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

The method of reactor and its elimination VOCs for gas-solid phase electrocatalytic reaction Download PDF

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CN106732238A
CN106732238A CN201611003102.4A CN201611003102A CN106732238A CN 106732238 A CN106732238 A CN 106732238A CN 201611003102 A CN201611003102 A CN 201611003102A CN 106732238 A CN106732238 A CN 106732238A
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electro
catalysis
anode
negative electrode
reactor
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CN106732238B (en
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贺泓
张博
张长斌
王少莘
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Research Center for Eco Environmental Sciences of CAS
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    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • 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
    • B01D53/32—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 by electrical effects other than those provided for in group B01D61/00
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/80—Type of catalytic reaction
    • B01D2255/806—Electrocatalytic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/22—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/06—Polluted air
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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

The method of reactor and its elimination VOCs for vapor solid electrocatalytic reaction
Technical field
The invention belongs to electrolytic cell and purification of volatile organic pollutant technical field, it is related to a kind of for vapor solid electricity The reactor of catalytic reaction and its method for eliminating VOCs.
Background technology
Volatile organic matter (VOCs) is the main gaseous contaminant in room air, including formaldehyde and benzene homologues.These Pollutant, with very big harm, can cause a disease to health, carcinogenic or teratogenesis.In the market, VOCs's is net in elimination room air Change technology mainly includes physical absorption, ozone oxidation, photocatalysis, heat catalytic oxidation and plasma for purification technology.But these Technology generally existing high energy consumption, the problem with potential safety hazard and generation secondary pollution.
Heat catalytic oxidation method has the advantages that simple to operate, VOCs can be degraded into nontoxic CO2And water.At present, It just can be CO by formaldehyde complete oxidation to have under the conditions of room temperature2To the catalysis material of water and related indoor air purification product, but The product of oxidative degradation benzene homologues does not find also.Because benzene homologues molecular structure is complicated, heat catalytic oxidation is eliminated under room temperature condition Benzene homologues are also difficult to.At present, even active highest catalyst, the temperature of benzene homologues burning also wants 150 DEG C or so, hardly possible Purified with the benzene homologues being applied under indoor environmental condition.Therefore safety economy, the benzene homologues elimination side of non-secondary pollution are developed Method, has very important significance to improving IAQ.
The significant advantage of electro-catalytic oxidation technology is can be effective by changing Interface electric field under conditions of normal temperature and pressure Ground reduces the energy barrier of reaction system, is a kind of substantially environmentally safe, low energy consumption " green " technology, and all of organic Molecule can be aoxidized by electrochemical method.In recent years, electro-catalytic oxidation technology is applied to the elimination of liquid phase organic pollution Research is extensive, and from simple straight chain organic matter to complicated polycyclic arene compound, electro-catalytic process can have these Malicious pollutant is oxidized to CO2And water.
CN 103074638A disclose a kind of double optical window electrolytic cells of double air chambers for electrochemistry preparing gas, including anti- Ying Chi and cover plate, cover plate are arranged at the opening of reaction tank, are removably to be tightly connected between cover plate and reaction tank, the lid Plate is provided with some connectivity ports, and dividing plate is provided with the reaction tank, and it is anti-that the space in reaction tank is divided into working electrode by dividing plate Answer room and auxiliary electrode reaction room two parts, top edge and the reaction tank either flush, the forward and backward lateral edges of dividing plate of the dividing plate It is connected with the forward and backward inner wall sealing of reaction tank, being left between dividing plate lower edge and reaction tank bottom can make electrolyte in work electricity Between pole reative cell and auxiliary electrode reaction room flow freely space, on the side of reaction tank correspondence working electrode reative cell and The position of auxiliary electrode reaction room is inlaid with a glass window for light-permeable respectively.This pair of double optical window electrolytic cells of air chamber are realized Working electrode and auxiliary electrode Surface Creation gas are effectively isolated, consequently facilitating the accuracy of Control release result.
But, do not eliminate the research of degradation of indoor air VOCs using electro-catalytic oxidation technology still at present.
The content of the invention
In view of the shortcomings of the prior art, it is used for vapor solid electrocatalytic reaction it is an object of the invention to provide one kind Reactor and its method that eliminates VOCs, the structure of reactor is simple, can be used for room temperature and eliminates volatile organic contaminant, And the product of generation is most of for CO2。
Unless otherwise specified, the room temperature refers to 20-45 DEG C to the present invention, and the wt% refers to weight/mass percentage composition, described V% refers to volumn concentration.
It is that, up to this purpose, the present invention uses following technical scheme：
An object of the present invention is to provide a kind of reactor for vapor solid electrocatalytic reaction, the reactor Including anode gas chamber, cathode air chamber, electro-catalysis anode, barrier film and electro-catalysis negative electrode, the electro-catalysis anode and electro-catalysis negative electrode Breathe 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 anode gas chamber Through hole and the through hole of cathode air chamber between, 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, the first wire One end is connected with electro-catalysis anode, and 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, the second wire One end is connected with electro-catalysis negative electrode, and the other end is connected with the negative pole of power supply.
Those skilled in the art should be known, and barrier film should be the barrier film that proton should be able to pass through, while barrier film has certain thickness Degree and intensity.
The integrative-structure separates 2 air chambers gas, is conducive to anode reaction and the noiseless of cathode reaction to carry out, and carries System mineralising volatile organic matter efficiency high；The integrative-structure is easy to proton and electron transmission, reduces system resistance.The sun Gas in the air chamber of pole flows out after being reacted on electro-catalysis anode from the gas outlet of anode gas chamber；In the cathode air chamber Gas flows out after being reacted on electro-catalysis negative electrode from the gas outlet of cathode air chamber.Cathode air chamber and anode gas chamber do not connect each other It is logical.
The first air inlet pipe is also set up in first air inlet, the second air inlet pipe, institute are also set up in second air inlet To state the first air inlet pipe and the second air inlet pipe independently include diversion section and expanding reach, the expanding reach with diameter greater than diversion section Diameter, the expanding reach of first air inlet pipe is located in anode gas chamber, and the expanding reach of second air inlet pipe is located at cathode air chamber In.
First wire is connected along the inwall of anode gas chamber with electro-catalysis anode；Second wire is along cathode air chamber Inwall is connected 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 and power supply Positive pole be connected.
Preferably, the cathode air chamber also sets up the second binding post, and second wire passes through the second binding post and power supply Negative pole be connected.
Preferably, the anode gas chamber and cathode air chamber are tightly connected, and are connected such as by bolt seal.
The electro-catalysis anode includes metal Ti substrates and the active material layer positioned at Ti substrate surfaces, the active material Layer is the compacted zone piled up by nano particle, and the material of nano particle is the SnO of doping2, doped chemical include F and Sb, Described metal Ti substrates are titanium foam and/or titanium net, preferably titanium foam.
Preferably, the active material layer is 2-10mg cm in the load capacity of Ti substrate surfaces-2, such as 2.5mg cm-2、 3mg cm-2、3.5mg cm-2、4mg cm-2、4.5mg cm-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-2Or 9.5mg cm-2Deng.
Preferably, the SnO of the doping2Granular size be 1-10nm, such as 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm or 9.5nm etc..
Preferably, the mol ratio of the doped chemical and Sn is 0.04-0.5, such as 0.05,0.06,0.07,0.08,0.09, 0.1st, 02,0.3 or 0.4 etc..
Preferably, the mol ratio of the 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 electro-catalysis anode is prepared via a method which to obtain：
(1) metal Ti substrates are soaked under the conditions of 80 DEG C with the NaOH solution that concentration is 10wt%-20wt% first 10min；Concentration is immersed afterwards to boil 1-3h in the oxalic acid solution of 10wt%；It is cleaned by ultrasonic titanium substrate table with distilled water again The oxalic acid and titanium oxalate in face, obtain pretreated metal Ti substrates；
(2) to use and electroplate Sn and Sb in electro-deposition method Ti substrates after the pre-treatment, obtain the coated Ti bases in surface Bottom, wherein, electroplate liquid is to contain 1-2M SnCl4, 0.2-1M Sb soluble compound and 0.1-1M HNO3Ethylene glycol it is molten Liquid, the plating is anode using Pt pieces；The electric current of plating is 10-15mA cm-2；The time of plating is 15-60min；
(3) slurries are coated in the coated metal Ti substrates in surface, after drying 5min under the conditions of 100 DEG C, at 500 DEG C Under the conditions of be calcined, heating rate be 5 DEG C of min-1, electro catalytic electrode of the active ingredient layer positioned at Ti substrate surfaces is obtained, wherein, slurry Liquid is to contain 0.2-1M SnCl4, the soluble compound of 0.02-0.1M Sb, the soluble compound of 0.001-0.1M F and 0.1-1M HNO3Isopropanol and n-butanol mixed solution, active ingredient layer is to be piled up to form by nano particle, and activity into It is layered as the SnO of doping2Layer, doped chemical includes F and Sb.
The electro-catalysis negative electrode includes carbon paper, the graphene oxide and Pt of partial reduction, the oxidation stone of the partial reduction Black alkene is carried on carbon paper surface, and the Pt is carried on the surface of graphene oxide of partial reduction.
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 or 55:1 etc., preferably 50:1.
The load capacity of the graphene oxide of the partial reduction seldom, several layers of (>=1 layers, such as 1 is only loaded with carbon paper surface Layer, 2 layers, 3 layers, 5 layers, 6 layers, 8 layers, 10 layers or 15 layers etc.) partial reduction graphene oxide.
Preferably, the particle size of the Pt be 100-200nm, such as 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm or 190nm etc..
The electro-catalysis negative electrode is prepared via a method which to obtain：
(1) carbon paper is placed in the logical nonionic surface active agent of Qula and soaks 8-24h, with deionized water ultrasound after taking-up Cleaning 2-4h, obtains hydrophilic carbon paper；
(2) hydrophilic carbon paper is calcined 5h at 200-400 DEG C, obtains product of roasting；
(3) product of roasting is placed in the graphene oxide dispersion that concentration is 0.1-0.5wt%, ultrasonic 1-5h takes out Obtaining area load afterwards has the product of roasting of graphene oxide；
(4) product that step (3) is obtained is placed in concentration for 1-10mg mL-1Ascorbic acid solution in stand 8-24h, 2h is stood in 40-80 DEG C of water-bath afterwards, obtaining area load has the product of roasting of graphene oxide of partial reduction；
(5) area load is had the product of roasting of graphene oxide of partial reduction as negative electrode, with Pt pieces as anode, is adopted With the NH containing 10mM4The PtCl of Cl and 1mM4PH value be 1 electroplate liquid, 10-20min is electroplated with the electric current of 20mA, in part The surface of graphene oxide deposition Pt of reduction, obtains the cathode material.
The barrier film is PEM, preferably Nafion117.
The integrative-structure is pressed by by electro-catalysis anode, barrier film and electro-catalysis negative electrode under the pressure of 2-10MPa Arrive.
An object of the present invention is also resided in a kind of elimination using reactor electrocatalytic oxidation as described above of offer and volatilized The method of property organic pollution, methods described is：Volatile organic contaminant and oxygen-containing gas containing vapor are led to respectively Enter anode gas chamber and cathode air chamber, under power on condition, the vapor in volatile organic contaminant occurs in electro-catalysis anode Oxidation reaction produce active oxygen species and proton, active oxygen species mineralising volatile organic contaminant, proton by after barrier film There is reduction reaction generation water with oxygen in electro-catalysis negative electrode.
The voltage of the energization 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 under the conditions of 20-45 DEG C, such as 22 DEG C, 25 DEG C, 28 DEG C, 31 DEG C, 35 DEG C, 38 DEG C, 40 DEG C or 42 DEG C etc..
The volatile organic contaminant is benzene homologues.
Preferably, the flow velocity of the volatile organic contaminant containing 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 Deng.
Preferably, the volatile organic contaminant humidity containing vapor is 100%；
Preferably, the flow velocity 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-1Or 18mL min-1Deng.
Preferably, the content of oxygen described in the oxygen-containing gas be 10-20v%, such as 12v%, 15v%, 16v%, 17v% or 19v% etc..
Used as preferred technical scheme, methods described comprises the following steps：
(1) by electro-catalysis anode and electro-catalysis negative electrode respectively with voltage for the positive pole and negative pole of 2-4V dc sources are connected；
(2) volatile organic contaminant and oxygen-containing gas containing vapor are each led into anode gas chamber and negative electrode gas Room, the flow velocity of the volatile organic matter containing vapor is 20-100mL min-1, the volatile organic contaminant containing vapor Humidity is 100%；The flow velocity of oxygen-containing gas is 4-20mL min-1；The content of oxygen described in oxygen-containing gas is 10-20v%；Wave Active oxygen species and proton, active oxygen thing produced and oxidation reaction in electro-catalysis anode in the vapor in hair property organic pollution there is Mineralising volatile organic contaminant is planted, proton generates water, institute by there is reduction reaction in electro-catalysis negative electrode and oxygen after barrier film The temperature for stating oxidation reaction and reduction reaction is 20-45 DEG C.
Compared with prior art, beneficial effects of the present invention are：
Provided by the present invention for the reactor of vapor solid electrocatalytic reaction, simple structure can be used between vapor solid Electrocatalysis oxidation reaction；Because anode gas chamber and cathode air chamber are separately provided, be conducive to the nothing of anode reaction and cathode reaction Interference is carried out, and reaction rate is faster；Integrative-structure is easy to proton and transmission, reduces resistance；
The removing method of the volatile organic contaminant that the present invention is provided conveniently, safely, energy consumption it is small, it is only necessary to 2-4V is additional straight Stream voltage can just realize the oxidative degradation of VOCs；And can realize that room temperature (20-45 DEG C) aoxidizes VOCs, product is most of It is CO2With a small amount of CO.
Brief description of the drawings
Fig. 1 is the structural representation of the gas-solid electrocatalytic oxidation electrolytic cell that embodiment 1 is provided, wherein：1, the first outlet Mouthful；2, the first air inlet；3-1, the first binding post；3-2, the second binding post；3-3, the 3rd binding post；4, integrative-structure；5, sun Pole air chamber；6, cathode air chamber；7, the second gas outlet；8, the second air inlet；9-1, first seal；9-2, second seal；10- 1, the 3rd seal；10-2, the 4th seal.
Fig. 2 a are the SEM figures of pretreated Ti substrate surfaces.
Fig. 2 b and Fig. 2 c are SEM figure of the electro-catalysis anode obtained in embodiment 2 under the conditions of different amplification.
Fig. 3 is the XRD of electro-catalysis anode obtained in embodiment 2.
Fig. 4 a are SnO2-Sb2O3Load capacity is respectively 4.4mg cm-2With 7.7mg cm-2Ti/Sb-SnO2Electrode and right Electro catalytic electrode described in ratio 1 is used to eliminate the active testing curve map of benzene；Wherein：■ represents SnO2-Sb2O3Load capacity is 4.4mg cm-2Ti/Sb-SnO2The elimination factor of electrode pair benzene；Represents SnO2-Sb2O3Load capacity is 7.7mg cm-2Ti/ Sb-SnO2The elimination factor of electrode pair benzene；Represent the Ti/SnO described in comparative example 12The elimination factor of electrode pair benzene.
Fig. 4 b are SnO2-Sb2O3Load capacity is respectively 4.4mg cm-2With 7.7mg cm-2Ti/Sb-SnO2Electrode and right Electro catalytic electrode described in ratio 1 is used to eliminate benzene CO and CO2Generation yield curve map, wherein, zero represent SnO2-Sb2O3It is negative Carrying capacity is 7.7mg cm-2Ti/Sb-SnO2Electrode is used to eliminate benzene CO2Generation yield；△ represents SnO2-Sb2O3Load capacity It is 7.7mg cm-2Ti/Sb-SnO2Electrode is used to eliminate the generation yield of benzene CO；● represent SnO2-Sb2O3Load capacity is 4.4mg cm-2Ti/Sb-SnO2Electrode is used to eliminate benzene CO2Generation yield；▲ represent SnO2-Sb2O3Load capacity is 4.4mg cm-2Ti/Sb-SnO2Electrode is used to eliminate the generation yield of benzene CO；⊕ represents that the electro catalytic electrode described in comparative example 1 is used to disappear Except benzene CO2Generation yield；Represent that the electro catalytic electrode described in comparative example 1 is used to eliminate the generation yield of benzene CO.
Fig. 5 is the SEM figures of the carbon paper that embodiment 11 is provided.
Fig. 6 is the SEM figures of the carbon paper of the graphene oxide for having loaded partial reduction that embodiment 11 is provided.
Fig. 7 is that the low power of the cathode material of the electro-catalysis reduction oxygen that embodiment 11 is provided amplifies SEM figures.
Fig. 8 is the magnification at high multiple SEM figures of the cathode material of the electro-catalysis reduction oxygen that embodiment 11 is provided.
Specific embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by specific embodiment.
Embodiment 1
A kind of reactor for vapor solid electrocatalytic reaction, as shown in Figure 1.The electrolytic cell include anode gas chamber 5, Cathode air chamber 6, electro-catalysis anode, barrier film and electro-catalysis negative electrode, the electro-catalysis anode and electro-catalysis negative electrode are ventilative；It is described Barrier film is airtight, and proton can be by the barrier film；
The barrier film is placed between electro-catalysis anode and electro-catalysis negative electrode, and three's composition is overall, is integrally formed structure 4； The integrative-structure 4 is obtained by the way that electro-catalysis anode, barrier film and electro-catalysis negative electrode are pressed under 2-10 kilograms of pressure；
The anode gas chamber 5 and cathode air chamber 6 independently are the cavity for being provided with through hole, and the integrative-structure 4 is placed in anode Between the through hole of air chamber 5 and the through hole of cathode air chamber 6, and the through hole of the through hole of anode gas chamber 5 and cathode air chamber 6 is covered；
The anode gas chamber 5 is provided with the first air inlet 2, the first gas outlet 1 and the first wire, one end of the first wire with Electro-catalysis anode is connected, and the other end is connected along the inwall of anode gas chamber 5 with the positive pole of power supply；Also set in first air inlet 2 Put the first air inlet pipe, first air inlet pipe includes diversion section and expanding reach, the expanding reach it is straight with diameter greater than diversion section Footpath, the expanding reach of first air inlet pipe is located in anode gas chamber 5；
Preferably, the anode gas chamber 5 also sets up the first binding post 3-1；The first wire salt anode gas chamber 5 it is interior Wall, one end is connected with electro-catalysis anode, and the other end is connected with the first binding post 3-1；
Preferably, the anode gas chamber 5 is additionally provided with first seal 9-1 and the 3rd seal 10-1；
The cathode air chamber 6 is provided with the second air inlet 8, the second gas outlet 7 and the second wire, one end of the second wire with Electro-catalysis negative electrode is connected, and the other end is connected along the inwall of cathode air chamber 6 with the negative pole of power supply；Also set in second air inlet 8 Put the second air inlet pipe, second air inlet pipe includes diversion section and expanding reach, the expanding reach it is straight with diameter greater than diversion section Footpath, the expanding reach of second air inlet pipe is located in cathode air chamber 6.
Preferably, the cathode air chamber 6 also sets up the second binding post 3-2 and the 3rd binding post 3-3, second wire Along the inwall of anode gas chamber 5, one end is connected with electro-catalysis negative electrode, and the other end is connected with the second binding post 3-2；3rd wiring Post 3-3 is used to connect reference electrode；
Preferably, the cathode air chamber 6 also sets up second seal 9-2 and the 4th seal 10-2；Described first is close Sealing 9-1 and second seal 9-2 coordinates；The 3rd seal 10-1 and the 4th seal 10-2 coordinates；So that anode gas Room 5 is tightly connected with cathode air chamber 6；
The barrier film is PEM, such as Nafion117.
Preferably, the electro-catalysis anode includes metal Ti substrates and the active material layer positioned at Ti substrate surfaces, institute It is the compacted zone piled up by nano particle to state active material layer, and the material of nano particle is the SnO of doping2, doped chemical Including F and Sb；The active material layer is 2-10mg cm in the load capacity of Ti substrate surfaces-2；The SnO of the doping2Particle Size is 1-10nm；The doped chemical is 0.04-0.1 with the mol ratio of Sn；The mol ratio of the Sb and F is (5-50):1； Described metal Ti substrates are titanium foam and/or titanium net, preferably titanium foam；
The electro-catalysis anode is prepared via a method which to obtain：
(1) metal Ti substrates are soaked under the conditions of 80 DEG C with the NaOH solution that concentration is 10wt%-20wt% first 10min；Concentration is immersed afterwards to boil 1-3h in the oxalic acid solution of 10wt%；It is cleaned by ultrasonic titanium substrate table with distilled water again The oxalic acid and titanium oxalate in face, obtain pretreated metal Ti substrates；
(2) to use and electroplate Sn and Sb in electro-deposition method Ti substrates after the pre-treatment, obtain the coated Ti bases in surface Bottom, wherein, electroplate liquid is to contain 1-2M SnCl4, 0.2-1M Sb soluble compound and 0.1-1M HNO3Ethylene glycol it is molten Liquid, the plating is anode using Pt pieces；The electric current of plating is 10-15mA cm-2；The time of plating is 15-60min；
(3) slurries are coated in the coated metal Ti substrates in surface, after drying 5min under the conditions of 100 DEG C, at 500 DEG C Under the conditions of be calcined, heating rate be 5 DEG C of min-1, electro catalytic electrode of the active ingredient layer positioned at Ti substrate surfaces is obtained, wherein, slurry Liquid is to contain 0.2-1M SnCl4, the soluble compound of 0.02-0.1M Sb, the soluble compound of 0.001-0.1M F and 0.1-1M HNO3Isopropanol and n-butanol mixed solution, active ingredient layer is to be piled up to form by nano particle, and activity into It is layered as the SnO of doping2Layer, doped chemical includes F and Sb.
Preferably, the electro-catalysis negative electrode includes carbon paper, the graphene oxide and Pt of partial reduction, the partial reduction It is graphene oxide-loaded in carbon paper surface, the Pt is carried on the surface of graphene oxide of partial reduction；The carbon paper and Pt Mass ratio be 10-65:1, preferably 50:1；The particle size of the Pt is that remaining is same as Example 1 outside 100-200nm.
The electro-catalysis negative electrode is prepared via a method which to obtain：
(1) carbon paper is placed in the logical nonionic surface active agent of Qula and soaks 8-24h, with deionized water ultrasound after taking-up Cleaning 2-4h, obtains hydrophilic carbon paper；
(2) hydrophilic carbon paper is calcined 5h at 200-400 DEG C, obtains product of roasting；
(3) product of roasting is placed in the graphene oxide dispersion that concentration is 0.1-0.5wt%, ultrasonic 1-5h takes out Obtaining area load afterwards has the product of roasting of graphene oxide；
(4) product that step (3) is obtained is placed in concentration for 1-10mg mL-1Ascorbic acid solution in stand 8-24h, 2h is stood in 40-80 DEG C of water-bath afterwards, obtaining area load has the product of roasting of graphene oxide of partial reduction；
(5) area load is had the product of roasting of graphene oxide of partial reduction as negative electrode, with Pt pieces as anode, is adopted With the NH containing 10mM4The PtCl of Cl and 1mM4PH value be 1 electroplate liquid, 10-20min is electroplated with the electric current of 20mA, in part The surface of graphene oxide deposition Pt of reduction, obtains the cathode material.
The method that volatile organic contaminant is eliminated using reactor electrocatalytic oxidation as described above, methods described is included Following steps：
(1) dc source is connected；
(2) to being passed through the volatile organic contaminant containing vapor in anode gas chamber；It is oxygen-containing to being passed through in cathode air chamber The gas of gas；Active oxygen species and matter produced and oxidation reaction in electro-catalysis anode in the vapor in volatile organic contaminant there is Son, active oxygen species voloxidation organic pollution, proton is anti-by there is reduction in electro-catalysis negative electrode and oxygen after barrier film Water should be generated.
Specifically, methods described comprises the following steps：
(1) by electro-catalysis anode and electro-catalysis negative electrode respectively with voltage for the positive pole and negative pole of 2-4V dc sources are connected；
(2) volatile organic contaminant and oxygen-containing gas containing vapor are each led into anode gas chamber and negative electrode gas Room, the flow velocity of the volatile organic matter containing vapor is 20-100mL min-1, the volatile organic contaminant containing vapor Humidity is 100%；The flow velocity of oxygen-containing gas is 4-20mL min-1；The content of oxygen described in oxygen-containing gas is 10-20v%；Wave Active oxygen species and proton, active oxygen thing produced and oxidation reaction in electro-catalysis anode in the vapor in hair property organic pollution there is Mineralising volatile organic contaminant is planted, proton generates water, institute by there is reduction reaction in electro-catalysis negative electrode and oxygen after barrier film The temperature for stating oxidation reaction and reduction reaction is 20-45 DEG C.
Embodiment 2
A kind of Ti/Sb-SnO2Preparation method, comprise the following steps：
(1) substrate is done using titanium foam, substrate 10min is soaked at 80 DEG C with 20wt%NaOH solution first, remove table Face greasy dirt；3h is boiled with 10wt% oxalic acid solutions afterwards, through the titanium foam surface gray pitted skin that oxalic acid is etched, such as Fig. 2 a；With Distilled water is cleaned by ultrasonic the oxalic acid and titanium oxalate of titanium-based basal surface, obtains pretreated foam Ti substrates；
(2) Sn and Sb is electroplated in foam Ti substrates after the pre-treatment, plating solution is：1M SnCl4、0.2M SbCl3And 0.1M HNO3Ethylene glycol solution, Pt pieces be anode, electric current be 15mA cm-2, electroplating time is 60min；Afterwards in 500 DEG C of roastings 30min, obtaining to surface has SnO2And Sb2O3Ti substrates；
(3) there is SnO on surface2And Sb2O3Ti substrates on swabbing, slurries composition：0.5M SnCl4、0.02M SbCl3、 0.001M NaF、0.1M HNO350mL isopropanols and n-butanol mixed solution, 100 DEG C of oven drying 5min are put into after swabbing； Swabbing again, dries afterwards；
(4) 4.4mg cm are generated in foam Ti substrates in 500 DEG C of roastings after repeat step (3) 6 times-2SnO2-Sb2O3 Oxide layer, as Ti/Sb-SnO2Electrode.
To the Ti/Sb-SnO for obtaining2Electrode carries out XRD and SEM tests, as a result as shown in Fig. 3, Fig. 2 b and Fig. 2 c.From Fig. 3 It can be seen that the oxide layer for obtaining all covers foam Ti substrates, Sb enters SnO2Lattice causes SnO2Diffraction maximum red shift；From figure 2b and Fig. 2 c can be seen that the oxide layer densification no cracking for obtaining, and is piled up by nano particle and formed, the SnO of doping2Particle it is big Small is 1-10nm, such as 2nm, 5nm, 7nm or 9nm.Through analysis, the doped chemical includes the integral molar quantity of F and Sb, F and Sb It is 0.04 with the ratio between the mole of Sn；The mol ratio of the Sb and F is 10:1.
Embodiment 3
A kind of Ti/Sb-SnO2Preparation method, the preparation method except step (4) for after repeat step (3) 10 times 500 DEG C of roastings are outer, and remaining is same as Example 1.7.7mgcm is generated in Ti substrates-2SnO2-Sb2O3Oxide layer, as Ti/ Sb-SnO2Electrode.
To the Ti/Sb-SnO for obtaining2Electrode carry out XRD and SEM test, as a result for：The oxide layer for obtaining is by foam Ti bases Bottom all covers, and Sb enters SnO2Lattice causes SnO2Diffraction maximum red shift；The oxide layer densification no cracking for obtaining, by nano particle Pile up and form, the SnO of doping2Granular size be 1-10nm, such as 2nm, 5nm, 7nm or 9nm.Through analysis, the doping unit The ratio between the mole of integral molar quantity and Sn of element including F and Sb, F and Sb is 0.04；The mol ratio of the Sb and F is 10:1.
Embodiment 4
A kind of Ti/Sb-SnO2Preparation method, the preparation method in addition to 1 time swabbing being carried out in step (3) and is dried, Remaining is same as Example 1.
2mgcm is generated in foam Ti substrates-2SnO2-Sb2O3Oxide layer, as Ti/Sb-SnO2Electrode.
To the Ti/Sb-SnO for obtaining2Electrode carry out XRD and SEM test, as a result for：The oxide layer for obtaining is by foam Ti bases Bottom all covers, and Sb enters SnO2Lattice causes SnO2Diffraction maximum red shift；The oxide layer densification no cracking for obtaining, by nano particle Pile up and form, the SnO of doping2Granular size be 1-10nm, such as 2nm, 5nm, 7nm or 9nm.Through analysis, the doping unit The ratio between the mole of integral molar quantity and Sn of element including F and Sb, F and Sb is 0.04；The mol ratio of the Sb and F is 10:1.
Embodiment 5
A kind of Ti/Sb-SnO2Preparation method, the preparation method in addition to 20 times swabbings being carried out in step (3) and are dried, Remaining is same as Example 1.
10mgcm is generated in foam Ti substrates-2SnO2-Sb2O3Oxide layer, as Ti/Sb-SnO2Electrode.
To the Ti/Sb-SnO for obtaining2Electrode carry out XRD and SEM test, as a result for：The oxide layer for obtaining is by foam Ti bases Bottom all covers, and Sb enters SnO2Lattice causes SnO2Diffraction maximum red shift；The oxide layer densification no cracking for obtaining, by nano particle Pile up and form, the SnO of doping2Granular size be 1-10nm, such as 2nm, 5nm, 7nm or 9nm.Through analysis, the doping unit The ratio between the mole of integral molar quantity and Sn of element including F and Sb, F and Sb is 0.04；The mol ratio of the Sb and F is 10:1.
Embodiment 6
A kind of electro catalytic electrode, its preparation method comprises the following steps：
(1) foam Ti substrates 10min is soaked under the conditions of 80 DEG C with the NaOH solution that concentration is 20wt% first；Soak afterwards Enter concentration to boil 3h in the oxalic acid solution of 10wt%；It is cleaned by ultrasonic the oxalic acid and oxalic acid of titanium foam substrate surface with distilled water again Titanium, obtains pretreated foam Ti substrates；
(2) to use and electroplate Sn and Sb in electro-deposition method foam Ti substrates after the pre-treatment, obtain surface coated Foam Ti substrates, electroplate liquid is to contain 1M SnCl4、1M SbCl3With 0.1M HNO3Ethylene glycol solution, the plating uses Pt Piece is anode；The electric current of plating is 15mA cm-2；The time of plating is 60min；
(3) slurries are coated in the coated foam Ti substrates in surface, 5min is dried under the conditions of 100 DEG C, wherein, slurries It is to contain 0.2M SnCl4、0.1M SbCl3, 0.001M NaF and 1M HNO3Isopropanol and n-butanol mixed solution；
(4) after repeat step (3) 4 times, product is calcined under the conditions of 500 DEG C, heating rate is 5 DEG C of min-1, lived Property into layering positioned at Ti substrate surfaces electro catalytic electrode, active ingredient layer is to be piled up to form by nano particle, and active component Layer is the SnO of doping2Layer, doped chemical includes the first doped chemical and the second doped chemical, and the first doped chemical is selected from F, the Two doped chemicals are selected from Sb.3.2mg cm are generated in foam Ti substrates-2SnO2-Sb2O3Oxide layer, as Ti/Sb-SnO2 Electrode.
To the Ti/Sb-SnO for obtaining2Electrode carry out XRD and SEM test, as a result for：The oxide layer for obtaining is by foam Ti bases Bottom all covers, and Sb enters SnO2Lattice causes SnO2Diffraction maximum red shift；The oxide layer densification no cracking for obtaining, by nano particle Pile up and form, the SnO of doping2Granular size be 1-10nm, such as 2nm, 5nm, 7nm or 9nm.Through analysis, the doping unit The ratio between the mole of integral molar quantity and Sn of element including F and Sb, F and Sb is 0.5；The mol ratio of the Sb and F is 100:1.
Embodiment 7
A kind of electro catalytic electrode, its preparation method comprises the following steps：
(1) foam Ti substrates 10min is soaked under the conditions of 80 DEG C with the NaOH solution that concentration is 20wt% first；Soak afterwards Enter concentration to boil 3h in the oxalic acid solution of 10wt%；It is cleaned by ultrasonic the oxalic acid and oxalic acid of titanium foam substrate surface with distilled water again Titanium, obtains pretreated foam Ti substrates；
(2) to use and electroplate Sn and Sb in electro-deposition method foam Ti substrates after the pre-treatment, obtain surface coated Foam Ti substrates, electroplate liquid is to contain 2M SnCl4、0.2M SbCl3With 0.5M HNO3Ethylene glycol solution, the plating uses Pt pieces are anode；The electric current of plating is 15mA cm-2；The time of plating is 15min；
(3) slurries are coated in the coated foam Ti substrates in surface, 5min is dried under the conditions of 100 DEG C, wherein, slurries It is to contain 1M SnCl4、0.02M SbCl3, 0.1M NaF and 0.1M HNO3Isopropanol and n-butanol mixed solution；
(4) after repeat step (3) 4 times, product is calcined under the conditions of 500 DEG C, heating rate is 5 DEG C of min-1, lived Property into layering positioned at Ti substrate surfaces electro catalytic electrode, active ingredient layer is to be piled up to form by nano particle, and active component Layer is the SnO of doping2Layer, doped chemical includes the first doped chemical and the second doped chemical, and the first doped chemical is selected from F, the Two doped chemicals are selected from Sb.2.6mg cm are generated in foam Ti substrates-2SnO2-Sb2O3Oxide layer, as Ti/Sb-SnO2 Electrode.
To the Ti/Sb-SnO for obtaining2Electrode carry out XRD and SEM test, as a result for：The oxide layer for obtaining is by foam Ti bases Bottom all covers, and Sb enters SnO2Lattice causes SnO2Diffraction maximum red shift；The oxide layer densification no cracking for obtaining, by nano particle Pile up and form, the SnO of doping2Granular size be 1-10nm, such as 2nm, 5nm, 7nm or 9nm.Through analysis, the doping unit The ratio between the mole of integral molar quantity and Sn of element including F and Sb, F and Sb is 0.12:1；The mol ratio of the Sb and F is 0.2:1.
Embodiment 8
A kind of electro catalytic electrode, its preparation method comprises the following steps：
(1) foam Ti substrates 10min is soaked under the conditions of 80 DEG C with the NaOH solution that concentration is 15wt% first；Soak afterwards Enter concentration to boil 3h in the oxalic acid solution of 10wt%；It is cleaned by ultrasonic the oxalic acid and oxalic acid of titanium foam substrate surface with distilled water again Titanium, obtains pretreated foam Ti substrates；
(2) to use and electroplate Sn and Sb in electro-deposition method foam Ti substrates after the pre-treatment, obtain surface coated Foam Ti substrates, electroplate liquid is to contain 1.5M SnCl4、0.5M SbCl3With 0.3M HNO3Ethylene glycol solution, the plating makes It is anode with Pt pieces；The electric current of plating is 15mA cm-2；The time of plating is 30min；
(3) slurries are coated in the coated foam Ti substrates in surface, 5min is dried under the conditions of 100 DEG C, wherein, slurries It is to contain 0.5M SnCl4、0.05M SbCl3, 0.05M NaF and 0.3M HNO3Isopropanol and n-butanol mixed solution；
(4) after repeat step (3) 4 times, product is calcined under the conditions of 500 DEG C, heating rate is 5 DEG C of min-1, lived Property into layering positioned at Ti substrate surfaces electro catalytic electrode, active ingredient layer is to be piled up to form by nano particle, and active component Layer is the SnO of doping2Layer, doped chemical includes the first doped chemical and the second doped chemical, and the first doped chemical is selected from F, the Two doped chemicals are selected from Sb.3.0mg cm are generated in foam Ti substrates-2SnO2-Sb2O3Oxide layer, as Ti/Sb-SnO2 Electrode.
To the Ti/Sb-SnO for obtaining2Electrode carry out XRD and SEM test, as a result for：The oxide layer for obtaining is by foam Ti bases Bottom all covers, and Sb enters SnO2Lattice causes SnO2Diffraction maximum red shift；The oxide layer densification no cracking for obtaining, by nano particle Pile up and form, the SnO of doping2Granular size be 1-10nm, such as 2nm, 5nm, 7nm or 9nm.Through analysis, the doping unit The ratio between the mole of integral molar quantity and Sn of element including F and Sb, F and Sb is 0.2:1；The mol ratio of the Sb and F is 1:1.
Comparative example 1
A kind of electro catalytic electrode, the electro catalytic electrode includes foam titanium substrate and is carried in foam titanium substrate SnO2.The preparation method of the electro catalytic electrode comprises the following steps：
(1) substrate is done using titanium foam, substrate 10min is soaked at 80 DEG C with 20wt%NaOH solution first, remove table Face greasy dirt；3h is boiled with 10wt% oxalic acid solutions afterwards, through the titanium foam surface gray pitted skin that oxalic acid is etched；It is super with distilled water Sound cleans the oxalic acid and titanium oxalate of titanium-based basal surface, obtains pretreated foam Ti substrates；
(2) Sn is electroplated in foam Ti substrates after the pre-treatment, plating solution is：1M SnCl4With 0.1M HNO3Ethylene glycol it is molten Liquid, Pt pieces are anode, and electric current is 15mA cm-2, electroplating time is 60min；30min is calcined at 500 DEG C afterwards, obtaining to surface has SnO2Ti substrates；
(3) there is SnO on surface2Ti substrates on swabbing, slurries composition：0.5M SnCl4、0.1M HNO350mL isopropyls Alcohol and n-butanol mixed solution, are put into 100 DEG C of oven drying 5min after swabbing；Swabbing again, dries afterwards；
(4) SnO is generated in foam Ti substrates in 500 DEG C of roastings after repeat step (3) 6 times2Oxide layer, as Ti/ SnO2Electrode.
Embodiment 9
A kind of cathode material of electro-catalysis reduction oxygen includes carbon paper, the graphene oxide and Pt of partial reduction, the portion Divide the graphene oxide-loaded in carbon paper surface of reduction, the Pt is carried on the surface of graphene oxide of partial reduction, the carbon The quality of paper and Pt is respectively 76mg and 1.5mg, and the particle diameter average-size of the Pt is 150nm.
A kind of preparation method of the cathode material of electro-catalysis reduction oxygen, comprises the following steps：
(1) carbon paper is placed in triton x-100 nonionic surface active agent and soaks 8h, soaked with deionized water after taking-up Bubble 2h, obtains hydrophilic carbon paper after ultrasonic cleaning；
(2) hydrophilic carbon paper 5h is calcined, product of roasting is obtained；
(3) product of roasting is placed in the graphene oxide dispersion that concentration is 0.3wt%, ultrasonic 1h is obtained after taking-up Area load has the product of roasting of graphene oxide；
(4) product that step (3) is obtained is placed in concentration for 5mg mL-1Ascorbic acid solution in stand 24h, obtain table Face is loaded with the product of roasting of the graphene oxide of partial reduction；
(5) area load is had the product of roasting of graphene oxide of partial reduction as negative electrode, with Pt pieces as anode, is adopted With the NH containing 10mM4The PtCl of Cl and 1mM4PH value be 1 electroplate liquid, 10min is electroplated with the electric current of 20mA, in part also Former surface of graphene oxide deposition Pt, obtains the cathode material that the electro-catalysis reduces oxygen.
Embodiment 10
A kind of cathode material of electro-catalysis reduction oxygen includes carbon paper, the graphene oxide and Pt of partial reduction, the portion Divide the graphene oxide-loaded in carbon paper surface of reduction, the Pt is carried on the surface of graphene oxide of partial reduction, the carbon The quality of paper and Pt is respectively 76mg and 4.5mg, and the particle diameter average-size of the Pt is 100nm.
A kind of preparation method of the cathode material of electro-catalysis reduction oxygen, comprises the following steps：
(1) carbon paper is placed in triton x-100 nonionic surface active agent and soaks 24h, deionized water is used after taking-up Immersion 2h, obtains hydrophilic carbon paper after ultrasonic cleaning；
(2) hydrophilic carbon paper 5h is calcined, product of roasting is obtained；
(3) product of roasting is placed in the graphene oxide dispersion that concentration is 0.5wt%, ultrasonic 5h is obtained after taking-up Area load has the product of roasting of graphene oxide；
(4) product that step (3) is obtained is placed in concentration for 10mg mL-1Ascorbic acid solution in stand 8h, obtain table Face is loaded with the product of roasting of the graphene oxide of partial reduction；
(5) area load is had the product of roasting of graphene oxide of partial reduction as negative electrode, with Pt pieces as anode, is adopted With the NH containing 10mM4The PtCl of Cl and 1mM4PH value be 1 electroplate liquid, 30min is electroplated with the electric current of 20mA, in part also Former surface of graphene oxide deposition Pt, obtains the cathode material that the electro-catalysis reduces oxygen.
Embodiment 11
A kind of electro-catalysis reduces the cathode material of oxygen, including carbon paper, the graphene oxide and Pt of partial reduction, the portion Divide the graphene oxide-loaded in carbon paper surface of reduction, the Pt is carried on the surface of graphene oxide of partial reduction, the carbon The quality of paper and Pt is respectively 76mg and 7.5mg, and the particle diameter average-size of the Pt is 200nm.
A kind of preparation method of the cathode material of electro-catalysis reduction oxygen, comprises the following steps：
(1) carbon paper is placed in triton x-100 nonionic surface active agent and soaks 12h, deionized water is used after taking-up Immersion 2h, obtains hydrophilic carbon paper after ultrasonic cleaning；
(2) hydrophilic carbon paper 5h is calcined, product of roasting is obtained；
(3) product of roasting is placed in the graphene oxide dispersion that concentration is 0.1wt%, ultrasonic 3h is obtained after taking-up Area load has the product of roasting of graphene oxide；
(4) product that step (3) is obtained is placed in concentration for 1mg mL-1Ascorbic acid solution in stand 12h, obtain table Face is loaded with the product of roasting of the graphene oxide of partial reduction；
(5) area load is had the product of roasting of graphene oxide of partial reduction as negative electrode, with Pt pieces as anode, is adopted With the NH containing 10mM4The PtCl of Cl and 1mM4PH value be 1 electroplate liquid, 120min is electroplated with the electric current of 20mA, in part also Former surface of graphene oxide deposition Pt, obtains the cathode material that the electro-catalysis reduces oxygen.Such as Fig. 5 for the SEM of carbon paper schemes, It can be seen that its surface is smooth；Fig. 6 is the SEM figures of the carbon paper of the graphene oxide that deposited partial reduction, its surface It is coarse.As shown in FIG. 7 and 8, as can be seen from the figure Pt is in carbon fiber surface for the cathode material of the electro-catalysis reduction oxygen Growth is formed thin slice and is erected at graphenic surface by the induction of graphene film Rotating fields, and width is about 200nm.
Embodiment 12
Using the Ti/Sb-SnO described in embodiment 2 and embodiment 32And the electrode that comparative example 4 is obtained is urged respectively as electricity Change anode, the cathode material of the electro-catalysis reduction oxygen described in embodiment 11 is used as electro-catalysis negative electrode；Using described in embodiment 1 For vapor solid electrocatalytic reaction reactor eliminate degradation of indoor air VOCs, comprise the following steps：
(1) by electro-catalysis anode and electro-catalysis negative electrode respectively with voltage for the positive pole and negative pole of 2-4V dc sources are connected；
(2) volatile organic contaminant and oxygen-containing gas containing vapor are each led into anode gas chamber and negative electrode gas Room, the flow velocity of the volatile organic matter containing vapor is 20-100mL min-1, the volatile organic contaminant containing vapor Humidity is 100%；The flow velocity of oxygen-containing gas is 4-20mL min-1；The content of oxygen described in oxygen-containing gas is 10-20v%；Wave Active oxygen species and proton, active oxygen thing produced and oxidation reaction in electro-catalysis anode in the vapor in hair property organic pollution there is Mineralising volatile organic contaminant is planted, proton generates water, institute by there is reduction reaction in electro-catalysis negative electrode and oxygen after barrier film The temperature for stating oxidation reaction and reduction reaction is 20-45 DEG C.
Wherein, anode gas chamber each component concentration is：30ppm benzene, room temperature saturated steam, air, gas flow rate is 100mL min-1；Cathode air chamber：80%N2And 20%O2.The voltage of dc source is 2V.Reacting gas and product gas-chromatography and PTR-QTOF mass spectrometer detectors detect, test result as shown in figures 4 a and 4b, wherein, 4.4CO2Activity is respectively with 4.4CO The mass density of material is 4.4 Ti/Sb-SnO2The CO that electrode is produced2With the content of CO；7.7CO2Activity is respectively with 7.7CO The mass density of material is 7.7 Ti/Sb-SnO2The CO that electrode is produced2With the content of CO；As can be seen from the figure：Embodiment 2 30ppm benzene can be fully converted into CO by the electro-catalysis anode obtained with embodiment 32And CO, and CO2Volume more than 80%；It is right With benzene is eliminated at room temperature, elimination factor during its 7h is only 35% to the electro catalytic electrode that ratio 4 is obtained, well below embodiment 2 With the electro catalytic electrode described in embodiment 3 to the elimination factor of benzene.
The electro-catalysis that the electrode that embodiment 4-8 is obtained is obtained as anode, embodiment 9-10 reduces the moon of oxygen Pole material is degraded benzene, test condition and test device and reality respectively as electro-catalysis negative electrode according to the method described in embodiment 12 The test condition applied described in example 12 is identical with device, as a result shows, it equally can at room temperature be completely eliminated benzene, and react Bulk product more than 80% be CO2。
In addition, the voltage in adjustment embodiment 12 is adjusted to any one point value in 2-4V；By waving containing vapor The flow velocity of hair property organic matter is adjusted to 20-100mL min-1In any one point value；The flow velocity of oxygen-containing gas is adjusted to 4- 20mL min-1In any one point value；The content of oxygen described in oxygen-containing gas is adjusted to any one in 10-20v% Individual point value；The temperature of oxidation reaction and reduction reaction is adjusted to any one point value in 20-45 DEG C, test effect with implementation Test result in example 12 is essentially identical.
Applicant states, the foregoing is only specific embodiment of the invention, but protection scope of the present invention not office It is limited to this, person of ordinary skill in the field is it will be clearly understood that any belong to those skilled in the art and taken off in the present invention In the technical scope of dew, the change or replacement that can be readily occurred in, within the scope of all falling within protection scope of the present invention and disclosing.

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%.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110559853A (en) * 2019-09-30 2019-12-13 华中师范大学 Method and device for removing gaseous pollutants by anode and cathode synchronous electrochemical method
CN110585917A (en) * 2019-09-30 2019-12-20 华中师范大学 Electrode for degrading gas-phase organic pollutants, preparation method thereof, method for degrading gas-phase organic pollutants and device thereof
CN110585916A (en) * 2019-09-30 2019-12-20 华中师范大学 Method and device for removing gaseous pollutants through electro-Fenton catalytic oxidation
CN111282410A (en) * 2020-02-19 2020-06-16 华中师范大学 Device and method for degrading gaseous pollutants by electrochemical method
CN113019082A (en) * 2021-01-11 2021-06-25 东莞市普锐美泰环保科技有限公司 Device and method for degrading gaseous organic pollutants by electrochemical method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040110052A1 (en) * 2002-05-23 2004-06-10 Bollepalli Srinivas Conducting polymer-grafted carbon material for fuel cell applications
US20070212594A1 (en) * 2006-03-09 2007-09-13 Permelec Electrode Ltd. Electrode catalyst for electrochemical reaction, process for producing the electrode catalyst and electrode for electrochemical reaction having the electrode catalyst
CN101434429A (en) * 2008-12-12 2009-05-20 清华大学 Apparatus and method for processing chlorine-containing organic wastewater by electrochemical reduction and oxidation
CN102205996A (en) * 2010-03-30 2011-10-05 北京理工大学 Chambered electrolysis wastewater device and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040110052A1 (en) * 2002-05-23 2004-06-10 Bollepalli Srinivas Conducting polymer-grafted carbon material for fuel cell applications
US20070212594A1 (en) * 2006-03-09 2007-09-13 Permelec Electrode Ltd. Electrode catalyst for electrochemical reaction, process for producing the electrode catalyst and electrode for electrochemical reaction having the electrode catalyst
CN101434429A (en) * 2008-12-12 2009-05-20 清华大学 Apparatus and method for processing chlorine-containing organic wastewater by electrochemical reduction and oxidation
CN102205996A (en) * 2010-03-30 2011-10-05 北京理工大学 Chambered electrolysis wastewater device and application thereof

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN110585917A (en) * 2019-09-30 2019-12-20 华中师范大学 Electrode for degrading gas-phase organic pollutants, preparation method thereof, method for degrading gas-phase organic pollutants and device thereof
CN110585916A (en) * 2019-09-30 2019-12-20 华中师范大学 Method and device for removing gaseous pollutants through electro-Fenton catalytic oxidation
CN110559853B (en) * 2019-09-30 2020-11-10 华中师范大学 Method and device for removing gaseous pollutants by anode and cathode synchronous electrochemical method
WO2021062907A1 (en) * 2019-09-30 2021-04-08 华中师范大学 Method and device for removing gaseous pollutants by using anode-cathode synchronous electrochemical method
WO2021062908A1 (en) * 2019-09-30 2021-04-08 华中师范大学 Method and device for removing gaseous pollutant by means of electro-fenton catalytic oxidation
CN111282410A (en) * 2020-02-19 2020-06-16 华中师范大学 Device and method for degrading gaseous pollutants by electrochemical method
CN111282410B (en) * 2020-02-19 2021-07-06 华中师范大学 Device and method for degrading gaseous pollutants by electrochemical method
WO2021164073A1 (en) * 2020-02-19 2021-08-26 华中师范大学 Device and method for degrading gaseous pollutants by using electrochemical method
CN113019082A (en) * 2021-01-11 2021-06-25 东莞市普锐美泰环保科技有限公司 Device and method for degrading gaseous organic pollutants by electrochemical method
WO2022148169A1 (en) * 2021-01-11 2022-07-14 深圳市普瑞美泰环保科技有限公司 Apparatus for degrading gaseous organic pollutants by electrochemical process, and method therefor
CN113019082B (en) * 2021-01-11 2022-10-04 深圳市普瑞美泰环保科技有限公司 Device and method for degrading gaseous organic pollutants by electrochemical method

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