pb (NO) 3 ) 2 、Ce(NO 3 ) 3 Adding a proper amount of NaF into deionized water, stirring until the NaF is fully dissolved, then adding concentrated nitric acid to adjust the pH to 2-3, preparing a solution C, and then adding a proper amount of boron alkene nanosheet dispersion liquid to obtain a solution D;
step S33, using the electrode sheet prepared in the step S2 as an anode, using a stainless steel sheet as a cathode, using the solution D as an electroplating solution, and using 10-30mA/cm at 20-40 DEG C 2 Is electrodeposited for 1-2h;
step S34, taking out the electrode plate after the reaction is finished, flushing and drying at normal temperature to obtain boron modified Ti/SnO 2 -Sb 2 O 5 /PbO 2 -CeO 2 Electrocatalytic composite anodes.
4. The method for preparing an electrocatalytic composite anode according to claim 3, wherein in step S2, snCl 4 ·5H 2 O and SbCl 3 The mass ratio of (2) is 10:1.
5. The method for preparing an electrocatalytic composite anode according to claim 3, wherein in step S3, pb (NO 3 ) 2 The concentration is 0.3mol/L, ce (NO) 3 ) 3 The concentration is 1.5g/L, the concentration of NaF is 0.4g/L, the concentration of concentrated nitric acid is 16mol/L, and the concentration of the boron alkene nanosheet dispersion liquid is 0.8mg/mL.
6. The method for preparing an electrocatalytic composite anode according to claim 3, wherein in step S1, the titanium plate pretreatment process comprises:
step S11, putting the titanium polar plate into NaOH solution, soaking for 20-60min at 70-100 ℃, taking out and cleaning with deionized water;
and step S12, placing the titanium polar plate in oxalic acid solution, etching for 2-3 hours at the temperature of 80-100 ℃, and washing the titanium polar plate with deionized water after the reaction is finished.
7. The method for preparing an electrocatalytic composite anode according to claim 6, wherein the concentration of NaOH solution is 14mol/L and the solubility of oxalic acid solution is 1mol/L.
8. Use of the electrocatalytic composite anode of claim 1 for degradation of high concentration dye wastewater.
9. The use according to claim 1, wherein the electrocatalytic composite anode is used for degrading high concentration dye waste water, comprising the steps of:
step S1, respectively adding acid/alkali into the anionic/cationic dye wastewater, regulating the pH value to 1-3 or 12-14, uniformly stirring, aging for 36-72h, filtering, and removing bottom sediment to obtain supernatant;
step S2, adding sodium sulfate as electrolyte into the supernatant of the step S1, taking the composite anode of claim 1 as an anode, taking a stainless steel plate as a cathode, and taking 10-30mA/cm 2 And performing electrochemical oxidation treatment for 1-3h in a constant-current mode to obtain degraded dye wastewater.
10. The use according to claim 9, characterized in that in step S2 the concentration of sodium sulphate is 0.012mol/L.
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