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CN112807995B - Device and method for degrading gaseous pollutants by electrochemical method - Google Patents

Device and method for degrading gaseous pollutants by electrochemical method Download PDF

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Publication number
CN112807995B
CN112807995B CN202110124234.7A CN202110124234A CN112807995B CN 112807995 B CN112807995 B CN 112807995B CN 202110124234 A CN202110124234 A CN 202110124234A CN 112807995 B CN112807995 B CN 112807995B
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electrode
gaseous pollutants
gaseous
pollutants
degrading
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CN112807995A (en
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刘超城
崔结东
严方升
刘德桃
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South China University of Technology SCUT
Shenzhen Puremate Technology Co Ltd
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South China University of Technology SCUT
Shenzhen Puremate Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium

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Abstract

The invention discloses a device and a method for degrading gaseous pollutants by an electrochemical method. The device for degrading gaseous pollutants by using the electrochemical method comprises a power supply, a first electrode, a second electrode and an induction electrode, wherein the first electrode and the second electrode are electrically connected to the power supply, the induction electrode is arranged between the first electrode and the second electrode, the induction electrode and the first electrode as well as the induction electrode and the second electrode are enclosed to form an airflow channel, and the induction electrode can generate active species when the power supply is switched on so as to degrade the gaseous pollutants in the airflow channel. The technical scheme of the invention can improve the degradation efficiency of the gaseous pollutants and is suitable for degrading the gaseous organic pollutants with poor water solubility.

Description

Device and method for degrading gaseous pollutants by electrochemical method
Technical Field
The invention relates to the technical field of gaseous pollutant degradation, in particular to a device and a method for degrading gaseous pollutants by an electrochemical method.
Background
The air mainly contains formaldehyde, benzene series, organic chloride, organic ketone, alcohol, ether,Gaseous pollutants such as petroleum hydrocarbon compounds, sulfur dioxide and nitrogen oxides not only cause pollution hazards to the atmospheric environment, but also seriously threaten the health of people. The degradation method for the gaseous pollutants mainly comprises an adsorption and fixation technology and a reaction degradation technology, wherein the reaction degradation technology can realize the degradation of volatile organic compounds, and the adopted catalyst material can be used for a long time, so the method is widely applied. The existing reaction degradation technology generally adopts low-temperature plasma and catalytic oxidation technology, has the problems of secondary pollution, catalyst service life and the like, and also adopts an electrochemical method in liquid-phase electrolyte to degrade gaseous pollutants, namely, the gaseous pollutants are introduced into the liquid-phase electrolyte, the gaseous pollutants are degraded by oxidation through an anode in the liquid-phase electrolyte and H is generated by cathodic electro-Fenton 2 O 2 Hydroxyl radicals are further generated to degrade gaseous pollutants, but the method has low degradation efficiency for degrading gaseous pollutants and is not suitable for electrochemically degrading gaseous organic pollutants with poor water solubility.
Disclosure of Invention
The invention mainly aims to provide a device and a method for degrading gaseous pollutants by an electrochemical method, aiming at improving the degradation efficiency of the gaseous pollutants and being suitable for degrading gaseous organic pollutants with poor water solubility.
In order to achieve the above purpose, the device for electrochemically degrading gaseous pollutants provided by the present invention includes a power supply, a first electrode, a second electrode, and an induction electrode, wherein the first electrode and the second electrode are both connected to the power supply, the induction electrode is disposed between the first electrode and the second electrode, and the induction electrode and the first electrode, the induction electrode and the second electrode all enclose to form an airflow channel, and the induction electrode can generate active species when the power supply is turned on, so as to degrade gaseous pollutants.
In an alternative embodiment, the induction electrode is a porous material electrode supporting a catalyst, and the catalyst is an iron-containing catalyst and a metal oxidant catalyst.
In an optional embodiment, the iron-containing catalyst is a composite catalyst of an iron-containing material and a porous conductive adsorption material carrier, wherein the iron-containing material is at least one of nano iron, ferric chloride, ferric oxide, ferroferric oxide, ferric nitrate and a metal organic framework material, and the porous conductive adsorption material carrier is at least one of nitrogen-doped carbon, carbon nitride, activated carbon, carbon nanotubes, graphene and graphite felt; and/or the metal oxide catalyst is at least one of a manganese oxide catalyst, a cobalt oxide catalyst, a copper oxide catalyst, an indium oxide catalyst, a titanium oxide catalyst and a titanium oxide catalyst.
In an alternative embodiment, the loading of the iron-containing catalyst is 0.1% to 50%, and the loading of the metal oxide catalyst is 0.1% to 50%.
In an optional embodiment, the first electrode is at least one of a stainless steel electrode, an iron electrode, a copper electrode, an aluminum alloy electrode, a copper alloy electrode, a zinc alloy electrode, a titanium foam supported titanium suboxide electrode, a platinum-based titanium electrode, an iridium-based titanium electrode, and an iridium-tantalum electrode; and/or the second electrode is at least one of a stainless steel electrode, an iron electrode, a copper electrode, an aluminum alloy electrode, a copper alloy electrode, a zinc alloy electrode, a titanium foam supported titanium suboxide electrode, a platinum-based titanium electrode, an iridium-based titanium electrode and an iridium tantalum electrode.
In an optional embodiment, the first electrode, the second electrode and the sensing electrode have the same shape, and the first electrode is at least one of a cylindrical sheet, a zigzag sheet, a long strip sheet, a circular sheet and a linear shape.
In an optional embodiment, a distance between the sensing electrode and the first electrode ranges from 0.1mm to 100mm, and a distance between the sensing electrode and the second electrode ranges from 0.1mm to 100mm.
In an optional embodiment, the device for degrading gaseous pollutants by using an electrochemical method further comprises an insulating support, and the first electrode, the second electrode and the sensing electrode are all fixed on the insulating support.
In an alternative embodiment, a plurality of devices for degrading gaseous pollutants by the electrochemical method are arranged, and the plurality of devices for degrading gaseous pollutants by the electrochemical method are arranged in series or in parallel.
In an alternative embodiment, a plurality of the devices for degrading gaseous pollutants by the electrochemical method are arranged in series or in parallel, and two adjacent sensing electrodes share one first electrode, and/or two adjacent sensing electrodes share one second electrode.
The invention also provides a method for removing gaseous pollutants by an electrochemical method, which is applied to the device for removing gaseous pollutants by the electrochemical method, and the method for degrading gaseous pollutants by the electrochemical method comprises the following steps:
applying a direct or alternating voltage between the first and second electrodes;
gaseous pollutants or air containing the gaseous pollutants are introduced into the airflow channel, and the induction electrode generates active species to degrade the gaseous pollutants.
In an optional embodiment, the voltage range of the direct current voltage or the alternating current voltage is 0.5V-30000V, and the temperature range in the process of removing the gaseous pollutants is controlled to be minus 20 ℃ to 120 ℃; and/or the flow rate of the gaseous pollutant or the air containing the gaseous pollutant ranges from 0.001m/s to 20m/s, the humidity ranges from 0% to 99.9%, and the oxygen volume content of the air containing the gaseous pollutant ranges from 2% to 28%.
According to the technical scheme, gaseous pollutants are degraded by adopting a catalytic mechanism of a gaseous three-dimensional electrode, wherein the three-dimensional electrode comprises a first electrode, a second electrode and an induction electrode, the first electrode and the second electrode are respectively and electrically connected to a power supply, the induction electrode is arranged between the first electrode and the second electrode, and the induction electrode and the first electrode, the induction electrode and the second electrode are enclosed to form an airflow channel. When gaseous pollutants are degraded, the first electrode and the second electrode are connected with a power supply, the gaseous pollutants or air containing the gaseous pollutants are introduced into the airflow channel, under the action of an electric field formed by voltage between the first electrode and the second electrode, induced charges are generated at two ends of the induction electrode, and redox reaction is generated on the surface of the induction electrode, so that active species such as hydroxyl radicals with high flux and strong oxidizing property are generated, and the active species can realize efficient and rapid decomposition on the gaseous pollutants or the gaseous pollutants in the air in the airflow channel, so that the purpose of degrading the gaseous pollutants is achieved. In addition, the induction electrode can realize the efficient degradation of organic matters with poor water solubility in air, and has a wide application range. The three-dimensional electrode is adopted to remove gaseous pollutants, the first electrode and the second electrode do not have the functions of a cathode and an anode of a conventional electrochemical reactor, the first electrode and the second electrode only have the function of providing an electric field, the induction electrode has the function of forming the induction cathode and the induction anode under the action of an external induction electric field, and can generate movement of positive and negative charges in the induction electric field, so that a key basis is provided for the redox reaction and the sustainable propulsion of catalytic metal ions, a proton exchange membrane is omitted, the preparation is convenient, the degradation efficiency and the space utilization rate are improved, and the reaction area is increased. In addition, the device for degrading the gaseous pollutants can realize the effect of removing the gaseous pollutants by the induction electrode, and provides a new technical approach for preventing and treating the atmospheric pollution and breaking through the indoor air purification industry.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a schematic structural diagram of an apparatus for electrochemically degrading gaseous pollutants according to the present invention;
FIG. 2 is a perspective view of a portion of FIG. 1 of an apparatus for electrochemically degrading gaseous pollutants in accordance with the present invention;
FIG. 3 is a schematic view of the construction of a plurality of combinations of FIG. 1 of the apparatus for electrochemically degrading gaseous pollutants according to the present invention;
FIG. 4 is a schematic view of another combination of the apparatus for electrochemically degrading gaseous pollutants according to the present invention;
FIG. 5 is a schematic view of an apparatus for electrochemically degrading gaseous pollutants according to the present invention, showing a plurality of combinations of the structures shown in FIG. 4;
FIG. 6 is a schematic cross-sectional view of the housing of FIGS. 4 and 5 illustrating an apparatus for electrochemically degrading gaseous pollutants according to the present invention;
FIG. 7 is a perspective view of a portion of another embodiment of the apparatus for electrochemically degrading gaseous pollutants according to the present invention.
The reference numbers illustrate:
reference numerals Name (R) Reference numerals Name (R)
1 A first electrode 6 Air inlet
2 A second electrode 7 Air outlet
3 Induction electrode 8 Insulating support
4 A air flow channel 9 Electrode assembly
5 B airflow channel
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that all directional indicators (such as upper, lower, left, right, front, and rear … …) in the embodiment of the present invention are only used to explain the relative position relationship between the components, the movement situation, and the like in a specific posture (as shown in the drawing), and if the specific posture is changed, the directional indicator is changed accordingly.
In addition, the descriptions related to "first", "second", etc. in the present invention are only for descriptive purposes and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the present invention, unless otherwise expressly stated or limited, the terms "connected," "secured," and the like are to be construed broadly, and for example, "secured" may be a fixed connection, a removable connection, or an integral part; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood according to specific situations by those of ordinary skill in the art.
In addition, the technical solutions in the embodiments of the present invention may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination of technical solutions should not be considered to exist, and is not within the protection scope of the present invention.
The invention provides a device for degrading gaseous pollutants by an electrochemical method, which adopts a three-dimensional electrode and is used for degrading the gaseous pollutants or gaseous pollutants in air, wherein the gaseous pollutants comprise gaseous organic pollutants.
The three-dimensional electrode is formed by filling a certain kind of granular filler or other crumbly electrode material between two-dimensional electrodes, so that the surfaces of the two-dimensional electrodes are charged under the action of an electric field to form countless tiny electrochemical systems, thereby promoting the progress of electrochemical reaction and forming a new electrode (three-dimensional electrode). However, the application of the three-dimensional electrode is mainly applied to the field of wastewater degradation or reaction in an aqueous phase, and the application of removing gaseous pollutants in the air is not available. The three-dimensional electrode is applied to degrading gaseous pollutants or gaseous pollutants in the air, so that the application field of the three-dimensional electrode for treating the pollutants is widened.
In an embodiment of the present invention, the apparatus for electrochemically degrading gaseous pollutants includes a power supply, a first electrode, a second electrode, and an induction electrode, wherein the first electrode and the second electrode are respectively electrically connected to the power supply, the induction electrode is disposed between the first electrode and the second electrode, and the induction electrode, the first electrode, the induction electrode, and the second electrode enclose to form an airflow channel, the through pore channel of the induction electrode itself also forms the airflow channel, and the induction electrode can generate active species when the power supply is turned on, so as to degrade gaseous pollutants in the airflow channel.
Referring to fig. 1, the sensing electrodes 3 are spaced between the first electrode 1 and the second electrode 2, the a airflow channel 4 is a flow channel formed between the first electrode 1 and the sensing electrodes 3, and the B airflow channel 5 is a flow channel formed between the second electrode 2 and the sensing electrodes 3. The three-dimensional electrode is adopted, the induction electrode is arranged between the first electrode 1 and the second electrode 2 and is respectively enclosed with the first electrode 1 and the second electrode 2 to form an airflow channel, when gaseous pollutants are degraded, the first electrode 1 and the second electrode 2 are powered on, and the gaseous pollutants or air containing the gaseous pollutants are introduced into the airflow channel, under the action of an electric field formed by voltage between the first electrode 1 and the second electrode 2, induction charges are generated at two ends of the induction electrode and are subjected to redox reaction on the surface of the induction electrode to generate active species such as high-flux strong-oxidability hydroxyl radicals, and the active species can realize efficient and rapid decomposition on the gaseous pollutants in the airflow channel to achieve the purpose of purification. Especially gaseous organic pollutants in the air are decomposed, a large number of reaction active sites are generated on the surface and inside of the induction electrode, and the organic pollutants are finally degraded into H through direct oxidation or indirect oxidation 2 O and CO 2 So as to realize the degradation of the organic pollutants.
It can be understood that, in the technical solution of the present invention, the gaseous pollutants and the gaseous pollutants in the air are degraded by using the three-dimensional electrode, wherein the three-dimensional electrode includes a first electrode, a second electrode and an induction electrode, the first electrode and the second electrode are respectively electrically connected to a power supply (including a dc power supply and an ac power supply), the induction electrode is disposed between the first electrode and the second electrode, and the induction electrode and the first electrode, the induction electrode and the second electrode all enclose to form an airflow channel. When gaseous pollutants are removed, the first electrode and the second electrode are connected with a power supply, the gaseous pollutants or air containing the gaseous pollutants are introduced into the airflow channel, under the action of an electric field formed by voltage between the first electrode and the second electrode, induction charges are generated at two ends of the induction electrode, redox reaction is carried out on the surface of the induction electrode, active species such as high-flux strong-oxidability hydroxyl radicals are generated, and the active species can realize efficient and rapid decomposition on the gaseous pollutants or the air containing the gaseous pollutants in the airflow channel, so that the purpose of degrading the gaseous pollutants is achieved. In addition, the induction electrode can realize the efficient removal of organic matters with poor water solubility in air, and has a wide application range. The three-dimensional electrode is adopted to degrade gaseous pollutants, wherein the first electrode and the second electrode are not an anode and a cathode in a conventional electrochemical reactor, the first electrode and the second electrode play a role in providing an electric field, the functions of the cathode and the anode are realized inside the induction electrode, and the movement of positive and negative charges can be generated in the induction electric field, so that a key basis is provided for the redox reaction and the sustainable propulsion of catalytic metal ions, a proton exchange membrane is omitted, the preparation is convenient, the degradation rate and the space utilization rate are improved, and the reaction area is increased. In addition, the device for degrading the gaseous pollutants can realize the effect of the induction electrode on the degradation of the gaseous pollutants, and provides a new technical approach for the prevention and control of the atmospheric pollution and the breakthrough of the indoor air purification industry.
In an alternative embodiment, the induction electrode is a porous material electrode supporting a catalyst, the catalyst being an iron-containing catalyst and a metal oxidant catalyst.
The induction electrode is made of a porous material electrode loaded with a catalyst, the porous material induction electrode can efficiently reduce oxygen input in air or manually to generate hydrogen peroxide in a high-flux manner, the hydrogen peroxide and the iron-containing and metal oxide catalyst generate high-flux active species such as hydroxyl radicals through an electro-Fenton reaction, the active species such as the hydroxyl radicals rapidly react with gaseous organic pollutants, and the organic pollutants are degraded to finally generate water and carbon dioxide, so that the air purification effect is realized.
It should be noted that both the iron-containing catalyst and the metal oxide catalyst have high activity, good stability and dispersibility, and are helpful for improving the removal rate of pollutants. The catalyst can efficiently catalyze and decompose various gaseous pollutants, and has a wide application range.
In an optional embodiment, the iron-containing catalyst is a composite catalyst comprising an iron-containing material and a porous conductive adsorption material carrier, wherein the iron-containing material is at least one of nano iron, ferric chloride, ferric oxide, ferroferric oxide, ferric nitrate and a metal organic framework material, and the porous conductive adsorption material carrier is at least one of nitrogen-doped carbon, carbon nitride, activated carbon, carbon nanotubes, graphene and graphite felt.
The iron-containing catalyst takes a porous material as a carrier, has a large specific surface area, and can better load the iron-containing catalyst, so that the obtained composite material catalyst has high activity and good stability, and is beneficial to the improvement of the removal rate of pollutants. Wherein, the iron-containing material can be selected from one or more combinations of the materials, and the porous material carrier is selected from one or more combinations of the materials.
In alternative embodiments, the loading of the iron-containing catalyst ranges from 0.1wt% to 50wt%, such as 0.1wt%, 1wt%, 10wt%, 20wt%, 30wt%, 40wt%, or 50wt% loading of the iron-containing catalyst. Preferably, the loading of iron containing catalyst is 1wt% to 5wt%, such as 1wt%, 2wt%, 3wt%, 4wt% or 5wt%.
In an alternative embodiment, the metal oxide catalyst is at least one of a manganese oxide catalyst, a cobalt oxide catalyst, a copper oxide catalyst, an indium oxide catalyst, and a titanium oxide catalyst.
In alternative embodiments, the metal oxide catalyst loading is from 0.1wt% to 50wt%. The loading amount to the metal oxide catalyst is 0.1wt%, 1wt%, 10wt%, 20wt%, 30wt%, 40wt%, or 50wt%. Preferably, the loading of the metal oxide catalyst is from 1wt% to 5wt%, such as 1wt%, 2wt%, 3wt%, 4wt% or 5wt%.
In alternative embodiments, the porous material electrode is one or more of a carbon paper electrode, a carbon cloth electrode, a carbon fiber cloth electrode, a carbon-polytetrafluoroethylene electrode, a carbon particle cloth electrode, and an activated carbon cloth electrode.
According to the invention, the induction electrode adopts the porous material electrode loaded with the iron-containing and metal oxide catalyst, the porous material electrode can reduce oxygen at high flux and high efficiency to generate hydrogen peroxide, the metal oxide catalyst can reduce the pH requirement on the reaction environment, the hydrogen peroxide, the iron-containing and metal oxide generate active species such as hydroxyl radicals through the Fenton reaction, and the active species such as the hydroxyl radicals react with gaseous pollutants to realize effective removal of the gaseous pollutants. Therefore, the device for removing the gaseous pollutants can realize the effect of the induction electrode on removing the gaseous pollutants and realize the catalytic degradation of the organic pollutants with poor water solubility in the air.
In an optional embodiment, the first electrode is at least one of a stainless steel electrode, an iron electrode, a copper electrode, an aluminum alloy electrode, a copper alloy electrode, a zinc alloy electrode, a titanium-supported titanium oxide foamed electrode, a platinum-based titanium electrode, an iridium-based titanium electrode, and an iridium-tantalum electrode; the second electrode is at least one of a stainless steel electrode, an iron electrode, a copper electrode, an aluminum alloy electrode, a copper alloy electrode, a zinc alloy electrode, a titanium-supported titanium oxide electrode, a platinum-based titanium electrode, an iridium-based titanium electrode and an iridium-tantalum electrode.
The first electrode and the second electrode are made of metal electrodes, and one or more of the above electrodes can be selected.
In an alternative embodiment, the first electrode, the second electrode and the sensing electrode are the same in shape, and the first electrode is at least one of a cylindrical sheet, a zigzag sheet, a strip sheet, a circular sheet and a linear shape. The first electrode, the second electrode and the induction electrode are the same in shape, and the shape can be selected from one or more combinations of the first electrode, the second electrode and the induction electrode, so that the manufacturing and the assembly of the induction electrode are convenient.
When the first electrode, the second electrode and the induction electrode are in the shape of a zigzag sheet, the tooth angle ranges from 30 degrees to 120 degrees.
In an optional embodiment, the distance between the sensing electrode and the first electrode and the distance between the sensing electrode and the second electrode are both 0.1mm-100mm. For example, the distance between the first electrode and the sensing electrode and the distance between the second electrode and the sensing electrode are 0.1mm, 4mm, 6mm, 8mm, 12mm, 16mm, 20mm, 40mm, 80mm and 100mm.
In an alternative embodiment, referring again to fig. 1 and 2, the apparatus for electrochemically removing gaseous pollutants further comprises an insulating support to which the first and second electrodes and the sensing electrode are fixed.
The insulating support is used for installing and fixing the first electrode, the second electrode and the induction electrode, and the shape of the insulating support can be set according to the shape of the electrodes. Of course, in some embodiments, the apparatus for electrochemically removing gaseous pollutants further comprises a housing, the housing may also be shaped according to the shape of the electrodes, the insulating support is fixed in the housing, and the first electrode and the second electrode and the sensing electrode are fixed in the insulating support. In order to facilitate the assembly operation, the housing is usually a split structure, the housing has two opposite surfaces along the extending direction of the airflow channel, and the two opposite surfaces are respectively provided with an air inlet and an air outlet which are communicated with the airflow channel. When the air containing the gaseous pollutants is treated, the air containing the gaseous pollutants flows into the air flow channel from the air inlet, effectively removes the gaseous pollutants under the action of the induction electrode, and then flows out from the air outlet.
In an alternative embodiment, a plurality of devices for degrading gaseous pollutants by an electrochemical method are arranged, and the plurality of devices for degrading gaseous pollutants by an electrochemical method are arranged in parallel or in series.
The plurality of devices for degrading the gaseous pollutants by the electrochemical method are arranged in a ring-by-ring manner or a layer-by-layer overlapping manner, so that the gaseous pollutants can be degraded by the plurality of devices for degrading the gaseous pollutants by the electrochemical method, and the treatment capacity of gas in unit time can be increased.
The gaseous pollutant degrading devices adopting the electrochemical methods are connected in series, so that the gas containing pollutants sequentially passes through the gaseous pollutant degrading devices adopting the electrochemical methods, and finally, the pollutants are thoroughly removed.
In alternative embodiments, a plurality of the devices for electrochemically degrading gaseous pollutants are arranged in parallel, and two adjacent sensing electrodes share one first electrode, and/or. Two adjacent induction electrodes share one second electrode.
The device for degrading gaseous pollutants by the electrochemical method is arranged in a ring-by-ring or layer-by-layer overlapping (parallel connection) mode, and the adjacent induction electrodes share the same first electrode and/or second electrode, so that the device for degrading gaseous pollutants by the electrochemical method can be used for simultaneously degrading gaseous pollutants, the gas treatment capacity in unit time can be increased, the number of electrodes is reduced, and the removal efficiency is improved.
Referring to fig. 3, in an embodiment of the present invention, a plurality of devices for degrading gaseous pollutants by an electrochemical method are provided, and a plurality of electrodes of the devices for degrading gaseous pollutants by an electrochemical method are integrated, so that electrode wires are reduced, and an assembly process is greatly simplified.
The induction electrode can be prepared by the following steps:
(1) Preparing modified reduced graphene oxide: adding 10-1000mg of graphene oxide into ethylene glycol (10-1000 mL), and performing ultrasonic oscillation for 1h to obtain a uniform precursor solution. Then adding Co (NO) 3 ) 3 ·6H 2 O(0.1g-20g)、Fe(NO 3 ) 3 ·9H 2 O (0.1 g to 20 g), anhydrous sodium acetate (0.1 g to 20 g), polyethylene glycol 4000 (0.1 g to 20 g) and urea (10 mg to 1000 mg) were dispersed in the above solution and stirred until completely dissolved. In a 50mL-500mL polytetrafluoroethylene-sealed autoclave, heat was applied at 180 ℃ for 24h. And (3) annealing and cooling to room temperature, repeatedly rinsing with deionized water and ethanol, and drying in vacuum (80 ℃,24 h) to obtain the modified reduced graphene oxide.
(2) Preparing an induction electrode: weighing modified reduced graphite oxide and a porous conductive adsorption material, placing the modified reduced graphite oxide and the porous conductive adsorption material in a beaker, wherein the mass ratio of the modified reduced graphite oxide to the porous conductive adsorption material is 1:1-1:8, adding a proper amount of polytetrafluoroethylene emulsion (the solid content is 60%, namely polytetrafluoroethylene: deionized water = 6:4) in proportion, the mass ratio of the porous conductive adsorption material to the polytetrafluoroethylene in the polytetrafluoroethylene emulsion is 0.5-6:1, carrying out ultrasonic treatment for 20min at room temperature to uniformly disperse catalyst material powder, then adding a proper amount of absolute ethyl alcohol, wherein the mass ratio of the absolute ethyl alcohol to the polytetrafluoroethylene in the polytetrafluoroethylene emulsion is 1:1-6:1, and continuing ultrasonic treatment for 15min. Continuously stirring the mixture into a wet paste at 80 ℃ in a constant-temperature water bath, then putting the wet paste into a stainless steel pressing mould with a prepared inner concave of 0.1-5 mm, carrying out cold pressing on the wet paste for 1min under the pressure of 10MPa on an oil press, coiling the wet paste by using a ceramic cylinder with the diameter of 1-200 mm, calcining the ceramic cylinder in a muffle furnace for 1h at 350 ℃, taking out the ceramic cylinder, and cutting the length of an electrode according to the length of the electrode to obtain an annular flaky electrode with the thickness of 0.1-5 mm, the diameter of 1-200 mm and the length of 1-200 mm; and/or continuously stirring the mixture in a constant-temperature water bath kettle at 80 ℃ to form wet paste, putting the wet paste into a prepared stainless steel fold-line-shaped tooth pressing die (with the tooth angle of 30-120 degrees and the height of 1-20 mm), cold-pressing the paste on an oil press for 1min under the pressure of 10MPa, placing the die in a muffle furnace, calcining the die for 1h at 350 ℃, and cutting the length and width of the electrode according to a device to obtain the fold-line-shaped sheet electrode with the thickness of 0.1-5 mm, the diameter of 1-200 mm, the length of 1-200 mm and the width of 1-200 mm. And (3) soaking the calcined induction electrode in ethanol for 10min to remove organic matters on the surface of the electrode, and then drying the electrode in an oven at 100 ℃ for 60min to obtain the induction electrode.
The invention also provides a method for degrading gaseous pollutants by an electrochemical method, which is applied to the device for degrading gaseous pollutants by the electrochemical method, and the method for degrading gaseous pollutants by the electrochemical method comprises the following steps:
applying a direct or alternating voltage between the first and second electrodes;
gaseous pollutants or air containing the gaseous pollutants are introduced into the airflow channel, and the induction electrode generates active species to degrade the gaseous pollutants.
Referring to fig. 1 and 2, when the gaseous pollutants are removed by the electrochemical method, firstly, a direct current voltage or an alternating current voltage of 0.5V-30000V is applied between the first electrode 1 and the second electrode 2, then, air containing the gaseous pollutants is continuously led into the air flow channel a 4 and the air flow channel B5 through the air inlet 6, and the reaction temperature range in the removing process is controlled to be-20 ℃ to 120 ℃, the distance between the first electrode 1 and the sensing electrode and between the second electrode 2 and the sensing electrode 3 is controlled to be 0.1mm to 100mm, the flow rate of the air containing the gaseous pollutants is controlled to be 0.001m/s to 20m/s, the humidity range is 0% to 99.9%, and the volume content of oxygen in the air containing the gaseous pollutants is controlled to be 2% to 28%. After the gas is stabilized, the concentration of gaseous pollutants at the gas port 7 is detected by an instrument. Of course, it is also possible to detect the concentration of gaseous pollutants in the air treated by the device.
Wherein the DC voltage or AC power supply is preferably in the range of 1000-9000V, such as 1000V, 2000V, 6000V or 9000V, and the reaction temperature is preferably in the range of 5-45 deg.C, such as 5 deg.C, 15 deg.C, 25 deg.C, 35 deg.C or 45 deg.C. The distance between the first electrode 1 and the sensing electrode 3 and between the second electrode 2 and the sensing electrode 3 is preferably in the range of 1-10mm, such as 1mm, 4mm, 8mm or 10mm. The gas flow rate is preferably in the range of 0.2m/s to 3m/s, such as 0.2m/s, 1m/s, 2m/s or 3m/s. The oxygen content of the gaseous contaminants is from 2V% to 28V%, preferably from 15V% to 20V%, such as an oxygen content of 15V%, 17V%, 18V% or 20V%. The removal efficiency of the gaseous pollutants is optimized by adjusting the power supply voltage, the distance between the electrode plates, the catalyst loading proportion, the electrode manufacturing and solvent proportion, the reaction temperature, the gas flow and the oxygen content.
The method for electrochemically degrading gaseous pollutants and the device thereof according to the present invention are described in detail by the following embodiments.
Example 1
(1) Preparing modified reduced graphene oxide: 60mg of graphene oxide is added into ethylene glycol (60 mL), and the mixture is subjected to ultrasonic oscillation for 1h to obtain a uniform precursor solution. Then mixing Co (NO) 3 ) 3 ·6H 2 O(0.4g)、Fe(NO 3 ) 3 ·9H 2 O (0.3 g), anhydrous sodium acetate (1.6 g), polyethylene glycol 4000 (0.3 g) and urea (50 mg) were dispersed in the precursor solution and stirred until completely dissolved. In a 100mL polytetrafluoroethylene-sealed autoclave, heat was applied at 180 ℃ for 24h. And after annealing and cooling to room temperature, repeatedly rinsing with deionized water and ethanol, and then drying in vacuum at the temperature of 80 ℃ for 12 hours to obtain the modified reduced graphene oxide.
(2) Preparing an induction electrode: weighing modified reduced graphite oxide and graphite, placing the modified reduced graphite oxide and the graphite in a beaker, wherein the mass ratio of the modified reduced graphite oxide to the graphite is 1:6, adding polytetrafluoroethylene emulsion (the solid content is 60 percent, namely the mass ratio of the polytetrafluoroethylene to deionized water is 6:4), the mass ratio of the graphite to the polytetrafluoroethylene in the polytetrafluoroethylene emulsion is 2:1, carrying out ultrasonic treatment for 20min at room temperature to realize uniform dispersion of the materials, then adding absolute ethyl alcohol, wherein the mass ratio of the absolute ethyl alcohol to the polytetrafluoroethylene in the polytetrafluoroethylene emulsion is 1:4, and continuing the ultrasonic treatment for 15min. Continuously stirring the obtained mixture in a constant-temperature water bath kettle at 80 ℃ to form wet paste, putting the wet paste into a pre-prepared stainless steel pressing mould with the thickness of 0.5mm, carrying out cold pressing on the wet paste for 1min under the pressure of 10MPa on an oil press, coiling the wet paste by using a ceramic cylinder with the diameter of 10mm, calcining the ceramic cylinder in a muffle furnace at the temperature of 350 ℃ for 1h, taking out the ceramic cylinder, and cutting the length of the electrode according to a device to obtain the annular sheet electrode with the thickness of 0.5mm, the diameter of 10mm and the length of 30 mm. And (3) soaking the calcined induction electrode in ethanol for 10min to remove organic matters on the surface of the electrode, and then drying the electrode in an oven at 100 ℃ for 60min to obtain the induction electrode.
(3) Assembling a device for degrading gaseous pollutants by an electrochemical method: referring to fig. 1 and 2, only one group of the first electrode 1, the second electrode 2 and the sensing electrode 3 is combined, the sensing electrode 3 prepared in step (2) and the first electrode 1 and the second electrode 2 are supported and fixed by an insulating support 8, when the first electrode 1, the second electrode 2 and the sensing electrode 3 are annular sheet electrodes, the first electrode 1 is made of stainless steel (inner diameter 19mm × length 30 mm), the second electrode 2 is made of stainless steel (diameter 2mm × length 30 mm), the second electrode 2 is made of solid cylindrical electrodes with diameter 2mm, the first electrode 1 or the second electrode 2 is made of stainless steel, the first electrode 1 or the second electrode 2 is 1mm, and the distance between the first electrode 1 and the sensing electrode 3 and the distance between the second electrode 2 and the sensing electrode 3 are both 4mm. The annular gap between the first electrode 1 and the induction electrode 3 is an A airflow channel 4, and the annular gap between the induction electrode 3 and the second electrode 2 is a B airflow channel 5,A airflow channel 4 and a B airflow channel 5 which are annular channels. Meanwhile, the first electrode 1 or the second electrode 2 is respectively connected with the positive electrode and the second electrode of the direct-current power supply through leads, the positive electrode and the second electrode are placed in a shell (a cylindrical cabin with the outer diameter of 80mm multiplied by 300 mm), the periphery of the shell is plugged by an annular rubber strip, so that gas passes through the gas flow channel A4 and the gas flow channel B5, and a device for degrading gaseous pollutants by an electrochemical method can be obtained, and the gas inlet 6 and the gas outlet 7 are respectively arranged at the circle center positions of the two bottom surfaces of the cylindrical shell.
(4) The method for degrading gaseous pollutants by using the device in the step (3) through an electrochemical method comprises the following steps: introducing air containing formaldehyde into the air inlet 6 at a flow rate of 20 mL/min -1 The gas humidity is 50%, the oxygen content in the gas is 20V%, the concentration of gaseous pollutant formaldehyde is 10ppm, 1000V direct current voltage is applied between the first electrode 1 and the second electrode 2, and the temperature in the reaction process is controlled to be 20 ℃. Under the action of wind speed, the induction electrode 3 absorbs organic pollutants through the absorption effect through the air flow channels A4 and B5, and under the action of moisture and a catalyst, a plurality of reaction sites are formed on the surface and inside of the induction electrode 3, and the organic pollutants are finally degraded into H through direct oxidation and indirect oxidation 2 O and CO 2 And flows out through the air outlet 7. And the concentration of the gas pollutants at the gas outlet 7 during the stable reaction is detected by using a macro-graph SP-502 type Gas Chromatograph (GC), and the catalytic performance is shown in Table 1 when the air pressure is 0.1MPa, the temperature of a gasification chamber is 120 ℃, and the column temperature is 100 ℃.
Example 2
(1) Preparing modified reduced graphene oxide: 100mg of graphene oxide is added into ethylene glycol (90 mL), and the mixture is subjected to ultrasonic oscillation for 1 hour to obtain a uniform precursor solution. Then adding Co (NO) 3 ) 3 ·6H 2 O(0.6g)、Fe(NO 3 ) 3 ·9H 2 O (0.3 g), sodium acetate anhydrous (2.36 g), polyethylene glycol 4000 (0.7 g) and urea (100 mg) were dispersed in the above solution and stirred until completely dissolved. In a 150mL polytetrafluoroethylene-sealed autoclave, heat was applied at 180 ℃ for 24h. And (3) annealing and cooling to room temperature, repeatedly rinsing with deionized water and ethanol, and drying in vacuum (80 ℃,24 h) to obtain the modified reduced graphene oxide.
(2) Preparing an induction electrode: weighing modified reduced graphene oxide and carbon nanotubes, and placing the weighed modified reduced graphene oxide and carbon nanotubes in a beaker, wherein the ratio of the modified reduced graphene oxide to the carbon nanotubes is 1: and 6, adding a proper amount of polytetrafluoroethylene emulsion (the solid content is 60 percent, namely polytetrafluoroethylene: deionized water = 6:4) in proportion, wherein the mass ratio of the carbon nano tube to the polytetrafluoroethylene in the polytetrafluoroethylene emulsion is 1:1, carrying out ultrasonic treatment for 20min at room temperature to uniformly disperse catalyst material powder, then adding a proper amount of absolute ethyl alcohol, wherein the mass ratio of the absolute ethyl alcohol to the polytetrafluoroethylene in the polytetrafluoroethylene emulsion is 1:3, and continuing carrying out ultrasonic treatment for 15min. Continuously stirring the mixture into a wet paste in a constant-temperature water bath kettle at 80 ℃, then putting the wet paste into a stainless steel pressing mould with the prepared inner dimension of 0.5mm, cold-pressing the wet paste on an oil press for 1min under the pressure of 10MPa, respectively coiling the wet paste by using ceramic cylinders with the diameters of 14mm, 40mm and 66mm, putting the ceramic cylinders into a muffle furnace, calcining the ceramic cylinders for 1h at 350 ℃, and taking out the ceramic cylinders to obtain annular flaky electrodes with the thicknesses of 0.5mm and the inner diameters of 11.5mm, 24.5mm and 37.5 mm. And (3) soaking the calcined induction electrode in ethanol for 10min to remove organic matters on the surface of the electrode, and then drying the electrode in an oven at 100 ℃ for 60min to finish the preparation of the induction electrode.
(3) Assembling a device for degrading gaseous pollutants by an electrochemical method: referring to fig. 3, the sensing electrode 3 prepared in step (2) is supported and fixed with the first electrode 1 and the second electrode 2, sequentially from inside to outside, the second electrode 2, the sensing electrode 3, the first electrode 1, the sensing electrode 3, the second electrode 2, the sensing electrode 3 and the first electrode 1 are combined, the first electrode 1, the second electrode 2 and the sensing electrode 3 are both annular sheet electrodes, the second electrode 2 is an annular sheet electrode and a solid cylindrical electrode, the size of the second electrode 2 (the inner diameter is 27mm × the length is 30mm, the inner diameter is 79mm × the length is 30 mm), the size of the first electrode (the diameter is 2mm × the length is 30mm, the inner diameter is 53mm × the length is 30 mm), the material of the first electrode 1 and the material of the second electrode 2 is red copper, the thickness of the first electrode 1 and the thickness of the second electrode 2 is 0.5mm, and the distance between the first electrode 1 or the second electrode 2 and the sensing electrode 3 is 6mm. The surface of the first electrode 1 is provided with an A airflow channel 4, the surface of the second electrode 2 is provided with a B airflow channel 5, and the airflow channels are in the shape of annular channels. Meanwhile, the first electrode 1 and the second electrode 2 are respectively connected with a first electrode and a second electrode of a direct-current power supply through leads, the first electrode and the second electrode are placed in a shell (a cylindrical cabin with the outer diameter of 80mm multiplied by 300 mm), the periphery of the shell is plugged by an annular rubber strip, and gas passes through the gas flow channel A4 and the gas flow channel B5, so that the device for degrading gaseous pollutants by an electrochemical method can be obtained. The degradation principle is the same as in example 1.
(4) The method for degrading gaseous pollutants by using the device in the step (3) through an electrochemical method comprises the following steps: introducing air containing formaldehyde into the air inlet 6 at a flow rate of 10 mL/min -1 The gas humidity is 50%, the oxygen content in the gas is 20V%, the concentration of gaseous pollutant formaldehyde is 30ppm, 2000V direct current voltage is applied between the first electrode 1 and the second electrode 2, and the temperature in the reaction process is controlled to be 20 ℃. Under the action of wind speed, the induction electrode 3 absorbs organic pollutants through the absorption effect through the air flow channels A4 and B5, and under the action of moisture and a catalyst, a plurality of reaction sites are formed on the surface and inside of the induction electrode 3, and the organic pollutants are finally degraded into H through direct oxidation and indirect oxidation 2 O and CO 2 And flows out through the air outlet 7. And the concentration of the gas pollutants at the gas outlet 7 during the stable reaction is detected by using a macro graph SP-502 type Gas Chromatograph (GC), and the catalytic performance is shown in table 1 when the air pressure is 0.1MPa, the temperature of the gasification chamber is 120 ℃, and the column temperature is 100 ℃.
Example 3
(1) Preparing modified reduced graphene oxide: 160mg of graphene oxide is added into ethylene glycol (120 mL), and the mixture is subjected to ultrasonic oscillation for 1 hour to obtain a uniform precursor solution. Then adding Co (NO) 3 ) 3 ·6H 2 O(0.9g)、Fe(NO 3 ) 3 ·9H 2 O (1.2 g), anhydrous sodium acetate (5.63 g), polyethylene glycol 4000 (1.3 g) and urea (160 mg) were dispersed in the above solution and stirred until completely dissolved. In a 200mL polytetrafluoroethylene-sealed autoclave, heat was applied at 180 ℃ for 24h. And after annealing and cooling to room temperature, repeatedly rinsing with deionized water and ethanol, and then drying in vacuum (80 ℃,24 hours) to obtain the modified reduced graphene oxide.
(2) Preparing an induction electrode: weighing modified reduced graphene oxide and acetylene black, and placing the modified reduced graphene oxide and the acetylene black in a beaker, wherein the ratio of the modified reduced graphene oxide to the acetylene black is 1: and 6, adding a proper amount of polytetrafluoroethylene emulsion (the solid content is 60 percent, namely polytetrafluoroethylene: deionized water = 6:4) in proportion, wherein the mass ratio of the acetylene black to the polytetrafluoroethylene in the polytetrafluoroethylene emulsion is 3:1, carrying out ultrasonic treatment for 20min at room temperature to uniformly disperse catalyst material powder, then adding a proper amount of absolute ethyl alcohol, wherein the mass ratio of the absolute ethyl alcohol to the polytetrafluoroethylene in the polytetrafluoroethylene emulsion is 1:2, and continuing carrying out ultrasonic treatment for 15min. Continuously stirring the mixture into a wet paste at 80 ℃ in a constant-temperature water bath, putting the wet paste into a stainless steel fold-line-shaped tooth pressing die (with the tooth angle of 60 degrees and the height of 8 mm) which is prepared in advance, and carrying out cold pressing on the mixture for 1min on an oil press under the pressure of 10MPa to obtain the fold-line-shaped sheet electrode with the thickness of 0.5mm, the tooth angle of 60 degrees and the height of 8mm. The prepared electrode was calcined in a muffle furnace at 350 ℃ for 1h. And (3) soaking the calcined induction electrode in ethanol for 10min to remove organic matters on the surface of the electrode, and then drying the electrode in an oven at 100 ℃ for 60min to finish the preparation of the induction electrode.
(3) Assembling a device for degrading gaseous pollutants by an electrochemical method: referring to fig. 4 and fig. 6, in order to form a set of electrode assembly 9, the sensing electrode 3 prepared in step (2) is supported and fixed with the first electrode 1 and the second electrode 2, the first electrode 1, the second electrode 2 and the sensing electrode 3 both use zigzag sheet electrodes, the first electrode 1 and the second electrode 2 have the dimensions (tooth angle 60 degrees, height 8mm, length 80mm, width 30 mm), the first electrode 1 and the second electrode 2 are made of titanium sheets, the first electrode 1 and the second electrode 2 have the thickness of 1mm, and the first electrode 1 and the second electrode 2 are spaced from the sensing electrode 3 by 8mm. The surface of the first electrode 1 is provided with an A airflow channel 4, the surface of the second electrode 2 is provided with a B airflow channel 5, and the airflow channels are in a zigzag channel shape. Meanwhile, the first electrode 1 and the second electrode 2 are respectively connected with a first electrode and a second electrode of a direct-current power supply through leads, the first electrode and the second electrode are placed in a shell (a cuboid cabin with the length of 100mm, the width of 80mm and the height of 80 mm), the periphery of the shell is plugged by rubber strips, and gas passes through the gas flow channel A4 and the gas flow channel B5, so that the device for degrading gaseous pollutants by the electrochemical method can be obtained. The degradation principle is the same as in example 1.
(4) The device for degrading gaseous pollutants by using the electrochemical method in the step (3) comprises the following steps: introducing air containing formaldehyde into the air inlet 6, wherein the flow rate of the air is 20 mL/min < -1 >, the humidity of the air is 50%, the oxygen content in the air is 20V%, the concentration of gaseous pollutant formaldehyde is 20ppm, and the first electrode 1 and the second electrodeA DC voltage of 6000V is applied between the electrodes 2, and the temperature in the reaction process is controlled to be 20 ℃. Under the action of wind speed, the induction electrode 3 absorbs organic pollutants through the absorption effect through the air flow channels A4 and B5, and under the action of moisture and a catalyst, a plurality of reaction sites are formed on the surface and inside of the induction electrode 3, and the organic pollutants are finally degraded into H through direct oxidation and indirect oxidation 2 O and CO 2 And flows out through the air outlet 7. And the concentration of the gas pollutants at the gas outlet 7 during the stable reaction is detected by using a macro-graph SP-502 type Gas Chromatograph (GC), and the catalytic performance is shown in Table 1 when the air pressure is 0.1MPa, the temperature of a gasification chamber is 120 ℃, and the column temperature is 100 ℃.
Example 4
(1) Preparing modified reduced graphene oxide: 180mg of graphene oxide is added into ethylene glycol (150 mL), and the mixture is subjected to ultrasonic oscillation for 1h to obtain a uniform precursor solution. Then adding Co (NO) 3 ) 3 ·6H 2 O(1.3g)、Fe(NO 3 ) 3 ·9H 2 O (1.5 g), anhydrous sodium acetate (7.63 g), polyethylene glycol 4000 (1.6 g) and urea (200 mg) were dispersed in the above solution and stirred until completely dissolved. In a 200mL polytetrafluoroethylene-sealed autoclave, heat was applied at 180 ℃ for 24h. And (3) annealing and cooling to room temperature, repeatedly rinsing with deionized water and ethanol, and drying in vacuum (80 ℃,24 h) to obtain the modified reduced graphene oxide.
(2) Preparing an induction electrode: weighing modified reduced graphene oxide and activated carbon, and placing the weighed modified reduced graphene oxide and activated carbon in a beaker, wherein the ratio of the modified reduced graphene oxide to the activated carbon is 1: and 6, adding a proper amount of polytetrafluoroethylene emulsion (the solid content is 60 percent, namely polytetrafluoroethylene: deionized water = 6:4) in proportion, wherein the mass ratio of the activated carbon to the polytetrafluoroethylene in the polytetrafluoroethylene emulsion is 4:1, carrying out ultrasonic treatment for 20min at room temperature to uniformly disperse catalyst material powder, then adding a proper amount of absolute ethyl alcohol, wherein the mass ratio of the absolute ethyl alcohol to the polytetrafluoroethylene in the polytetrafluoroethylene emulsion is 1:1, and continuing carrying out ultrasonic treatment for 15min. Continuously stirring the mixture in a constant temperature water bath kettle at 80 ℃ to form wet paste, putting the wet paste into a pre-prepared stainless steel fold line-shaped tooth pressing mould (the tooth angle is 90 degrees, and the height is 8 mm), and carrying out cold pressing on the mixture for 1min on an oil press under the pressure of 10MPa to obtain the fold line-shaped sheet electrode with the thickness of 0.5mm, the tooth angle is 90 degrees, and the height is 8mm. The prepared electrode was calcined in a muffle furnace at 350 ℃ for 1h. And (3) soaking the calcined induction electrode in ethanol for 10min to remove organic matters on the surface of the electrode, and then drying the electrode in an oven at 100 ℃ for 60min to finish the preparation of the induction electrode.
(3) Assembling a device for degrading gaseous pollutants by an electrochemical method: referring to fig. 5 and fig. 6, the sensing electrode 3 prepared in step (2) is supported and fixed with the first electrode 1 and the second electrode 2, and the sensing electrode 3, the first electrode 1, the sensing electrode 3, the second electrode 2, the sensing electrode 3, and the second electrode 2 are sequentially combined from bottom to top, the first electrode 1, the second electrode 2, and the sensing electrode 3 are both zigzag sheet-shaped electrodes, the sizes of the first electrode 1 and the second electrode 2 (the tooth angle is 90 ° × height is 8mm × length is 80mm × width is 30 mm), the first electrode 1 and the second electrode 2 are made of iridium titanium, the thicknesses of the first electrode 1 and the second electrode 2 are 1mm, and the distance between the first electrode 1 and the sensing electrode 2 and the sensing electrode 3 is 10mm. The surface of the first electrode 1 is provided with an A airflow channel 4, the surface of the second electrode 2 is provided with a B airflow channel 5, and the airflow channels are in a zigzag channel shape. Meanwhile, the first electrode 1 and the second electrode 2 are respectively connected with a first electrode and a second electrode of a direct-current power supply through leads, the first electrode and the second electrode are placed in a shell (a cuboid cabin with the length of 100mm, the width of 80mm and the height of 80 mm), the periphery of the shell is plugged by rubber strips, and gas passes through the gas flow channel A4 and the gas flow channel B5, so that the device for degrading gaseous pollutants by the electrochemical method can be obtained. The degradation principle is the same as in example 1.
(4) The device for degrading gaseous pollutants by using the electrochemical method in the step (3) comprises the following steps: introducing air containing formaldehyde into the air inlet 6, wherein the flow rate of the air is 10 mL/min < -1 >, the humidity of the air is 50%, the oxygen content in the air is 20V%, the concentration of gaseous pollutant formaldehyde is 60ppm, 9000V alternating voltage is applied to the first electrode 1 and the second electrode 2, and the temperature in the reaction process is controlled to be 20 ℃. Under the action of wind speed, the organic pollutants are adsorbed by the induction electrode 3 through the air flow channels A and B4 and 5, and the action of moisture and catalystWith this, a plurality of reaction sites are formed on the surface and inside of the induction electrode 3 and the organic contaminants are finally degraded into H by direct oxidation and indirect oxidation 2 O and CO 2 And flows out through the air outlet 7. And the concentration of the gas pollutants at the gas outlet 7 during the stable reaction is detected by using a macro-graph SP-502 type Gas Chromatograph (GC), and the catalytic performance is shown in Table 1 when the air pressure is 0.1MPa, the temperature of a gasification chamber is 120 ℃, and the column temperature is 100 ℃.
TABLE 1 Formaldehyde degradation rates for examples 1 to 4
Figure BDA0002921679430000171
Figure BDA0002921679430000181
As can be seen from table 1, compared with the three combinations of the devices for electrochemically degrading gaseous pollutants in examples 1 and 3 and in examples 2 and 4, the formaldehyde degrading effects in examples 2 and 4 are better than those in examples 1 and 3, because the contact area of the reaction is increased by the combination of the devices for electrochemically removing gaseous pollutants, and thus the formaldehyde degrading rate is increased; example 4 the effect of degrading formaldehyde was superior to that of example 2 because the same volume contact area of the zigzag-shaped sheet electrode was superior to that of the circular sheet electrode. Compare with current air purifier device, adopted the reaction degradation technique, can effectively degrade gaseous pollutants such as formaldehyde, thereby prevent to lead to the secondary pollution of desorption like the adsorption saturation of adsorption fixation technique, solve the problem from the source. In addition, the invention has low requirements on the materials of the first electrode and the second electrode, is mainly used for preparing a single induction electrode, reduces the production requirements, has higher activity of the iron-containing catalyst and the metal oxide catalyst, has better stability, and is beneficial to the improvement of the pollutant removal rate. The catalyst can efficiently catalyze and decompose various gaseous pollutants, and has a wide application range.
Example 5
The same preparation method of the induction electrode as that of the example 1 is adopted;
assembling the device for removing the gaseous pollutants by the electrochemical method: referring to fig. 7, only one set of the first electrode 1, the sensing electrode 3 and the second electrode 2 is combined, the sensing electrode 3 prepared in step (1) and the first electrode 1 and the second electrode 2 are supported and fixed by the insulating support 8, the first electrode 1, the second electrode 2 and the sensing electrode 3 are annular sheet electrodes, the first electrode 1 is made of stainless steel (with an inner diameter of 35mm × a length of 30 mm), the second electrode 2 is made of stainless steel (with a diameter of 2mm × a length of 30 mm), the second electrode 2 is made of solid cylindrical electrodes with a diameter of 2mm, the first electrode 1 and the second electrode 2 are made of 1mm, and the distance between the first electrode 1 and the sensing electrode 3 and the distance between the second electrode 2 and the sensing electrode 3 are 8mm. The annular gap between the first electrode 1 and the induction electrode 3 is an A airflow channel 4, and the annular gap between the induction electrode 3 and the second electrode 2 is a B airflow channel 5,A airflow channel 4 and a B airflow channel 5, which are in the shape of annular channels. Four same blocks for degrading gaseous pollutants by an electrochemical method are manufactured, meanwhile, a first electrode 1 and a second electrode 2 of the four blocks are respectively connected with a positive electrode and a negative electrode of a direct-current power supply in series through leads and are placed in a shell (a cylindrical cabin with the outer diameter of 80mm multiplied by 300 mm), the periphery of the shell is plugged by an annular rubber strip, gas passes through an air flow channel A4 and an air flow channel B5, a device for degrading gaseous pollutants by the electrochemical method can be obtained, and a gas inlet 6 and a gas outlet 7 are respectively arranged at the circle center positions of two bottom surfaces of the cylindrical shell.
(3) The device for removing the gaseous pollutants by using the electrochemical method in the step (2) comprises the following steps: introducing air containing toluene or formaldehyde or acetone or n-hexane or cyclohexanone into the gas inlet 6 at a flow rate of 30 mL/min -1 The humidity of the gas is 50%, the oxygen content in the gas is 20V%, the concentration of toluene, formaldehyde, acetone, normal hexane or cyclohexanone is 20ppm, 5000V direct current voltage is applied between the second electrode and the first electrode, and the temperature in the reaction process is controlled to be 20 ℃. The induction electrode 3 absorbs organic pollutants through the adsorption effect through the air flow channel A4 and the air flow channel B5 under the action of wind speed, and the induction electrode 3 is used for measuring the air flow rate under the action of moisture and a catalystA plurality of reaction sites are formed on the surface and inside, and the organic pollutants are finally degraded into H through direct oxidation and indirect oxidation 2 O and CO 2 And flows out through the air outlet 7. And the concentration of the gas pollutants at the gas outlet 7 during the stable reaction is detected by using a macro-graph SP-502 type Gas Chromatograph (GC), and the catalytic performance is shown in Table 2 when the air pressure is 0.1MPa, the temperature of the gasification chamber is 120 ℃, and the column temperature is 100 ℃.
TABLE 2 degradation rates (%)
Toluene Formaldehyde (I) Acetone (II) N-hexane Cyclohexanone
Degradation ratio of organic contaminants (%) 93 95 89 92 90
As can be seen from Table 2, the device for degrading gaseous pollutants by using an electrochemical method can realize the effect of removing different gaseous pollutants by using the sensing electrode. Compared with porous materials such as nitrogen-doped carbon, carbon nitride, activated carbon, graphite felt, graphite-polytetrafluoroethylene and the like which cannot adsorb toluene gas, the device for degrading gaseous pollutants by the electrochemical method cannot effectively adsorb toluene gas in some air purification devices based on adsorption and fixation technologies, and the device for degrading gaseous pollutants by the electrochemical method can effectively degrade the gaseous pollutants which are difficult to adsorb and degrade, such as benzene, toluene, xylene and the like, by active species such as hydroxyl radicals.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (10)

1. An apparatus for electrochemically degrading gaseous pollutants, comprising a power supply, a first electrode, a second electrode and a sensing electrode, wherein the first electrode and the second electrode are electrically connected to the power supply, the sensing electrode is disposed between the first electrode and the second electrode, and the sensing electrode and the first electrode, the sensing electrode and the second electrode enclose a gas flow channel, and the sensing electrode can generate active species when the power supply is turned on, so as to degrade gaseous pollutants in the gas flow channel;
the induction electrode is a porous material electrode loaded with a catalyst, and the catalyst is an iron-containing catalyst and a metal oxidant catalyst; the induction electrode can reduce oxygen in air or manually input oxygen to generate hydrogen peroxide, and the hydrogen peroxide and the iron-containing and metal oxide catalyst generate hydroxyl radicals through electro-Fenton reaction so as to react with gaseous organic pollutants, so that the gaseous organic pollutants are degraded to finally generate water and carbon dioxide;
the iron-containing catalyst is a composite catalyst of an iron-containing material and a porous conductive adsorption material carrier, wherein the iron-containing material is at least one of nano iron, ferric chloride, ferric oxide, ferroferric oxide, ferric nitrate and a metal organic framework material, and the porous conductive adsorption material carrier is at least one of nitrogen-doped carbon, carbon nitride, activated carbon, a carbon nanotube, graphene and a graphite felt;
the metal oxide catalyst is at least one of a manganese oxide catalyst, a cobalt oxide catalyst, a copper oxide catalyst, an indium oxide catalyst, a titanium oxide catalyst and a titanium oxide catalyst.
2. The apparatus for electrochemically degrading gaseous pollutants according to claim 1, wherein the loading amount of the iron-containing catalyst is 0.1-50%, and the loading amount of the metal oxide catalyst is 0.1-50%.
3. The apparatus for electrochemically degrading gaseous pollutants according to claim 1, wherein the first electrode is at least one of a stainless steel electrode, an iron electrode, a copper electrode, an aluminum alloy electrode, a copper alloy electrode, a zinc alloy electrode, a titanium foam supported titanium suboxide electrode, a platinum-based titanium electrode, an iridium-based titanium electrode, and an iridium-tantalum electrode;
and/or the second electrode is at least one of a stainless steel electrode, an iron electrode, a copper electrode, an aluminum alloy electrode, a copper alloy electrode, a zinc alloy electrode, a titanium foam titanium-supported titanium suboxide electrode, a platinum-group titanium electrode, an iridium-group titanium electrode and an iridium-tantalum electrode.
4. The apparatus for electrochemically degrading gaseous pollutants according to claim 1, wherein the first electrode, the second electrode and the sensing electrode have the same shape, and the shape of the first electrode is at least one of a cylindrical sheet, a zigzag sheet, a strip sheet, a circular sheet and a linear shape.
5. The apparatus for electrochemically degrading gaseous pollutants according to claim 1, wherein the distance between the sensing electrode and the first electrode is in a range from 0.1mm to 100mm, and the distance between the sensing electrode and the second electrode is in a range from 0.1mm to 100mm.
6. The apparatus for electrochemically degrading a gaseous pollutant according to claim 1, further comprising an insulating support to which the first electrode, the second electrode, and the sensing electrode are affixed.
7. The apparatus for electrochemically degrading gaseous pollutants according to any one of claims 1 to 6, wherein a plurality of the apparatus for electrochemically degrading gaseous pollutants are provided, and a plurality of the apparatus for electrochemically degrading gaseous pollutants are provided in series or in parallel.
8. The apparatus for electrochemically degrading a gaseous pollutant according to claim 7, wherein a plurality of said apparatus for electrochemically degrading a gaseous pollutant are arranged in series or in parallel, and wherein two adjacent sensing electrodes share a first electrode and/or two adjacent sensing electrodes share a second electrode.
9. A method for electrochemically degrading gaseous pollutants, which is applied to the device for electrochemically degrading gaseous pollutants according to any one of claims 1 to 8, and comprises the following steps:
applying a direct or alternating voltage between the first and second electrodes;
gaseous pollutants or air containing the gaseous pollutants are introduced into the airflow channel, and the induction electrode generates active species to degrade the gaseous pollutants.
10. The method for electrochemically degrading gaseous pollutants according to claim 9, wherein the voltage range of the direct current voltage or the alternating current voltage is 0.5V-30000V, and the temperature range during the process of degrading gaseous pollutants is controlled to be minus 20 ℃ to 120 ℃;
and/or the flow rate of the gaseous pollutant or the air containing the gaseous pollutant ranges from 0.001m/s to 20m/s, the humidity ranges from 0% to 99.9%, and the volume content of oxygen in the air containing the gaseous pollutant ranges from 2% to 28%.
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