CN106732238B - The method of reactor and its elimination VOCs for vapor solid electrocatalytic reaction - Google Patents

The method of reactor and its elimination VOCs for vapor solid electrocatalytic reaction Download PDF

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CN106732238B
CN106732238B CN201611003102.4A CN201611003102A CN106732238B CN 106732238 B CN106732238 B CN 106732238B CN 201611003102 A CN201611003102 A CN 201611003102A CN 106732238 B CN106732238 B CN 106732238B
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cathode
catalysis
anode
reactor according
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CN106732238A (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 present invention provides a kind of reactor for vapor solid electrocatalytic reaction and its methods for eliminating VOCs (volatile organic contaminant), the reactor includes anode gas chamber, cathode air chamber, electro-catalysis anode, diaphragm and electro-catalysis cathode, and electro-catalysis anode and electro-catalysis cathode are ventilative；Diaphragm is placed between electro-catalysis anode and electro-catalysis cathode, and three's group is integral, is integrally formed structure；Anode gas chamber and cathode air chamber independently are the cavity equipped with through-hole, and integral structure is placed between the through-hole of anode gas chamber and the through-hole of cathode air chamber, and the through-hole of anode gas chamber and the through-hole of cathode air chamber are covered.The electrolytic cell can eliminate degradation of indoor air VOCs at room temperature, and the product generated is largely CO2；In addition, the electrolytic cell for eliminate degradation of indoor air VOCs conveniently, safely, energy consumption it is small --- only need 2V impressed DC voltage that can realize VOCs oxidative degradation.

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 fields, are related to a kind of for vapor solid electricity The method for being catalyzed the reactor of reaction and its eliminating VOCs.
Background technique
Volatile organic matter (VOCs) is the main gaseous pollutant in room air, including formaldehyde and benzene homologues.These Pollutant has very big harm to human health, can cause a disease, carcinogenic or teratogenesis.In the market, eliminate room air in VOCs it is net Change technology mainly includes physical absorption, ozone oxidation, photocatalysis, heat catalytic oxidation and plasma for purification technology.But these The generally existing energy consumption of technology is high, has security risk and leads to the problem of secondary pollution.
Heat catalytic oxidation method has the advantages that easy to operate, and VOCs can be degraded to nontoxic CO2And water.Currently, Having under room temperature can be CO by formaldehyde complete oxidation2To the catalysis material of water and related indoor air purification product, but The product of oxidative degradation benzene homologues is not found also.Since benzene homologues molecular structure is complicated, heat catalytic oxidation is eliminated under room temperature Benzene homologues are also difficult to realize.Even the temperature of benzene homologues burning also wants 150 DEG C or so, hardly possible currently, activity highest catalyst With the benzene homologues purification being applied under indoor environmental condition.Therefore exploitation safety economy, benzene homologues elimination side without secondary pollution Method has very important significance to indoor air quality is improved.
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 basic no pollution to the environment, low energy consumption " green " technology, and all organic Molecule can be aoxidized by electrochemical method.In recent years, electro-catalytic oxidation technology is applied to what liquid phase organic pollutant was eliminated Extensively, from simple straight chain organic matter to complicated polycyclic arene compound, electro-catalytic process can have these for research Malicious pollutant is oxidized to CO2And water.
CN 103074638A discloses a kind of double optical window electrolytic cells of double gas chambers for electrochemistry preparing gas, including anti- Ying Chi and cover board, cover board are set to the opening of reaction tank, are removably to be tightly connected between cover board and reaction tank, the lid Plate is equipped with several connectivity ports, is equipped with partition in the reaction tank, and it is anti-that the space in reaction tank is divided into working electrode by partition Answer room and auxiliary electrode reaction room two parts, the top edge of the partition and reaction tank either flush, the forward and backward side edge of partition Be tightly connected with the forward and backward inner wall of reaction tank, partition lower edge with react between bottom of pond portion that there are electrolyte can be made electric in work The space flowed freely between pole reaction chamber and auxiliary electrode reaction room, correspond on the side of reaction tank working electrode reaction chamber and The position of auxiliary electrode reaction room is inlaid with the glass window of a light-permeable respectively.The double optical window electrolytic cells of double gas chambers realize Working electrode and auxiliary electrode Surface Creation gas are effectively isolated, consequently facilitating the accuracy of control experimental result.
But the research still without eliminating degradation of indoor air VOCs using electro-catalytic oxidation technology at present.
Summary of the invention
It is a kind of for vapor solid electrocatalytic reaction in view of the deficiencies of the prior art, the present invention intends to provide Reactor and its eliminate VOCs method, the structure of reactor is simple, can be used for room temperature eliminate volatile organic contaminant, And the product generated is largely CO2。
Unless otherwise specified, the room temperature refers to 20-45 DEG C to the present invention, and the wt% refers to mass percentage, described V% refers to volumn concentration.
To achieve this purpose, the present invention adopts the following technical scheme:
One of the objects of the present invention is to provide a kind of reactor for vapor solid electrocatalytic reaction, the reactors Including anode gas chamber, cathode air chamber, electro-catalysis anode, diaphragm and electro-catalysis cathode, the electro-catalysis anode and electro-catalysis cathode It is ventilative；
The diaphragm is placed between electro-catalysis anode and electro-catalysis cathode, and three's group is integral, is integrally formed structure；
The anode gas chamber and cathode air chamber independently are the cavity equipped with through-hole, and the integral structure is placed in anode gas chamber Through-hole and cathode air chamber through-hole between, and the through-hole of anode gas chamber and the through-hole of cathode air chamber are covered；
The anode gas chamber is additionally provided with the first air inlet, the first gas outlet and optionally the first conducting wire, the first conducting wire One end is connected with electro-catalysis anode, and the other end is connected with the anode of power supply；
The cathode air chamber is additionally provided with the second air inlet, the second gas outlet and optionally the second conducting wire, the second conducting wire One end is connected with electro-catalysis cathode, and the other end is connected with the cathode of power supply.
Those skilled in the art answer it is known, diaphragm should be proton should be able to by diaphragm, while diaphragm have it is certain thick Degree and intensity.
The integral structure separates 2 air chambers gas, is conducive to the noiseless progress of anode reaction and cathode reaction, mentions High system mineralising volatile organic matter efficiency；The integral structure is convenient for proton and electron transmission, reduces system resistance.The sun Gas in the gas 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 cathode 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, and the second air inlet pipe, institute are also set up in second air inlet It states the first air inlet pipe and the second air inlet pipe independently includes diversion section and expanding reach, the diameter of the expanding reach is greater than diversion section The expanding reach of diameter, 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 conducting wire is connected along the inner wall of anode gas chamber with electro-catalysis anode；Second conducting wire is along cathode air chamber Inner wall is connected with electro-catalysis cathode.
Preferably, the anode gas chamber also sets up the first binding post, and first conducting wire passes through the first binding post and power supply Anode be connected.
Preferably, the cathode air chamber also sets up the second binding post, and second conducting wire passes through the second binding post and power supply Cathode be connected.
Preferably, the anode gas chamber and cathode air chamber are tightly connected, and can such as be connected by bolt seal.
The electro-catalysis anode includes metal Ti substrate and the active material layer positioned at Ti substrate surface, the active material Layer is compacted zone made of being piled up as nano particle, and the material of nano particle is the SnO of doping2, doped chemical includes F and Sb, The metal Ti substrate is 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 surface-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, as 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm or 9.5nm etc..
Preferably, the doped chemical and the molar ratio of Sn are 0.04-0.5, such as 0.05,0.06,0.07,0.08,0.09, 0.1,02,0.3 or 0.4 etc..
Preferably, the molar ratio of the Sb and F be (0.2-100): 1, 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) NaOH solution for being first 10wt%-20wt% with concentration impregnates metal Ti substrate under the conditions of 80 DEG C 10min；It is immersed in the oxalic acid solution that concentration is 10wt% later and boils 1-3h；It is cleaned by ultrasonic titanium substrate table with distilled water again The oxalic acid and titanium oxalate in face obtain pretreated metal Ti substrate；
(2) using Sn and Sb is electroplated in the Ti substrate of electro-deposition method after the pre-treatment, the coated Ti base in surface is obtained 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 are anode using Pt piece；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 substrate in surface, under the conditions of 100 DEG C after dry 5min, at 500 DEG C Under the conditions of roast, heating rate be 5 DEG C of min-1, obtain the electro catalytic electrode that active ingredient layer is located at Ti substrate surface, 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 be piled up by nano particle, and activity at It is layered as the SnO of doping2Layer, doped chemical includes F and Sb.
The electro-catalysis cathode includes the graphene oxide and Pt of carbon paper, 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 be 10-65:1, 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 is seldom, and only loading in carbon paper surface has several layers of (>=1 layers, such as 1 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, as 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm or 190nm etc..
The electro-catalysis cathode is prepared via a method which to obtain:
(1) carbon paper is placed in the logical nonionic surface active agent of Qula and impregnates 8-24h, with deionized water ultrasound after taking-up 2-4h is cleaned, hydrophilic carbon paper is obtained；
(2) hydrophilic carbon paper is obtained into product of roasting in 200-400 DEG C of roasting 5h；
(3) product of roasting is placed in the graphene oxide dispersion that concentration is 0.1-0.5wt%, ultrasonic 1-5h takes out The product of roasting that area load has graphene oxide is obtained afterwards；
(4) product that step (3) obtains is placed in concentration is 1-10mg mL-1Ascorbic acid solution in stand 8-24h, 2h is stood in 40-80 DEG C of water-bath later, obtaining area load has the product of roasting of graphene oxide of partial reduction；
(5) product of roasting of graphene oxide of partial reduction adopts as cathode using Pt piece as anode area load 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 of reduction deposits Pt, obtains the cathode material.
The diaphragm is proton exchange membrane, preferably Nafion117.
The integral structure under the pressure of 2-10MPa by pressing electro-catalysis anode, diaphragm and electro-catalysis cathode It arrives.
An object of the present invention, which also resides in provide a kind of utilization reactor electrocatalytic oxidation as described above and eliminate, volatilizees The method of property organic pollutant, the method are as follows: lead to the volatile organic contaminant containing vapor and oxygen-containing gas 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 generates active oxygen species and proton, active oxygen species mineralising volatile organic contaminant, proton pass through after diaphragm Electro-catalysis cathode and oxygen occur reduction reaction and generate water.
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 independently carry 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%, as 12v%, 15v%, 16v%, 17v% or 19v% etc..
Described method includes following steps as a preferred technical solution:
It (1) is respectively that the anode of 2-4V DC power supply and cathode are connected with voltage with electro-catalysis cathode by electro-catalysis anode；
(2) volatile organic contaminant containing vapor and oxygen-containing gas are each led into anode gas chamber and cathode gas Room, the flow velocity of the volatile organic matter containing vapor are 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%；It waves Vapor in hair property organic pollutant occurs oxidation reaction in electro-catalysis anode and generates active oxygen species and proton, active oxygen object Kind mineralising volatile organic contaminant, proton generate water, institute by the way that reduction reaction occurs in electro-catalysis cathode and oxygen after diaphragm The temperature for stating oxidation reaction and reduction reaction is 20-45 DEG C.
Compared with prior art, the invention has the benefit that
Provided by the present invention for the reactor of vapor solid electrocatalytic reaction, structure is simple, can be used between vapor solid Electrocatalysis oxidation reaction；Since anode gas chamber and cathode air chamber are separately provided, be conducive to the nothing of anode reaction and cathode reaction Interference carries out, and reaction rate is faster；Integral structure is convenient for proton and transmitting, reduces resistance；
The removing method of volatile organic contaminant provided by the invention conveniently, safely, energy consumption it is small, it is only necessary to 2-4V is additional straight Galvanic electricity pressure can realize the oxidative degradation of VOCs；And it can be realized room temperature (20-45 DEG C) to aoxidize VOCs, product is most of For CO2With a small amount of CO.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the gas-solid electrocatalytic oxidation electrolytic cell that embodiment 1 provides, in which: 1, the first outlet Mouthful；2, the first air inlet；3-1, the first binding post；3-2, the second binding post；3-3, third binding post；4, integral structure；5, sun Pole gas 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, third sealing element；10-2, the 4th sealing element.
Fig. 2 a is that the SEM of pretreated Ti substrate surface schemes.
Fig. 2 b and Fig. 2 c are SEM figure of the electro-catalysis anode made from embodiment 2 under the conditions of different amplification.
Fig. 3 is the XRD diagram of electro-catalysis anode made from embodiment 2.
Fig. 4 a is 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 graph of benzene；Wherein: ■ indicates SnO2-Sb2O3Load capacity is 4.4mg cm-2Ti/Sb-SnO2Elimination factor of the electrode to benzene；Indicates SnO2-Sb2O3Load capacity is 7.7mg cm-2Ti/ Sb-SnO2Elimination factor of the electrode to benzene；Indicate Ti/SnO described in comparative example 12Elimination factor of the electrode to benzene.
Fig. 4 b is 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 for eliminating benzene CO and CO2Generation yield curve graph, wherein zero indicate SnO2-Sb2O3It is negative Carrying capacity is 7.7mg cm-2Ti/Sb-SnO2Electrode is for eliminating benzene CO2Generation yield；△ indicates SnO2-Sb2O3Load capacity For 7.7mg cm-2Ti/Sb-SnO2Electrode is used to eliminate the generation yield of benzene CO；● indicate SnO2-Sb2O3Load capacity is 4.4mg cm-2Ti/Sb-SnO2Electrode is for eliminating benzene CO2Generation yield；▲ indicate SnO2-Sb2O3Load capacity is 4.4mg cm-2Ti/Sb-SnO2Electrode is used to eliminate the generation yield of benzene CO；⊕ indicates electro catalytic electrode described in comparative example 1 for disappearing Except benzene CO2Generation yield；Indicate that electro catalytic electrode described in comparative example 1 is used to eliminate the generation yield of benzene CO.
Fig. 5 is the SEM figure for the carbon paper that embodiment 11 provides.
Fig. 6 is the SEM figure of the carbon paper for the graphene oxide for having loaded partial reduction that embodiment 11 provides.
Fig. 7 is that the low power for the cathode material that the electro-catalysis that embodiment 11 provides restores oxygen amplifies SEM figure.
Fig. 8 is the magnification at high multiple SEM figure for the cathode material that the electro-catalysis that embodiment 11 provides restores oxygen.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
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, diaphragm and electro-catalysis cathode, the electro-catalysis anode and electro-catalysis cathode are ventilative；It is described Diaphragm is airtight, and proton can pass through the diaphragm；
The diaphragm is placed between electro-catalysis anode and electro-catalysis cathode, and three's group is integral, is integrally formed structure 4； The integral structure 4 is obtained by pressing electro-catalysis anode, diaphragm and electro-catalysis cathode under 2-10 kilograms of pressure；
The anode gas chamber 5 and cathode air chamber 6 independently are the cavity equipped with through-hole, and the integral structure 4 is placed in anode Between the through-hole of gas chamber 5 and the through-hole of cathode air chamber 6, and the through-hole of anode gas chamber 5 and the through-hole of cathode air chamber 6 are covered；
The anode gas chamber 5 is provided with the first air inlet 2, the first gas outlet 1 and the first conducting wire, one end of the first conducting wire with Electro-catalysis anode is connected, and the other end is connected along the inner wall of anode gas chamber 5 with the anode of power supply；It is also set in first air inlet 2 The first air inlet pipe is set, first air inlet pipe includes diversion section and expanding reach, and the diameter of the expanding reach is greater than the straight of diversion section The expanding reach of diameter, 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 conducting wire salt anode gas chamber 5 it is interior Wall, one end are 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 third sealing element 10-1；
The cathode air chamber 6 is provided with the second air inlet 8, the second gas outlet 7 and the second conducting wire, one end of the second conducting wire with Electro-catalysis cathode is connected, and the other end is connected along the inner wall of cathode air chamber 6 with the cathode of power supply；It is also set in second air inlet 8 The second air inlet pipe is set, second air inlet pipe includes diversion section and expanding reach, and the diameter of the expanding reach is greater than the straight of diversion section The expanding reach of diameter, 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 third binding post 3-3, second conducting wire Along the inner wall of anode gas chamber 5, one end is connected with electro-catalysis cathode, and the other end is connected with the second binding post 3-2；The third wiring Column 3-3 is for connecting reference electrode；
Preferably, the cathode air chamber 6 also sets up second seal 9-2 and the 4th sealing element 10-2；Described first is close Sealing 9-1 and second seal 9-2 cooperates；The third sealing element 10-1 and the 4th sealing element 10-2 cooperates；So that anode gas Room 5 and cathode air chamber 6 are tightly connected；
The diaphragm is proton exchange membrane, such as Nafion117.
Preferably, the electro-catalysis anode includes metal Ti substrate and the active material layer positioned at Ti substrate surface, institute Stating active material layer is compacted zone made of being piled up as nano particle, 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 surface-2；The SnO of the doping2Particle Size is 1-10nm；The doped chemical and the molar ratio of Sn are 0.04-0.1；The molar ratio of the Sb and F is (5-50): 1； The metal Ti substrate is titanium foam and/or titanium net, preferably titanium foam；
The electro-catalysis anode is prepared via a method which to obtain:
(1) NaOH solution for being first 10wt%-20wt% with concentration impregnates metal Ti substrate under the conditions of 80 DEG C 10min；It is immersed in the oxalic acid solution that concentration is 10wt% later and boils 1-3h；It is cleaned by ultrasonic titanium substrate table with distilled water again The oxalic acid and titanium oxalate in face obtain pretreated metal Ti substrate；
(2) using Sn and Sb is electroplated in the Ti substrate of electro-deposition method after the pre-treatment, the coated Ti base in surface is obtained 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 are anode using Pt piece；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 substrate in surface, under the conditions of 100 DEG C after dry 5min, at 500 DEG C Under the conditions of roast, heating rate be 5 DEG C of min-1, obtain the electro catalytic electrode that active ingredient layer is located at Ti substrate surface, 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 be piled up by nano particle, and activity at It is layered as the SnO of doping2Layer, doped chemical includes F and Sb.
Preferably, the electro-catalysis cathode includes the graphene oxide and Pt of carbon paper, 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 outside 100-200nm, remaining is same as Example 1.
The electro-catalysis cathode is prepared via a method which to obtain:
(1) carbon paper is placed in the logical nonionic surface active agent of Qula and impregnates 8-24h, with deionized water ultrasound after taking-up 2-4h is cleaned, hydrophilic carbon paper is obtained；
(2) hydrophilic carbon paper is obtained into product of roasting in 200-400 DEG C of roasting 5h；
(3) product of roasting is placed in the graphene oxide dispersion that concentration is 0.1-0.5wt%, ultrasonic 1-5h takes out The product of roasting that area load has graphene oxide is obtained afterwards；
(4) product that step (3) obtains is placed in concentration is 1-10mg mL-1Ascorbic acid solution in stand 8-24h, 2h is stood in 40-80 DEG C of water-bath later, obtaining area load has the product of roasting of graphene oxide of partial reduction；
(5) product of roasting of graphene oxide of partial reduction adopts as cathode using Pt piece as anode area load 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 of reduction deposits Pt, obtains the cathode material.
The method for eliminating volatile organic contaminant using reactor electrocatalytic oxidation as described above, the method includes Following steps:
(1) DC power supply is connected；
(2) volatile organic contaminant containing vapor is passed through into anode gas chamber；It is passed through into cathode air chamber oxygen-containing The gas of gas；Vapor in volatile organic contaminant occurs oxidation reaction in electro-catalysis anode and generates active oxygen species and matter Son, active oxygen species voloxidation organic pollutant, proton occur to restore instead after passing through diaphragm in electro-catalysis cathode and oxygen Water should be generated.
Specifically, described method includes following steps:
It (1) is respectively that the anode of 2-4V DC power supply and cathode are connected with voltage with electro-catalysis cathode by electro-catalysis anode；
(2) volatile organic contaminant containing vapor and oxygen-containing gas are each led into anode gas chamber and cathode gas Room, the flow velocity of the volatile organic matter containing vapor are 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%；It waves Vapor in hair property organic pollutant occurs oxidation reaction in electro-catalysis anode and generates active oxygen species and proton, active oxygen object Kind mineralising volatile organic contaminant, proton generate water, institute by the way that reduction reaction occurs in electro-catalysis cathode and oxygen after diaphragm The temperature for stating oxidation reaction and reduction reaction is 20-45 DEG C.
Embodiment 2
A kind of Ti/Sb-SnO2Preparation method, include the following steps:
(1) substrate is done using titanium foam, impregnates substrate 10min at 80 DEG C with 20wt%NaOH solution first, removes table Face greasy dirt；3h is boiled with 10wt% oxalic acid solution later, the titanium foam surface gray pitted skin etched through oxalic acid, such as Fig. 2 a；With Distilled water is cleaned by ultrasonic the oxalic acid and titanium oxalate of titanium-based bottom surface, obtains pretreated foam Ti substrate；
(2) Sn and Sb, plating solution are as follows: 1M SnCl are electroplated in foam Ti substrate after the pre-treatment4、0.2M SbCl3And 0.1M HNO3Ethylene glycol solution, Pt piece be anode, electric current be 15mA cm-2, electroplating time 60min；It is roasted later at 500 DEG C 30min, obtaining to surface has SnO2And Sb2O3Ti substrate；
(3) there is SnO on surface2And Sb2O3Ti substrate on swabbing, slurries composition: 0.5M SnCl4、0.02M SbCl3、 0.001M NaF、0.1M HNO350mL isopropanol and n-butanol mixed solution, be put into 100 DEG C of oven drying 5min after swabbing； Swabbing again later, it is dry；
(4) it is roasted after repeating step (3) 6 times at 500 DEG C, 4.4mg cm is generated in foam Ti substrate-2SnO2-Sb2O3 Oxide layer, as Ti/Sb-SnO2Electrode.
To obtained Ti/Sb-SnO2Electrode carries out XRD and SEM test, as a result as shown in Fig. 3, Fig. 2 b and Fig. 2 c.From Fig. 3 It can be seen that obtained oxide layer all covers foam Ti substrate, Sb enters SnO2Lattice causes SnO2Diffraction maximum red shift；From figure The oxide layer densification no cracking that 2b and Fig. 2 c can be seen that, is piled up, the SnO of doping by nano particle2Particle it is big Small is 1-10nm, such as 2nm, 5nm, 7nm or 9nm.Through analyzing, the doped chemical includes F and Sb, the integral molar quantity of F and Sb It is 0.04 with the ratio between the mole of Sn；The molar ratio of the Sb and F is 10:1.
Embodiment 3
A kind of Ti/Sb-SnO2Preparation method, the preparation method except step (4) be repeat step (3) 10 times after 500 DEG C of roastings are outer, remaining is same as Example 1.7.7mgcm is generated in Ti substrate-2SnO2-Sb2O3Oxide layer, as Ti/ Sb-SnO2Electrode.
To obtained Ti/Sb-SnO2Electrode carries out XRD and SEM test, as a result are as follows: obtained oxide layer is by foam Ti base Bottom all covers, and Sb enters SnO2Lattice causes SnO2Diffraction maximum red shift；Obtained oxide layer densification no cracking, by nano particle It piles up, the SnO of doping2Granular size be 1-10nm, such as 2nm, 5nm, 7nm or 9nm.Through analyzing, the doping member Element includes F and Sb, and the ratio between mole of integral molar quantity and Sn of F and Sb is 0.04；The molar ratio of the Sb and F is 10:1.
Embodiment 4
A kind of Ti/Sb-SnO2Preparation method, the preparation method carry out in the step (3) 1 time swabbing and it is dry in addition to, Remaining is same as Example 1.
2mgcm is generated in foam Ti substrate-2SnO2-Sb2O3Oxide layer, as Ti/Sb-SnO2Electrode.
To obtained Ti/Sb-SnO2Electrode carries out XRD and SEM test, as a result are as follows: obtained oxide layer is by foam Ti base Bottom all covers, and Sb enters SnO2Lattice causes SnO2Diffraction maximum red shift；Obtained oxide layer densification no cracking, by nano particle It piles up, the SnO of doping2Granular size be 1-10nm, such as 2nm, 5nm, 7nm or 9nm.Through analyzing, the doping member Element includes F and Sb, and the ratio between mole of integral molar quantity and Sn of F and Sb is 0.04；The molar ratio of the Sb and F is 10:1.
Embodiment 5
A kind of Ti/Sb-SnO2Preparation method, the preparation method carry out in the step (3) 20 times swabbings and it is dry in addition to, Remaining is same as Example 1.
10mgcm is generated in foam Ti substrate-2SnO2-Sb2O3Oxide layer, as Ti/Sb-SnO2Electrode.
To obtained Ti/Sb-SnO2Electrode carries out XRD and SEM test, as a result are as follows: obtained oxide layer is by foam Ti base Bottom all covers, and Sb enters SnO2Lattice causes SnO2Diffraction maximum red shift；Obtained oxide layer densification no cracking, by nano particle It piles up, the SnO of doping2Granular size be 1-10nm, such as 2nm, 5nm, 7nm or 9nm.Through analyzing, the doping member Element includes F and Sb, and the ratio between mole of integral molar quantity and Sn of F and Sb is 0.04；The molar ratio of the Sb and F is 10:1.
Embodiment 6
A kind of electro catalytic electrode, preparation method include the following steps:
(1) NaOH solution for being first 20wt% with concentration impregnates foam Ti substrate 10min under the conditions of 80 DEG C；It soaks later Enter in the oxalic acid solution that concentration is 10wt% and boils 3h；Again with the oxalic acid and oxalic acid of distilled water ultrasonic cleaning titanium foam substrate surface Titanium obtains pretreated foam Ti substrate；
(2) using Sn and Sb is electroplated in the foam Ti substrate of electro-deposition method after the pre-treatment, it is coated to obtain surface Foam Ti substrate, electroplate liquid are to contain 1M SnCl4、1M SbCl3With 0.1M HNO3Ethylene glycol solution, it is described plating use 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 substrate in surface, dry 5min under the conditions of 100 DEG C, wherein slurries To contain 0.2M SnCl4、0.1M SbCl3, 0.001M NaF and 1M HNO3Isopropanol and n-butanol mixed solution；
(4) after repeating step (3) 4 times, product is roasted under the conditions of 500 DEG C, heating rate is 5 DEG C of min-1, lived Property be located at the electro catalytic electrode of Ti substrate surface at layering, active ingredient layer is piled up by nano particle, and active constituent Layer is the SnO of doping2Layer, doped chemical include 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 is generated in foam Ti substrate-2SnO2-Sb2O3Oxide layer, as Ti/Sb-SnO2 Electrode.
To obtained Ti/Sb-SnO2Electrode carries out XRD and SEM test, as a result are as follows: obtained oxide layer is by foam Ti base Bottom all covers, and Sb enters SnO2Lattice causes SnO2Diffraction maximum red shift；Obtained oxide layer densification no cracking, by nano particle It piles up, the SnO of doping2Granular size be 1-10nm, such as 2nm, 5nm, 7nm or 9nm.Through analyzing, the doping member Element includes F and Sb, and the ratio between mole of integral molar quantity and Sn of F and Sb is 0.5；The molar ratio of the Sb and F is 100:1.
Embodiment 7
A kind of electro catalytic electrode, preparation method include the following steps:
(1) NaOH solution for being first 20wt% with concentration impregnates foam Ti substrate 10min under the conditions of 80 DEG C；It soaks later Enter in the oxalic acid solution that concentration is 10wt% and boils 3h；Again with the oxalic acid and oxalic acid of distilled water ultrasonic cleaning titanium foam substrate surface Titanium obtains pretreated foam Ti substrate；
(2) using Sn and Sb is electroplated in the foam Ti substrate of electro-deposition method after the pre-treatment, it is coated to obtain surface Foam Ti substrate, electroplate liquid are to contain 2M SnCl4、0.2M SbCl3With 0.5M HNO3Ethylene glycol solution, the plating uses Pt piece is 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 substrate in surface, dry 5min under the conditions of 100 DEG C, wherein slurries To contain 1M SnCl4、0.02M SbCl3, 0.1M NaF and 0.1M HNO3Isopropanol and n-butanol mixed solution；
(4) after repeating step (3) 4 times, product is roasted under the conditions of 500 DEG C, heating rate is 5 DEG C of min-1, lived Property be located at the electro catalytic electrode of Ti substrate surface at layering, active ingredient layer is piled up by nano particle, and active constituent Layer is the SnO of doping2Layer, doped chemical include 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 is generated in foam Ti substrate-2SnO2-Sb2O3Oxide layer, as Ti/Sb-SnO2 Electrode.
To obtained Ti/Sb-SnO2Electrode carries out XRD and SEM test, as a result are as follows: obtained oxide layer is by foam Ti base Bottom all covers, and Sb enters SnO2Lattice causes SnO2Diffraction maximum red shift；Obtained oxide layer densification no cracking, by nano particle It piles up, the SnO of doping2Granular size be 1-10nm, such as 2nm, 5nm, 7nm or 9nm.Through analyzing, the doping member Element includes F and Sb, and the ratio between mole of integral molar quantity and Sn of F and Sb is 0.12:1；The molar ratio of the Sb and F is 0.2:1.
Embodiment 8
A kind of electro catalytic electrode, preparation method include the following steps:
(1) NaOH solution for being first 15wt% with concentration impregnates foam Ti substrate 10min under the conditions of 80 DEG C；It soaks later Enter in the oxalic acid solution that concentration is 10wt% and boils 3h；Again with the oxalic acid and oxalic acid of distilled water ultrasonic cleaning titanium foam substrate surface Titanium obtains pretreated foam Ti substrate；
(2) using Sn and Sb is electroplated in the foam Ti substrate of electro-deposition method after the pre-treatment, it is coated to obtain surface Foam Ti substrate, electroplate liquid are to contain 1.5M SnCl4、0.5M SbCl3With 0.3M HNO3Ethylene glycol solution, the plating makes It is anode with Pt piece；The electric current of plating is 15mA cm-2；The time of plating is 30min；
(3) slurries are coated in the coated foam Ti substrate in surface, dry 5min under the conditions of 100 DEG C, wherein slurries To contain 0.5M SnCl4、0.05M SbCl3, 0.05M NaF and 0.3M HNO3Isopropanol and n-butanol mixed solution；
(4) after repeating step (3) 4 times, product is roasted under the conditions of 500 DEG C, heating rate is 5 DEG C of min-1, lived Property be located at the electro catalytic electrode of Ti substrate surface at layering, active ingredient layer is piled up by nano particle, and active constituent Layer is the SnO of doping2Layer, doped chemical include 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 is generated in foam Ti substrate-2SnO2-Sb2O3Oxide layer, as Ti/Sb-SnO2 Electrode.
To obtained Ti/Sb-SnO2Electrode carries out XRD and SEM test, as a result are as follows: obtained oxide layer is by foam Ti base Bottom all covers, and Sb enters SnO2Lattice causes SnO2Diffraction maximum red shift；Obtained oxide layer densification no cracking, by nano particle It piles up, the SnO of doping2Granular size be 1-10nm, such as 2nm, 5nm, 7nm or 9nm.Through analyzing, the doping member Element includes F and Sb, and the ratio between mole of integral molar quantity and Sn of F and Sb is 0.2:1；The molar ratio of the Sb and F is 1:1.
Comparative example 1
A kind of electro catalytic electrode, the electro catalytic electrode include foam titanium substrate and are carried in foam titanium substrate SnO2.The preparation method of the electro catalytic electrode includes the following steps:
(1) substrate is done using titanium foam, impregnates substrate 10min at 80 DEG C with 20wt%NaOH solution first, removes table Face greasy dirt；3h is boiled with 10wt% oxalic acid solution later, the titanium foam surface gray pitted skin etched through oxalic acid；It is super with distilled water Sound cleans the oxalic acid and titanium oxalate of titanium-based bottom surface, obtains pretreated foam Ti substrate；
(2) Sn, plating solution is electroplated in foam Ti substrate after the pre-treatment are as follows: 1M SnCl4With 0.1M HNO3Ethylene glycol it is molten Liquid, Pt piece are anode, and electric current is 15mA cm-2, electroplating time 60min；Later in 500 DEG C of roasting 30min, obtaining to surface has SnO2Ti substrate；
(3) there is SnO on surface2Ti substrate on swabbing, slurries composition: 0.5M SnCl4、0.1M HNO350mL isopropyl Pure and mild n-butanol mixed solution is put into 100 DEG C of oven drying 5min after swabbing；Swabbing again later, it is dry；
(4) it is roasted after repeating step (3) 6 times at 500 DEG C, generates SnO in foam Ti substrate2Oxide layer, as Ti/ SnO2Electrode.
Embodiment 9
A kind of cathode material of electro-catalysis reduction oxygen includes the graphene oxide and Pt of carbon paper, 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 are respectively 76mg and 1.5mg, and the partial size average-size of the Pt is 150nm.
A kind of preparation method of the cathode material of electro-catalysis reduction oxygen, includes the following steps:
(1) carbon paper is placed in triton x-100 nonionic surface active agent and impregnates 8h, soaked after taking-up with deionized water 2h is steeped, obtains hydrophilic carbon paper after ultrasonic cleaning；
(2) hydrophilic carbon paper 5h is roasted, 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) obtains is placed in concentration is 5mg mL-1Ascorbic acid solution in stand for 24 hours, obtain table Face load has the product of roasting of the graphene oxide of partial reduction；
(5) product of roasting of graphene oxide of partial reduction adopts as cathode using Pt piece as anode area load With the NH containing 10mM4The PtCl of Cl and 1mM4PH value be 1 electroplate liquid, 10min is electroplated with the electric current of 20mA, part also Former surface of graphene oxide deposits Pt, obtains the cathode material of the electro-catalysis reduction oxygen.
Embodiment 10
A kind of cathode material of electro-catalysis reduction oxygen includes the graphene oxide and Pt of carbon paper, 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 are respectively 76mg and 4.5mg, and the partial size average-size of the Pt is 100nm.
A kind of preparation method of the cathode material of electro-catalysis reduction oxygen, includes the following steps:
(1) carbon paper is placed in triton x-100 nonionic surface active agent and is impregnated for 24 hours, deionized water is used after taking-up 2h is impregnated, obtains hydrophilic carbon paper after ultrasonic cleaning；
(2) hydrophilic carbon paper 5h is roasted, 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) obtains is placed in concentration is 10mg mL-1Ascorbic acid solution in stand 8h, obtain table Face load has the product of roasting of the graphene oxide of partial reduction；
(5) product of roasting of graphene oxide of partial reduction adopts as cathode using Pt piece as anode area load With the NH containing 10mM4The PtCl of Cl and 1mM4PH value be 1 electroplate liquid, 30min is electroplated with the electric current of 20mA, part also Former surface of graphene oxide deposits Pt, obtains the cathode material of the electro-catalysis reduction oxygen.
Embodiment 11
A kind of cathode material of electro-catalysis reduction oxygen, graphene oxide and Pt including carbon paper, 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 are respectively 76mg and 7.5mg, and the partial size average-size of the Pt is 200nm.
A kind of preparation method of the cathode material of electro-catalysis reduction oxygen, includes the following steps:
(1) carbon paper is placed in triton x-100 nonionic surface active agent and impregnates 12h, use deionized water after taking-up 2h is impregnated, obtains hydrophilic carbon paper after ultrasonic cleaning；
(2) hydrophilic carbon paper 5h is roasted, 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) obtains is placed in concentration is 1mg mL-1Ascorbic acid solution in stand 12h, obtain table Face load has the product of roasting of the graphene oxide of partial reduction；
(5) product of roasting of graphene oxide of partial reduction adopts as cathode using Pt piece as anode area load With the NH containing 10mM4The PtCl of Cl and 1mM4PH value be 1 electroplate liquid, 120min is electroplated with the electric current of 20mA, part also Former surface of graphene oxide deposits Pt, obtains the cathode material of the electro-catalysis reduction oxygen.SEM if Fig. 5 is carbon paper schemes, It can be seen from the figure that its surface is smooth；Fig. 6 is the SEM figure that deposited the carbon paper of graphene oxide of partial reduction, surface It is coarse.The cathode material of the electro-catalysis reduction oxygen is as shown in FIG. 7 and 8, and as can be seen from the figure Pt is in carbon fiber surface Growth is induced by graphene sheet layer structure, is formed thin slice and is erect on the surface of graphene, width is about 200nm.
Embodiment 12
Utilize embodiment 2 and Ti/Sb-SnO described in embodiment 32And the electrode that comparative example 4 obtains is urged respectively as electricity Change anode, using the cathode material of the reduction oxygen of electro-catalysis described in embodiment 11 as electro-catalysis cathode；Using described in embodiment 1 For vapor solid electrocatalytic reaction reactor eliminate degradation of indoor air VOCs, include the following steps:
It (1) is respectively that the anode of 2-4V DC power supply and cathode are connected with voltage with electro-catalysis cathode by electro-catalysis anode；
(2) volatile organic contaminant containing vapor and oxygen-containing gas are each led into anode gas chamber and cathode gas Room, the flow velocity of the volatile organic matter containing vapor are 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%；It waves Vapor in hair property organic pollutant occurs oxidation reaction in electro-catalysis anode and generates active oxygen species and proton, active oxygen object Kind mineralising volatile organic contaminant, proton generate water, institute by the way that reduction reaction occurs in electro-catalysis cathode and oxygen after diaphragm The temperature for stating oxidation reaction and reduction reaction is 20-45 DEG C.
Wherein, anode gas chamber each component concentration are as follows: 30ppm benzene, room temperature saturated steam, air, gas flow rate 100mL min-1；Cathode air chamber: 80%N2And 20%O2.The voltage of DC power supply is 2V.Reaction gas and product gas-chromatography and The detection of PTR-QTOF mass spectrometer detector, test result is as shown in figures 4 a and 4b, wherein 4.4CO2It is respectively activity with 4.4CO The Ti/Sb-SnO that the mass density of substance is 4.42The CO that electrode generates2With the content of CO；7.7CO2It is respectively activity with 7.7CO The Ti/Sb-SnO that the mass density of substance is 7.72The CO that electrode generates2With 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 be more than 80%；It is right The electro catalytic electrode that ratio 4 obtains with eliminating benzene at room temperature, and elimination factor when 7h is only 35%, well below embodiment 2 With electro catalytic electrode described in embodiment 3 to the elimination factor of benzene.
The yin of the electro-catalysis reduction oxygen obtained using the electrode that embodiment 4-8 is obtained as anode, embodiment 9-10 Pole material is degraded benzene, test condition and test device and reality according to method described in embodiment 12 respectively as electro-catalysis cathode It is identical with device to apply test condition described in example 12, the results showed that, benzene can be equally completely eliminated at room temperature, and is reacted Bulk product 80% the above are 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% A 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.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.

Claims (19)

1. a kind of reactor for vapor solid electrocatalytic reaction, which is characterized in that the reactor includes anode gas chamber, yin Pole gas chamber, electro-catalysis anode, diaphragm and electro-catalysis cathode, the electro-catalysis anode and electro-catalysis cathode are ventilative；
The diaphragm is placed between electro-catalysis anode and electro-catalysis cathode, and three's group is integral, is integrally formed structure；
The anode gas chamber and cathode air chamber independently are the cavity equipped with through-hole, and the integral 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 anode gas chamber and the through-hole of cathode air chamber are covered；
The anode gas chamber is additionally provided with the first air inlet, the first gas outlet and optionally the first conducting wire, one end of the first conducting wire It is connected with electro-catalysis anode, the other end is connected with the anode of power supply；
The cathode air chamber is additionally provided with the second air inlet, the second gas outlet and optionally the second conducting wire, one end of the second conducting wire It is connected with electro-catalysis cathode, the other end is connected with the cathode of power supply；
The first air inlet pipe is also set up in first air inlet, also sets up the second air inlet pipe in second air inlet, described One air inlet pipe and the second air inlet pipe independently include diversion section and expanding reach, and the diameter of the expanding reach is greater than the straight of diversion section The expanding reach of diameter, first air inlet pipe is located in anode gas chamber, and the expanding reach of second air inlet pipe is located in cathode air chamber.
2. reactor according to claim 1, which is characterized in that first conducting wire is urged along the inner wall of anode gas chamber with electricity Change anode to be connected；Second conducting wire is connected along the inner wall of cathode air chamber with electro-catalysis cathode.
3. according to claim 1 or the reactor, which is characterized in that the anode gas chamber also sets up the first binding post, institute The first conducting wire is stated to be connected by the first binding post with the anode of power supply.
4. reactor according to claim 1, which is characterized in that the cathode air chamber also sets up the second binding post, described Second conducting wire is connected by the second binding post with the cathode of power supply.
5. reactor according to claim 1, which is characterized in that the anode gas chamber and cathode air chamber are tightly connected.
6. reactor according to claim 1, which is characterized in that the electro-catalysis anode includes metal Ti substrate and is located at The active material layer of Ti substrate surface, the active material layer are compacted zones made of being piled up as nano particle, nano particle Material is the SnO of doping2, doped chemical includes F and Sb；The metal Ti substrate is titanium foam and/or titanium net.
7. reactor according to claim 6, which is characterized in that the metal Ti substrate is titanium foam.
8. reactor according to claim 6, which is characterized in that load capacity of the active material layer in Ti substrate surface For 2-10mg cm-2。
9. reactor according to claim 6, which is characterized in that the SnO of the doping2Granular size be 1-10nm.
10. reactor according to claim 6, which is characterized in that the doped chemical and the molar ratio of Sn are 0.04- 0.5。
11. reactor according to claim 6, which is characterized in that the molar ratio of the Sb and F is (0.2-100): 1.
12. reactor according to claim 1, which is characterized in that the electro-catalysis cathode includes carbon paper, partial reduction Graphene oxide and Pt, the partial reduction it is graphene oxide-loaded in carbon paper surface, the Pt is carried on partial reduction Surface of graphene oxide.
13. reactor according to claim 12, which is characterized in that the mass ratio of the carbon paper and Pt are 10-65:1.
14. reactor according to claim 12, which is characterized in that the mass ratio of the carbon paper and Pt are 50:1.
15. reactor according to claim 12, which is characterized in that the particle size of the Pt is 100-200nm.
16. reactor according to claim 1, which is characterized in that the diaphragm is proton exchange membrane.
17. reactor according to claim 1, which is characterized in that the diaphragm is Nafion117.
18. reactor according to claim 1, which is characterized in that the integral structure is by by electro-catalysis anode, diaphragm It presses and obtains under the pressure of 2-10MPa with electro-catalysis cathode.
19. the method for eliminating volatile organic contaminant using reactor electrocatalytic oxidation described in one of claim 1-18, It is characterized in that, described method includes following steps:
It (1) is respectively that the anode of 2-4V DC power supply and cathode are connected with voltage with electro-catalysis cathode by electro-catalysis anode；
(2) volatile organic contaminant containing vapor and oxygen-containing gas are each led into anode gas chamber and cathode air chamber, contained The flow velocity for having the volatile organic matter of vapor is 20-100mL min-1, the volatile organic contaminant humidity containing vapor It 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%；Volatility Vapor in organic pollutant occurs oxidation reaction in electro-catalysis anode and generates active oxygen species and proton, active oxygen species mine Change volatile organic contaminant, proton generates water, the oxygen by the way that reduction reaction occurs in electro-catalysis cathode and oxygen after diaphragm The temperature for changing reaction and reduction reaction is 20-45 DEG C.
CN201611003102.4A 2016-11-09 2016-11-09 The method of reactor and its elimination VOCs for vapor solid electrocatalytic reaction Active CN106732238B (en)

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