CN106299418B - Strengthen the photocatalysis wastewater fuel cell, manufacture and preparation method and application of radical reaction - Google Patents
Strengthen the photocatalysis wastewater fuel cell, manufacture and preparation method and application of radical reaction Download PDFInfo
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- CN106299418B CN106299418B CN201610674001.3A CN201610674001A CN106299418B CN 106299418 B CN106299418 B CN 106299418B CN 201610674001 A CN201610674001 A CN 201610674001A CN 106299418 B CN106299418 B CN 106299418B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
A kind of photocatalysis wastewater fuel cell, manufacture for strengthening radical reaction, including light anode, cathode, persistent organic pollutant wastewater, light source, electrolyte solution, quartz reaction pond and air vent；Wherein, light anode and cathode are inserted into quartz reaction pond respectively and include in the electrolyte solution of persistent organic pollutant wastewater, and it is connected to by external circuit, it is added with 0.1~0.4mM ferrous ion in electrolyte solution and pH is adjusted to 1.0~4.0, the cathode is close to the air vent for being continually fed into air, open light source irradiation light anode and cathode, ferrous ion and the free radical and related substances generated in light anode and cathode surface, the circular response of Fenton-like occurs under the automatic bias effect of photocatalytic fuel cell, to the radical reaction in fortification system, greatly improve the performance of photocatalytic fuel cell.The present invention provides a kind of methods of sewage treatment and energy regenerating more efficiently, economic, gather around and have broad application prospects.
Description
Technical field
The present invention relates to a kind of photocatalysis wastewater fuel cell, manufactures and preparation method and application for strengthening radical reaction, belong to
Organic pollutant disposition and resource utilization field.
Background technique
The rapid development of modern industry causes a large amount of toxic, harmful organic contaminants to be discharged into water environment, causes serious
Pollution.However, the organic principle in sewage contains a large amount of energy or even some organic pollutants difficult to degrade are contained
The some easily biological-degradables of energy ratio organic matter it is taller.For example, 3050.6KJ mol can be discharged after phenol degrading-1Change
Energy is learned, and glucose can only discharge 2808KJ mol-1Chemical energy.Develop a kind of cleaning, efficient technology is handled in waste water
Organic pollutant, especially persistent organic pollutants, to realize organic-matter chemical can comprehensive utilization there is important meaning
Justice.
Using organic wastewater as resource, using the principle of chemical primary cell, wastewater through organic matter is allowed " to burn " in the battery, having
The chemical energy of machine object is converted into electric energy, achievees the purpose that the organic pollutant in not only purified water but also comprehensively utilizes chemical energy, this is
A kind of water treatment technology with Significance of Sustainable Development.B.X.Zhou et al. is based on photocatalysis principle and establishes with metal titanium-based
TiO2Nano-tube array is light anode, and using Pt/ platinum black electrode as the photocatalysis wastewater fuel cell, manufacture of cathode, which can be fast
Speed, efficiently degradable organic pollutant and (the Water Res.2011,45,3991 that externally generates electricity simultaneously；
Chem.Commun.2011,47,10314).But the free radical of degradable organic pollutant is anti-in existing photocatalytic fuel cell
The surface of light anode or cathode should be occurred mainly in, this leads to the property of existing photocatalytic fuel cell system degradation of organic substances
The specific surface area of electrode can be depended critically upon, and the specific surface area of electrode can not infinitely increase, and become and promote existing photocatalysis
The technical bottleneck of fuel cell system performance.
Summary of the invention
It is an object of the present invention to which radical reaction is limited in existing photocatalysis wastewater fuel cell, manufacture system
The deficiency of illumination electrode area provides the photocatalysis wastewater fuel cell, manufacture and preparation method of radical reaction in a kind of fortification system
And application, by adding ferrous ion into battery system, to promote the performance of photocatalysis wastewater fuel cell, manufacture.
To achieve the above object, the present invention is by the following technical programs to solve its technical problem:
A kind of photocatalysis wastewater fuel cell, manufacture for strengthening radical reaction, including light anode, cathode, organic contamination difficult to degrade
Object waste water, light source, electrolyte solution, quartz reaction pond and air vent, the light anode and cathode are inserted into the stone respectively
English reaction tank includes in the electrolyte solution of the persistent organic pollutant wastewater, and is connected to by external circuit, the yin
Extremely close to the air vent for being continually fed into air, the light source irradiates the light anode or irradiates the light sun simultaneously
Pole and cathode with photoresponse；It is characterized by: in the electrolyte solution simultaneously added with 0.1~0.4mM ferrous ion
PH is adjusted to 1.0~4.0, under the automatic bias effect of the photocatalysis wastewater fuel cell, manufacture, the ferrous ion and the light
Free radical and related substances that the electrode surface of anode and cathode generates generate the circular response of Fenton-like, thus fortification system
Interior radical reaction.
Further, the ferrous ion is green vitriol.
Further, the light anode is TiO2Nanotube array photo-anode, the cathode are Pt/PVC (Pt modification
Si solar battery sheet) photocathode or platinum black electrode, the electrolyte solution is 0.1M metabisulfite solution.
Further, the light source is simulated solar irradiation, light intensity 100mW/cm2(AM1.5)。
Another technical solution of the invention are as follows:
A kind of preparation method of the photocatalysis wastewater fuel cell, manufacture of above-mentioned reinforcing radical reaction, includes the following steps:
1) traditional TiO is prepared2Nanotube array photo-anode, production method are: using clean metal titanium sheet as sun
Pole is placed in the hydrofluoric acid aqueous solution of 0.5wt%, is to electrode with platinum electrode, control voltage raising speed is 1V s-1, and accompany by magnetic
Power stirring, in 20V, anodic oxidation 30min, then takes out metal titanium sheet, is rinsed 2~3 times with deionized water, air-dries and is placed on
In Muffle furnace, 3h is sintered at 450 DEG C, muffle furnace climbing speed and fall off rate are 1 DEG C of min-1, after sintering to obtain the final product
Required TiO2Nanotube array photo-anode；
2) Pt/PVC photocathode or platinum black electrode are prepared, wherein the production method of Pt/PVC photocathode is: first in silicon
Copper conductor is welded out on the back surface field silver grid of cell piece, the closing of entire back surface field epoxy resin adhesive is then prepared into PVC
Photocathode, then using the PVC photocathode as working electrode, in K2PtCl6Content is the 0.5mol/L K of 1mmol/L2SO4Solution
In, the K2SO4Solution H2SO4Adjust pH to 1, under the irradiation of simulated solar irradiation, regulating illumination intensity 100mW/cm2, control
Current potential processed is that -0.2V deposits 20min, just obtains the Pt/PVC photocathode of Pt modification PVC；Platinum black electrode directly buys institute by market
?；
3) by TiO prepared by step 1)2Nanotube array photo-anode is as light anode, by Pt/ prepared by step 2)
PVC photocathode or platinum black electrode are inserted into the quartz reaction pond respectively and have included the organic contamination difficult to degrade as cathode
In the 0.1M sodium sulphate electrolyte solution of object waste water, 0.1~0.4mM ferrous ion is added simultaneously into the sodium sulphate electrolyte solution
PH is adjusted to 1.0~4.0, is continually fed into air, the light anode and cathode in the air vent being located near the cathode
Pass through external circuit to be connected to and irradiated by the light source and is generated photogenerated charge, at the same the ferrous ion of addition with described
Free radical and related substances that the electrode surface of light anode and cathode generates generate the circular response of Fenton-like, to strengthen body
Radical reaction in system.
Another technical solution of the invention are as follows:
A kind of photocatalysis wastewater fuel cell, manufacture of above-mentioned reinforcing radical reaction wastewater treatment and electric energy recycling at the same time
In application.
Present invention has the main advantage that
(1) by adding ferrous ion to photocatalysis wastewater fuel cell, manufacture, the Fenton-like for forming automatic bias follows the present invention
Ring reaction, is extended to entire solution system for the radical reaction for occurring mainly in photocatalysis wastewater fuel cell, manufacture electrode surface
In, relative to traditional photocatalysis wastewater fuel cell, manufacture, organic pollutant degradation is obviously improved with generating capacity.
For example, the Fenton-like circulation that the automatic bias formed after ferrous ion is added in photocatalysis wastewater fuel cell, manufacture is anti-
It answers are as follows:
Fe2++H2O2→Fe3++OH-+HO· (1)
Fe2++HO·→Fe3++OH- (2)
Fe2++HO2·→Fe3++HO2 - (3)
Fe3++O2 -·→Fe2++O2 (4)
Fe3++HO2·→Fe2++O2+H+ (5)
Fe3++H2O2→Fe2++HO2·+H+ (6)
The reaction can expand radical reaction to entire solution system from electrode surface, and will have by chain reaction
The degradation of machine object:
RH+HO·→R·+H2O (7)
R·+O2→RO2·→R1·+CO2 (8)
RO2·+Fe2++H+→Fe3++RO2H (9)
RO2H+Fe2+→Fe3++RO·+HO· (10)
RO·+HO·+O2→…→CO2+H2O (11)
And the radical reaction of traditional photocatalytic fuel cell takes place mostly in photoanode surface, reaction is also mainly
The degradation of HO:
RH+HO·→R·+H2O (12)
(2) the Fenton-like circular response process of automatic bias does not need additionally to add hydrogen peroxide as oxidant, and hydroxyl is certainly
It can be spontaneously generated, be reduced in the photocatalytic process by oxidants such as base, peroxy radical, superoxide radical, hydrogen peroxide
Cost.
(3) it does not need additionally to add voltage and persistently puts into ferrous ion, because photocatalytic fuel cell under light illumination can
Enough generate automatic bias, and the circular regeneration of spontaneous realization ferrous ion.
(4) adding a small amount of ferrous ion can be realized the efficient degradation of organic pollutant, hardly produce in whole process
Primary sludge.
Therefore the present invention wastewater treatment and electric energy recycling in while apply, performance it is more traditional photocatalysis waste water combustion
Material battery is obviously improved.
Detailed description of the invention
Fig. 1 is structure and working principle diagram of the invention.
Fig. 2 is the present invention in simulated solar irradiation AM1.5 (100mW/cm2) light of strengthening radical reaction under irradiation condition urges
Change the comparison of fuel cell and traditional photocatalytic fuel cell in organic matter degradation performance.
Fig. 3 is the present invention in simulated solar irradiation AM1.5 (100mW/cm2) light of strengthening radical reaction under irradiation condition urges
Change the comparison of fuel cell and traditional photocatalytic fuel cell on power generation performance.
In figure, 1 is TiO2Nanotube array photo-anode, 2 be Pt/PVC photocathode, and 3 be external circuit, and 4 be ferrous ion.
Specific embodiment
It elaborates below with reference to embodiment and attached drawing to the present invention, but protection model of the invention should not be limited with this
It encloses.
First referring to Fig. 1, Fig. 1 be it is of the present invention strengthen radical reaction photocatalysis wastewater fuel cell, manufacture structure and
Working principle diagram.As seen from Figure 1, it is of the present invention strengthen radical reaction photocatalysis wastewater fuel cell, manufacture include light anode 1,
Cathode 2, persistent organic pollutant wastewater, light source, electrolyte solution, quartz reaction pond and air vent.The light sun
Pole 1 is TiO2Nanotube array photo-anode, the cathode 2 are that platinum black electrode or Pt modify Si solar battery sheet (Pt/
PVC) photocathode, the light anode 1 and cathode 2 are inserted into the quartz reaction pond respectively and have included the organic contamination difficult to degrade
In the 0.1M sodium sulphate electrolyte solution of object waste water, and it is connected to by external circuit 3.The 0.1M sodium sulphate electrolyte solution
In added with 0.1~0.4mM ferrous ion 4 and by pH be adjusted to 1.0~4.0, the ferrous ion 4 is that seven hydrated sulfuric acids are sub-
Iron.The light source irradiation optoelectronic pole is opened, which is simulated solar irradiation, and light intensity is AM1.5 (100mW/cm2).Light anode 1 produces
Raw photohole is attached to 1 surface of light anode and water oxygen is turned to hydroxyl radical free radical, organic matter will 1 surface of light anode by hydroxyl from
It is aoxidized by base, while being continually fed into air in the air vent being located near cathode 2, being passed through oxygen in air at this time will be with
It is that the light anode 1 generates and combined by the light induced electron that external circuit 3 is transferred to the cathode 2 and generate water and be consequently formed back
Road.Meanwhile on 2 surface of cathode, from light anode 1 by external circuit 3 shift to light induced electron and the oxygen that is passed through in air
Solid/liquid/gas reactions generate the oxidants such as hydroxyl radical free radical, peroxy radical, superoxide radical, hydrogen peroxide again, ferrous ion 4 in light
The free radical and related substances of 2 Surface Creation of anode 1 and cathode generate class under the automatic bias effect of photocatalytic fuel cell
The circular response of Fenton is expanded radical reaction into whole system from light anode 1 and 2 surface of cathode, to enhance
Radical reaction in system, making photocatalytic fuel cell, degradation of organic substances and the ability of power generation are obviously improved simultaneously.
The preparation method of the photocatalysis wastewater fuel cell, manufacture of the present invention for strengthening radical reaction comprising following step
It is rapid:
1) light anode 1 described in is traditional TiO2Nano-tube array, production method are: clean metal titanium sheet is made
It for anode, is placed in the hydrofluoric acid aqueous solution of 0.5wt%, is to electrode with platinum electrode, control voltage raising speed is 1V s-1, and companion
With magnetic agitation, in 20V, anodic oxidation 30min, then takes out metal titanium sheet, is rinsed 2~3 times with deionized water, after air-drying
It is placed in Muffle furnace, 3h is sintered at 450 DEG C, muffle furnace climbing speed and fall off rate are 1 DEG C of min-1, after sintering
Up to required TiO2Nanotube array photo-anode.
2) cathode 2 described in is Pt/PVC (Pt modifies Si solar battery sheet) photocathode or platinum black electrode, wherein Pt/
The production method of PVC photocathode is: copper conductor is welded out on the back surface field silver grid of silicon cell, by entire back surface field epoxy resin
It is that cementing agent closing prepares silicon cell (PVC) photocathode, then using the silicon cell photocathode as working electrode, in K2PtCl6
Content is the 0.5mol/LK of 1mmol/L2SO4Solution (uses H2SO4PH is adjusted in 1), under the irradiation of simulated solar irradiation, is adjusted
Intensity of illumination is 100mW/cm2, controlling potential is that -0.2V deposits 20min, and PVC (Pt/PVC) time of Pt modification has just been made
Pole；Platinum black electrode can be directly commercially available by market.
3) by TiO prepared by step 1)2Nanotube array photo-anode is as light anode 1, by Pt/ prepared by step 2)
PVC photocathode or platinum black electrode are inserted into the quartz reaction pond respectively and have included the organic contamination difficult to degrade as cathode 2
In the 0.1M sodium sulphate electrolyte solution of object waste water, (seven hydrations of 0.1~0.4mM ferrous ion 4 are added into the electrolyte solution
Ferrous sulfate) and pH is adjusted to 1.0~4.0, while it being continually fed into air in the air vent being located near cathode 2, it is described
Light anode 1 is connected to by external circuit with cathode 2 and is irradiated by the light source and generated photogenerated charge, while being added in system
The ferrous ion 4 generates class with the free radical and related substances generated in the electrode surface of the light anode 1 and cathode 2
The circular response of Fenton, thus the radical reaction in fortification system.
Wastewater treatment and electric energy return the photocatalysis wastewater fuel cell, manufacture of the present invention for strengthening radical reaction at the same time
The more traditional photocatalysis wastewater fuel cell, manufacture of the performance of receipts is obviously improved.
The contents of the present invention are illustrated with embodiment below.
Embodiment 1
It first using clean metal titanium sheet as anode, is placed in the hydrofluoric acid aqueous solution of 0.5wt%, is to electricity with platinum electrode
Pole, control voltage raising speed are 1V s-1, and magnetic agitation is accompanied by, in 20V, anodic oxidation 30min, then takes out titanium sheet, spends
Ionized water rinses 2~3 times, air-dries and is placed in Muffle furnace, 3h, muffle furnace climbing speed and lower reduction of speed are sintered at 450 DEG C
Rate is 1 DEG C of min-1, up to required TiO after sintering2Nanotube array photo-anode.
Copper conductor is welded out on the back surface field silver grid of silicon cell, entire back surface field is closed with epoxy resin adhesive and is made
Standby silicon cell (PVC) photocathode, then using the PVC photocathode as working electrode, in K2PtCl6Content is 1mmol/L's
0.5mol/LK2SO4(use H2SO4PH is adjusted into 1) solution, under the irradiation of simulated solar irradiation, regulating illumination intensity is
100mW/cm2, controlling potential is that required Pt/PVC photocathode has just been made in -0.2V deposition 20min；
By TiO obtained2Nano-tube array is as light anode 1, using Pt/PVC photocathode obtained as cathode 2, respectively
It is inserted into the 0.1M metabisulfite solution of the methylene blue containing 20mg/L, 0.2mM ferrous ion 4 and will be electric is added into electrolyte solution
The pH of electrolyte solution is adjusted to 3.0, is connected to by external circuit 3.Opening simulated solar light source, (light intensity is 100mW cm-2) irradiation,
Ferrous ion 4 with 2 Surface Creation of light anode 1 and cathode free radical and related substances photocatalytic fuel cell automatic bias
The lower circular response for generating Fenton-like of effect, so that the radical reaction in fortification system, realizes that photocatalytic fuel cell exists
Greatly improving in the ability of degradation and the power generation of methylene blue.
The photocatalysis wastewater fuel cell, manufacture of reinforcing radical reaction described in the present embodiment will be difficult to degrade organic in 90min
Methylene blue removal 91.97% in pollutant waste water, while being measured through electrochemical workstation, electric current output density of the invention
For 0.322mAcm-2；With traditional photocatalysis wastewater fuel cell, manufacture (53.61%, 0.228mA cm-2) significantly mention compared to having
It is high, wherein the methylene blue removal rate in 90min improves 38.36%, and current density expands 1.41 times.As a result it sees
Fig. 2 and Fig. 3.In Fig. 2, curve 1,2 is respectively in simulated solar irradiation AM1.5 (100mW/cm2) under irradiation condition, traditional light is urged
Change fuel cell and strengthens the rate curve of the photocatalytic fuel cell degradation 20mg/L methylene blue of radical reaction；In Fig. 3,
Curve 3,4 is respectively in simulated solar irradiation AM1.5 (100mW/cm2) under irradiation condition, traditional photocatalytic fuel cell and strong
Change current -voltage curve of the photocatalytic fuel of radical reaction in degradation process.
Illustrate the effect of embodiment 1 with 3 reference examples below.
Reference examples 1
As control, in the case where the other conditions of embodiment 1 are constant, electrolyte solution pH is adjusted to 1.0, measures battery
90min methylene blue removal rate is 80.23%, reduces 11.74% than embodiment 1, density of photocurrent is 0.263mA cm-2,
It is the 4/5 of embodiment 1；With traditional photocatalysis wastewater fuel cell, manufacture (46.59%, 0.209mA cm under the conditions of-2) compared to having
Methylene blue removal rate in 90min improves 33.64%, and current density expands 1.26 times.
Reference examples 2
As control, in the case where the other conditions of embodiment 1 are constant, electrolyte solution pH is adjusted to 2.0, measures battery
90min methylene blue removal rate is 91.45%, reduces 0.52% than embodiment 1, density of photocurrent is 0.280mA cm-2, it is
The 6/7 of embodiment 1；With traditional photocatalysis wastewater fuel cell, manufacture (51.01%, 0.217mA cm under the conditions of-2) compared to having
Methylene blue removal rate in 90min improves 40.44%, and current density expands 1.29 times.
Reference examples 3
As control, in the case where the other conditions of embodiment 1 are constant, electrolyte solution pH is adjusted to 4.0, measures battery
90min methylene blue removal rate is 53.70%, reduces 38.21% than embodiment 1, density of photocurrent is 0.223mA cm-2,
Only the 7/10 of embodiment 1；With traditional photocatalysis wastewater fuel cell, manufacture (49.76%, 0.212mA cm under the conditions of-2) compare
There is the methylene blue removal rate in 90min to improve 3.94%, current density expands 1.05 times.
Embodiment 2
By TiO obtained2Nano-tube array is inserted into as light anode 1 using Pt/PVC obtained as photocathode 2 respectively
In the 0.1M sodium sulphate electrolyte solution of the methylene blue containing 20mg/L, 0.1mM ferrous ion 4 is added into the solution and will be electrolysed
The pH of matter solution is adjusted to 4.0, is connected to by external circuit 3.Opening simulated solar light source, (light intensity is 100mW cm-2) irradiation, it is sub-
Iron ion 4 is made with the free radical and related substances in 2 Surface Creation of light anode 1 and cathode in the automatic bias of photocatalytic fuel cell
With the lower circular response for generating Fenton-like, thus the radical reaction in fortification system, realization photocatalytic fuel cell is in Asia
Greatly improving in the ability of degradation and the power generation of methyl blue.
The photocatalysis wastewater fuel cell, manufacture of reinforcing radical reaction described in the present embodiment will be difficult to degrade organic in 90min
Methylene blue removal 83.63% in pollutant waste water, while being measured through electrochemical workstation, electric current output density of the invention
For 0.274mA cm-2；With traditional photocatalysis wastewater fuel cell, manufacture (53.61%, 0.228mA cm-2) compare, in 90min
Methylene blue removal rate improves 22.02%, and current density expands 1.20 times.
Embodiment 3
By TiO obtained2Nano-tube array is inserted into as light anode 1 using Pt/PVC obtained as photocathode 2 respectively
In the 0.1M metabisulfite solution of the methylene blue containing 20mg/L, 0.4mM ferrous ion 4 is added into electrolyte solution and by electrolyte
The pH of solution is adjusted to 1.0, is connected to by external circuit 3.Opening simulated solar light source, (light intensity is 100mW cm-2) irradiation, it is ferrous
Ion 4 is acted on the free radical and related substances in 2 Surface Creation of light anode 1 and cathode in the automatic bias of photocatalytic fuel cell
The lower circular response for generating Fenton-like, so that the radical reaction in fortification system, realizes photocatalytic fuel cell in methylene
Greatly improving in the ability of degradation and the power generation of base indigo plant.
The photocatalysis wastewater fuel cell, manufacture of reinforcing radical reaction described in the present embodiment will be difficult to degrade organic in 90min
Methylene blue removal 70.51% in pollutant waste water, while being measured through electrochemical workstation, electric current output density of the invention
For 0.259mA cm-2；With traditional photocatalysis wastewater fuel cell, manufacture (53.61%, 0.228mA cm-2) compare, in 90min
Methylene blue removal rate improves 16.90%, and current density expands 1.14 times.
Embodiment 4
By TiO obtained2Nano-tube array will directly buy resulting platinum black electrode conduct as light anode 1 in the market
Cathode 2 is inserted into respectively in the 0.1M metabisulfite solution of the methylene blue containing 20mg/L, and it is ferrous that 0.2mM is added into electrolyte solution
The pH of electrolyte solution is simultaneously adjusted to 1.5 by ion 4, is connected to by external circuit 3.It is ultraviolet to open the 4W that central wavelength is 254nm
Lamp (1.0mW cm-2) irradiation light anode 1, ferrous ion 4 and the free radical and correlative in 2 Surface Creation of light anode 1 and cathode
Matter generates the circular response of Fenton-like under the automatic bias effect of photocatalytic fuel cell, thus the free radical in fortification system
Photocatalytic fuel cell greatly improving in the ability of degradation and the power generation of methylene blue is realized in reaction.
The photocatalysis wastewater fuel cell, manufacture organic contamination difficult to degrade in 60min of the present invention for strengthening radical reaction
Methylene blue removal 95.36% in object waste water, while being measured through electrochemical workstation, electric current output density of the invention is
0.59mA cm-2；With traditional photocatalysis wastewater fuel cell, manufacture (43.75%, 0.42mA cm-2) compare, the methylene in 60min
Base indigo plant removal rate improves 51.61%, and current density expands 1.40 times.
Claims (6)
1. a kind of photocatalysis wastewater fuel cell, manufacture for strengthening radical reaction, including light anode, cathode, persistent organic pollutants
Waste water, light source, electrolyte solution, quartz reaction pond and air vent, the light anode and cathode are inserted into the quartz respectively
Reaction tank includes in the electrolyte solution of the persistent organic pollutant wastewater, and is connected to by external circuit, the cathode
Close to the air vent for being continually fed into air, the light source irradiates the light anode or irradiates the light anode simultaneously
With the cathode with photoresponse；It is characterized by: added with 0.1~0.4mM ferrous ion and being incited somebody to action in the electrolyte solution
PH is adjusted to 1.0~4.0, under the automatic bias effect of the photocatalysis wastewater fuel cell, manufacture, the ferrous ion and light sun
Free radical and related substances that the electrode surface of pole and cathode generates generate the circular response of Fenton-like, thus in fortification system
Radical reaction.
2. the photocatalysis wastewater fuel cell, manufacture according to claim 1 for strengthening radical reaction, it is characterised in that: described
Light anode is TiO2Nanotube array photo-anode, the cathode are Pt/PVC photocathode or platinum black electrode, the electrolysis
Matter solution is 0.1M metabisulfite solution.
3. the photocatalysis wastewater fuel cell, manufacture according to claim 1 for strengthening radical reaction, it is characterised in that: described
Light source is simulated solar irradiation, light intensity 100mW/cm2。
4. a kind of preparation method of the photocatalysis wastewater fuel cell, manufacture described in claim 1 for strengthening radical reaction, feature
Be: the preparation method includes the following steps:
1) traditional TiO is prepared2Nanotube array photo-anode, production method are: using clean metal titanium sheet as anode, setting
It is to electrode with platinum electrode, control voltage raising speed is 1V s in the hydrofluoric acid aqueous solution of 0.5wt%-1, and accompany by magnetic force and stir
It mixes, in 20V, anodic oxidation 30min, then takes out metal titanium sheet, is rinsed 2~3 times with deionized water, air-dries and is placed on Muffle
In furnace, 3h is sintered at 450 DEG C, muffle furnace climbing speed and fall off rate are 1 DEG C of min-1, up to required after sintering
TiO2Nanotube array photo-anode；
2) Pt/PVC photocathode or platinum black electrode are prepared, wherein the production method of Pt/PVC photocathode is: first in silion cell
Copper conductor is welded out on the back surface field silver grid of piece, the closing of entire back surface field epoxy resin adhesive is then prepared into PVC time
Pole, then using the PVC photocathode as working electrode, in K2PtCl6Content is the 0.5mol/L K of 1mmol/L2SO4It, should in solution
K2SO4Solution H2SO4Adjust pH to 1, under the irradiation of simulated solar irradiation, regulating illumination intensity 100mW/cm2, controlling potential
20min is deposited for -0.2V, just obtains the Pt/PVC photocathode of Pt modification PVC；Platinum black electrode directly buys gained by market；
3) by TiO prepared by step 1)2Nanotube array photo-anode is as light anode, by Pt/PVC light prepared by step 2)
Cathode or platinum black electrode are inserted into the quartz reaction pond respectively and have included the persistent organic pollutant wastewater as cathode
0.1M sodium sulphate electrolyte solution in, 0.1~0.4mM ferrous ion is added into the sodium sulphate electrolyte solution and by pH tune
It is 1.0~4.0, is continually fed into air, the light anode and cathode outside in the air vent being located near the cathode
Portion's circuit communication is simultaneously irradiated by the light source and is generated photogenerated charge, at the same add the ferrous ion in the light anode
The free radical and related substances that generate with the electrode surface of cathode generate the circular response of Fenton-like, thus in fortification system
Radical reaction.
5. the preparation method of the photocatalysis wastewater fuel cell, manufacture according to claim 4 for strengthening radical reaction, feature
Be: in the step 3), the light source is simulated solar irradiation, light intensity 100mW/cm2。
6. a kind of photocatalysis wastewater fuel cell, manufacture described in claim 1 for strengthening radical reaction wastewater treatment and electricity at the same time
Application in capable of recycling.
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