CN104724788B - A kind of visible light-responded electrode of ferrum oxide, graphene oxide and N, F codope and preparation method and application - Google Patents
A kind of visible light-responded electrode of ferrum oxide, graphene oxide and N, F codope and preparation method and application Download PDFInfo
- Publication number
- CN104724788B CN104724788B CN201510076147.3A CN201510076147A CN104724788B CN 104724788 B CN104724788 B CN 104724788B CN 201510076147 A CN201510076147 A CN 201510076147A CN 104724788 B CN104724788 B CN 104724788B
- Authority
- CN
- China
- Prior art keywords
- electrode
- tio
- codope
- graphene
- electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses visible light-responded electrode of a kind of ferrum oxide, graphene oxide and N, F codope and preparation method and application, including: (1) is by TiO2NTs electrode and NH4F is blended under air atmosphere and calcines to obtain N, F TiO2Electrode；(2) by N, F TiO2Electrode is soaked in Fe (NO3)3In；With graphite electrode as anode, platinized platinum as negative electrode, Na2SO4For electrolyte, dissolve Graphene and obtain Graphene electrolyte；(3) by the electrode after immersion treatment air-dry make negative electrode, anode made by graphite electrode, electro-deposition in Graphene electrolyte；(4) with step (3) process after electrode as anode, graphite as negative electrode, KOH be electrolyte electro-deposition, clean air-dry.Light induced electron and hole good separating effect after ferrum oxide, graphene oxide codope in electrode of the present invention, photoelectric current is high, by photoelectric-synergetic effect processing waste water containing chrome, effective, and non-secondary pollution can be used for multiple times.
Description
Technical field
The present invention relates to catalysis material technical field, be specifically related to a kind of ferrum oxide, graphene oxide
Visible light-responded electrode of codope and preparation method and application.
Background technology
While facing mankind environmental pollution, also face energy starved problem.On the one hand, environment is dirty
Dye, especially water are polluted, and increasingly aggravate, the Health and Living of the serious threat mankind.Wherein, containing weight
Metallic wastewater, toxicity is big, and microorganism is difficult to degrade, it is more difficult to process.On the other hand, urge along with light
The development of technology, utilizes photocatalyst decomposition water to prepare hydrogen, is expected to alleviating energy crisis problem.
Nanotube titanium dioxide film is the Novel Titanium dioxide nano material of development in recent years, and it is in reduction
Heavy metal ion Cr (VI) aspect has good effect.But due to energy gap width, only with accounting for too
The less ultraviolet region of sunlight gross energy, by TiO2The element that middle doping is appropriate so that it is forbidden band
Narrowing, the light that absorbing wavelength is longer, such that it is able to utilize more visible ray.Such as, Publication No.
The Chinese invention application of CN 103523826A discloses the preparation method of a kind of tin dope titanium dioxide,
Method is as follows: join in dehydrated alcohol by Butyl Phthalate and stannic chloride pentahydrate, adds ethylene glycol,
Sequentially add concentrated hydrochloric acid and deionized water, add polyvinylpyrrolidone, stirring, obtain stablizing
Bright yellow sol, anti-in yellow sol is transferred to the stainless steel cauldron of teflon lined
Should, naturally cool to room temperature, with dehydrated alcohol and distilled water wash, filter, collect white precipitate,
White precipitate is dried, grinds, encapsulation, obtain tin dope titanium dioxide.
The Chinese invention application of Publication No. CN 103908962A discloses a kind of Ag doping titanium dioxide
Titanium aeroge preparation technology of coating and equipment, technique includes the system of Ag doping nano titania aqueous solution
The step of the preparation of standby step and nano titanium oxide aeroge coating；Equipment includes for storing silver
The liquid material tank of doping titanium dioxide nano aqueous solution, spray gun tank connected with liquid material, spray gun
There is nozzle, for transmitting the transmission part of base material and drying the Ag doping titanium dioxide of spraying on base material
The baking oven of nano aqueous solution layer.
During dual element codope, strengthening further that it is visible light-responded, photocatalytic activity significantly improves.
The Chinese invention application of such as Publication No. CN104258837A discloses a kind of carbon-silicon coblended and receives
The preparation method of rice titanium dioxide, makees with butyl titanate for titanium source, alkyl triethoxysilane simultaneously
For carbon source and silicon source, utilize alkyl triethoxysilane to prepare silicon with butyl titanate cohydrolysis polycondensation and mix
Miscellaneous TiO 2 precursor, utilizes the silicon-alkyl bond in alkyl triethoxysilane (such as Si-CH3)
Regulate and control titania growth, utilize silicon-alkyl bond to introduce carbon source, at follow-up roasting process
Introduce in situ carbon, and then prepare the nano titanium oxide of carbon-silicon coblended.
Summary of the invention
The invention provides the visible light-responded of a kind of ferrum oxide, graphene oxide and N, F codope
Electrode and preparation method and application, the preparation method of photoelectrocatalysielectrode electrode is simple, ferrum oxide, oxidation
Light induced electron and hole good separating effect after Graphene codope, photoelectric current is high, is made by photoelectric-synergetic
By processing waste water containing chrome, effective, non-secondary pollution, can be used for multiple times.
Prepared by its of the visible light-responded electrode of a kind of ferrum oxide, graphene oxide and N, F codope
Method, comprises the steps:
(1) by TiO2-NTs electrode and NH4F solids mixing is placed in Muffle furnace, in air atmosphere
Enclose lower calcining 2～3 hours, washing surface impurity after cooling, after air-drying NF-TiO2Electrode；
(2) by described NF-TiO2Electrode is soaked in the Fe (NO of supersound process3)3In solution；
(3) with graphite electrode as anode, platinized platinum as negative electrode, Na2SO4Solution is electrolyte, powers up
Pressure makes graphite dissolve, and controls dissolution time, obtains the Graphene electrolyte of variable concentrations；
(4) by the NF-TiO after immersion treatment in step (2)2Electrode air-dries makees negative electrode, graphite electricity
Anode is made in pole, carries out electro-deposition for several times in (3) gained Graphene electrolyte；
(5) with step (4) process after electrode as anode, graphite as negative electrode, KOH solution be
Electrolyte carries out electrodeposition process, cleans after air-drying that i.e. to obtain ferrum oxide, graphene oxide and N, F common
The visible light-responded electrode of doping.
The visible light-responded electrode of ferrum oxide, graphene oxide and N, F codope is designated as
Fe2O3-GO/NF-TiO2Electrode.
TiO described in step (1)2The preparation method of-NTs electrode is as follows:
By seamless to surface for pure Ti sheet sand papering, the most successively with acetone, dehydrated alcohol with go
Ionized water each ultrasonic cleaning 10min, with Ti sheet as anode, Cu sheet is negative electrode, in 0.5wt%NaF
With 0.5mol/L Na2SO4Mixed solution, in addition 20V constant voltage, anodic oxidation 5h, will prepare
Sample clean, air-dry, obtain TiO2-NTs electrode.
Research finds in lattice titania-doped for F codope to N, can not only promote N
Doping, promote visible absorption, moreover it is possible to strengthen hole oxidability, improve photocatalysis effect；
Fe2O3It is a kind of narrow-band semiconductor material, ultraviolet light and visible ray is all had response in various degree,
Stable chemical nature, nontoxic simultaneously, but its light induced electron and hole produced in photocatalytic process is easy
Compound, the absorption coefficient of light is little.Research discovery Fe2O3To titania nanotube (TiO2-NTs)
It is modified preparing combination electrode, recuperability can be improved, and suppression electron-hole pair is multiple further
Close, improve the absorption efficiency of visible ray；It is successfully separated out Graphene in the lab to open from scientist
Beginning, Graphene is always the focus of people's research, and its resistivity is extremely low, and electron transfer rate is exceedingly fast.
Graphene oxide, as the oxide of Graphene, is the new carbon of a kind of excellent performance, has higher
Specific surface area and abundant functional group, in photocatalyst, doping can help to improve light induced electron
Being combined of transfer, further suppression electronics and hole.The present invention is in the titanium dioxide of N, F codope
On the basis of titanium nanometer tube combination electrode, by ferrum oxide and graphene oxide being collectively incorporated into, it is expected to carry
The response to visible ray of the high photochemical catalyst electrode, by photoelectric-synergetic effect, improves photochemical catalyst electrode to containing
The treatment effect of chrome waste water.
The present invention studies discovery TiO2In when carrying out N, F dual element codope effect be obviously improved,
Fe of the present invention2O3-GO/NF-TiO2Electrode is utilizing the TiO of nonmetalloid N, F doping vario-property2
On nanotube electrode material foundation, and it is aided with metal-oxide Fe2O3, nonmetal oxide oxidation stone
Ink alkene surface is synergistically modified, it is possible to suppression electron-hole pair is combined further, strengthens electron transfer speed
Rate, thus promote visible ray utilization rate.
The Fe of the present invention2O3-GO/NF-TiO2Electrode produce under the excitation of visible ray electronics and
Hole, Hole oxidation Organic substance, electron reduction heavy metal, Cr (VI) is reduced to toxicity little 100 times,
Easily there is the Cr (III) of coordination precipitation.
NH is used when electrode N, F of the present invention adulterates4F solid is raw material, finds in exploratory development
With NH4F solid is raw material, and nonmetalloid N, F codope is entered TiO2-NTs prepares
Electrode product shape corroded into irregularly shaped by original nano tube structure, and by follow-up should
Show there is this erose modified electrode and there are more preferable photoelectric properties, to visible with test
The utilization rate of light is higher, more preferable to the treatment effect of hexavalent chromium wastewater.
Described N, F is doped into TiO with the ratio of 1:12, wherein the doping of N, F is to compound
The performance of electrode has affected, for NH4The addition of F is forged through repetition test, step (1)
The NH added during burning4F mass is 0.04g～0.3g:1cm with the area ratio of electrode2；Most preferably
0.2g:1cm2。
As preferably, in step (1), calcining heat is 400～500 DEG C；More preferably 450
℃.The speed heated up is 5～10 DEG C/min, cooldown rate 5～10 DEG C/min.
As preferably, when preparing Graphene electrolyte in step (3), voltage is 4～9V；Temperature is 80～90
℃；Dissolution time is 5～30min.Na when preparing Graphene electrolyte2SO4The concentration of solution is
0.1mol/L, most preferably, when step (3) is prepared Graphene electrolyte in concentration be 0.1mol/L
And the Na that water temperature is 85 DEG C2SO4In electrolyte, 5V constant voltage 15min in addition.
NF-TiO in step (2)2Electrode is at Fe (NO3)3Soak time in solution is 8～15min；
Fe(NO3)3Solution concentration is 0.02～0.2mol/L, more preferably 0.02～0.08mol/L.
As preferably, in step (4), electro-deposition number of times is 1～5 time.More preferably 1～3 time,
It is preferably 1 time.
As preferably, in step (4), electro-deposition voltage is 4～9V；The time of electro-deposition is every time
10～20min.Most preferably with constant 5V voltage electro-deposition 20min.
As preferably, in step (5), electro-deposition voltage is 4～9V, and electrodeposition time is 1.5～2.5min.
In step (5), electrodeposition temperature is room temperature, it is highly preferred that step (5) is to exist at room temperature
In 1mol/L KOH electrolyte, 5V constant voltage anodic oxidation 2min in addition.
A kind of preferably technical scheme, the Fe of the present invention2O3-GO/NF-TiO2Electrode is by the following method
Preparation:
(1) by TiO2-NTs electrode and NH4F solids mixing is placed in Muffle furnace, in air atmosphere
Enclosing lower calcining 2～3 hours, calcining heat is 400～500 DEG C, washing surface impurity after cooling, wind
NF-TiO is obtained after Gan2Electrode；The NH added4F mass is 0.04g～0.3g with the area ratio of electrode:
1cm2；
(2) by described NF-TiO2Electrode is soaked in the Fe (NO of supersound process3)3In solution,
NF-TiO2Electrode is at Fe (NO3)3Soak time in solution is 8～15min；Fe(NO3)3
Solution concentration is 0.02～0.2mol/L；
With graphite electrode as anode, platinized platinum as negative electrode, Na2SO4Solution is electrolyte, and making alive makes stone
Ink alkene dissolves, and obtains Graphene electrolyte；When preparing Graphene electrolyte, voltage is 4～9V；Temperature is
80～90 DEG C；Dissolution time is 5～30min；
(3) by the NF-TiO after immersion treatment in step (2)2Electrode air-dries makees negative electrode, graphite electricity
Anode is made in pole, carries out 1～5 electro-deposition in described Graphene electrolyte；Electro-deposition voltage is 4～9V；
The time of electro-deposition is 10～20min every time；
(4) with step (3) process after electrode as anode, graphite as negative electrode, KOH solution be
Electrolyte carries out electrodeposition process, and electro-deposition voltage is 4～9V, and electrodeposition time is 1.5～2.5min,
Temperature is 20～30 DEG C, and electrodeposition process afterwash air-dries and i.e. obtains ferrum oxide, graphene oxide codope
Visible light-responded electrode, i.e. Fe2O3-GO/NF-TiO2Electrode.
The core of the present invention is to build the photoelectrocatalysis body of visible ray-catalysis electrode-applying bias combination
System.Utilize Fe2O3-GO/NF-TiO2The combination electrode response to visible ray, promotes that electron-hole divides
From, and the graphene oxide of area load can accelerate electron transport rate, thus effectively suppress photoproduction
Electronics and hole compound, substantially increases the effect that Cr in water (VI) is reduced to hypotoxic Cr (III)
Rate.Under the combination of above-mentioned each optimum condition, treatment effect is more preferable.
A kind of most preferably technical scheme, described Fe2O3-GO/NF-TiO2Electrode is by the following method
Preparation:
(1) by TiO2-NTs electrode and NH4F solids mixing is placed in Muffle furnace, in air atmosphere
Enclosing lower calcining 2～3 hours, calcining heat is 450 DEG C, washing surface impurity after cooling, after air-drying
Obtain NF-TiO2Electrode；The NH added4F mass is 0.2:1cm with the area ratio of electrode2；
(2) by described NF-TiO2Electrode is soaked in the Fe (NO of supersound process3)3In solution, N,
F-TiO2Electrode is at Fe (NO3)3Soak time in solution is 10min；Fe(NO3)3Solution concentration
It is 0.02～0.08mol/L；
With graphite electrode as anode, platinized platinum as negative electrode, Na2SO4Solution is electrolyte, and making alive makes stone
Ink alkene dissolves, and obtains Graphene electrolyte；When preparing Graphene electrolyte, voltage is 5V；Temperature is 85
℃；Dissolution time is 15min；
(3) by N, the F-TiO after immersion treatment in step (2)2Electrode air-dries makees negative electrode, graphite
Electrode makees anode, carries out 1 electro-deposition in described Graphene electrolyte；Electro-deposition voltage is 5V；
The time of electro-deposition is 15min every time；
(4) with step (3) process after electrode as anode, graphite as negative electrode, KOH solution be
Electrolyte carries out electrodeposition process, and electro-deposition voltage is 5V, electrodeposition time 2min, and temperature is 20～30
DEG C, electrodeposition process afterwash air-dry i.e. obtain ferrum oxide, graphene oxide codope visible light-responded
Electrode, i.e. Fe2O3-GO/NF-TiO2Electrode.
It is common that the present invention also provides for a kind of ferrum oxide of preparing such as described preparation method, graphene oxide
The visible light-responded electrode of doping.
The combination electrode of the present invention is at the synergism of metal-oxide, graphene oxide and N, F
Under, the response to visible ray promotes that electron-hole separates, and the graphene oxide of area load is permissible
Accelerate electron transport rate, thus effectively suppression light induced electron and hole is compound, therefore combination electrode
The electric current density that detection obtains is big, and hole-electron pair good separating effect, optical Response is good.Present invention electricity
Stabilizer pole is good, still has higher Cr (VI) reduction efficiency after being recycled for multiple times.
Present invention also offers a kind of method utilizing described visible light-responded Electrode treatment chromate waste water,
Comprise the steps:
Equipped with the most described visible light-responded electrode as anode, Ti sheet is in the reactor of negative electrode, Gu
Distance between fixed two electrodes, adds containing electrolyte and the chromate waste water of EDTA, and regulation pH value is extremely
Acidity, stirs in dark place, after adsorption equilibrium, and in addition voltage, open light source, react.
As preferably, the hexavalent chromium concentration in described chromate waste water is 8 × 10-5mol/L。
As preferably, the hole agent for capturing added in described chromate waste water is EDTA, more as preferably
EDTA concentration is 1 × 10-3mol/L。
As preferably, described light source is to utilize optical filter to filter off the wavelength X < Halogen light of 420nm part.
As preferably, on described working electrode, institute's making alive is 0.5～3V, more preferably 2～3V.
As preferably, the pH value of waste water is adjusted to 2～5.
As preferably, fixing the distance between two electrodes is 1～2cm.
Beneficial effects of the present invention has:
(1) with low cost, preparation method is simple, green cleaning；
(2) light induced electron and hole good separating effect, photoelectric current is high, has the highest going back to Cr (VI)
Proper energy power；
(3) combination electrode prepared, stable performance, can realize repeatedly utilizing.
Accompanying drawing explanation
Fig. 1 a and Fig. 1 b is Fe2O3/TiO2-NTs and Fe2O3-GO/NF-TiO2Pattern comparison diagram.
Fig. 2 is Fe under different voltages in the embodiment of the present invention 12O3-GO/NF-TiO2Electrode time m-
Current curve
Fig. 3-a is Different electrodes AC impedance contrast under visible light illumination in the embodiment of the present invention 2
Figure.
Fig. 3-b is Fe in the embodiment of the present invention 22O3-GO/NF-TiO2Combination electrode is in dark and illumination
Under the conditions of AC impedance comparison diagram
Fig. 4 is the Fe of different frequency of depositing in the embodiment of the present invention 32O3-GO/NF-TiO2Electrode
Photoelectric current comparison diagram.
Fig. 5 is Different electrodes Cr (VI) reduction effect under same reaction condition in the embodiment of the present invention 4
Really comparison diagram.
Fig. 6 is Fe in the embodiment of the present invention 42O3-GO/NF-TiO2The optical, electrical synergism of electrode
Process containing Cr (VI) waste water design sketch.
Fig. 7 is Fe in the embodiment of the present invention 42O3-GO/NF-TiO2Electrode is under different voltages
Cr (VI) reduction effect contrasts.
Fig. 8 is Fe in the embodiment of the present invention 42O3-GO/NF-TiO2Electrode cycle using effect figure.
Detailed description of the invention
In conjunction with Figure of description and specific embodiment, the present invention is further described.
Fe in the embodiment of the present invention2O3-GO/NF-TiO2Electrode production process is as follows:
1, by seamless to surface with sand papering, the most successively with third for pure Ti sheet (2cm × 2.5cm)
The ultrasonic cleaning successively of ketone, dehydrated alcohol and deionized water, clean to titanium plate surface.With Ti sheet as sun
Pole, Cu sheet is negative electrode, with 0.5wt%NaF and 0.5mol/L Na2SO4For electrolyte solution, additional
20V constant voltage, anodic oxidation 5h.Prepared sample is cleaned, air-dries, obtain TiO2-NTs。
2, by TiO2-NTs is placed in crucible, and crucible bottom addition is a certain amount of, and (0.2～1.5g is preferably
NH 1.0g)4F solid, 450 DEG C of cycle annealings process 2h (7 DEG C/min of heating rate, cooling
10 DEG C/min of speed), obtain NF-TiO2。
3, by NF-TiO2Being immersed in solution concentration is 0.05mol/L and the most ultrasonic 10min
Fe(NO3)310min in solution, air-dries.Using platinized platinum as negative electrode, graphite is as anode, in concentration
For 0.1mol/L and Na that water temperature is 85 DEG C2SO4In electrolyte, 5V constant voltage 15min in addition,
Close power supply.
4, with above-mentioned obtained solution as electrolyte, the NF-TiO that will have soaked2As negative electrode, graphite
Electrode is as anode, with constant 5V voltage electro-deposition 20min.
5, using this electrode as anode, graphite is negative electrode, in room temperature 1mol/L KOH electrolyte,
In addition 5V constant voltage anodic oxidation 2min, closes power supply, cleans and obtains after air-drying
Fe2O3-GO/NF-TiO2。
Fe2O3-GO/NF-TiO2Electrode treatment chromate waste water process is as follows:
Adding chromate waste water and EDTA in the reactor, regulation pH value is the most acid, with
Fe2O3-GO/NF-TiO2Electrode is working electrode, and Ti sheet is to electrode, balances in dark place stirring and adsorbing
After, certain voltage in addition, and open light source, react.And with diphenyl phosphinylidyne two hydrazine, dense sulfur
Acid, strong phosphoric acid, as developer, use spectrophotometry.
Embodiment 1
By Fe2O3-GO/NF-TiO2Electrode is placed in the Na that concentration is 0.1mol/L2SO4In solution, add
Enter sacrifice agent Na2SO3(0.1mol/L), under electrochemical workstation 3 electrode system, with
Fe2O3-GO/NF-TiO2-NTs electrode is working electrode, and platinized platinum is to electrode, and silver electrode is reference electricity
Pole, xenon lamp is light source, and filters off the ultraviolet light of below 420nm with optical filter.
It will be seen that TiO from Fig. 1-a, Fig. 1-b2-NTs is at NH4Under F modifies, high-temperature calcination
There is change greatly in the pattern of rear surface, tubulose is changed into irregular, meanwhile photoproduction electricity
There is change greatly in sub-transmission means and electrode performance.Fig. 2 is for setting electricity in different electrochemical workstations
Pressure Fe2O3-GO/NF-TiO2The time current curve of electrode, can be obtained by Fig. 2, this compound electric
The electric current density that pole detection obtains is big, and hole-electron pair good separating effect, optical Response is good.Along with outward
Biased improving constantly, the recombination rate of hole-electron pair declines, and photoelectric properties have promoted.
Embodiment 2
Under electrochemical workstation 3 electrode system, electrolyte be concentration be the Na of 0.5mol/L2SO4
Solution, respectively with Fe2O3-GO/NF-TiO2Electrode is working electrode, and platinum electrode is to electrode, silver
Electrode is reference electrode.Measure the AC impedance of combination electrode under dark place and radiation of visible light respectively.
Fig. 3-a is Different electrodes AC impedance comparison diagram under visible light illumination.Various electrodes
In Nyquist figure, Fe2O3-GO/NF-TiO2The impedance ring radius of combination electrode is minimum, and this electricity is described
The interface charge transmission resistance of pole is less.
Fig. 3-b is Fe2O3-GO/NF-TiO2Electrode AC impedance pair under dark and illumination condition
Than figure.As seen from the figure, the impedance under illumination condition of this electrode is changed radius and is reduced, and photoelectric properties are carried
Rise.
Embodiment 3
The different frequency of depositing of research is to preparation Fe2O3-GO/NF-TiO2The impact of combination electrode.By N,
F-TiO2It is immersed in the Fe (NO of the most ultrasonic 10min3)3In solution, air-dry.Using platinized platinum as negative electrode,
Graphite is as anode, in the Na that concentration is 0.1mol/L and water temperature is 85 DEG C2SO4In electrolyte, add
With 5V constant voltage 15min, close power supply.With above-mentioned obtained solution as electrolyte, will soak
NF-TiO2As negative electrode, graphite electrode is as anode, with constant 5V voltage electro-deposition 20min.
Using this electrode as anode, graphite is negative electrode, in room temperature 1mol/L KOH electrolyte, and 5V in addition
Constant voltage anodic oxidation 2min, closes power supply.Repeat above-mentioned 4,5 steps, different heavyly final
The Fe of long-pending number of times2O3-GO/NF-TiO2Combination electrode.
Fig. 4 is the Fe of different frequency of depositing2O3-GO/NF-TiO2The photoelectric current comparison diagram of electrode.By
Figure understands, and frequency of depositing is many, Fe2O3And the increase of graphene oxide-loaded amount does not promote electrode
Photoelectric properties, therefore frequency of depositing is to be preferred for 1～2 time.
Embodiment 4
Take the Cr of 50mL6+(8×10-5mol/L)、Na2SO4(0.2mol/L)、EDTA(10-3mol/L)
Mixed solution, regulation pH value is to acid (pH is 3), with catalysis electrode as anode, clean Ti sheet
For negative electrode, the distance between distance and working electrode and light source between regulating YIN and YANG pole.Dark place is anti-
After answering adsorption equilibrium, 2V constant voltage open light source in addition, react, after reacting 80 minutes,
Sample and use spectrophotometry.Change Different electrodes or regulate applied voltage size, change light source,
Power supply, Organic substance addition condition etc., other steps are ibid.
Fig. 5 is Different electrodes Cr (VI) reduction effect contrast under same reaction condition.As seen from the figure,
Under same reaction condition, Fe2O3-GO/NF-TiO2Electrode is up to 94% to the clearance of Cr (VI),
Compared with similar catalysis electrode, there is remarkable result.
Fig. 6 is Fe2O3-GO/NF-TiO2The optical, electrical synergism of electrode processes containing Cr (VI) waste water
Design sketch.As seen from the figure, when reducing Cr (VI), optical, electrical there is synergism, can be substantially improved
Reduction efficiency.Fe2O3-GO/NF-TiO2Combination electrode can reduce Cr (VI) simultaneously, oxidation of organic compounds,
All heavy metals have synergism with Organic substance in the presence of simultaneously.
Fig. 7 is Fe2O3-GO/NF-TiO2Electrode Cr (VI) under common power difference applied voltage
Reduction effect contrasts.As seen from the figure, along with the raising of applying bias, Cr (VI) reduction effect has carried
Rise.
Fig. 8 is Fe2O3-GO/NF-TiO2Electrode cycle using effect.As seen from the figure, this electrode is steady
Qualitative good, after being recycled for multiple times, the clearance range of decrease of Cr (VI) is less than 5%.Have higher
Cr (VI) reduction efficiency.
Embodiment 5
By TiO2-NTs (2cm × 2.5cm) is placed in 6 crucibles, be separately added into 0.2g, 0.5g,
The NH of 0.7g, 1.0g, 1.2g, 1.5g4F solid, sets heating rate as 7 DEG C/min, annealing perseverance
450 DEG C of 2h of temperature, lower the temperature with 10 DEG C/min, obtain the NF-TiO of different N, F doping2。
With NF-TiO2For substrate, by above-mentioned steps 3-5 final different N, F dopings
Fe2O3-GO/NF-TiO2Combination electrode, and it is applied to the process of chromate waste water.Result of study table
Bright: along with NH4The increase of F content, same reaction time Cr (VI) clearance is gradually incremented by, and works as NH4F
Content is that 1.0g, Cr (VI) clearance is maximum, increases NH further4F content, electrode easily peels off,
Instability, Cr (VI) clearance declines on the contrary.
Embodiment 6
By TiO2-NTs is placed in crucible, adds the NH of 1.0g4F solid, set heating rate as
7 DEG C/min, anneal under specified temp (350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C) constant temperature 2h, with 10
DEG C/min cooling, obtain the NF-TiO of specific calcining heat2。
With NF-TiO2For substrate, by above-mentioned steps 3-5 final different calcining heats
Fe2O3-GO/NF-TiO2Combination electrode, and it is applied to the process of chromate waste water.Result of study table
Bright: along with the increase of calcining heat, same reaction time Cr (VI) clearance is gradually incremented by, 450 DEG C
Process catalysis electrode removal Cr (VI) efficiency obtained optimal.
Embodiment 7
Preparing 6 parts of volumes is 100mL, and concentration is the Na of 0.1mol/L2SO4Solution is as electrolyte.
Respectively with platinized platinum as negative electrode, graphite electrode is anode, and 5V constant voltage, dissolves 5min respectively in addition,
10min, 15min, 20min, 25min, 30min, obtain the graphene solution of variable concentrations gradient.
By TiO2-NTs is placed in crucible, adds the NH of 1.0g4F solid, sets heating rate as 7 DEG C/min,
Anneal at specified temp 450 DEG C constant temperature 2h, lowers the temperature with 10 DEG C/min, obtains NF-TiO2。
By NF-TiO2It is immersed in the Fe (NO that solution concentration is 0.05mol/L the most ultrasonic 10min3)3
10min in solution, air-dries, and then immerses above-mentioned graphene solution, graphite electrode conduct as negative electrode
Anode, with constant 5V voltage electro-deposition 20min.
By the final Fe obtaining different graphene-supported amounts of above-mentioned steps 52O3-GO/NF-TiO2Compound electric
Pole, and it is applied to the process of chromate waste water.Result of study shows: when dissolving with 15min graphite
Between prepare graphene solution be immersion fluid prepare the electrode that meets there is optimal PhotoelectrocatalytiPerformance Performance.
After visible ray-electricity synergy 80 minutes, the clearance of Cr (VI) reaches 94%.
Claims (9)
1. the preparation of the visible light-responded electrode of a ferrum oxide, graphene oxide and N, F codope
Method, it is characterised in that comprise the steps:
(1) by TiO2-NTs electrode and NH4F solids mixing is placed in Muffle furnace, in air atmosphere
Enclose lower calcining 2～3 hours, washing surface impurity after cooling, after air-drying NF-TiO2Electrode；
Described TiO2The preparation method of-NTs electrode is as follows:
By seamless to surface for pure Ti sheet sand papering, the most successively with acetone, dehydrated alcohol with go
Ionized water each ultrasonic cleaning 10min, with Ti sheet as anode, Cu sheet is negative electrode, in 0.5wt%NaF
With 0.5mol/L Na2SO4In mixed solution, in addition 20V constant voltage, anodic oxidation 5h, will system
The sample obtained is cleaned, is air-dried, and obtains TiO2-NTs electrode；
(2) by described NF-TiO2Electrode is soaked in the Fe (NO of supersound process3)3In solution；
(3) with graphite electrode as anode, platinized platinum as negative electrode, Na2SO4Solution is electrolyte, powers up
Pressure makes graphite dissolve, and controls dissolution time, obtains the Graphene electrolyte of variable concentrations；
(4) by the NF-TiO after immersion treatment in step (2)2Electrode air-dries makees negative electrode, graphite electricity
Anode is made in pole, carries out electro-deposition for several times in (3) gained Graphene electrolyte；
(5) with step (4) process after electrode as anode, graphite as negative electrode, KOH solution be
Electrolyte carries out electrodeposition process, cleans after air-drying that i.e. to obtain ferrum oxide, graphene oxide and N, F common
The visible light-responded electrode of doping.
Ferrum oxide, graphene oxide and the visible ray of N, F codope the most according to claim 1
The preparation method of response electrode, it is characterised in that the NH added during step (1) calcining4F mass
It is 0.04g～0.3g:1cm with the area ratio of electrode2。
Ferrum oxide, graphene oxide and the visible ray of N, F codope the most according to claim 1
The preparation method of response electrode, it is characterised in that in step (1), calcining heat is 400～500 DEG C.
Ferrum oxide, graphene oxide and the visible ray of N, F codope the most according to claim 1
The preparation method of response electrode, it is characterised in that electricity when preparing Graphene electrolyte in step (3)
Pressure is 4～9V；Temperature is 80～90 DEG C；Dissolution time is 5～30min.
Ferrum oxide, graphene oxide and the visible ray of N, F codope the most according to claim 1
The preparation method of response electrode, it is characterised in that in step (4), electro-deposition number of times is 1～5 time.
Ferrum oxide, graphene oxide and the visible ray of N, F codope the most according to claim 1
The preparation method of response electrode, it is characterised in that in step (4), electro-deposition voltage is 4～9V；Often
The time of secondary electro-deposition is 10～20min.
Ferrum oxide, graphene oxide and the visible ray of N, F codope the most according to claim 1
The preparation method of response electrode, it is characterised in that in step (5), electro-deposition voltage is 4～9V, electricity
Sedimentation time is 1.5～2.5min.
8. the oxidation that a preparation method as described in claim 1～7 any claim prepares
The visible light-responded electrode of ferrum, graphene oxide and N, F codope.
9. utilize a method for visible light-responded Electrode treatment chromate waste water described in claim 8,
It is characterized in that, comprise the steps:
Equipped with visible light-responded electrode as claimed in claim 8 as anode, Ti sheet is the anti-of negative electrode
Answer in device, fix the distance between two electrodes, add containing electrolyte and the chromate waste water of EDTA, adjust
Joint pH value, to acid, stirs in dark place, after adsorption equilibrium, and in addition voltage, open light source, carry out
Reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510076147.3A CN104724788B (en) | 2015-02-12 | 2015-02-12 | A kind of visible light-responded electrode of ferrum oxide, graphene oxide and N, F codope and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510076147.3A CN104724788B (en) | 2015-02-12 | 2015-02-12 | A kind of visible light-responded electrode of ferrum oxide, graphene oxide and N, F codope and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104724788A CN104724788A (en) | 2015-06-24 |
| CN104724788B true CN104724788B (en) | 2016-08-24 |
Family
ID=53449291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510076147.3A Expired - Fee Related CN104724788B (en) | 2015-02-12 | 2015-02-12 | A kind of visible light-responded electrode of ferrum oxide, graphene oxide and N, F codope and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104724788B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104984756B (en) * | 2015-07-10 | 2018-07-31 | 浙江工商大学 | A kind of NF-Bi2O3- SBA visible light responsive photocatalysts and its preparation method and application |
| CN105420794B (en) * | 2015-11-13 | 2018-01-26 | 上海应用技术学院 | A kind of preparation method of graphene/ferriferrous oxide composite material |
| CN107081153B (en) * | 2017-06-15 | 2020-02-18 | 青岛理工大学 | Method for reducing Cr (VI) based on catalyst photocatalysis |
| CN110860312A (en) * | 2019-11-27 | 2020-03-06 | 湖南大学 | Visible light response semiconductor-MOFs hybrid photoelectrocatalysis material electrode and preparation method thereof |
| CN114772683B (en) * | 2022-04-26 | 2023-06-13 | 南京理工大学 | Titanium-based antimony-doped tin dioxide microporous whole electrode and preparation method and application thereof |
| CN116161750B (en) * | 2023-01-29 | 2023-07-25 | 上海宁和环境科技发展有限公司 | Electrochemical wastewater treatment process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102485969A (en) * | 2010-12-06 | 2012-06-06 | 长沙理工大学 | Method for preparing nitrogen and gadolinium co-doped titania nano-tube array |
| CN102500406A (en) * | 2011-10-26 | 2012-06-20 | 辽宁大学 | Iron, nitrogen and fluoride co-doped titanium dioxide (TiO2) photocatalyst and application thereof in degrading organic pollutants in visible light |
| CN102553627A (en) * | 2012-02-22 | 2012-07-11 | 福建农林大学 | N and F-codoped visible-light-responsive TiO2 photocatalyst and preparation method thereof |
| CN103372424A (en) * | 2012-04-12 | 2013-10-30 | 沈阳理工大学 | Synthetic method for high-activity N-F co-doped bismuth vanadate visible light photocatalytic material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI455889B (en) * | 2008-08-05 | 2014-10-11 | Nat Univ Tsing Hua | Carbon-coated metal oxide nano-particles and method of preparing the same |
-
2015
- 2015-02-12 CN CN201510076147.3A patent/CN104724788B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102485969A (en) * | 2010-12-06 | 2012-06-06 | 长沙理工大学 | Method for preparing nitrogen and gadolinium co-doped titania nano-tube array |
| CN102500406A (en) * | 2011-10-26 | 2012-06-20 | 辽宁大学 | Iron, nitrogen and fluoride co-doped titanium dioxide (TiO2) photocatalyst and application thereof in degrading organic pollutants in visible light |
| CN102553627A (en) * | 2012-02-22 | 2012-07-11 | 福建农林大学 | N and F-codoped visible-light-responsive TiO2 photocatalyst and preparation method thereof |
| CN103372424A (en) * | 2012-04-12 | 2013-10-30 | 沈阳理工大学 | Synthetic method for high-activity N-F co-doped bismuth vanadate visible light photocatalytic material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104724788A (en) | 2015-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104724788B (en) | A kind of visible light-responded electrode of ferrum oxide, graphene oxide and N, F codope and preparation method and application | |
| Wu et al. | A solar-driven photocatalytic fuel cell with dual photoelectrode for simultaneous wastewater treatment and hydrogen production | |
| CN103818986B (en) | Photocatalytic electrode responding to visible lights and application thereof on chromium-containing wastewater treatment | |
| CN102941077A (en) | Preparation method of titanium dioxide nanotube thin film with visible-light activity | |
| He et al. | Highly efficient AgBr/BiVO4 photoanode for photocatalytic fuel cell | |
| CN101844077B (en) | Preparation method of carbon and nitrogen modified nano-titanium dioxide thin film with visible light activity | |
| CN106794459A (en) | The manufacture method and composite photo-catalyst of composite photo-catalyst | |
| CN101773841A (en) | Photocatalyst for water treatment | |
| CN109402656A (en) | A kind of preparation method of phosphatization cobalt modification molybdenum doping pucherite optoelectronic pole | |
| CN108212192A (en) | A kind of light-fenton catalyst and preparation method thereof | |
| CN105597784A (en) | MoS2-doped iron oxide photocatalytic thin film and preparation method as well as application thereof to treatment of phenolic waste water | |
| CN104667951A (en) | Preparation and application method of bismuthyl bromide highlight catalyst | |
| CN103964563A (en) | Visible-light photoelectric-Fenton method for efficiently degrading organic substances | |
| CN103489651A (en) | Preparing method for embellish titanium dioxide nanotube array electrode material embellished by cadmium selenide nano-particles | |
| CN109989088A (en) | A kind of TiO2Nanotube and MoSe2The preparation of nanosheet composite material | |
| CN103320839B (en) | Go the preparation method of the titanium dioxide nanotube array photoelectrode of removal organic polluter | |
| CN106431005A (en) | Strontium titanate-titanium dioxide composite nanotube array film and preparation method and application thereof | |
| CN108511198A (en) | Ni-doped BiVO4Thin-film photoelectric anode, preparation method and application thereof | |
| CN104098134A (en) | Preparation method and application of TiO2 nanotube coated with amorphous layer | |
| CN104709961B (en) | A kind of Fe2O3-Bi2O3/NF-TiO2Combination electrode and its preparation method and application | |
| CN107020103A (en) | A kind of iron oxide molybdenum sulfide cuprous oxide photocatalysis film and its preparation method and application | |
| CN104465101A (en) | Method for manufacturing metal-ion-doped {001}-face-exposed TiO2 nanosheet | |
| CN108273486B (en) | Carbon nano tube/secondary anode oxidized TiO2Nanotube photocatalyst material and preparation method and application thereof | |
| CN104028309B (en) | A kind of compound visible light catalyst and preparation method thereof | |
| CN102614877B (en) | Preparation method of transition metallic element and non-metallic element doped nano titanium dioxide modified photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160824 Termination date: 20170212 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |