CN115159631B - Double-sided electrocatalytically-active ceramic membrane, preparation method thereof and water treatment application - Google Patents
Double-sided electrocatalytically-active ceramic membrane, preparation method thereof and water treatment application Download PDFInfo
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
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Abstract
The utility model discloses a double-sided electrocatalytic active ceramic membrane, a preparation method and water treatment application thereof. The ceramic membrane is composed of a substrate ceramic membrane and has double-sided electrochemical activity. Sputtering Magneli phase Ti on the surface of the film 4 O 7 As an electrocatalytic film anode, and deposit CuFe 2 O 4 As an electrocatalytic membrane cathode. The double-sided electrocatalytic active ceramic membrane has rapid decontamination rate and mineralization rate on organic pollution in water, and can be used for rapidly and efficiently removing the organic pollution in water. The double-sided electrocatalytic active ceramic membrane is suitable for multi-pollution coexistence and micro-pollution treatment, and is beneficial to reducing environmental risks.
Description
Technical Field
The utility model relates to the technical field of environmental organic pollution restoration, in particular to a double-sided electrocatalytic active ceramic membrane, and a preparation method and application thereof.
Background
Porous electrocatalytic membranes are of great interest for water treatment. The electrocatalytic film technology can quantitatively regulate electrode potential to controllably degrade refractory organic matters, so that the electrocatalytic film technology has higher oxidizing capacity compared with the traditional advanced oxidation technology for generating, for example, OH and Cl. Exposing the membrane pores to the electrolyte, the electrocatalytic membrane overcomes the contaminant diffusion limitations in conventional flat plate electrodes by shortening the charge and mass transport distance. However, the existing electrocatalytic membrane technology relies on high doses of chemical precursors, which is detrimental to environmental sustainability. In addition, the reaction residence time during filtration is limited, and the electrocatalytic membrane cannot generate enough active radicals (such as hydroxyl radicals, hydrogen peroxide, O 3 Etc.) to effectively oxidize persistent organic pollutants. Thus, practical applications of electromembrane technology face challenges of low efficiency of degradation and mineralization of persistent organic pollutants.
The Janus electrocatalytic film has double-sided electrochemical reaction surfaces, and the unique structure is beneficial to improving the pollution removal performance of the electrocatalytic film. The double-sided electrocatalytically active membrane can take full advantage of electrode redox reactions within the membrane matrix with enhanced faraday efficiency as compared to electrocatalytic membranes that provide only single-sided cathodic reduction or anodic oxidation. The double-sided electrocatalytically-active ceramic membranes avoid distance limitations between electrode pairs and allow for shorter diffusion distances to achieve rapid electrochemical oxidation compared to electrocatalytic membranes due to the electrically insulating nature of the substrate. Zhang et al first reported that double-sided electrocatalytically active membranes produced singlet oxygen in situ; and the mass transfer effect in the membrane is proved to enhance the electrocatalytic efficiency, and the reactive free radical ROS finite field effect is proved to enhance the reaction efficiency. Singlet oxygen is inert to a variety of organic contaminants. For example, sulfamethoxazole degrades relatively slowly in the presence of singlet oxygen, and intermediates are more toxic than the parent. Electrocatalytic oxidation includes both direct oxidation (direct electron loss reaction of organic matter at the anode) and indirect oxidation (oxidation of contaminants by active radicals generated by the electrode, such as hydroxyl radicals, etc.). However, the effect of direct anodic oxidation is often neglected, but is very important. For example, hydroxyl groups cannot degrade PFOA directly unless combined with anodic direct oxidation. However, the research of the current double-sided electrocatalytic membrane is only focused on indirect oxidation (such as researching the limiting field effect of the indirect oxidation to improve the electrocatalytic efficiency), and the research of the Janus electrocatalytic membrane for fully utilizing the oxidation-reduction reaction of the two sides of the membrane is still in an early stage, and the development of the double-sided electrocatalytic membrane capable of efficiently removing pollutants has great challenges and opportunities. First, in practical applications, it is necessary to generate active oxygen sufficiently strong. Secondly, careful selection of electrode materials is critical to improving electrocatalytic efficiency, which is yet to be explored. Furthermore, electrochemical oxidation is inefficient in its use and the important role of direct electrochemical oxidation is ignored.
The utility model with publication number of CN108543423A provides an electrocatalytic membrane filter device and a preparation method of an electrocatalytic filter membrane. The electrocatalytic membrane filter device can couple membrane filtration with an electrocatalytic mechanism and be applied to degrading organic matters and other wastewater. The utility model discloses a preparation method of an electrocatalytic membrane filter membrane, which is a preparation method of a thermal reduction graphene oxide/carbon nano tube electrocatalytic filter membrane carrying titanium dioxide. In practical application, compared with the existing membrane filtration and electrocatalytic technology, the electrocatalytic membrane filter device can remove the micromolecular pollutants difficult to degrade in water in real time, has low energy consumption and high efficiency, and has potential industrial application value. The electrocatalytic filtration membrane prepared by the utility model not only can obtain higher water flux than the existing graphene oxide or reduced graphene oxide film, but also can effectively degrade organic pollutants with smaller molecular radius in a membrane channel by combining electrocatalytic effect. However, the film is a flexible film, and the practical application lacks mechanical strength.
The utility model patent with publication number of CN211886777U discloses a multistage electrocatalytic membrane reactor, which comprises: a reactor body having a chamber in which an electrochemical reaction is performed; two or more porous membrane electrode pairs disposed within the chamber; the feeding unit is arranged on one side of the reactor body and communicated with the cavity and is used for providing reaction raw materials for the cavity; the product collecting unit is arranged on the other side of the reactor body and communicated with the cavity and is used for collecting products generated in the cavity; and a power source whose positive and negative electrodes are connected to the porous membrane electrode and the auxiliary electrode of each stage of the porous membrane electrode pair, or the auxiliary electrode and the porous membrane electrode, respectively, to form an electrode pair. The multistage electrocatalytic membrane reactor has the advantages of high conversion rate, good stability, safety, reliability, environment friendliness, repeated use and the like. However, the membrane described in the utility model is a porous membrane electrode pair of two or more stages, and there is a limit to the electrode spacing in practical use.
Disclosure of Invention
The utility model aims to solve the technical problems and provide a double-sided electrocatalytically active ceramic membrane as well as a preparation method and application thereof. The double-sided electrocatalytic active ceramic membrane provided by the utility model has rapid decontamination rate and mineralization rate on organic pollution in water, and can be used for rapidly and efficiently removing the organic pollution in water. The double-sided electrocatalytic active ceramic membrane provided by the utility model is suitable for multi-pollution coexistence and micro-pollution treatment, and is beneficial to reducing environmental risks.
In order to achieve the above purpose, the specific technical scheme to be adopted by the utility model is as follows:
in a first aspect, the present utility model provides a double-sided electrocatalytically-active ceramic membrane, which is composed of an insulating substrate, an electrocatalytic membrane anode layer and a cathode layer, wherein the insulating substrate is an insulating ceramic membrane with a pore diameter of 1-5 microns; the anode layer is a conductive coating sputtered on one side of the ceramic film and is used for connecting with the positive electrode of a power supply; the cathode layer is a catalyst layer deposited on the other side of the ceramic membrane and is used for connecting with a power supply cathode; the catalyst is a heterogeneous catalyst with electro-Fenton activity.
As a preference of the first aspect, the material of the conductive coating is preferably Ti of the Magneli phase 4 O 7 The method comprises the steps of carrying out a first treatment on the surface of the The heterogeneous catalyst with electro-Fenton activity is preferably an iron-based heterogeneous catalyst, and further preferably copper ferrite.
In a second aspect, the utility model provides a method for preparing a double-sided electrocatalytically-active ceramic membrane, which comprises the following steps:
s1, taking an insulating ceramic film as a substrate, dissolving copper nitrate, ferric nitrate, citric acid and ethylene glycol in water to form sol, continuously stirring to form gel-like precursors, coating the gel-like precursors on one side of the substrate to form a film, and heating the film to 350-450 ℃ in a gradient way to calcine the gel-like precursors to form a catalyst layer serving as a cathode layer;
s2, sputtering a titanium dioxide coating on the other side of the substrate film to serve as an anode layer, so that the ceramic film with double-sided electrocatalytically active properties is obtained.
As a preferable mode of the second aspect, the sol is prepared by dissolving copper nitrate, ferric nitrate, citric acid and glycol in deionized water, wherein the concentrations are respectively 0.02mol/L of copper nitrate, 0.04mol/L of ferric nitrate, 0.072mol/L of citric acid and 0.144mol/L of glycol.
Preferably, in the second aspect, the sol is stirred at 60 to 100 ℃ for 4 to 6 hours to form a gel-like precursor.
As a preferable aspect of the above second aspect, the precursor is subjected to three spin coating rounds, each of which is to place 0.1 to 0.7mL of the precursor on the upper surface of the base ceramic film, and then spin-coating is performed with a spin coater at 500 to 6000rpm for 30 seconds.
As a preferable aspect of the above second aspect, the calcination process is performed by gradient heating at a heating rate of 2 to 7 ℃/min, and maintaining at 100 ℃,300 ℃ and 450 ℃ for 1.5 hours, respectively, to complete the calcination process.
As a preferable aspect of the second aspect, the sputtering method of the titanium oxide coating layer is laser sputtering; preferably, the technological parameters of laser sputtering are current of 350-550A, voltage of 55-65V, argon flow of 45-55L/min, hydrogen flow of 3-5L/min, titanium oxide powder supply rate of 20-50 g/min and sputtering distance of 70-100 mm.
In a third aspect, the present utility model provides a double-sided electrocatalytically-active ceramic membrane prepared by a method according to any one of the above second aspects.
In a fourth aspect, the utility model provides an application of a double-sided electrocatalytically-active ceramic membrane in water treatment, which comprises the following specific steps:
introducing a solution to be treated containing organic pollutant molecules into treatment equipment for treatment; the treatment apparatus forms a supply side and an outflow side which are not directly connected, the supply side being located on the anode layer side and the outflow side being located on the cathode layer side, with the double-sided electrocatalytically active ceramic membrane of claim 1 or 2 or 9; the anode layer is connected with a power supply anode, and the cathode layer is connected with a power supply cathode; the solution to be treated is introduced from the supply side, organic pollutant molecules therein sequentially pass through the anode layer, the ceramic membrane and the cathode layer, are removed through direct anode oxidation and indirect cathode oxidation reactions, and finally are discharged from the outflow meter.
As a preferable aspect of the above fourth aspect, the solution to be treated is medical wastewater, printing and dyeing wastewater or domestic wastewater containing multi-pollution co-organic pollutants;
as a preferable aspect of the fourth aspect, the organic contaminant molecule in the medical wastewater, the printing wastewater or the domestic wastewater is one or more of phenol, sulfamethoxazole, carbamazepine and perfluorooctanoic acid.
Compared with the prior art, the double-sided electrocatalytic active ceramic membrane provided by the utility model has rapid decontamination rate and mineralization rate on organic pollution in water, and can be used for rapidly and efficiently removing the organic pollution in water. The double-sided electrocatalytic active ceramic membrane is suitable for multi-pollution coexistence and micro-pollution treatment, and is beneficial to reducing environmental risks.
Drawings
FIG. 1 is a graph showing the results of a property measurement of a double-sided electrocatalytically-active ceramic membrane; wherein: a is a preparation method of a double-sided electrocatalytically active ceramic membrane and a cross-section optical photograph; b-c are two-sided electrocatalytically active ceramic membrane section scanning electron micrographs; d-e is an optical and scanning electron microscope photograph of the surface of the double-sided electrocatalytically-active ceramic film; f, g are XRD results for the double-sided electrocatalytically-active ceramic membranes implemented.
FIG. 2 is a schematic illustration of a double-sided electrocatalytically-active ceramic membrane operating device.
FIG. 3 is a graph showing contaminant removal performance of the present utility model; wherein: (a) For the removal performance of the double-sided electrocatalytically active ceramic membrane for coexistence of various pollutants, the reaction conditions are 1mg/L of perfluorooctanoic acid (PFOA), sulfamethoxazole (SMX), carbamazepine (CBZ) and phenol (phenol). The electrolyte was 100mM sodium sulfate, the applied voltage was 10V, and the flow rate was 0.5mL/min. (b) For the removal of CBZ and phenol by the double-sided electrocatalytically-active ceramic membrane, the electrolyte used was 100mM sodium sulfate, the applied voltage was 10V, and the flow rate was 2ml/min.
Detailed Description
In order that the above objects, features and advantages of the utility model will be readily understood, a more particular description of the utility model will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present utility model. The present utility model may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the utility model, whereby the utility model is not limited to the specific embodiments disclosed below. The technical features of the embodiments of the utility model can be combined correspondingly on the premise of no mutual conflict.
The double-sided electrocatalytically-active ceramic membranes provided by the utility model and their preparation and use will be further described below.
The utility model provides a double-sided electrocatalytically-active ceramic membrane, which consists of an insulating substrate, an electrocatalytic membrane anode layer and a cathode layer, wherein the insulating substrate is an insulating ceramic membrane with the aperture of 1-5 microns; the anode layer is a conductive coating sputtered on one side of the ceramic film and is used for connecting with the positive electrode of a power supply; the cathode layer is a catalyst layer deposited on the other side of the ceramic membrane and is used for connecting with a power supply cathode; the catalyst is a heterogeneous catalyst with electro-Fenton activity.
The three-layer structure of the double-sided electrocatalytically-active ceramic membrane plays different roles respectively, and is specifically introduced as follows:
first, the ceramic substrate is used as a support structure for the monolithic catalytic membrane, and the remaining layers are built on the basis of the substrate.
Secondly, the anode layer is used for connecting with a power anode and simultaneously performing the function of enabling pollutants to be in electron oxidation at the power anode.
Again, the cathode layer functions to connect to the power cathode while oxidizing contaminants in the pores near the cathode and at the cathode film surface by the hydroxyl groups generated by the electro-Fenton reaction.
Therefore, in the double-sided electrocatalytic active ceramic membrane, the ceramic base layer, the cathode layer and the anode layer respectively have different insulation, hydroxyl indirect oxidation and electrode direct oxidation functions, so that the electrocatalytic membrane has rapid decontamination rate and mineralization rate, coexists with micro-pollution and is used for rapidly and efficiently removing organic pollution in water. The double-sided electrocatalytic active ceramic membrane is suitable for multi-pollution coexistence and micro-pollution treatment, and is beneficial to reducing environmental risks.
It should be noted that any heterogeneous iron-based catalyst capable of generating hydroxyl groups by electro-Fenton may be used in the cathode layer according to the present utility model, and the specific conditions may depend on the pollutant to be treated and the catalyst selected, so as to achieve efficient catalysis of the pollutant in the electro-Fenton advanced oxidation system. In the present utility model, such a catalyst is preferably an iron-based catalyst, and further preferably a heterogeneous catalyst such as copper ferrite, which contains a co-doped material of iron and copper as a precursor.
The following describes the preparation method of the double-sided electrocatalytically-active ceramic membrane in detail, which adopts a sol-gel-sintering method and a laser sputtering technology, and comprises the following steps:
s1, taking an insulating ceramic film as a substrate, dissolving copper nitrate, ferric nitrate, citric acid and ethylene glycol in water to form sol, continuously stirring to form gel-like precursors, coating the gel-like precursors on one side of the substrate to form a film, and heating the film to 350-450 ℃ in a gradient way to calcine the gel-like precursors to form a catalyst layer serving as a cathode layer;
in the utility model, the sol is prepared by dissolving copper nitrate, ferric nitrate, citric acid and glycol in deionized water, wherein the concentrations are respectively 0.02mol/L of copper nitrate, 0.04mol/L of ferric nitrate, 0.072mol/L of citric acid and 0.144mol/L of glycol. After the sol is prepared, the sol can be stirred for 4-6 hours at 60-100 ℃ to form a gel precursor.
In the utility model, since the gel viscosity of the precursor solution is not high, excessive single spin coating can overflow, the precursor needs to be subjected to three rounds of spin coating, and 0.1-0.7 mL of precursor is placed on the upper surface of the substrate ceramic film in each round of spin coating, and then the spin coating is carried out for 30s by using a spin coater at the rotating speed of 500-6000 rpm.
In the utility model, in the process of calcining by gradient heating, the temperature is gradually raised at the heating rate of 2-7 ℃/min, and the temperature is maintained at 100 ℃,300 ℃ and 450 ℃ for 1.5 hours respectively, thus completing the calcining procedure.
S2, sputtering a titanium dioxide coating on the other side of the substrate film to serve as an anode layer, so that the ceramic film with double-sided electrocatalytically active properties is obtained.
In the present utility model, the sputtering method of the titanium oxide coating layer is laser sputtering. Preferably, the technological parameters of laser sputtering are current of 350-550A, voltage of 55-65V, argon flow of 45-55L/min, hydrogen flow of 3-5L/min, titanium oxide powder supply rate of 20-50 g/min and sputtering distance of 70-100 mm.
Of course, in the steps S1 to S2, the process parameters and the material selection in each step may be optimized and adjusted according to the actual effect.
The double-sided electrocatalytically-active ceramic membrane can be used as a membrane component to construct double-sided electrocatalytically-active ceramic membrane treatment equipment for repairing environmental organic pollution. The double-sided electrocatalytically-active ceramic membrane is used as a filtering membrane in the treatment equipment for introducing organic pollution solution to be treated.
In the utility model, the specific organic pollution solution to be treated can be selected according to actual conditions, and specifically, the solution to be treated can be medical wastewater, printing and dyeing wastewater and domestic wastewater containing multi-pollution co-organic pollutants and trace pollution. Wherein the organic pollutant molecules of the medical wastewater, the printing and dyeing wastewater and the domestic wastewater can be phenol, sulfamethoxazole, carbamazepine or perfluorooctanoic acid, and the target organic pollutant molecules and the interference components are not limited to the above in the practical application.
In order to further demonstrate the performance of the above-described double-sided electrocatalytically-active ceramic membranes of the present utility model, the present utility model is further illustrated by way of example for its actions and effects.
Example 1
In this example, a double-sided electrocatalytically-active ceramic membrane was prepared using electrospinning and electrostatic spray printing techniques, according to the following procedure. The specific steps are described below:
s1, taking an insulating ceramic film (with the thickness of 2.03 micrometers and 300 kDa) as a substrate, and depositing a precursor containing an iron element on the substrate by a sol-gel-sintering method, wherein the specific steps are as follows:
copper nitrate, ferric nitrate, citric acid and glycol are dissolved in deionized water according to the proportion to form sol. The concentration of each solute in the sol is respectively 0.02mol/L of copper nitrate, 0.04mol/L of ferric nitrate, 0.072mol/L of citric acid and 0.144mol/L of glycol. The sol was stirred at 90 ℃ for 5 hours to form a gel-like precursor. Placing 0.7mL of the precursor on the upper surface of the substrate ceramic film, and then performing spin coating for 30 seconds by using a spin coater at a rotating speed of 1500 rpm; and then, under the condition that the quantity of the added precursor is the same as the spin coating parameters, carrying out two-round spin coating on the substrate ceramic film. And then heating the coating formed by spin coating to 450 ℃ in a gradient way through temperature programming at a heating rate of 3.5 ℃/min for calcination, so as to form the catalyst layer serving as the cathode layer. Wherein, in the calcining process of gradient heating, the temperature is gradually increased at a heating rate of 3 ℃/min, and the temperature is maintained at 100 ℃,300 ℃ and 450 ℃ for 1.5 hours respectively, so as to complete the calcining procedure, and finally, the mass of the copper ferrite film layer attached on the ceramic film is about 0.6g.
S2, sputtering titanium dioxide Ti on the other side of the substrate ceramic film 4 O 7 The coating is used as an anode layer to obtain the ceramic membrane with double-sided electrocatalytically active.
In the step, the titanium dioxide coating is sputtered by laser, the process parameters are current 500A, voltage 60V, argon flow 50L/min, hydrogen flow 4L/min, titanium dioxide powder supply rate 30 g/min and sputtering distance 90 mm.
The results of various characterizations of the double-sided electrocatalytically-active ceramic membranes prepared by this example are shown in fig. 1.
A double-sided electrocatalytically active ceramic membrane with a copper ferrite coating is produced on the water outlet side [ JPEM (-), FIG. 1a ] by means of sol-gel sintering, and titanium dioxide is sputtered on the water inlet side surface of the membrane [ JPEM (+) ] by means of laser sputtering. The base ceramic membrane has electrical insulation and a thickness of 2.42mm (fig. 1b and 1 c), so that anodic oxidation and cathodic reduction can occur continuously in different areas within the pores during electrocatalytic filtration. The different colours of the copper ferrite coating and the titanium suboxide sputtered film surface confirm the corresponding metal deposition (fig. 1a, 1d and 1 e). Titanium is the main metal element of the titanium sub-oxide anode surface (fig. 1 f). SEM-EDS mapping results show the presence of copper and iron elements in the membrane pore structure (fig. 1 e), indicating that copper ferrite is deposited in the membrane surface and its nearby internal pores. XRD patterns of the copper ferrite cathode surface showed that diffraction peaks of 18.398 °, 30.242 °, 35.560 °, 43.333 °, 57.262 °, 61.333 °, 62.869 ° and 73.626 ° were copper ferrite spinel structures (fig. 1 g). Titanium dioxide and copper ferrite nano particles are uniformly coated on the surface of the membrane, have larger specific surface area and are excellent active oxygen activation catalysts.
Example 2
In order to evaluate the efficiency of the double-sided electrocatalytically-active ceramic membrane in removing organic pollutants in water, a degradation experiment is carried out by taking sulfamethoxazole, phenol, perfluoro caprylic acid and carbamazepine as typical pollutants. The double-sided electrocatalytically-active ceramic membrane used in this example was the membrane prepared in example 1.
The degradation test adopts a flow-through electric filtration test, and the specific method comprises the following steps: electrofiltration experiments were performed using a flow membrane filtration system. The copper ferrite coating and the titanium suboxide sputtered surface were used as cathode and anode and connected to a direct current power supply (fig. 2) via a stainless steel strip.
To further compare the performance of the double-sided electrocatalytically-active ceramic membranes prepared in example 1 of this utility model with other electrocatalytic membranes reported in the prior art, a number of different sets of experiments were further set up in this example. Wherein different active electrodes and sequence tests are also provided for the same membrane material, wherein the anode is denoted as +, and the cathode is denoted as +. "+/-" represents that the wastewater to be treated flows in from the anode surface of the membrane and flows out from the cathode surface of the membrane, and the anode and the cathode of the membrane are both communicated with the anode and the cathode of the power supply; "-/+" represents that the wastewater to be treated flows in from the cathode surface of the membrane and flows out from the anode surface of the membrane, and the anode and the cathode of the membrane are communicated with the anode and the cathode of the power supply; "+ & -" represents that the wastewater to be treated passes through the membrane but the active electrodes have no sequence; the individual "+" indicates that the wastewater to be treated passes through the membrane, but only the anode of the membrane is communicated with the anode of the power supply, while the cathode of the membrane is not communicated with the cathode of the power supply, and a titanium mesh with the same area (the titanium mesh is not contacted with the cathode) is arranged at the cathode of the membrane for connecting the cathode of the power supply and forming current; the separate "-" indicates that the wastewater to be treated passes through the membrane, but only the cathode of the membrane is connected to the negative electrode of the power supply, while the anode of the membrane is not connected to the positive electrode of the power supply, and a titanium mesh of the same area (the titanium mesh is not in contact with the anode) is arranged at the anode of the membrane for connecting the positive electrode of the power supply and forming a current.
The pollution degradation performance of other electrochemical methods, mainly electrocatalytic membranes, is shown in table 1. In the method listed in the utility model, the double-sided electrocatalytically-active ceramic membranes of the utility model require a relatively short time (2.165 s) to remove more than 90% of the contaminants and 68.7% of the Total Organic Carbon (TOC), showing the potential for rapid contaminant removal. In addition, the double-sided electrocatalytically-active ceramic membranes of the present utility model can eliminate multi-contaminant coexistence during one electrofiltration process (fig. 3 a). Then electrons extracted from phenol, carbamazepine, sulfamethoxazole and perfluoro caprylic acid are transferred to a cathode for electro-Fenton method production of OH, and the final removal rates are 93.23%, 80%, 58.94% and 24.83%, respectively. Furthermore, the removal rate of carbamazepine and phenol was 100% at microgram level in a single filtration process with the double-sided electrocatalytically active ceramic membranes of the present utility model (fig. 3 b). Thus, an effective charged membrane helps minimize the additional or synergistic negative impact of the coexistence of numerous contaminants on human health, as well as the ecological risk of micro-contaminants in the environment.
TABLE 1 comparative pollution removal for different electrochemical processes
In conclusion, the double-sided electrocatalytic active ceramic membrane provided by the utility model has a rapid decontamination rate and mineralization rate for organic pollution in water, is coexisting for micro-pollution, and is used for rapidly and efficiently removing the organic pollution in water. The double-sided electrocatalytic active ceramic membrane is suitable for multi-pollution coexistence and micro-pollution treatment, and is beneficial to reducing environmental risks.
The above embodiment is only a preferred embodiment of the present utility model, but it is not intended to limit the present utility model. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present utility model. Therefore, all the technical schemes obtained by adopting the equivalent substitution or equivalent transformation are within the protection scope of the utility model.
Claims (8)
1. The double-sided electrocatalytic active ceramic membrane is characterized by comprising an insulating substrate, an electrocatalytic membrane anode layer and a cathode layer, wherein the insulating substrate is an insulating ceramic membrane with the aperture of 1-5 microns; the anode layer is a conductive coating sputtered on one side of the ceramic film and is used for connecting with the positive electrode of a power supply; the cathode layer is a catalyst layer deposited on the other side of the ceramic membrane and is used for connecting with a power supply cathode; the catalyst is a heterogeneous catalyst with electro-Fenton activity;
the material of the conductive coating is Ti of magneli phase 4 O 7 The method comprises the steps of carrying out a first treatment on the surface of the The heterogeneous catalyst with the electro-Fenton activity is an iron-based heterogeneous catalyst; the iron-based heterogeneous catalyst is copper ferrite;
the preparation method of the double-sided electrocatalytically-active ceramic membrane comprises the following steps:
s1, taking an insulating ceramic film as a substrate, dissolving copper nitrate, ferric nitrate, citric acid and ethylene glycol in water to form sol, continuously stirring to form a gel precursor, coating the gel precursor on one side of the substrate to form a film, and heating to 350-450 ℃ in a gradient manner to calcine the gel precursor to form a catalyst layer serving as a cathode layer;
s2, sputtering a titanium dioxide coating on the other side of the substrate film to serve as an anode layer, so that the ceramic film with double-sided electrocatalytically active properties is obtained.
2. The double-sided electrocatalytically-active ceramic membrane of claim 1, wherein the sol is prepared by dissolving copper nitrate, ferric nitrate, citric acid and ethylene glycol in deionized water at a concentration of 0.02mol/L copper nitrate, 0.04mol/L ferric nitrate, 0.072mol/L citric acid and 0.144mol/L ethylene glycol, respectively.
3. The double-sided electrocatalytically-active ceramic film as claimed in claim 1, wherein the sol is stirred at 60-100 ℃ for 4-6 hours to form a gel-like precursor.
4. The two-sided electrocatalytically-active ceramic film of claim 1, wherein the precursor is spun on three rounds of spin coating, each round of spin coating placing 0.1-0.7 mL of precursor on the upper surface of the base ceramic film, and then spin coating 30s with a spin coater at 500-6000 rpm.
5. The double-sided electrocatalytically-active ceramic membrane as claimed in claim 1, wherein the calcination procedure is completed by gradually heating at a heating rate of 2-7 ℃/min for 1.5 hours at 100 ℃,300 ℃ and 450 ℃ respectively during the calcination procedure.
6. The double-sided electrocatalytically-active ceramic film as claimed in claim 1, wherein the sputtering method of the titanium suboxide coating is laser sputtering; the technological parameters of laser sputtering are 350-550A of current, 55-65V of voltage, 45-55L/min of argon flow, 3-5L/min of hydrogen flow, 20-50 g/min of titanium dioxide powder supply rate and 70-100 mm of sputtering distance.
7. An application of a double-sided electrocatalytically-active ceramic membrane in water treatment is characterized in that:
introducing a solution to be treated containing organic pollutant molecules into treatment equipment for treatment; the treatment apparatus forms a supply side and an outflow side that are not directly connected with the double-sided electrocatalytically-active ceramic membrane of claim 1, the supply side being located on the anode layer side and the outflow side being located on the cathode layer side; the anode layer is connected with a power supply anode, and the cathode layer is connected with a power supply cathode; the solution to be treated is introduced from the supply side, organic pollutant molecules therein sequentially pass through the anode layer, the ceramic membrane and the cathode layer, are removed through direct anode oxidation and indirect cathode oxidation reactions, and finally are discharged from the outflow meter.
8. The use of a double-sided electrocatalytically-active ceramic membrane according to claim 7, wherein the solution to be treated is medical wastewater, printing wastewater or domestic wastewater containing multi-pollution co-organic pollutants; the organic pollutant molecules in the medical wastewater, the printing and dyeing wastewater or the domestic wastewater are one or more of phenol, sulfamethoxazole, carbamazepine and perfluoro caprylic acid.
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| CN107930414A (en) * | 2017-11-06 | 2018-04-20 | 中国矿业大学(北京) | A kind of electrochemical membrane, preparation method and reaction unit for being suitable for processing strong brine |
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| CN111054341A (en) * | 2020-01-10 | 2020-04-24 | 北京工业大学 | Preparation method and application of bimetal oxide loaded activated carbon fiber composite electrode |
| US20200407248A1 (en) * | 2019-06-25 | 2020-12-31 | California Institute Of Technology | Reactive electrochemical membrane for wastewater treatment |
| CN113019082A (en) * | 2021-01-11 | 2021-06-25 | 东莞市普锐美泰环保科技有限公司 | Device and method for degrading gaseous organic pollutants by electrochemical method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107930414A (en) * | 2017-11-06 | 2018-04-20 | 中国矿业大学(北京) | A kind of electrochemical membrane, preparation method and reaction unit for being suitable for processing strong brine |
| US20200407248A1 (en) * | 2019-06-25 | 2020-12-31 | California Institute Of Technology | Reactive electrochemical membrane for wastewater treatment |
| CN110820030A (en) * | 2019-11-14 | 2020-02-21 | 西安建筑科技大学 | Titanium-based PbO for preparing conducting ceramic membrane intermediate layer based on in-situ thermal reaction2Anode preparation method |
| CN111054341A (en) * | 2020-01-10 | 2020-04-24 | 北京工业大学 | Preparation method and application of bimetal oxide loaded activated carbon fiber composite electrode |
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