CN106732238A - The method of reactor and its elimination VOCs for gas-solid phase electrocatalytic reaction - Google Patents

Abstract

The invention provides a kind of reactor for gas-solid phase electrocatalytic reaction and its method for eliminating VOCs (volatile organic contaminant), the reactor includes anode gas chamber, cathode air chamber, electro-catalysis anode, barrier film and electro-catalysis negative electrode, and electro-catalysis anode and electro-catalysis negative electrode are breathed freely；Barrier film is placed between electro-catalysis anode and electro-catalysis negative electrode, and three's composition is overall, is integrally formed structure；Anode gas chamber and cathode air chamber independently are the cavity for being provided with through hole, and integrative-structure is placed between the through hole of anode gas chamber and the through hole of cathode air chamber, and the through hole of the through hole of anode gas chamber and cathode air chamber is covered.The electrolytic cell can at room temperature eliminate degradation of indoor air VOCs, and the product of generation is most of for CO₂；In addition, the electrolytic cell be used to eliminating degradation of indoor air VOCs conveniently, safely, energy consumption it is small --- only need the 2V impressed DC voltages can just to realize VOCs oxidative degradations.

Description

Reactor for gas-solid phase electrocatalytic reaction and method for eliminating VOCs

technical field

The invention belongs to the technical field of electrolytic cells and purification of volatile organic pollutants, and relates to a reactor for gas-solid phase electrocatalytic reaction and a method for eliminating VOCs.

Background technique

Volatile organic compounds (VOCs) are the main gaseous pollutants in indoor air, including formaldehyde and benzene series. These pollutants are very harmful to human health and can cause disease, cancer or teratogenicity. On the market, the purification technologies for eliminating VOCs in indoor air mainly include physical adsorption, ozone oxidation, photocatalysis, thermal catalytic oxidation and plasma purification technologies. However, these technologies generally have the problems of high energy consumption, potential safety hazards and secondary pollution.

The thermocatalytic oxidation method has the advantage of simple operation and can degrade VOCs into nontoxic _CO2 and water. At present, there are catalytic materials and related indoor air purification products that can completely oxidize formaldehyde to CO ₂ and water at room temperature, but products that oxidatively degrade benzene series have not been found. Due to the complex molecular structure of benzene series, it is still difficult to eliminate benzene series by thermal catalytic oxidation at room temperature. At present, even for the catalyst with the highest activity, the combustion temperature of benzene series is about 150°C, which is difficult to apply to the purification of benzene series under indoor environmental conditions. Therefore, it is of great significance to develop safe, economical and non-secondary pollution-free benzene series elimination methods to improve indoor air quality.

The remarkable advantage of electrocatalytic oxidation technology is that it can effectively reduce the energy barrier of the reaction system by changing the interface electric field under the condition of normal temperature and pressure. Organic molecules can be oxidized electrochemically. In recent years, the application of electrocatalytic oxidation technology to the elimination of liquid-phase organic pollutants has been extensively studied. From simple straight-chain organic compounds to complex polycyclic aromatic hydrocarbons, electrocatalytic methods can oxidize these toxic pollutants into _CO2 and water. .

CN 103074638A discloses an electrolytic cell with double gas chambers and double light windows for electrochemical gas production, including a reaction cell and a cover plate, the cover plate is arranged at the opening of the reaction cell, and the cover plate and the reaction cell are detachable Sealed connection, the cover plate is provided with a number of connection ports, the reaction tank is provided with a partition, the partition divides the space in the reaction tank into two parts, the working electrode reaction chamber and the auxiliary electrode reaction chamber, the upper part of the partition The edge is flush with the top surface of the reaction pool, and the front and rear side edges of the partition are sealed and connected with the front and rear inner walls of the reaction pool. In the free-flowing space between the auxiliary electrode reaction chambers, a transparent glass window is inlaid on the side of the reaction pool corresponding to the positions of the working electrode reaction chamber and the auxiliary electrode reaction chamber. The double-gas-chamber double-light-window electrolytic cell realizes the effective isolation of the gas generated on the surface of the working electrode and the auxiliary electrode, thereby facilitating the control of the accuracy of the experimental results.

However, there is no research on the use of electrocatalytic oxidation technology to eliminate indoor volatile organic pollutants.

Contents of the invention

In view of the deficiencies in the prior art, the object of the present invention is to provide a reactor for gas-solid phase electrocatalytic reaction and a method for eliminating VOCs thereof. The reactor has a simple structure and can be used for eliminating volatile organic pollution at room temperature substances, and most of the generated products are CO ₂ .

In the present invention, unless otherwise specified, the room temperature refers to 20-45°C, the wt% refers to the mass percentage, and the v% refers to the volume percentage.

For reaching this purpose, the present invention adopts following technical scheme:

One of the purposes of the present invention is to provide a reactor for gas-solid phase electrocatalytic reaction, said reactor comprising anode gas chamber, cathode gas chamber, electrocatalytic anode, diaphragm and electrocatalytic cathode, said electrocatalytic Both the anode and the electrocatalytic cathode are breathable;

The diaphragm is placed between the electrocatalytic anode and the electrocatalytic cathode, and the three form a whole to form an integrated structure;

The anode gas chamber and the cathode gas chamber are independently cavities provided with through holes, the integrated structure is placed between the through holes of the anode gas chamber and the through holes of the cathode gas chamber, and the through holes of the anode gas chamber and through-hole coverage of the cathode gas chamber;

The anode gas chamber is also provided with a first air inlet, a first air outlet and optionally a first wire, one end of the first wire is connected to the electrocatalytic anode, and the other end is connected to the positive pole of the power supply;

The cathode air chamber is also provided with a second air inlet, a second air outlet and optionally a second wire, one end of the second wire is connected to the electrocatalytic cathode, and the other end is connected to the negative electrode of the power supply.

Those skilled in the art should know that the diaphragm should be a diaphragm through which protons can pass, and the diaphragm should have a certain thickness and strength.

The integrated structure separates the gas in the two chambers, which is beneficial to the uninterrupted progress of the anode reaction and the cathode reaction, and improves the efficiency of mineralization of volatile organic compounds in the system; the integrated structure facilitates the transfer of protons and electrons and reduces the system resistance. The gas in the anode gas chamber flows out from the gas outlet of the anode gas chamber after reacting on the electrocatalytic anode; the gas in the cathode gas chamber flows out from the gas outlet of the cathode gas chamber after reacting on the electrocatalytic cathode. The cathode gas chamber and the anode gas chamber are not in communication with each other.

A first air intake pipe is also provided in the first air inlet, a second air intake pipe is also provided in the second air intake port, and the first air intake pipe and the second air intake pipe independently include a diversion section and an expansion section, so The diameter of the enlarged section is greater than that of the guide section, the enlarged section of the first air intake pipe is located in the anode gas chamber, and the enlarged section of the second air intake pipe is located in the cathode air chamber.

The first wire is connected to the electrocatalytic anode along the inner wall of the anode gas chamber; the second wire is connected to the electrocatalytic cathode along the inner wall of the cathode gas chamber.

Preferably, the anode gas chamber is further provided with a first terminal, and the first wire is connected to the positive pole of the power supply through the first terminal.

Preferably, the cathode gas chamber is further provided with a second terminal, and the second wire is connected to the negative pole of the power supply through the second terminal.

Preferably, the anode gas chamber and the cathode gas chamber are hermetically connected, such as by bolts.

The electrocatalytic anode includes a metal Ti substrate and an active material layer located on the surface of the Ti substrate. The active material layer is a dense layer formed by stacking nanoparticles. The material of the nanoparticles is doped SnO ₂ , and the doping elements include F and Sb, the metal Ti substrate is titanium foam and/or titanium mesh, preferably titanium foam.

Preferably, the loading amount of the active material layer on the surface of the Ti substrate is 2-10 mg cm ^-2 , such as 2.5 mg cm ^-2 , 3 mg cm ^-2 , 3.5 mg cm ^-2 , 4 mg cm ^-2 , 4.5 mg cm ^{-2 2} , 5mg cm ^-2 , 5.5mg cm ^-2 , 6mg cm ^-2 , 6.5mg cm ^-2 , 7mg cm ^-2 , 7.5mg cm ^-2 , 8mg cm ^-2 , 8.5mg cm ^-2 or 9.5mg cm ^{-2 2} etc.

Preferably, the particle size of the doped SnO ₂ is 1-10nm, such as 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm or 9.5nm.

Preferably, the molar ratio of the doping element to Sn is 0.04-0.5, such as 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 02, 0.3 or 0.4.

Preferably, the molar ratio of Sb and F is (0.2-100):1, such as 0.5:1, 0.8:1, 1:1, 3:1, 5:1, 6:1, 8:1, 10 :1, 12:1, 15:1, 18:1, 20:1, 25:1, 28:1, 30:1, 32:1, 35:1, 38:1, 40:1, 42:1 , 45:1, 48:1, 50:1, 60:1, 70:1, 80:1, 90:1 or 95:1, etc.

The electrocatalytic anode is prepared by the following method:

(1) First soak the metal Ti substrate with a concentration of 10wt%-20wt% NaOH solution at 80°C for 10min; then immerse in a 10wt% oxalic acid solution and boil for 1-3h; then ultrasonically clean the surface of the metal titanium substrate with distilled water Oxalic acid and titanium oxalate to obtain a pretreated metal Ti substrate;

(2) Electroplating Sn and Sb on the pretreated Ti substrate by electrodeposition to obtain a Ti substrate with a coating on the surface, wherein the electroplating solution is a soluble compound containing 1-2M SnCl ₄ , 0.2-1M Sb and 0.1- 1M HNO ₃ ethylene glycol solution, the electroplating uses Pt sheet as the anode; the electroplating current is 10-15mA cm ^-2 ; the electroplating time is 15-60min;

(3) Coating the slurry on the metal Ti substrate with a coating on the surface, drying at 100°C for 5 minutes, and then firing at 500°C with a heating rate of 5°C min ^-1 , to obtain the active ingredient layer on the surface of the Ti substrate Electrocatalytic electrode, wherein the slurry is a mixed solution of isopropanol and n-butanol containing 0.2-1M SnCl ₄ , 0.02-0.1M Sb soluble compound, 0.001-0.1MF soluble compound and 0.1-1M HNO ₃ , the active ingredient The layer is formed by stacking nanoparticles, and the active component layer is a doped SnO ₂ layer, and the doping elements include F and Sb.

The electrocatalytic cathode comprises carbon paper, partially reduced graphene oxide and Pt, the partially reduced graphene oxide is loaded on the surface of the carbon paper, and the Pt is loaded on the surface of the partially reduced graphene oxide.

Preferably, the mass ratio of the carbon paper and Pt is 10-65:1, such as 12:1, 15:1, 18:1, 20:1, 25:1, 30:1, 40:1, 45:1 1 or 55:1 etc., preferably 50:1.

The loading capacity of the graphene oxide of described partial reduction is very little, and only several layers (≥1 layer, such as 1 layer, 2 layers, 3 layers, 5 layers, 6 layers, 8 layers, 10 layers or more are loaded on the carbon paper surface. 15 layers, etc.) partially reduced graphene oxide.

Preferably, the particle size of the Pt is 100-200nm, such as 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm or 190nm.

The electrocatalytic cathode is prepared by the following method:

(1) Soak the carbon paper in Triton non-ionic surfactant for 8-24 hours, take it out and ultrasonically clean it with deionized water for 2-4 hours to obtain hydrophilic carbon paper;

(2) Calcining the hydrophilic carbon paper at 200-400°C for 5 hours to obtain a calcined product;

(3) placing the calcined product in a graphene oxide dispersion with a concentration of 0.1-0.5 wt%, ultrasonication for 1-5h, and taking it out to obtain a calcined product with graphene oxide loaded on its surface;

(4) Put the product obtained in step (3) in an ascorbic acid solution with a concentration of 1-10 mg mL ^-1 and let it stand for 8-24 hours, and then let it stand in a water bath at 40-80° C. for 2 hours to obtain partially reduced surface-loaded The calcined product of graphene oxide;

(5) The surface is loaded with the roasted product of partially reduced graphene oxide as the cathode, and the Pt sheet is used as the anode, adopting an electroplating solution containing 10mM NH ₄ Cl and 1mM PtCl ₄ with a pH value of 1, and using a current of 20mA After electroplating for 10-20 minutes, Pt is deposited on the surface of the partially reduced graphene oxide to obtain the cathode material.

The membrane is a proton exchange membrane, preferably Nafion117.

The integrated structure is obtained by pressing the electrocatalytic anode, the diaphragm and the electrocatalytic cathode under a pressure of 2-10 MPa.

One of the objects of the present invention is also to provide a method for eliminating volatile organic pollutants by using the electrocatalytic oxidation of the above-mentioned reactor, the method is: the volatile organic pollutants containing water vapor and the oxygen-containing gas are respectively It is connected to the anode gas chamber and the cathode gas chamber. Under the condition of electrification, the water vapor in the volatile organic pollutants undergoes an oxidation reaction at the electrocatalyzed anode to generate active oxygen species and protons. The active oxygen species mineralizes the volatile organic pollutants and protons. After passing through the diaphragm, a reduction reaction occurs with oxygen at the electrocatalytic cathode to generate water.

The energized voltage is 2-4V, such as 2.2V, 2.5V, 2.8V, 3V, 3.2V, 3.5V or 3.8V.

Preferably, the oxidation reaction and reduction reaction are independently carried out at 20-45°C, such as 22°C, 25°C, 28°C, 31°C, 35°C, 38°C, 40°C or 42°C.

The volatile organic pollutants are benzene series.

Preferably, the flow rate of the volatile organic pollutants containing water vapor is 20-100mL min ^-1 , such as 25mL min ^-1 , 30mL min ^-1 , 40mL min ^-1 , 50mL min ^-1 , 60mL min ^-1 , 70mL min ^-1 , 80mL min ^-1 , 90mL min ^-1 , etc.

Preferably, the humidity of the volatile organic pollutants containing water vapor is 100%;

Preferably, the flow rate of the oxygen-containing gas is 4-20mL min ^-1 , such as 5mL min ^-1 , 6mL min ^-1 , 8mL min ^-1 , 10mL min ^-1 , 12mL min ^-1 , 15mL min ^-1 or 18mL min ^-1 etc.

Preferably, the oxygen content in the oxygen-containing gas is 10-20v%, such as 12v%, 15v%, 16v%, 17v% or 19v%.

As a preferred technical solution, the method comprises the steps of:

(1) Connecting the electrocatalytic anode and the electrocatalytic cathode to the positive pole and the negative pole of a 2-4V direct current power supply respectively;

(2) Pass volatile organic pollutants containing water vapor and oxygen-containing gas into the anode gas chamber and cathode gas chamber respectively, the flow rate of volatile organic compounds containing water vapor is 20-100mL min ^-1 The humidity of volatile organic pollutants is 100%; the flow rate of oxygen-containing gas is 4-20mL min ^-1 ; the content of oxygen in oxygen-containing gas is 10-20v%; the water vapor in volatile organic pollutants is An oxidation reaction occurs to generate active oxygen species and protons. The active oxygen species mineralizes volatile organic pollutants. After passing through the diaphragm, the protons undergo a reduction reaction with oxygen at the electrocatalytic cathode to generate water. The temperature of the oxidation reaction and reduction reaction is 20-45 ℃.

Compared with prior art, the beneficial effect of the present invention is:

The reactor for the gas-solid phase electrocatalytic reaction provided by the present invention has a simple structure and can be used for the electrocatalytic oxidation reaction between the gas-solid phase; since the anode gas chamber and the cathode gas chamber are separately arranged, it is beneficial to the anode reaction and The cathode reaction is carried out without interference, and the reaction rate is faster; the integrated structure is convenient for proton and transfer, and reduces resistance;

The method for eliminating volatile organic pollutants provided by the present invention is safe, convenient, and low in energy consumption. It only needs 2-4V external DC voltage to realize the oxidative degradation of VOCs; and it can realize the oxidation of VOCs at room temperature (20-45° C.), The product is mostly _CO2 and a small amount of CO.

Description of drawings

Fig. 1 is the schematic structural diagram of the gas-solid electrocatalytic oxidation electrolytic cell provided in Example 1, wherein: 1, the first gas outlet; 2, the first air inlet; 3-1, the first terminal; 3-2, The second terminal; 3-3, the third terminal; 4, integrated structure; 5, the anode chamber; 6, the cathode chamber; 7, the second air outlet; 8, the second air inlet; 9-1, First seal; 9-2, second seal; 10-1, third seal; 10-2, fourth seal.

Figure 2a is a SEM image of the pretreated Ti substrate surface.

Figure 2b and Figure 2c are SEM images of the electrocatalytic anode prepared in Example 2 under different magnification conditions.

FIG. 3 is an XRD pattern of the electrocatalytic anode prepared in Example 2.

Figure 4a is the Ti/Sb-SnO ₂ electrode with SnO ₂ -Sb ₂ O ₃ loadings of 4.4 mg cm ^-2 and 7.7 mg cm ^-2 respectively, and the electrocatalytic electrode described in Comparative Example 1 for the activity test of benzene elimination Graph; where: ■ indicates the elimination rate of benzene on the Ti/Sb-SnO ₂ electrode with a loading capacity of SnO ₂ -Sb ₂ O ₃ of 4.4 mg cm ^-2 ; □ indicates that the loading capacity of SnO ₂ -Sb ₂ O ₃ is 7.7 mg cm ^-2 Ti/Sb-SnO ₂ electrode to the elimination rate of benzene; Represents the Ti/SnO ₂ electrode described in Comparative Example 1 to the elimination rate of benzene.

Figure 4b shows the Ti/Sb-SnO ₂ electrodes with SnO ₂ -Sb ₂ O ₃ loadings of 4.4 mg cm ^-2 and 7.7 mg cm ^-2 respectively and the electrocatalytic electrode described in Comparative Example 1 for the elimination of benzene CO and CO The production yield curve of ₂ , in which, ○ indicates that the Ti/Sb-SnO ₂ electrode with SnO ₂ -Sb ₂ O ₃ loading capacity of 7.7 mg cm ^-2 is used to eliminate the production yield of benzene CO ₂ ; △ indicates the production yield of SnO ₂ - Ti/Sb ^- _{SnO 2} electrode with Sb ₂ O ₃ loading _of 7.7 mg cm ^-2 is used to eliminate the yield of benzene CO formation _; /Sb-SnO ₂ electrode is used to eliminate the production yield of benzene CO ₂ ; ▲ indicates that the Ti/Sb-SnO ₂ electrode with SnO ₂ -Sb ₂ O ₃ loading capacity of 4.4 mgcm ^-2 is used to eliminate the production yield of benzene CO ; ⊕ represents that the electrocatalytic electrode described in Comparative Example 1 is used to eliminate benzene CO ₂ generation yield; Indicates that the electrocatalytic electrode described in Comparative Example 1 is used to eliminate the production yield of benzene CO.

FIG. 5 is an SEM image of the carbon paper provided in Example 11.

FIG. 6 is an SEM image of the carbon paper loaded with partially reduced graphene oxide provided in Example 11. FIG.

7 is a low-magnification SEM image of the cathode material for electrocatalytic reduction of oxygen provided in Example 11.

FIG. 8 is a high-magnification SEM image of the cathode material for electrocatalytic reduction of oxygen provided in Example 11. FIG.

detailed description

The technical solutions of the present invention will be further described below in conjunction with the accompanying drawings and through specific implementation methods.

Example 1

A reactor for gas-solid phase electrocatalytic reaction, as shown in Figure 1. The electrolytic cell comprises an anode gas chamber 5, a cathode gas chamber 6, an electrocatalytic anode, a diaphragm and an electrocatalytic cathode, and both the electrocatalytic anode and the electrocatalytic cathode are breathable; the diaphragm is airtight, and protons can pass through the diaphragm;

The diaphragm is placed between the electrocatalytic anode and the electrocatalytic cathode, and the three form a whole to form an integrated structure 4; the integrated structure 4 is formed by placing the electrocatalytic anode, diaphragm and electrocatalytic cathode under a pressure of 2-10 kg Pressed to get;

The anode gas chamber 5 and the cathode gas chamber 6 are independently cavities provided with through holes, the integrated structure 4 is placed between the through holes of the anode gas chamber 5 and the through holes of the cathode gas chamber 6, and the anode The through holes of the gas chamber 5 and the through holes of the cathode gas chamber 6 are covered;

The anode gas chamber 5 is provided with a first air inlet 2, a first gas outlet 1 and a first wire, one end of the first wire is connected to the electrocatalytic anode, and the other end is connected to the positive pole of the power supply along the inner wall of the anode gas chamber 5 The first air intake pipe is also set in the first air inlet 2, the first air intake pipe includes a diversion section and an expansion section, the diameter of the expansion section is greater than the diameter of the diversion section, and the first air intake pipe The enlarged section of is located in the anode gas chamber 5;

As a preference, the anode gas chamber 5 is also provided with a first terminal 3-1; the inner wall of the first wire salt anode gas chamber 5 is connected to the electrocatalytic anode at one end and connected to the first terminal 3-1 at the other end ;

Preferably, the anode gas chamber 5 is also provided with a first seal 9-1 and a third seal 10-1;

The cathode gas chamber 6 is provided with a second air inlet 8, a second gas outlet 7 and a second wire, one end of the second wire is connected to the electrocatalytic cathode, and the other end is connected to the negative pole of the power supply along the inner wall of the cathode gas chamber 6 A second air intake pipe is also set in the second air inlet 8, and the second air intake pipe includes a diversion section and an expansion section, and the diameter of the expansion section is greater than the diameter of the flow diversion section, and the second air intake pipe The enlarged section of is located in the cathode gas chamber 6.

As preferably, the cathode gas chamber 6 is also provided with a second terminal 3-2 and a third terminal 3-3, and the second wire is along the inner wall of the anode gas chamber 5, and one end is connected with the electrocatalytic cathode, and the other end is connected with the electrocatalytic cathode. The second terminal 3-2 is connected; the third terminal 3-3 is used to connect the reference electrode;

Preferably, the cathode gas chamber 6 is also provided with a second seal 9-2 and a fourth seal 10-2; the first seal 9-1 cooperates with the second seal 9-2; the third The sealing member 10-1 cooperates with the fourth sealing member 10-2; so that the anode gas chamber 5 and the cathode gas chamber 6 are hermetically connected;

The membrane is a proton exchange membrane, such as Nafion117.

Preferably, the electrocatalytic anode includes a metal Ti substrate and an active material layer located on the surface of the Ti substrate. The active material layer is a dense layer formed by stacking nanoparticles. The material of the nanoparticles is doped SnO ₂ . The heteroelement includes F and Sb; the loading amount of the active material layer on the surface of the Ti substrate is 2-10 mg cm ^-2 ; the particle size of the doped SnO ₂ is 1-10 nm; the doping element and Sn The molar ratio is 0.04-0.1; the molar ratio of Sb and F is (5-50): 1; the metal Ti substrate is titanium foam and/or titanium mesh, preferably titanium foam;

The electrocatalytic anode is prepared by the following method:

(1) First soak the metal Ti substrate with a concentration of 10wt%-20wt% NaOH solution at 80°C for 10min; then immerse in a 10wt% oxalic acid solution and boil for 1-3h; then ultrasonically clean the surface of the metal titanium substrate with distilled water Oxalic acid and titanium oxalate to obtain a pretreated metal Ti substrate;

(2) Electroplating Sn and Sb on the pretreated Ti substrate by electrodeposition to obtain a Ti substrate with a coating on the surface, wherein the electroplating solution is a soluble compound containing 1-2M SnCl ₄ , 0.2-1M Sb and 0.1- 1M HNO ₃ ethylene glycol solution, the electroplating uses Pt sheet as the anode; the electroplating current is 10-15mA cm ^-2 ; the electroplating time is 15-60min;

(3) Coating the slurry on the metal Ti substrate with a coating on the surface, drying at 100°C for 5 minutes, and then firing at 500°C with a heating rate of 5°C min ^-1 , to obtain the active ingredient layer on the surface of the Ti substrate Electrocatalytic electrode, wherein the slurry is a mixed solution of isopropanol and n-butanol containing 0.2-1M SnCl ₄ , 0.02-0.1M Sb soluble compound, 0.001-0.1MF soluble compound and 0.1-1M HNO ₃ , the active ingredient The layer is formed by stacking nanoparticles, and the active component layer is a doped SnO ₂ layer, and the doping elements include F and Sb.

Preferably, the electrocatalytic cathode includes carbon paper, partially reduced graphene oxide and Pt, the partially reduced graphene oxide is loaded on the surface of carbon paper, and the Pt is loaded on the partially reduced graphene oxide surface; the The mass ratio of carbon paper to Pt is 10-65:1, preferably 50:1; the particle size of the Pt is 100-200nm, and the rest are the same as in Example 1.

The electrocatalytic cathode is prepared by the following method:

(1) Soak the carbon paper in Triton non-ionic surfactant for 8-24 hours, take it out and ultrasonically clean it with deionized water for 2-4 hours to obtain hydrophilic carbon paper;

(2) Calcining the hydrophilic carbon paper at 200-400°C for 5 hours to obtain a calcined product;

(3) placing the calcined product in a graphene oxide dispersion with a concentration of 0.1-0.5 wt%, ultrasonication for 1-5h, and taking it out to obtain a calcined product with graphene oxide loaded on its surface;

(4) Put the product obtained in step (3) in an ascorbic acid solution with a concentration of 1-10 mg mL ^-1 and let it stand for 8-24 hours, and then put it in a water bath at 40-80° C. for 2 hours to obtain partially reduced surface-loaded The calcined product of graphene oxide;

(5) The surface is loaded with the roasted product of partially reduced graphene oxide as the cathode, and the Pt sheet is used as the anode, adopting an electroplating solution containing 10mM NH ₄ Cl and 1mM PtCl ₄ with a pH value of 1, and using a current of 20mA After electroplating for 10-20 minutes, Pt is deposited on the surface of the partially reduced graphene oxide to obtain the cathode material.

Utilize the method for eliminating volatile organic pollutants by electrocatalytic oxidation of the above-mentioned reactor, said method comprises the following steps:

(1) Connect the DC power supply;

(2) Pass volatile organic pollutants containing water vapor into the anode chamber; pass oxygen-containing gas into the cathode chamber; the water vapor in the volatile organic pollutants is oxidized at the electrocatalyzed anode to generate activity Oxygen species and protons, active oxygen species oxidize volatile organic pollutants, and protons undergo a reduction reaction with oxygen at the electrocatalytic cathode to generate water after passing through the diaphragm.

Specifically, the method includes the steps of:

(1) Connecting the electrocatalytic anode and the electrocatalytic cathode to the positive pole and the negative pole of a 2-4V direct current power supply respectively;

(2) Pass volatile organic pollutants containing water vapor and oxygen-containing gas into the anode gas chamber and cathode gas chamber respectively, the flow rate of volatile organic compounds containing water vapor is 20-100mL min ^-1 The humidity of volatile organic pollutants is 100%; the flow rate of oxygen-containing gas is 4-20mL min ^-1 ; the content of oxygen in oxygen-containing gas is 10-20v%; the water vapor in volatile organic pollutants is An oxidation reaction occurs to generate active oxygen species and protons. The active oxygen species mineralizes volatile organic pollutants. After passing through the diaphragm, the protons undergo a reduction reaction with oxygen at the electrocatalytic cathode to generate water. The temperature of the oxidation reaction and reduction reaction is 20-45 ℃.

Example 2

A preparation method of Ti/Sb- _SnO , comprising the steps of:

(1) Use foamed titanium as the base, first soak the base with 20wt% NaOH solution at 80°C for 10min, remove surface oil; then boil with 10wt% oxalic acid solution for 3h, the surface of the foamed titanium etched by oxalic acid is gray and pockmarked, as Figure 2a; oxalic acid and titanium oxalate on the surface of the titanium substrate were ultrasonically cleaned with distilled water to obtain a pretreated foamed Ti substrate;

(2) Electroplating Sn and Sb on the pretreated foam Ti substrate, the plating solution is: ethylene glycol solution of 1M SnCl ₄ , 0.2M SbCl ₃ and 0.1M HNO ₃ , the Pt sheet is used as the anode, and the current is 15mA cm ^-2 , the electroplating time is 60min; then baked at 500°C for 30min to obtain a Ti substrate with SnO ₂ and Sb ₂ O ₃ on the surface;

(3) Brush slurry on the Ti substrate with SnO ₂ and Sb ₂ O ₃ on the surface, slurry composition: 50mL isopropanol and n-butanol mixed with 0.5M SnCl ₄ , 0.02M SbCl ₃ , 0.001M NaF, 0.1M HNO ₃ Solution, after brushing, put it in a 100°C oven to dry for 5 minutes; then brush and dry;

(4) Repeat step (3) 6 times and bake at 500°C to form a 4.4 mg cm ^-2 SnO ₂ -Sb ₂ O ₃ oxide layer on the foamed Ti substrate, which is the Ti/Sb-SnO ₂ electrode.

The obtained Ti/Sb-SnO ₂ electrodes were tested by XRD and SEM, and the results are shown in Figure 3, Figure 2b and Figure 2c. It can be seen from Figure 3 that the obtained oxide layer completely covers the foamed Ti substrate, and Sb enters the SnO ₂ lattice to cause a red shift of the SnO ₂ diffraction peak; it can be seen from Figure 2b and Figure 2c that the obtained oxide layer is dense and free of cracks. Nanoparticles are stacked, and the particle size of doped SnO ₂ is 1-10nm, such as 2nm, 5nm, 7nm or 9nm. After analysis, the doping elements include F and Sb, the ratio of the total molar weight of F and Sb to the molar weight of Sn is 0.04; the molar ratio of Sb and F is 10:1.

Example 3

A preparation method of Ti/Sb-SnO ₂ , the preparation method is the same as that of Example 1 except that step (4) is roasted at 500° C. after repeating step (3) 10 times. A 7.7 mgcm ^-2 SnO ₂ -Sb ₂ O ₃ oxide layer is formed on the Ti substrate, which is the Ti/Sb-SnO ₂ electrode.

XRD and SEM tests were carried out on the obtained Ti/Sb-SnO ₂ electrode. The results are: the obtained oxide layer covers the foamed Ti substrate completely, and Sb enters the SnO ₂ lattice to cause the red shift of the SnO ₂ diffraction peak; the obtained oxide layer is dense and without Cracks are formed by stacking nanoparticles, and the particle size of doped SnO ₂ is 1-10nm, such as 2nm, 5nm, 7nm or 9nm. After analysis, the doping elements include F and Sb, the ratio of the total molar weight of F and Sb to the molar weight of Sn is 0.04; the molar ratio of Sb and F is 10:1.

Example 4

A preparation method of Ti/Sb-SnO ₂ , the preparation method is the same as that of Example 1 except for one pass of brushing and drying in step (3).

A 2 mgcm ^-2 SnO ₂ -Sb ₂ O ₃ oxide layer is formed on the foamed Ti substrate, which is a Ti/Sb-SnO ₂ electrode.

XRD and SEM tests were carried out on the obtained Ti/Sb-SnO ₂ electrode. The results are: the obtained oxide layer covers the foamed Ti substrate completely, and Sb enters the SnO ₂ lattice to cause the red shift of the SnO ₂ diffraction peak; the obtained oxide layer is dense and without Cracks are formed by stacking nanoparticles, and the particle size of doped SnO ₂ is 1-10nm, such as 2nm, 5nm, 7nm or 9nm. After analysis, the doping elements include F and Sb, the ratio of the total molar weight of F and Sb to the molar weight of Sn is 0.04; the molar ratio of Sb and F is 10:1.

Example 5

A kind of Ti/Sb-SnO ₂ preparation method, described preparation method carries out 20 times brushing and drying in step (3), all the other are the same as embodiment 1.

A 10 mgcm ^-2 SnO ₂ -Sb ₂ O ₃ oxide layer is formed on the foamed Ti substrate, which is a Ti/Sb-SnO ₂ electrode.

XRD and SEM tests were carried out on the obtained Ti/Sb-SnO ₂ electrode. The results are: the obtained oxide layer covers the foamed Ti substrate completely, and Sb enters the SnO ₂ lattice to cause the red shift of the SnO ₂ diffraction peak; the obtained oxide layer is dense and without Cracks are formed by stacking nanoparticles, and the particle size of doped SnO ₂ is 1-10nm, such as 2nm, 5nm, 7nm or 9nm. After analysis, the doping elements include F and Sb, the ratio of the total molar weight of F and Sb to the molar weight of Sn is 0.04; the molar ratio of Sb and F is 10:1.

Example 6

A kind of electrocatalytic electrode, its preparation method comprises the steps:

(1) First soak the foamed Ti substrate with a concentration of 20wt% NaOH solution at 80°C for 10min; then immerse in a 10wt% oxalic acid solution and boil for 3h; then ultrasonically clean the oxalic acid and titanium oxalate on the surface of the foamed titanium substrate with distilled water , to obtain the pretreated foamed Ti substrate;

(2) Electroplating Sn and Sb on the pretreated foamed Ti substrate by electrodeposition to obtain a foamed Ti substrate with a coating on the surface. The electroplating solution is ethylene glycol containing 1M SnCl ₄ , 1M SbCl ₃ and 0.1M HNO ₃ solution, the electroplating uses a Pt sheet as the anode; the electroplating current is 15mA cm ^-2 ; the electroplating time is 60min;

(3) Coat the slurry on the foamed Ti substrate with a coating on the surface, and dry it at 100°C for 5 minutes, wherein the slurry is isopropanol containing 0.2M SnCl ₄ , 0.1M SbCl ₃ , 0.001M NaF and 1M HNO ₃ and Mixed solution of n-butanol;

(4) After repeating step (3) four times, the product was calcined at 500°C with a heating rate of 5°C min ^-1 to obtain an electrocatalytic electrode with an active component layer on the surface of the Ti substrate. The active component layer was composed of nanoparticles stacked, and the active component layer is a doped _SnO2 layer, the doping elements include a first doping element and a second doping element, the first doping element is selected from F, and the second doping element is selected from Sb. A 3.2 mg cm ^-2 SnO ₂ -Sb ₂ O ₃ oxide layer is formed on the foamed Ti substrate, which is the Ti/Sb-SnO ₂ electrode.

XRD and SEM tests were carried out on the obtained Ti/Sb-SnO ₂ electrode. The results are: the obtained oxide layer covers the foamed Ti substrate completely, and Sb enters the SnO ₂ lattice to cause the red shift of the SnO ₂ diffraction peak; the obtained oxide layer is dense and without Cracks are formed by stacking nanoparticles, and the particle size of doped SnO ₂ is 1-10nm, such as 2nm, 5nm, 7nm or 9nm. After analysis, the doping elements include F and Sb, the ratio of the total molar weight of F and Sb to the molar weight of Sn is 0.5; the molar ratio of Sb and F is 100:1.

Example 7

A kind of electrocatalytic electrode, its preparation method comprises the steps:

(1) First soak the foamed Ti substrate with a concentration of 20wt% NaOH solution at 80°C for 10min; then immerse in a 10wt% oxalic acid solution and boil for 3h; then ultrasonically clean the oxalic acid and titanium oxalate on the surface of the foamed titanium substrate with distilled water , to obtain the pretreated foamed Ti substrate;

(2) Sn and Sb are electroplated on the pretreated foamed Ti substrate by electrodeposition to obtain a foamed Ti substrate with a coating on the surface. The electroplating solution is ethylenedioxide containing 2M SnCl ₄ , 0.2M SbCl ₃ and 0.5M HNO ₃ Alcohol solution, the electroplating uses a Pt sheet as the anode; the electroplating current is 15mA cm ^-2 ; the electroplating time is 15min;

(3) Coat the slurry on the foamed Ti substrate with a coating on the surface, and dry it at 100°C for 5 minutes, wherein the slurry is isopropanol containing 1M SnCl ₄ , 0.02M SbCl ₃ , 0.1M NaF and 0.1M HNO ₃ and Mixed solution of n-butanol;

(4) After repeating step (3) four times, the product was calcined at 500°C with a heating rate of 5°C min ^-1 to obtain an electrocatalytic electrode with an active component layer on the surface of the Ti substrate. The active component layer was composed of nanoparticles stacked, and the active component layer is a doped _SnO2 layer, the doping elements include a first doping element and a second doping element, the first doping element is selected from F, and the second doping element is selected from Sb. A 2.6mg cm ^-2 SnO ₂ -Sb ₂ O ₃ oxide layer is formed on the foamed Ti substrate, which is the Ti/Sb-SnO ₂ electrode.

XRD and SEM tests were carried out on the obtained Ti/Sb-SnO ₂ electrode. The results are: the obtained oxide layer covers the foamed Ti substrate completely, and Sb enters the SnO ₂ lattice to cause the red shift of the SnO ₂ diffraction peak; the obtained oxide layer is dense and without Cracks are formed by stacking nanoparticles, and the particle size of doped SnO ₂ is 1-10nm, such as 2nm, 5nm, 7nm or 9nm. After analysis, the doping elements include F and Sb, the ratio of the total molar weight of F and Sb to the molar weight of Sn is 0.12:1; the molar ratio of Sb and F is 0.2:1.

Example 8

A kind of electrocatalytic electrode, its preparation method comprises the steps:

(1) First soak the foamed Ti substrate with a concentration of 15wt% NaOH solution at 80°C for 10min; then immerse in a 10wt% oxalic acid solution and boil for 3h; then ultrasonically clean the oxalic acid and titanium oxalate on the surface of the foamed titanium substrate with distilled water , to obtain the pretreated foamed Ti substrate;

(2) Sn and Sb are electroplated on the pretreated foamed Ti substrate by electrodeposition to obtain a foamed Ti substrate with a coating on the surface. The electroplating solution is ethyl alcohol containing 1.5M SnCl ₄ , 0.5M SbCl ₃ and 0.3M HNO ₃ Diol solution, the electroplating uses a Pt sheet as the anode; the electroplating current is 15mA cm ^-2 ; the electroplating time is 30min;

(3) Coat the slurry on the foamed Ti substrate with a coating on the surface, and dry it at 100°C for 5 minutes, wherein the slurry is isopropanol containing 0.5M SnCl ₄ , 0.05M SbCl ₃ , 0.05M NaF and 0.3M HNO ₃ Mixed solution of alcohol and n-butanol;

(4) After repeating step (3) four times, the product was calcined at 500°C with a heating rate of 5°C min ^-1 to obtain an electrocatalytic electrode with an active component layer on the surface of the Ti substrate. The active component layer was composed of nanoparticles stacked, and the active component layer is a doped _SnO2 layer, the doping elements include a first doping element and a second doping element, the first doping element is selected from F, and the second doping element is selected from Sb. A 3.0 mg cm ^-2 SnO ₂ -Sb ₂ O ₃ oxide layer is formed on the foamed Ti substrate, which is the Ti/Sb-SnO ₂ electrode.

XRD and SEM tests were carried out on the obtained Ti/Sb-SnO ₂ electrode. The results are: the obtained oxide layer covers the foamed Ti substrate completely, and Sb enters the SnO ₂ lattice to cause the red shift of the SnO ₂ diffraction peak; the obtained oxide layer is dense and without Cracks are formed by stacking nanoparticles, and the particle size of doped SnO ₂ is 1-10nm, such as 2nm, 5nm, 7nm or 9nm. After analysis, the doping elements include F and Sb, the ratio of the total molar weight of F and Sb to the molar weight of Sn is 0.2:1; the molar ratio of Sb and F is 1:1.

Comparative example 1

An electrocatalytic electrode comprises a foamed titanium base and SnO ₂ supported on the foamed titanium base. The preparation method of the electrocatalytic electrode comprises the following steps:

(1) Adopt foamed titanium as substrate, first soak this substrate 10min at 80 ℃ with 20wt% NaOH solution, remove surface oil stain; Boil 3h with 10wt% oxalic acid solution afterwards, the surface of foamed titanium etched by oxalic acid is gray pitted surface; use Ultrasonic cleaning of oxalic acid and titanium oxalate on the surface of the titanium substrate with distilled water to obtain a pretreated foamed Ti substrate;

(2) Electroplating Sn on the pretreated foam Ti substrate, the plating solution is: ethylene glycol solution of 1M SnCl ₄ and 0.1M HNO ₃ , the Pt sheet is used as the anode, the current is 15mA cm ^-2 , and the plating time is 60min; Then bake at 500°C for 30min to obtain a Ti substrate with _SnO on the surface;

(3) Brush slurry on the Ti substrate with SnO ₂ on the surface, the slurry composition: 50mL isopropanol and n-butanol mixed solution of 0.5M SnCl ₄ , 0.1M HNO ₃ , after brushing, put it into a 100°C oven to dry for 5min; Repaint, dry;

(4) Repeat step (3) 6 times and bake at 500°C to form a SnO ₂ oxide layer on the foamed Ti substrate, which is the Ti/SnO ₂ electrode.

Example 9

A cathode material for electrocatalytic reduction of oxygen comprises carbon paper, partially reduced graphene oxide and Pt, the partially reduced graphene oxide is loaded on the surface of carbon paper, and the Pt is loaded on the surface of partially reduced graphene oxide, so The masses of the carbon paper and the Pt are 76 mg and 1.5 mg respectively, and the average particle size of the Pt is 150 nm.

A method for preparing a cathode material for electrocatalytic reduction of oxygen, comprising the steps of:

(1) Soak the carbon paper in Triton X-100 non-ionic surfactant for 8 hours, soak it in deionized water for 2 hours after taking it out, and obtain hydrophilic carbon paper after ultrasonic cleaning;

(2) roasting the hydrophilic carbon paper for 5 hours to obtain a roasted product;

(3) placing the calcined product in a graphene oxide dispersion with a concentration of 0.3wt%, ultrasonication for 1 h, and obtaining a calcined product with graphene oxide loaded on the surface after taking it out;

(4) placing the product obtained in step (3) in a solution of ascorbic acid with a concentration of 5 mg mL ^-1 and standing for 24 h to obtain a roasted product of partially reduced graphene oxide loaded on the surface;

(5) The surface is loaded with the roasted product of partially reduced graphene oxide as the cathode, and the Pt sheet is used as the anode, adopting an electroplating solution containing 10mM NH ₄ Cl and 1mM PtCl ₄ with a pH value of 1, and using a current of 20mA After electroplating for 10 minutes, Pt is deposited on the surface of the partially reduced graphene oxide to obtain the cathode material for the electrocatalytic reduction of oxygen.

Example 10

A cathode material for electrocatalytic reduction of oxygen comprises carbon paper, partially reduced graphene oxide and Pt, the partially reduced graphene oxide is loaded on the surface of carbon paper, and the Pt is loaded on the surface of partially reduced graphene oxide, so The masses of the carbon paper and the Pt are 76 mg and 4.5 mg respectively, and the average particle size of the Pt is 100 nm.

A method for preparing a cathode material for electrocatalytic reduction of oxygen, comprising the steps of:

(1) Soak carbon paper in Triton X-100 non-ionic surfactant for 24 hours, soak it in deionized water for 2 hours after taking it out, and obtain hydrophilic carbon paper after ultrasonic cleaning;

(2) roasting the hydrophilic carbon paper for 5 hours to obtain a roasted product;

(3) placing the calcined product in a graphene oxide dispersion with a concentration of 0.5 wt%, ultrasonicating for 5 hours, and obtaining a calcined product with graphene oxide loaded on the surface after taking it out;

(4) placing the product obtained in step (3) at a concentration of 10 mg mL ^-1 in an ascorbic acid solution and standing for 8 h to obtain a roasted product of partially reduced graphene oxide loaded on the surface;

(5) The surface is loaded with the roasted product of partially reduced graphene oxide as the cathode, and the Pt sheet is used as the anode, adopting an electroplating solution containing 10mM NH ₄ Cl and 1mM PtCl ₄ with a pH value of 1, and using a current of 20mA After electroplating for 30 minutes, Pt is deposited on the surface of the partially reduced graphene oxide to obtain the cathode material for the electrocatalytic reduction of oxygen.

Example 11

A cathode material for electrocatalytic oxygen reduction, comprising carbon paper, partially reduced graphene oxide and Pt, the partially reduced graphene oxide is supported on the surface of carbon paper, and the Pt is supported on the partially reduced graphene oxide surface, The masses of the carbon paper and the Pt are 76 mg and 7.5 mg respectively, and the average particle size of the Pt is 200 nm.

A method for preparing a cathode material for electrocatalytic reduction of oxygen, comprising the steps of:

(1) Soak carbon paper in Triton X-100 non-ionic surfactant for 12 hours, soak it in deionized water for 2 hours after taking it out, and obtain hydrophilic carbon paper after ultrasonic cleaning;

(2) roasting the hydrophilic carbon paper for 5 hours to obtain a roasted product;

(3) placing the calcined product in a graphene oxide dispersion with a concentration of 0.1 wt%, ultrasonication for 3 hours, and obtaining a calcined product with graphene oxide on the surface after taking it out;

(4) placing the product obtained in step (3) at a concentration of 1 mg mL ^-1 in an ascorbic acid solution and standing for 12 h to obtain a roasted product of partially reduced graphene oxide loaded on the surface;

(5) The surface is loaded with the roasted product of partially reduced graphene oxide as the cathode, and the Pt sheet is used as the anode, adopting an electroplating solution containing 10mM NH ₄ Cl and 1mM PtCl ₄ with a pH value of 1, with a current of 20mA After electroplating for 120 minutes, Pt was deposited on the surface of the partially reduced graphene oxide to obtain the cathode material for the electrocatalytic reduction of oxygen. Figure 5 is the SEM image of carbon paper, as can be seen from the figure, its surface is smooth; Figure 6 is the SEM image of carbon paper deposited with partially reduced graphene oxide, its surface is rough. The cathode material for the electrocatalytic reduction of oxygen is shown in Figures 7 and 8. It can be seen from the figures that the growth of Pt on the surface of the carbon fiber is induced by the graphene sheet structure, forming a thin sheet standing on the graphene surface with a width of about 200nm.

Example 12

Utilize the Ti/Sb-SnO described in embodiment 2 and embodiment 3 ₂ and the electrode that comparative example 4 obtains as electrocatalytic anode respectively, with the negative electrode material of electrocatalytic reduction oxygen described in embodiment 11 as electrocatalytic cathode; Utilize The reactor for gas-solid phase electrocatalytic reaction described in embodiment 1 eliminates indoor volatile organic pollutants, comprising the steps:

(1) Connecting the electrocatalytic anode and the electrocatalytic cathode to the positive pole and the negative pole of a 2-4V direct current power supply respectively;

(2) Pass volatile organic pollutants containing water vapor and oxygen-containing gas into the anode gas chamber and cathode gas chamber respectively, the flow rate of volatile organic compounds containing water vapor is 20-100mL min ^-1 The humidity of volatile organic pollutants is 100%; the flow rate of oxygen-containing gas is 4-20mL min ^-1 ; the content of oxygen in oxygen-containing gas is 10-20v%; the water vapor in volatile organic pollutants is An oxidation reaction occurs to generate active oxygen species and protons. The active oxygen species mineralizes volatile organic pollutants. After passing through the diaphragm, the protons undergo a reduction reaction with oxygen at the electrocatalytic cathode to generate water. The temperature of the oxidation reaction and reduction reaction is 20-45 ℃.

Among them, the concentration of each component in the anode gas chamber is: 30ppm benzene, room temperature saturated water vapor, air, and the gas flow rate is 100mLmin ^-1 ; the cathode gas chamber: 80% N ₂ and 20% O ₂ . The voltage of the DC power supply is 2V. The reaction gases and products were detected by gas chromatography and PTR-QTOF mass spectrometer, and the test results are shown in Figure 4a and Figure 4b, where 4.4CO ₂ and 4.4CO are Ti/Sb-SnO with a mass density of 4.4 as the active material respectively ₂ The content of _CO2 and CO produced by the electrode; _7.7CO2 and 7.7CO are the content of _CO2 and CO produced by the Ti/Sb- _SnO2 electrode with a mass density of active material of 7.7; it can be seen from the figure: The electrocatalytic anode obtained in embodiment 2 and embodiment 3 can completely convert 30ppm benzene into _CO and _CO , and the volume of CO exceeds 80%; the electrocatalytic electrode obtained in comparative example 4 is used to eliminate benzene at room temperature, and its 7h When the elimination rate is only 35%, it is far lower than the elimination rate of the electrocatalytic electrode described in embodiment 2 and embodiment 3 to benzene.

The electrodes obtained in Examples 4-8 are respectively used as anodes, and the cathode materials for the electrocatalytic reduction of oxygen obtained in Examples 9-10 are respectively used as electrocatalytic cathodes, and benzene is degraded according to the method described in Example 12. Test conditions and test equipment are the same as The test conditions and equipment described in Example 12 are the same, and the results show that it can also completely eliminate benzene at room temperature, and more than 80% of the volume of the reaction product is CO ₂ .

In addition, the voltage in Example 12 is adjusted to any point value in 2-4V; the flow rate of volatile organic compounds containing water vapor is adjusted to any point value in 20-100mL min ^-1 ; the oxygen-containing gas The flow rate is adjusted to any point value in 4-20mL min ^-1 ; the content of oxygen in the oxygen-containing gas is adjusted to any point value in 10-20v%; the temperature of oxidation reaction and reduction reaction is adjusted to For any point value in the range of 20-45°C, the test results are basically the same as those in Example 12.

The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, and those skilled in the art should understand that any person skilled in the art should be aware of any disclosure in the present invention Within the technical scope, easily conceivable changes or substitutions all fall within the scope of protection and disclosure of the present invention.

Claims (10)

1. a kind of reactor for vapor solid electrocatalytic reaction, it is characterised in that the reactor includes anode gas chamber, the moon Pole air chamber, electro-catalysis anode, barrier film and electro-catalysis negative electrode, the electro-catalysis anode and electro-catalysis negative electrode are breathed freely；

The barrier film is placed between electro-catalysis anode and electro-catalysis negative electrode, and three's composition is overall, is integrally formed structure；

The anode gas chamber and cathode air chamber independently are the cavity for being provided with through hole, and the integrative-structure is placed in the logical of anode gas chamber Between hole and the through hole of cathode air chamber, and the through hole of the through hole of anode gas chamber and cathode air chamber is covered；

The anode gas chamber is additionally provided with the first air inlet, the first gas outlet and alternatively the first wire, one end of the first wire It is connected with electro-catalysis anode, the other end is connected with the positive pole of power supply；

The cathode air chamber is additionally provided with the second air inlet, the second gas outlet and alternatively the second wire, one end of the second wire It is connected with electro-catalysis negative electrode, the other end is connected with the negative pole of power supply.

2. reactor according to claim 1, it is characterised in that also set up the first air inlet pipe in first air inlet, Also set up the second air inlet pipe in second air inlet, first air inlet pipe and the second air inlet pipe independently include diversion section and Expanding reach, the diameter with diameter greater than diversion section of the expanding reach, the expanding reach of first air inlet pipe is located in anode gas chamber, The expanding reach of second air inlet pipe is located in cathode air chamber.

3. reactor according to claim 1 and 2, it is characterised in that first wire along anode gas chamber inwall with Electro-catalysis anode is connected；Second wire is connected along the inwall of cathode air chamber with electro-catalysis negative electrode；

Preferably, the anode gas chamber also sets up the first binding post, and first wire passes through the first binding post with power supply just Extremely it is connected；

Preferably, the cathode air chamber also sets up the second binding post, and second wire is negative with power supply by the second binding post Extremely it is connected；

Preferably, the anode gas chamber and cathode air chamber are tightly connected.

4. according to the reactor that one of claim 1-3 is described, it is characterised in that the electro-catalysis anode includes metal Ti substrates With the active material layer positioned at Ti substrate surfaces, the active material layer is the compacted zone piled up by nano particle, nanometer The material of particle is the SnO of doping₂, doped chemical include F and Sb；Described metal Ti substrates be titanium foam and/or titanium net, it is excellent Elect titanium foam as；

Preferably, the active material layer is 2-10mg cm in the load capacity of Ti substrate surfaces^-2；

Preferably, the SnO of the doping₂Granular size be 1-10nm；

Preferably, the doped chemical and the mol ratio of Sn are 0.04-0.5；

Preferably, the mol ratio of the Sb and F is (0.2-100):1.

5. according to the reactor that one of claim 1-4 is described, it is characterised in that the electro-catalysis negative electrode includes carbon paper, part The graphene oxide and Pt of reduction, the partial reduction it is graphene oxide-loaded in carbon paper surface, the Pt is carried on part The surface of graphene oxide of reduction；

Preferably, the mass ratio of the carbon paper and Pt is 10-65:1, preferably 50:1；

Preferably, the particle size of the Pt is 100-200nm.

6. according to the reactor that one of claim 1-5 is described, it is characterised in that the barrier film is PEM, preferably Nafion117。

7. according to the reactor that one of claim 1-6 is described, it is characterised in that the integrative-structure is by positive by electro-catalysis Pole, barrier film and electro-catalysis negative electrode are pressed under the pressure of 2-10MPa and obtained.

8. the method that volatile organic contaminant is eliminated using one of claim 1-7 described reactor electrocatalytic oxidation, its It is characterised by, methods described is：Volatile organic contaminant and oxygen-containing gas containing vapor are each led into anode gas chamber And cathode air chamber, under power on condition, there is oxidation reaction and produce in the vapor in volatile organic contaminant in electro-catalysis anode Liveliness proof oxygen species and proton, active oxygen species mineralising volatile organic contaminant, proton by after barrier film in electro-catalysis negative electrode There is reduction reaction generation water with oxygen.

9. method according to claim 8, it is characterised in that the voltage of the energization is 2-4V；

Preferably, the oxidation reaction and reduction reaction are independently carried out under the conditions of 20-45 DEG C.

10. method according to claim 8 or claim 9, it is characterised in that the volatile organic contaminant is benzene homologues；

Preferably, the flow velocity of the volatile organic contaminant containing vapor is 20-100mL min^-1；

Preferably, the volatile organic contaminant humidity containing vapor is 100%；

Preferably, the flow velocity of the oxygen-containing gas is 4-20mL min^-1；

Preferably, the content of oxygen described in the oxygen-containing gas is 10-20v%.