CN113264573A - Bipolar electrode, preparation method thereof and wastewater treatment system - Google Patents

Bipolar electrode, preparation method thereof and wastewater treatment system Download PDF

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CN113264573A
CN113264573A CN202110411232.6A CN202110411232A CN113264573A CN 113264573 A CN113264573 A CN 113264573A CN 202110411232 A CN202110411232 A CN 202110411232A CN 113264573 A CN113264573 A CN 113264573A
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bipolar electrode
substrate
ceramic membrane
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intermediate layer
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CN113264573B (en
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李晓良
郑兴
张耀中
王一帆
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Xian University of Technology
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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
    • C02F2101/36—Organic compounds containing halogen

Abstract

The invention discloses a bipolar electrode, a preparation method thereof and a wastewater treatment system. The preparation method comprises the following steps: modifying the ceramic membrane to obtain a weakly conductive matrix; carrying out hydrothermal synthesis-hydrophobization treatment on the substrate, embedding GQDs into a skeleton of the substrate, and forming a hydrophobic intermediate layer on the surface of the substrate; and respectively loading metal oxide and metal on two sides of the middle layer to respectively form an anode catalyst layer and a cathode catalyst layer. Can realize the high-efficiency, low-consumption purification and effective detoxification of the halogenated pollutant wastewater with low salt content.

Description

Bipolar electrode, preparation method thereof and wastewater treatment system
Technical Field
The invention belongs to the technical field of treatment of refractory organic wastewater, and relates to a bipolar electrode, a preparation method of the bipolar electrode, and a wastewater treatment system using the bipolar electrode.
Background
Halogenated pollutants (HOPs) are widely used as important organic compounds in the fields of agriculture, medical treatment, chemical industry and the like. Due to the existence of carbon-halogen bonds, the substances have the characteristics of strong durability, wide accumulation range, high biotoxicity and the like, and potential threats are brought to water environment and human health by using and discharging a large amount of the substances. However, conventional processes (including filtration, coagulation, microbial metabolism, etc.) have poor dehalogenation degradation or do not eliminate HOPs at all. With the widespread and continuous use of current HOPs, how to develop efficient dehalogenation degradation technology is urgent.
Electrocatalysis (oxidation/reduction), one of the most potential environment-friendly technologies in the field of 'new pollutant' degradation in the 21 st century, has the advantages of quick reaction, convenience in operation, controllable conditions and the like. The process generates hydroxyl free radical (. OH), hydrogen peroxide (H)2O2) In the adsorption state [ H ]]adsThese active species promote the cleavage of carbon-halogen bonds and the further degradation of HOPs, and are a green technology with great potential. The electrode is used as a core component in the electrocatalytic reaction process and is crucial to the pollutant removal effect, wherein the removal of most organic pollutants depends on the catalytic oxidation capacity of the anode to realize self decomposition and even mineralization. However, for the persistent pollutants of HOPs, the carbon-halogen bond is difficult to break only by the oxidation of the anode, so that the dehalogenation rate is low and the water toxicity risk still exists. The electrocatalytic reduction can preferentially attack halogen atoms with stronger electronegativity and carbon atoms with lower electron cloud density, so that the carbon-halogen bonds in the HOPs are promoted to be broken, and the aim of quick dehalogenation is fulfilled.
In addition, in a traditional open type electrocatalysis reaction system, a cathode and an anode mostly exist separately, and organic matters which are difficult to degrade in the wastewater are mainly removed by contacting with the surface of the electrode. But because of the key active species generated by the reaction, OH free radical has extremely short half-life (10)-6～10-9s), the contact between pollutants in water and an electrode interface/free radical is limited, and even under good hydraulic conditions, the mass transfer process is still weak, so that the utilization efficiency of the free radical is low, and side reactions such as oxygen evolution, hydrogen evolution and the like are aggravated. Based on the above, how to realize a more efficient and low-consumption dehalogenation and degradation process of HOPs still has a plurality of key problems to be solved urgently, wherein the core problem is how to improve the efficient coordination of electrocatalytic reduction and oxidationAnd the mass transfer efficiency of the electrocatalytic reaction system.
Disclosure of Invention
The invention aims to provide a bipolar electrode, which solves the problem of poor dehalogenation and degradation effects of pollutants caused by insufficient oxidation-reduction synergistic effect and mass transfer efficiency in the prior art.
The technical scheme adopted by the invention is that the bipolar electrode comprises a substrate, wherein an intermediate layer is loaded on the surface of the substrate, and an anode catalyst layer and a cathode catalyst layer are respectively loaded on two sides of the intermediate layer.
The invention is also characterized in that:
the substrate is a ceramic membrane with titanium hydroxide loaded on the surface, the middle layer is made of Graphene Quantum Dots (GQDs), the anode catalyst layer is made of metal oxide with catalytic oxidation capability, and the cathode catalyst layer is made of metal with catalytic reduction capability.
The ceramic film material comprises Al2O3、TiO2、SiO2SiC or ZrO2。
The invention also aims to provide a preparation method of the bipolar electrode.
The invention adopts another technical scheme that a preparation method of a bipolar electrode comprises the following steps: modifying the ceramic membrane to obtain a weakly conductive matrix; carrying out hydrothermal synthesis-hydrophobization treatment on the substrate, embedding GQDs into a skeleton of the substrate, and forming a hydrophobic intermediate layer on the surface of the substrate; and respectively loading metal oxide and metal on two sides of the middle layer to respectively form an anode catalyst layer and a cathode catalyst layer.
The method specifically comprises the following steps:
step 1, cleaning a ceramic membrane, forming a titanium oxide layer on the surface of the ceramic membrane by adopting a dipping-thermal decomposition method, taking the ceramic membrane loaded with titanium oxide as a cathode and graphite as an anode, and carrying out electrochemical reduction to form a weakly conductive matrix;
step 2, preparing a precursor solution, pouring the precursor solution into a reaction kettle with a substrate for hydrothermal reaction, cooling, and dipping the substrate to form a hydrophobic intermediate layer on the surface of the substrate to obtain a ceramic membrane loaded with the intermediate layer;
step 3, dissolving the first metal salt to obtain a mixed solution, coating the mixed solution on one side of the middle layer, drying and calcining the mixed solution, and obtaining an anode catalyst layer on one side of the middle layer; and dissolving a second metal salt and a surfactant in deionized water to be used as an electrodeposition solution, using the catalytic film as a working electrode, performing pulse electrodeposition of a metal catalyst on the other side of the intermediate layer, and forming a cathode catalytic layer on the other side of the intermediate layer to obtain the bipolar electrode.
The cleaning process in the step 1 specifically comprises the following steps: the ceramic membrane is firstly placed in deionized water for ultrasonic cleaning for 5-15min, then placed in an acid solution, rinsed to be neutral by the deionized water, and dried.
In the process of the dipping-thermal decomposition method in the step 1: the impregnation liquid comprises the following components: tetrabutyl titanate with the volume fraction of 80 percent, ethanol with the volume fraction of 20 percent and HNO with the volume fraction of 0.1mol/L3The dipping time is 5 min; the drying temperature is 90-105 ℃; the calcination temperature is 500 ℃ and the calcination time is 15 min.
The preparation process of the precursor solution in the step 2 comprises the following steps: adding deionized water into a carbon source by taking citric acid or glucose as the carbon source, and fully stirring; and slowly adding concentrated sulfuric acid, continuously stirring, cooling to room temperature, slowly adding a NaOH solution, and adjusting the pH value of the solution to be neutral to obtain a precursor solution.
The dipping process in the step 2 is that the ceramic membrane loaded with the middle layer is dipped in an ethanol solution containing hexadecyl trimethoxy silane, then drying is carried out, and the dipping-drying process is repeated for 3-5 times.
A third object of the present invention is to provide a bipolar electrode based wastewater treatment system.
According to a third technical scheme adopted by the invention, the wastewater treatment system comprises the bipolar electrode and the electrolysis assembly, wherein the bipolar electrode is arranged in the electrolysis assembly, an inlet of the electrolysis assembly is connected with a wastewater pool through a pipeline, an outlet of the electrolysis assembly is connected with a water purification pool through a pipeline, and the bipolar electrode is connected with a power supply.
The invention has the beneficial effects that:
according to the bipolar electrode, the ceramic membrane, the Graphene Quantum Dots (GQDs) and the electrocatalyst are combined in situ to obtain the redox efficient synergistic bipolar functional membrane, so that the problems of mass transfer limitation and high energy consumption in the traditional electrocatalysis technology are solved, and efficient dehalogenation and degradation of the HOPs in the pore passage flow process are realized. According to the preparation method of the bipolar electrode, the ceramic membrane substrate is subjected to weak conduction treatment, so that the material impedance and the charge transmission energy barrier are reduced and the electron transfer rate is improved on the premise of not causing short circuit; an anode catalyst and a cathode catalyst are respectively loaded on two sides of the substrate, so that a bipolar electrode with efficient oxidation-reduction synergy is obtained, and the rapid dehalogenation and degradation of halogenated pollutants are promoted; zero-dimensional carbon nano-materials GQDs are introduced into the electro-catalytic material framework, so that the cathodic hydrogen evolution reaction can be inhibited, and meanwhile, the anodic byproduct O is realized2Is reduced into H by double electrons2O2Active species and energy utilization efficiency are improved. The bipolar electrode is applied to electrocatalytic degradation of halogenated pollutants in wastewater, and the mass transfer efficiency and the catalyst activity in the reaction process are improved by adopting a wastewater flow-through treatment mode and by means of a limited-area environment in a ceramic membrane pore channel, so that the high-efficiency, low-consumption purification and effective detoxification of the low-salt-content halogenated pollutant wastewater are realized.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a bipolar electrode according to the present invention;
FIG. 2 is a schematic view of a wastewater treatment system according to the present invention;
FIG. 3 is a graph showing the effect of a wastewater treatment system according to the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
A bipolar electrode comprises a substrate, wherein an intermediate layer is loaded on the surface of the substrate, and an anode catalyst layer and a cathode catalyst layer are respectively loaded on two sides of the intermediate layer.
The substrate is a ceramic membrane with titanium hydroxide loaded on the surface, the intermediate layer is made of GQDs, and the anode catalyst layer is made of a ceramic material with titanium hydroxide loaded on the surfaceThe material of the cathode catalyst layer is metal with catalytic reduction capability. The ceramic film material comprises Al2O3、TiO2、SiO2、SiC、ZrO2And the like.
A method of making a bipolar electrode, comprising: weak electrochemical modification is carried out on the ceramic membrane to obtain a matrix; carrying out hydro-thermal synthesis-hydrophobization treatment on the substrate, embedding GQDs into a framework of the substrate, and forming an intermediate layer on the surface of the substrate; and respectively loading metal oxide and metal on two sides of the middle layer, and forming an anode catalyst layer and a cathode catalyst layer on two sides of the middle layer.
Specifically, step 1, putting the ceramic membrane into deionized water, ultrasonically cleaning for 5-15min, keeping the ceramic membrane in an acid solution at 98 ℃ for 1-2h, rinsing the ceramic membrane to be neutral by using the deionized water, and drying the ceramic membrane at 90-105 ℃; forming a titanium oxide layer on the surface of the ceramic membrane by adopting an immersion-thermal decomposition method, wherein the immersion liquid comprises the following components: tetrabutyl titanate with the volume fraction of 80 percent, ethanol with the volume fraction of 20 percent and HNO with the volume fraction of 0.1mol/L3And soaking for 5min, taking out, drying at the temperature of 90-105 ℃, repeatedly soaking and drying for 2-3 times, and calcining at the calcining temperature of 500 ℃ for 15 min. Taking the ceramic membrane loaded with titanium oxide as a cathode and graphite as an anode, and adding the ceramic membrane into ammonium sulfate solution at a concentration of 10mA/cm2Electrochemically reducing for 5min under the cathode current density, wherein the titanium oxide layer on the surface of the ceramic membrane is converted into a hydroxide titanium layer to form a matrix;
step 2, adding deionized water into a carbon source by taking citric acid or glucose as the carbon source, and fully stirring for 10-15 min; slowly adding concentrated sulfuric acid, continuously stirring for 5-10min, cooling to room temperature, slowly adding 0.5mol/L NaOH solution, and adjusting the pH of the solution to be neutral to obtain a precursor solution; pouring the precursor solution into a polytetrafluoroethylene reaction kettle with a substrate for hydrothermal reaction at the reaction temperature of 200-260 ℃ for 3h, cooling to room temperature, taking out, cleaning, drying, and forming a hydrophobic intermediate layer on the surface of the substrate to obtain a ceramic membrane loaded with the intermediate layer; soaking the ceramic membrane loaded with the middle layer in an ethanol solution containing hexadecyl trimethoxy silane for 2-3h, then drying at 65 ℃, and repeating the soaking-drying process for 3-5 times to obtain the ceramic membrane loaded with the hydrophobic middle layer;
step 3, dissolving a first metal salt in a mixed solution of ethanol, n-butanol and isopropanol with equal volume fraction, adjusting the pH to 2 with concentrated nitric acid to obtain a mixed solution, brushing the mixed solution on one side of the intermediate layer, drying at 105 ℃ and 120 ℃, calcining in a 400 ℃ muffle furnace with 500 ℃, repeating the brushing-calcining process for 3-5 times, and calcining for the last time for 1h to obtain an anode catalyst layer on one side of the intermediate layer; dissolving a second metal salt and a surfactant in deionized water to be used as electrodeposition liquid, using a catalytic film as a working electrode, controlling the negative potential (-0.3V) - (-0.8V) (vs Ag/AgCl) of the working electrode by an electrochemical workstation, performing pulse electrodeposition of a metal catalyst on the other side of the middle layer by adopting a three-electrode system for 3-5min, and forming a cathode catalytic layer on the other side of the middle layer to obtain the bipolar electrode.
Wherein the first metal salt is one or a combination of Sn salt, Sb salt, Ru salt, Ir salt, Mn salt and Co salt. The second metal salt is one or a combination of Pd salt, Fe salt, Ni salt, Cu salt and Zn salt.
A wastewater treatment system is shown in figure 2 and comprises the bipolar electrode 1 and an electrolysis assembly 2, wherein the bipolar electrode 1 is arranged in the electrolysis assembly 2, the inlet of the electrolysis assembly 2 is connected with a wastewater tank 3 through a pipeline, a water pump 6 is connected on the pipeline between the electrolysis assembly 2 and the wastewater tank 3, the outlet of the electrolysis assembly 2 is connected with a water purifying tank 4 through a pipeline, and the bipolar electrode 1 is connected with a power supply 5.
Through the mode, the bipolar electrode combines the ceramic membrane, the Graphene Quantum Dots (GQDs) and the electrocatalyst in situ to obtain the redox efficient synergistic bipolar functional membrane, so that the problems of mass transfer limitation and high energy consumption in the traditional electrocatalysis technology are solved, and efficient dehalogenation and degradation of HOPs in the pore passage flow-through process are realized. According to the preparation method of the bipolar electrode, the ceramic membrane substrate is subjected to weak conduction treatment, so that the material impedance and the charge transmission energy barrier are reduced and the electron transfer rate is improved on the premise of not causing short circuit; the anode catalyst and the cathode catalyst are respectively loaded on two sides of the substrate to obtainThe bipolar electrode with efficient redox coordination is obtained, and the rapid dehalogenation and degradation of halogenated pollutants are promoted; zero-dimensional carbon nano-materials GQDs are introduced into the electro-catalytic material framework, so that the cathodic hydrogen evolution reaction can be inhibited, and meanwhile, the anodic byproduct O is realized2Is reduced into H by double electrons2O2Active species and energy utilization efficiency are improved. According to the wastewater treatment system, the bipolar electrode is used for electrocatalytic degradation of halogenated pollutants in wastewater, a wastewater flow-through treatment mode is adopted, and the mass transfer efficiency and the catalyst activity in the reaction process are improved by virtue of the limited-area environment in the ceramic membrane pore channel; realizes the high-efficiency, low-consumption purification and effective detoxification of the halogenated pollutant wastewater with low salt content.
Example 1
Step 1, selecting Al with the diameter of 3cm, the thickness of 2.5mm and the average pore diameter of 3 mu m2O3And (3) placing the ceramic membrane in deionized water for ultrasonic cleaning for 15min, then keeping the ceramic membrane in an acid solution with the pH value of 2 at 98 ℃ for 2h, then rinsing the ceramic membrane to be neutral by using the deionized water, and drying the ceramic membrane at the temperature of 105 ℃. Forming a titanium oxide layer on the surface of the ceramic membrane by adopting an immersion-thermal decomposition method, wherein the immersion liquid comprises the following components: tetrabutyl titanate with the volume fraction of 80 percent, ethanol with the volume fraction of 20 percent and HNO with the volume fraction of 0.1mol/L3The dipping time is 5min, the mixture is taken out and dried under the condition that the temperature is 105 ℃, and after the dipping-drying is repeated for 3 times, the mixture is calcined for 15min under the condition that the calcining temperature is 500 ℃. Taking the ceramic membrane loaded with titanium oxide as a cathode and graphite as an anode, and adding 10mA/cm in 0.1mol/L ammonium sulfate solution2Electrochemically reducing for 5min under the cathode current density, wherein the titanium oxide layer on the surface of the ceramic membrane is converted into a hydroxide titanium layer to form a matrix;
step 2, adding deionized water into citric acid, and fully stirring for 10 min; slowly adding concentrated sulfuric acid, continuously stirring for 10min, cooling to room temperature, slowly adding 0.5mol/L NaOH solution, and adjusting the pH of the solution to be neutral to obtain a precursor solution; pouring the precursor solution into a polytetrafluoroethylene reaction kettle with a substrate for hydrothermal reaction at 200 ℃ for 3h, cooling to room temperature, taking out, cleaning, drying, and forming on the surface of the substrateForming a hydrophobic intermediate layer, i.e. obtaining Al2O3a/GQDs membrane; mixing Al2O3Soaking the/GQDs membrane in ethanol solution containing hexadecyl trimethoxy silane for 2h, then drying at 65 ℃, and repeating the soaking-drying process for 3-5 times to obtain hydrophobic Al2O3a/GQDs membrane;
step 3, adding 1mol/L SnCl4、0.1mol/L SbCl3Dissolving in a mixed solution of ethanol, n-butanol and isopropanol with equal volume fraction, adjusting pH to 2 with concentrated nitric acid to obtain a mixed solution, coating the mixed solution on one side of the intermediate layer, drying at 120 ℃, calcining in a muffle furnace at 500 ℃, repeating the coating-calcining process for 3 times, calcining for 1h for the last time, and obtaining an anode catalyst layer on one side of the intermediate layer to obtain the Sb-SnO-loaded catalyst2Catalyst unipolar electrode (Sb-SnO)2@Al2O3/GQDs); 0.01mol/L H2PdCl4、0.2mol/L FeCl2Proper amount of sodium dodecyl sulfate is dissolved in deionized water to be used as electrodeposition liquid, and Sb-SnO is applied under the control of an electrochemical workstation2@Al2O3Adopting a three-electrode system to perform pulse electrodeposition of Pd-Fe catalyst on the other side of the middle layer for 5min, and forming a cathode catalyst layer on the other side of the middle layer to obtain the bipolar electrode (Sb-SnO)2@Al2O3/GQDs@Pd-Fe)。
Example 2
With Sb-SnO2@Al2O3the/GQDs @ Pd-Fe bipolar electrode is used as a core, and three typical halogenated pollutant simulated wastewater of perfluorooctanoic acid, m-chlorophenol and tetrabromobisphenol A are treated to evaluate the dehalogenation degradation effect of the three typical halogenated pollutant simulated wastewater. The specific treatment method comprises the following steps:
(1) Sb-SnO2@Al2O3the/GQDs @ Pd-Fe bipolar electrode 1 is arranged in the electrolytic component 1, and a flow-through type electro-catalysis wastewater treatment system shown in figure 2 is built;
(2) respectively preparing 1mg/L perfluorooctanoic acid solution, m-chlorophenol solution and tetrabromobisphenol solution, adding deionized water and 5mmol/L Na2SO4Respectively asA solvent and a supporting electrolyte;
(3) setting a continuous direct current power supply mode of the output of the power supply 5, wherein the applied voltage is 3.0V, the set flow rate of the water pump is 5mL/min, the wastewater in the wastewater tank 3 enters the electrolysis component 2 through the operation of the water pump 6, one part of the wastewater flows out of the electrolysis component 2 in a cross current mode and flows back to the wastewater tank 3, and the other part of the wastewater enters the water purifying tank 4 through the bipolar electrode 1.
As shown in fig. 3, the perfluorooctanoic acid-simulated wastewater, the m-chlorophenol-simulated wastewater, and the tetrabromobisphenol a-simulated wastewater all obtained good dehalogenation degradation effects in a single flow-through process under the same treatment conditions, and the dehalogenation rates (degradation rates) were 73.2% (92.3%), 93.6% (97.9%), and 81.3% (95.7%) in this order. The results show that the bipolar electrode and the treatment system thereof can well realize the high-efficiency dehalogenation degradation of halogenated pollutants, have obvious advantages compared with the traditional electrocatalysis system, and can be used for the purification treatment of wastewater containing halogenated pollutants.

Claims (10)

1. The bipolar electrode is characterized by comprising a substrate, wherein an intermediate layer is loaded on the surface of the substrate, and an anode catalyst layer and a cathode catalyst layer are respectively loaded on two sides of the intermediate layer.
2. The bipolar electrode according to claim 1, wherein the substrate is a ceramic membrane with titanium oxyhydroxide supported on the surface, the intermediate layer is made of GQDs, the anode catalyst layer is made of metal oxide with catalytic oxidation capability, and the cathode catalyst layer is made of metal with catalytic reduction capability.
3. The bipolar electrode of claim 2 wherein said ceramic membrane material comprises Al2O3、TiO2、SiO2SiC or ZrO2。
4. A method for preparing a bipolar electrode, comprising: weak electrochemical modification is carried out on the ceramic membrane to obtain a matrix; carrying out hydrothermal synthesis-hydrophobization treatment on the substrate, embedding GQDs into a framework of the substrate, and forming an intermediate layer on the surface of the substrate; and respectively loading metal oxide and metal on two sides of the middle layer, and forming an anode catalyst layer and a cathode catalyst layer on two sides of the middle layer.
5. The preparation method of the bipolar electrode according to claim 4, comprising the following steps:
step 1, cleaning a ceramic membrane, forming a titanium oxide layer on the surface of the ceramic membrane by adopting a dipping-thermal decomposition method, taking the ceramic membrane loaded with titanium oxide as a cathode and graphite as an anode, and carrying out electrochemical reduction to form a weakly conductive matrix;
step 2, preparing a precursor solution, pouring the precursor solution into a reaction kettle with a substrate for hydrothermal reaction, cooling, and dipping the substrate to form a hydrophobic intermediate layer on the surface of the substrate to obtain a ceramic membrane loaded with the intermediate layer;
step 3, dissolving the first metal salt to obtain a mixed solution, coating the mixed solution on one side of the middle layer, drying and calcining the mixed solution, and obtaining an anode catalyst layer on one side of the middle layer; and dissolving a second metal salt and a surfactant in deionized water to be used as an electrodeposition solution, using the catalytic film as a working electrode, performing pulse electrodeposition of a metal catalyst on the other side of the intermediate layer, and forming a cathode catalytic layer on the other side of the intermediate layer to obtain the bipolar electrode.
6. The method for preparing a bipolar electrode according to claim 4, wherein the cleaning process in step 1 is specifically as follows: the ceramic membrane is firstly placed in deionized water for ultrasonic cleaning for 5-15min, then placed in an acid solution, rinsed to be neutral by the deionized water, and dried.
7. The method for preparing a bipolar electrode according to claim 4, wherein during the dipping-thermal decomposition method in step 1: the impregnation liquid comprises the following components: tetrabutyl titanate with the volume fraction of 80 percent, ethanol with the volume fraction of 20 percent and HNO with the volume fraction of 0.1mol/L3At the time of impregnationThe time is 5 min; the drying temperature is 90-105 ℃; the calcination temperature is 500 ℃ and the calcination time is 15 min.
8. The method for preparing a bipolar electrode according to claim 4, wherein the precursor solution in step 2 is prepared by: adding deionized water into a carbon source by taking citric acid or glucose as the carbon source, and fully stirring; and slowly adding concentrated sulfuric acid, continuously stirring, cooling to room temperature, slowly adding a NaOH solution, and adjusting the pH value of the solution to be neutral to obtain a precursor solution.
9. The method for preparing a bipolar electrode according to claim 4, wherein the step 2 of dipping comprises dipping the ceramic membrane supporting the intermediate layer in an ethanol solution containing hexadecyl trimethoxy silane, drying, and repeating the dipping-drying process 3-5 times.
10. A wastewater treatment system, comprising a bipolar electrode (1) according to any one of claims 1 to 3 and an electrolysis module (2), wherein the bipolar electrode (1) is arranged in the electrolysis module (2), the inlet of the electrolysis module (2) is connected with a wastewater tank (3) through a pipeline, the outlet of the electrolysis module (2) is connected with a water purifying tank (4) through a pipeline, and the bipolar electrode (1) is connected with a power supply (5).
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CN114504952A (en) * 2022-03-24 2022-05-17 清华大学 Double-sided conductive film filtering assembly and water purification method
CN114715984A (en) * 2022-03-28 2022-07-08 昆明理工大学 Self-cleaning luminous photoelectric cooperative catalysis electrode and application thereof

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