CN114162912A - Preparation method of titanium dioxide particle electrode loaded with high {001} crystal face - Google Patents
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Abstract
A preparation method of a titanium dioxide particle electrode loaded with a high {001} crystal face is disclosed, wherein the particle electrode is composed of granular activated carbon and titanium dioxide loaded on the granular activated carbon and having a high {001} crystal face, and the preparation method comprises the following steps: the method comprises the steps of activated carbon pretreatment, hydrothermal reaction of a mixture of powdered activated carbon and titanium tetrafluoride, high-temperature heat treatment, extrusion molding of granular activated carbon and the like, wherein titanium tetrafluoride is used as a titanium source, and a {001} crystal face with high surface energy can be stably grown on titanium dioxide in a fluorine environment by utilizing higher binding energy between fluorine and titanium, so that the prepared particle electrode can remarkably improve electrocatalytic oxidation activity, promote degradation of organic pollutants difficult to biochemically generate, reduce treatment time and prolong service life in a three-dimensional electrolytic system in which the particle electrode is applied; the material is filled into a fixed bed of an up-flow three-dimensional electrode reactor to carry out an electrolytic oxidation experiment of electrolyzing the acid orange 7, and the removal rate of the acid orange 7 after 5min of electrolysis can reach 91.2%.
Description
Technical Field
The invention belongs to the field of particle electrode preparation, and particularly relates to a preparation method of a titanium dioxide particle electrode loaded with a high {001} crystal face.
Background
The industrial development of China is rapid, the national economic development and the improvement of material civilization are greatly driven, but at the same time, the direct discharge or substandard discharge of the industrial production wastewater not only causes serious environmental pollution, but also harms the physical health of people. According to the statistical data of the ministry of ecological environment of China, the discharge amount of industrial wastewater in China in 2018 still reaches 175 hundred million tons, wherein the discharge amount comprises a plurality of industries such as papermaking, printing and dyeing, pharmacy, chemical engineering and the like. The industrial wastewater has the characteristics of large water quantity, complex components, and various organic pollutants which are difficult to be biochemically degraded, such as colorant, dye, organic raw material, auxiliary agent and the like.
At present, methods for treating organic pollutants in industrial wastewater mainly comprise flocculation, membrane separation, photocatalysis, laser catalysis, advanced oxidation technology and electrochemical catalytic oxidation technology, wherein the electrochemical catalytic oxidation technology has the advantages of good treatment effect, simple process flow and small occupied area and is widely applied. The three-dimensional electrode method is to fill granular electrode materials, namely the third electrode, on the basis of the two-dimensional electrolytic cell, and compared with the two-dimensional electrode method, the three-dimensional electrode method has the advantages of reducing mass transfer resistance, improving current efficiency and space-time yield, reducing energy consumption and the like. The particle electrodes are polarized in an electric field, so that particles with opposite charges are enriched on two different surfaces of the particles, a micro-electrolysis cell is formed, and the efficiency of directly oxidizing organic matters in an electrolysis bath is improved; secondly, the particle electrode has larger specific surface area and can carry out effective physical adsorption and electric adsorption on organic pollutants; by carrying out catalyst loading on the particle electrode and utilizing the catalyst to catalyze water or oxygen to generate hydroxyl radicals, the concentration of the hydroxyl radicals in a system is improved, and the indirect catalysis effect on organic pollutants is enhanced.
Anatase type TiO2The crystal has important application value in the aspects of photocatalytic water decomposition and photocatalytic degradation of organic pollutants, but has little application research in the aspect of electrocatalytic oxidation of organic pollutants, mainly because TiO prepared by the prior art2Crystal surface throughIs usually composed of thermodynamically stable {101} plane (94%), and contains only a small amount of {001} crystal plane, resulting in poor electrical conductivity and low electrocatalytic activity. Therefore, how to prepare TiO accurately and controllably2The specific crystal face of the crystal, and the development of high-performance particle electrodes have important significance for the treatment of industrial wastewater.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a titanium dioxide particle electrode loaded with a high {001} crystal face.
The invention adopts the following technical scheme:
a preparation method of a titanium dioxide particle electrode loaded with a high {001} crystal face is disclosed, wherein the particle electrode is composed of granular activated carbon and titanium dioxide loaded on the granular activated carbon and having a high {001} crystal face, and the preparation method comprises the following steps:
step one, pretreatment of activated carbon: boiling powdered activated carbon and dilute hydrochloric acid solution at 100 ℃ for 2h, cooling, filtering, washing with deionized water until the pH of the filtrate is neutral, and then vacuum-drying at 110 ℃ for 24 h;
step two, hydrothermal reaction: dissolving titanium tetrafluoride in deionized water, adding a hydrochloric acid solution and sodium chloride solid particles, uniformly stirring, adding the powdered activated carbon obtained by the first step, uniformly mixing and stirring, pouring into a reaction kettle with polytetrafluoroethylene, and treating at 200 ℃ for 2-6 hours, wherein the molar ratio of the titanium tetrafluoride to the hydrochloric acid solution to the sodium chloride is 3-5:1:80, and the mass ratio of the titanium tetrafluoride to the powdered activated carbon is 1-2: 30;
step three, high-temperature heat treatment: filtering the mixed solution obtained by the reaction in the step two, washing with deionized water for 5-6 times, drying in vacuum at 110 ℃ for 20h, and then carrying out heat treatment at 450 ℃ for 2h to obtain modified activated carbon;
and step four, uniformly mixing and stirring the modified activated carbon obtained in the step three and coal tar, carrying out extrusion forming, placing at 110 ℃ for drying, and then carbonizing at 400 ℃ for 2h to obtain the particle electrode loaded with the titanium dioxide with the high {001} crystal face.
Further, the powdered activated carbon is made of coconut shells, fruit shells, wood or coal base.
Furthermore, the particle size of the powdered activated carbon is less than 200 meshes, the iodine adsorption value is greater than 950mg/L, and the methylene blue adsorption value is 10-15 ml.
Further, in the first step, the concentration of the dilute hydrochloric acid aqueous solution is 0.05-0.1 mol/L.
Further, in the second step, the concentration of the hydrochloric acid solution is 0.1 mol/L.
Further, in the fourth step, the content of the coal tar is 5-10% of the mass of the modified activated carbon.
Further, the crystal form of the titanium dioxide is anatase.
As can be seen from the above description of the present invention, compared with the prior art, the beneficial effects of the present invention are:
firstly, titanium tetrafluoride is used as a titanium source, and high bonding energy between fluorine and titanium is utilized to enable titanium dioxide to stably grow a {001} crystal face with high surface energy in a fluorine environment, so that the prepared particle electrode can obviously improve the electrocatalytic oxidation activity, promote the degradation of organic pollutants difficult to biochemically generate, reduce the treatment time and prolong the service life in a three-dimensional electrolytic system in which the particle electrode is applied; filling the mixture into a fixed bed of an up-flow three-dimensional electrode reactor to perform an electrolytic oxidation experiment of electrolyzing the acid orange 7, wherein the removal rate of the acid orange 7 after 5min of electrolysis can reach 91.2%;
secondly, adding sodium chloride solid particles to provide a stable environment for the stable growth of the {001} crystal face with high surface energy of titanium dioxide, and ensuring the characteristics of the prepared particle electrode;
thirdly, the coal tar is used as an adhesive to prepare the formed activated carbon electrode particles, so that the mechanical strength is high, and the particles cannot be lost or block a water outlet due to crushing in the actual application process;
fourthly, the powder activated carbon is washed by using dilute hydrochloric acid, so that inorganic ash and organic impurities in the pore channel of the activated carbon are effectively removed, the loading rate of the titanium dioxide is improved, and the titanium dioxide is firmly fixed in the pore channel.
Detailed Description
The invention is further described below by means of specific embodiments.
A titanium dioxide particle electrode loaded with high {001} crystal face is composed of granular activated carbon and titanium dioxide loaded on the granular activated carbon and having a high {001} crystal face, wherein the crystal form of the titanium dioxide is anatase; specifically, the powdered activated carbon is prepared from coconut shells, fruit shells, wood or coal-based materials, the particle size of the powdered activated carbon is less than 200 meshes, the iodine adsorption value is greater than 950mg/L, and the methylene blue adsorption value is 10-15 ml.
The preparation method comprises the following steps:
step one, pretreatment of activated carbon: boiling powdered activated carbon and dilute hydrochloric acid solution at 100 ℃ for 2h, cooling, filtering, washing with deionized water until the pH of the filtrate is neutral, and then vacuum-drying at 110 ℃ for 24 h;
step two, hydrothermal reaction: dissolving titanium tetrafluoride in deionized water, adding 0.1mol/L hydrochloric acid solution and sodium chloride solid particles, stirring uniformly, adding the powdered activated carbon obtained by the first step, mixing and stirring uniformly, pouring into a reaction kettle with polytetrafluoroethylene, and treating at 200 ℃ for 2-6h, wherein the molar ratio of the titanium tetrafluoride to the hydrochloric acid solution to the sodium chloride is 3-5:1:80, and the mass ratio of the titanium tetrafluoride to the powdered activated carbon is 1-2: 30;
step three, high-temperature heat treatment: filtering the mixed solution obtained by the reaction in the step two, washing with deionized water for 5-6 times, drying in vacuum at 110 ℃ for 20h, and then carrying out heat treatment at 450 ℃ for 2h to obtain modified activated carbon;
and step four, uniformly mixing and stirring the modified activated carbon obtained in the step three and coal tar, carrying out extrusion forming, placing at 110 ℃ for drying, and then carbonizing at 400 ℃ for 2h to obtain the particle electrode loaded with the titanium dioxide with the high {001} crystal face.
Specifically, in the step one, the concentration of the dilute hydrochloric acid aqueous solution is 0.05-0.1 mol/L.
In the fourth step, the content of the coal tar is 5-10% of the mass of the modified activated carbon.
Example 1
A titanium dioxide particle electrode loaded with a high {001} crystal face is composed of granular activated carbon and titanium dioxide loaded on the granular activated carbon and having a high {001} crystal face, wherein the crystal form of the titanium dioxide is anatase.
The preparation method comprises the following steps:
step one, pretreatment of activated carbon: boiling powdered activated carbon and dilute hydrochloric acid solution at 100 ℃ for 2h, cooling, filtering, washing with deionized water until the pH of the filtrate is neutral, and then vacuum-drying at 110 ℃ for 24 h;
step two, hydrothermal reaction: dissolving 0.3g of titanium tetrafluoride in 100ml of deionized water, adding 8ml of hydrochloric acid solution with the concentration of 0.1mol/L and 3.77g of sodium chloride solid particles, uniformly stirring, adding 9g of powdered activated carbon obtained by the first step, uniformly mixing and stirring, pouring into a reaction kettle with polytetrafluoroethylene, and treating for 2 hours at 200 ℃, wherein the molar ratio of the titanium tetrafluoride to the hydrochloric acid solution to the sodium chloride is 3:1:80, and the mass ratio of the titanium tetrafluoride to the powdered activated carbon is 1: 30;
step three, high-temperature heat treatment: filtering the mixed solution obtained by the reaction in the step two, washing with deionized water for 5-6 times, drying in vacuum at 110 ℃ for 20h, and then carrying out heat treatment at 450 ℃ for 2h to obtain modified activated carbon;
and step four, uniformly mixing and stirring the modified activated carbon obtained in the step three and coal tar, carrying out extrusion forming, placing at 110 ℃ for drying, and then carbonizing at 400 ℃ for 2h to obtain the particle electrode loaded with the titanium dioxide with the high {001} crystal face.
Specifically, in the step one, the concentration of the dilute hydrochloric acid aqueous solution is 0.05 mol/L.
In the fourth step, the content of the coal tar is 5 percent of the mass of the modified activated carbon.
The particle electrode prepared in the example is filled in a fixed bed of an up-flow three-dimensional electrode reactor to perform an electrolytic oxidation experiment of electrolyzing acid orange 7, wherein the electrolyte is 10g/L Na2SO4 solution, graphite is adopted as a cathode and an anode, the working voltage is 10V, and the removal rate of the acid orange 7 after 5min of electrolysis reaches 88.3%.
Example 2
A titanium dioxide particle electrode loaded with a high {001} crystal face is composed of granular activated carbon and titanium dioxide loaded on the granular activated carbon and having a high {001} crystal face, wherein the crystal form of the titanium dioxide is anatase.
The preparation method comprises the following steps:
step one, pretreatment of activated carbon: boiling powdered activated carbon and dilute hydrochloric acid solution at 100 ℃ for 2h, cooling, filtering, washing with deionized water until the pH of the filtrate is neutral, and then vacuum-drying at 110 ℃ for 24 h;
step two, hydrothermal reaction: dissolving 0.3g of titanium tetrafluoride in 100ml of deionized water, adding 8ml of hydrochloric acid solution with the concentration of 0.1mol/L and 3.77g of sodium chloride solid particles, uniformly stirring, adding 9g of powdered activated carbon obtained by the first step, uniformly mixing and stirring, pouring into a reaction kettle with polytetrafluoroethylene, and treating at 200 ℃ for 4 hours, wherein the molar ratio of the titanium tetrafluoride to the hydrochloric acid solution to the sodium chloride is 3:1:80, and the mass ratio of the titanium tetrafluoride to the powdered activated carbon is 1: 30;
step three, high-temperature heat treatment: filtering the mixed solution obtained by the reaction in the step two, washing with deionized water for 5-6 times, drying in vacuum at 110 ℃ for 20h, and then carrying out heat treatment at 450 ℃ for 2h to obtain modified activated carbon;
and step four, uniformly mixing and stirring the modified activated carbon obtained in the step three and coal tar, carrying out extrusion forming, placing at 110 ℃ for drying, and then carbonizing at 400 ℃ for 2h to obtain the particle electrode loaded with the titanium dioxide with the high {001} crystal face.
Specifically, in the step one, the concentration of the dilute hydrochloric acid aqueous solution is 0.1 mol/L.
In the fourth step, the content of the coal tar is 10 percent of the mass of the modified activated carbon.
The particle electrode prepared in the example is filled in a fixed bed of an up-flow three-dimensional electrode reactor to perform an electrolytic oxidation experiment of electrolyzing acid orange 7, wherein the electrolyte is 10g/L Na2SO4 solution, graphite is adopted as a cathode and an anode, the working voltage is 10V, and the removal rate of acid orange 7 after 5min of electrolysis reaches 89.7%.
Example 3
A titanium dioxide particle electrode loaded with a high {001} crystal face is composed of granular activated carbon and titanium dioxide loaded on the granular activated carbon and having a high {001} crystal face, wherein the crystal form of the titanium dioxide is anatase.
The preparation method comprises the following steps:
step one, pretreatment of activated carbon: boiling powdered activated carbon and dilute hydrochloric acid solution at 100 ℃ for 2h, cooling, filtering, washing with deionized water until the pH of the filtrate is neutral, and then vacuum-drying at 110 ℃ for 24 h;
step two, hydrothermal reaction: dissolving 0.3g of titanium tetrafluoride in deionized water, adding 8ml of hydrochloric acid solution with the concentration of 0.1mol/L and 3.77g of sodium chloride solid particles, uniformly stirring, adding 9g of powdered activated carbon obtained by the first step, uniformly mixing and stirring, pouring into a reaction kettle with polytetrafluoroethylene, and treating for 6 hours at 200 ℃, wherein the molar ratio of the titanium tetrafluoride to the hydrochloric acid solution to the sodium chloride is 3:1:80, and the mass ratio of the titanium tetrafluoride to the powdered activated carbon is 1: 30;
step three, high-temperature heat treatment: filtering the mixed solution obtained by the reaction in the step two, washing with deionized water for 5-6 times, drying in vacuum at 110 ℃ for 20h, and then carrying out heat treatment at 450 ℃ for 2h to obtain modified activated carbon;
and step four, uniformly mixing and stirring the modified activated carbon obtained in the step three and coal tar, carrying out extrusion forming, placing at 110 ℃ for drying, and then carbonizing at 400 ℃ for 2h to obtain the particle electrode loaded with the titanium dioxide with the high {001} crystal face.
Specifically, in the step one, the concentration of the dilute hydrochloric acid aqueous solution is 0.08 mol/L.
In the fourth step, the content of the coal tar is 8 percent of the mass of the modified activated carbon.
The particle electrode prepared in the example is filled in a fixed bed of an up-flow three-dimensional electrode reactor to perform an electrolytic oxidation experiment of electrolyzing acid orange 7, wherein the electrolyte is 10g/L Na2SO4 solution, graphite is adopted as a cathode and an anode, the working voltage is 10V, and the removal rate of acid orange 7 after 5min of electrolysis reaches 91.2%.
Example 4
A titanium dioxide particle electrode loaded with a high {001} crystal face is composed of granular activated carbon and titanium dioxide loaded on the granular activated carbon and having a high {001} crystal face, wherein the crystal form of the titanium dioxide is anatase.
The preparation method comprises the following steps:
step one, pretreatment of activated carbon: boiling powdered activated carbon and dilute hydrochloric acid solution at 100 ℃ for 2h, cooling, filtering, washing with deionized water until the pH of the filtrate is neutral, and then vacuum-drying at 110 ℃ for 24 h;
step two, hydrothermal reaction: dissolving 0.4g of titanium tetrafluoride in deionized water, adding 8ml of hydrochloric acid solution with the concentration of 0.1mol/L and 3.77g of sodium chloride solid particles, uniformly stirring, adding 8g of powdered activated carbon obtained by the first step, uniformly mixing and stirring, pouring into a reaction kettle with polytetrafluoroethylene, and treating at 200 ℃ for 2 hours, wherein the molar ratio of the titanium tetrafluoride to the hydrochloric acid solution to the sodium chloride is 4:1:80, and the mass ratio of the titanium tetrafluoride to the powdered activated carbon is 1.5: 30;
step three, high-temperature heat treatment: filtering the mixed solution obtained by the reaction in the step two, washing with deionized water for 5-6 times, drying in vacuum at 110 ℃ for 20h, and then carrying out heat treatment at 450 ℃ for 2h to obtain modified activated carbon;
and step four, uniformly mixing and stirring the modified activated carbon obtained in the step three and coal tar, carrying out extrusion forming, placing at 110 ℃ for drying, and then carbonizing at 400 ℃ for 2h to obtain the particle electrode loaded with the titanium dioxide with the high {001} crystal face.
Specifically, in the step one, the concentration of the dilute hydrochloric acid aqueous solution is 0.08 mol/L.
In the fourth step, the content of the coal tar is 8 percent of the mass of the modified activated carbon.
The particle electrode prepared in the example is filled in a fixed bed of an up-flow three-dimensional electrode reactor to perform an electrolytic oxidation experiment of electrolyzing acid orange 7, wherein the electrolyte is 10g/L Na2SO4 solution, graphite is adopted as a cathode and an anode, the working voltage is 10V, and the removal rate of acid orange 7 after 5min of electrolysis reaches 90.2%.
Example 5
A titanium dioxide particle electrode loaded with a high {001} crystal face is composed of granular activated carbon and titanium dioxide loaded on the granular activated carbon and having a high {001} crystal face, wherein the crystal form of the titanium dioxide is anatase.
The preparation method comprises the following steps:
step one, pretreatment of activated carbon: boiling powdered activated carbon and dilute hydrochloric acid solution at 100 ℃ for 2h, cooling, filtering, washing with deionized water until the pH of the filtrate is neutral, and then vacuum-drying at 110 ℃ for 24 h;
step two, hydrothermal reaction: dissolving 0.5g of titanium tetrafluoride in deionized water, adding 8ml of hydrochloric acid solution with the concentration of 0.1mol/L and 3.77g of sodium chloride solid particles, uniformly stirring, adding 7.5g of powdered activated carbon obtained by the first step, uniformly mixing and stirring, pouring into a reaction kettle with polytetrafluoroethylene, and treating for 6 hours at 200 ℃, wherein the molar ratio of the titanium tetrafluoride to the hydrochloric acid solution to the sodium chloride is 5:1:80, and the mass ratio of the titanium tetrafluoride to the powdered activated carbon is 2: 30;
step three, high-temperature heat treatment: filtering the mixed solution obtained by the reaction in the step two, washing with deionized water for 5-6 times, drying in vacuum at 110 ℃ for 20h, and then carrying out heat treatment at 450 ℃ for 2h to obtain modified activated carbon;
and step four, uniformly mixing and stirring the modified activated carbon obtained in the step three and coal tar, carrying out extrusion forming, placing at 110 ℃ for drying, and then carbonizing at 400 ℃ for 2h to obtain the particle electrode loaded with the titanium dioxide with the high {001} crystal face.
Specifically, in the step one, the concentration of the dilute hydrochloric acid aqueous solution is 0.08 mol/L.
In the fourth step, the content of the coal tar is 8 percent of the mass of the modified activated carbon.
The particle electrode prepared in the example is filled in a fixed bed of an up-flow three-dimensional electrode reactor to perform an electrolytic oxidation experiment of electrolyzing acid orange 7, wherein the electrolyte is 10g/L Na2SO4 solution, graphite is adopted as a cathode and an anode, the working voltage is 10V, and the removal rate of acid orange 7 after 5min of electrolysis reaches 91.1%.
Titanium tetrafluoride is used as a titanium source, and high bonding energy between fluorine and titanium is utilized to enable titanium dioxide to stably grow a {001} crystal face with high surface energy in a fluorine environment, so that the prepared particle electrode can obviously improve electrocatalytic oxidation activity, promote degradation of organic pollutants difficult to biochemically generate, reduce treatment time and prolong service life in a three-dimensional electrolytic system applied by the particle electrode; the material is filled into a fixed bed of an up-flow three-dimensional electrode reactor to carry out an electrolytic oxidation experiment of electrolyzing the acid orange 7, and the removal rate of the acid orange 7 after 5min of electrolysis can reach 91.2%.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents and modifications within the scope of the description.
Claims (7)
1. A preparation method of a titanium dioxide particle electrode loaded with a high {001} crystal face is characterized by comprising the following steps: the particle electrode consists of granular activated carbon and titanium dioxide loaded on the granular activated carbon and having a high {001} crystal face, and the preparation method comprises the following steps:
step one, pretreatment of activated carbon: boiling powdered activated carbon and dilute hydrochloric acid solution at 100 ℃ for 2h, cooling, filtering, washing with deionized water until the pH of the filtrate is neutral, and then vacuum-drying at 110 ℃ for 24 h;
step two, hydrothermal reaction: dissolving titanium tetrafluoride in deionized water, adding a hydrochloric acid solution and sodium chloride solid particles, uniformly stirring, adding the powdered activated carbon obtained by the first step, uniformly mixing and stirring, pouring into a reaction kettle with polytetrafluoroethylene, and treating at 200 ℃ for 2-6 hours, wherein the molar ratio of the titanium tetrafluoride to the hydrochloric acid solution to the sodium chloride is 3-5:1:80, and the mass ratio of the titanium tetrafluoride to the powdered activated carbon is 1-2: 30;
step three, high-temperature heat treatment: filtering the mixed solution obtained by the reaction in the step two, washing with deionized water for 5-6 times, drying in vacuum at 110 ℃ for 20h, and then carrying out heat treatment at 450 ℃ for 2h to obtain modified activated carbon;
and step four, uniformly mixing and stirring the modified activated carbon obtained in the step three and coal tar, carrying out extrusion forming, placing at 110 ℃ for drying, and then carbonizing at 400 ℃ for 2h to obtain the particle electrode loaded with the titanium dioxide with the high {001} crystal face.
2. The preparation method of the titanium dioxide particle electrode loaded with high {001} crystal plane according to claim 1, wherein: the powdered activated carbon is made of coconut shells, fruit shells, wood or coal base.
3. The preparation method of the titanium dioxide particle electrode loaded with high {001} crystal plane according to claim 2, wherein: the particle size of the powdered activated carbon is less than 200 meshes, the iodine adsorption value is greater than 950mg/L, and the methylene blue adsorption value is 10-15 ml.
4. The preparation method of the titanium dioxide particle electrode loaded with high {001} crystal plane according to claim 1, wherein: in the first step, the concentration of the dilute hydrochloric acid aqueous solution is 0.05-0.1 mol/L.
5. The preparation method of the titanium dioxide particle electrode loaded with high {001} crystal plane according to claim 1, wherein: in the second step, the concentration of the hydrochloric acid solution is 0.1 mol/L.
6. The preparation method of the titanium dioxide particle electrode loaded with high {001} crystal plane according to claim 1, wherein: in the fourth step, the content of the coal tar is 5-10% of the mass of the modified activated carbon.
7. The preparation method of the titanium dioxide particle electrode loaded with high {001} crystal plane according to claim 1, wherein: the crystal form of the titanium dioxide is anatase.
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| CN115849521A (en) * | 2023-02-22 | 2023-03-28 | 深圳永清水务有限责任公司北京分公司 | Three-dimensional electrocatalytic oxidation electrode for sewage treatment and application thereof |
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