CN104724788A - Ferric oxide, graphene oxide and N-F codoped visible light response electrode as well as preparation method and application thereof - Google Patents
Ferric oxide, graphene oxide and N-F codoped visible light response electrode as well as preparation method and application thereof Download PDFInfo
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- CN104724788A CN104724788A CN201510076147.3A CN201510076147A CN104724788A CN 104724788 A CN104724788 A CN 104724788A CN 201510076147 A CN201510076147 A CN 201510076147A CN 104724788 A CN104724788 A CN 104724788A
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Abstract
The invention discloses a ferric oxide, grapheme oxide and N-F codoped visible light response electrode as well as a preparation and application thereof. The method comprises the following steps: (1) mixing a TiO2-NTs electrode with NH4F under an air atmosphere, and calcining the mixture to obtain an N, F-TiO2 electrode; (2) immersing the N, F-TiO2 electrode in Fe(NO3)3, using a graphite electrode as an anode, using a platinum sheet as a cathode, using Na2SO4 as an electrolyte, and dissolving graphene to get a grapheme electrolyte; (3) drying the immersed electrode serving as a cathode, using the graphite electrode as a anode, and electrically depositing the electrodes in grapheme electrolyte; and (4) using the electrode which is processed in the step (3) as an anode, using graphite as a cathode, and using KOH as an electrolyte to perform electric deposition, cleaning and drying the electrically deposited electrode. In the electrode provided by the invention, after ferric oxide and grapheme oxide are codoped, the photo electron and cavity separation effect is good, the photo-electric current is high, the effect for treating chromium-containing wastewater through photo-electro cooperation is good, no secondary pollution exists, and the treated wastewater is reusable.
Description
Technical field
The present invention relates to photocatalyst material technical field, be specifically related to a kind of ferric oxide, the visible light-responded electrode and preparation method thereof of graphene oxide codoped and application.
Background technology
While facing mankind environmental pollution, also face energy starved problem.On the one hand, environmental pollution, especially water pollutions, aggravate increasingly, the Health and Living of the serious threat mankind.Wherein, heavy metal-containing waste water, toxicity is large, and microorganism is difficult to degraded, is more difficult to process.On the other hand, along with light urges the development of technology, utilize photocatalyst water of decomposition to prepare hydrogen, be expected to alleviating energy crisis problem.
Nanotube titanium dioxide film is the Novel Titanium dioxide nano material of development in recent years, and it has good effect in reducing heavy metal ion Cr (VI).But because energy gap is wide, can only utilize and account for the less ultraviolet region of sunlight total energy, by TiO
2the element that middle doping is appropriate, makes its forbidden band narrow, the light that absorbing wavelength is longer, thus can utilize more visible ray.Such as, publication number is the preparation method that the Chinese invention of CN 103523826A application discloses that a kind of tin dope titanium dioxide, method is as follows: join in dehydrated alcohol by Butyl Phthalate and stannic chloride pentahydrate, add ethylene glycol, add concentrated hydrochloric acid and deionized water successively again, add polyvinylpyrrolidone, stir, obtain the yellow sol of stable transparent, react in stainless steel cauldron yellow sol being transferred to teflon lined, naturally cool to room temperature, with dehydrated alcohol and distilled water wash, filter, collect white precipitate, white precipitate is dried, grinding, encapsulation, obtain tin dope titanium dioxide.
Publication number is that the Chinese invention of CN 103908962A application discloses that a kind of Ag doping titania aerogel preparation technology of coating and equipment, and technique comprises the step of the step of the preparation of the Ag doping nano titania aqueous solution and the preparation of nano titanium oxide aerogel coating; Equipment comprises the liquid raw material tank for storing the Ag doping nano titania aqueous solution, spray gun tank connected with liquid raw material, spray gun has nozzle, for transmitting the transmission part of base material and drying the baking oven of the Ag doping nano titania aqueous layer that base material sprays.
During dual element codoped, strengthen further that it is visible light-responded, photocatalytic activity significantly improves.Such as publication number is the preparation method that the Chinese invention of CN104258837A application discloses that a kind of carbon-silicon coblended nano TiO 2, take tetrabutyl titanate as titanium source, alkyl triethoxysilane is simultaneously as carbon source and silicon source, utilize alkyl triethoxysilane and the polycondensation of tetrabutyl titanate cohydrolysis to prepare the TiO 2 precursor of silicon doping, utilize silicon-alkyl bond in alkyl triethoxysilane (as Si-CH
3) regulate and control titania growth, utilize silicon-alkyl bond to introduce carbon source, introduce carbon in follow-up roasting process original position, and then prepare the nano titanium oxide of carbon-silicon coblended.
Summary of the invention
The invention provides visible light-responded electrode of a kind of ferric oxide, graphene oxide and N, F codoped and preparation method thereof and application, the preparation method of photoelectrocatalysielectrode electrode is simple, light induced electron and hole good separating effect after ferric oxide, graphene oxide codoped, photoelectric current is high, by photoelectric-synergetic effect processing waste water containing chrome, effective, non-secondary pollution, can repeatedly use.
An its preparation method for the visible light-responded electrode of ferric oxide, graphene oxide and N, F codoped, comprises the steps:
(1) by TiO
2-NTs electrode and NH
4f solids mixing is placed in retort furnace, calcines 2 ~ 3 hours under air atmosphere, and washing surface impurity after cooling obtains NF-TiO after air-dry
2electrode;
(2) by described NF-TiO
2electrode is soaked in the Fe (NO of supersound process
3)
3in solution;
(3) take Graphite Electrodes as anode, platinized platinum is negative electrode, Na
2sO
4solution is electrolytic solution, and making alive makes Graphite dissolution, controls dissolution time, obtains the Graphene electrolytic solution of different concns;
(4) by the NF-TiO after immersion treatment in step (2)
2electrode is air-dry makes negative electrode, anode made by Graphite Electrodes, in (3) gained Graphene electrolytic solution, carry out several galvanic deposit;
(5) with the electrode after step (4) process be anode, graphite is negative electrode, KOH solution is that electrolytic solution carries out electrodeposition process, clean air-dry after namely obtain the visible light-responded electrode of ferric oxide, graphene oxide and N, F codoped.
The visible light-responded electrode of ferric oxide, graphene oxide and N, F codoped is designated as Fe
2o
3-GO/NF-TiO
2electrode.
TiO described in step (1)
2the preparation method of-NTs electrode is as follows:
The sand papering of pure Ti sheet is seamless to surface, and then use each ultrasonic cleaning 10min of acetone, dehydrated alcohol and deionized water successively, with Ti sheet for anode, Cu sheet is negative electrode, in 0.5wt%NaF and 0.5mol/L Na
2sO
4mixing solutions, in addition 20V constant voltage, anodic oxidation 5h, cleans obtained sample, air-dry, obtains TiO
2-NTs electrode.
Research to find F codoped, in the titania-doped lattice of N, can not only promote the doping of N, promote visible absorption, can also strengthen the oxidation capacity in hole, improve photocatalysis effect; Fe
2o
3be a kind of narrow-band semiconductor material, all have response in various degree to UV-light and visible ray, simultaneously stable chemical nature, nontoxic, but the easy compound of its light induced electron produced in photocatalytic process and hole, photoabsorption coefficient is little.Research discovery Fe
2o
3to titania nanotube (TiO
2-NTs) carry out modification and prepare combined electrode, can returnability be improved, and suppress electron-hole pair compound further, improve the assimilated efficiency of visible ray; From scientist successfully isolates Graphene in the lab, Graphene is the focus that people study always, and its resistivity is extremely low, and electron transfer rate is exceedingly fast.Graphene oxide is as the oxide compound of Graphene, it is a kind of new carbon of excellent performance, have higher specific surface area and abundant functional group, in photocatalyst, doping can contribute to the transfer improving light induced electron, further suppresses the compound in electronics and hole.The present invention is on the titanium dioxide nanotube composite electrode basis of N, F codoped, by ferric oxide and graphene oxide are introduced jointly, be expected to improve photochemical catalyst electrode to the response of visible ray, by photoelectric-synergetic effect, improve photochemical catalyst electrode to the treatment effect of chromate waste water.
The present invention studies and finds TiO
2in when carrying out N, F dual element codoped effect have obvious lifting, Fe of the present invention
2o
3-GO/NF-TiO
2electrode is utilizing the TiO of non-metallic element N, F doping vario-property
2on nanotube electrode material foundation, and be aided with metal oxide Fe
2o
3, nonmetal oxide surface of graphene oxide is synergistically modified, can suppress electron-hole pair compound further, strengthens electron transfer rate, thus promotes visible ray utilization ratio.
Fe of the present invention
2o
3-GO/NF-TiO
2electrode produces electronics and hole under the excitation of visible ray, Hole oxidation organism, electron reduction heavy metal, Cr (VI) is reduced to toxicity little 100 times, and the Cr (III) of coordination precipitation easily occurs.
NH is adopted during electrode N, F doping of the present invention
4f solid is raw material, finds with NH in exploratory development
4f solid is raw material, and non-metallic element N, F codoped is entered TiO
2the electrode product shape prepared in-NTs is corroded into irregularly shaped by original nano tube structure, and shown by follow-up application test, there is this erose modified electrode there are better photoelectric properties, higher to the utilization ratio of visible ray, better to the treatment effect of hexavalent chromium wastewater.
Described N, F are doped into TiO with the ratio of 1:1
2, wherein the performance of doping on combined electrode of N, F affects, to some extent for NH
4the add-on of F through repetition test, the NH that adds during step (1) calcining
4the area ratio of F quality and electrode is 0.04g ~ 0.3g:1cm
2; Most preferably be 0.2g:1cm
2.
As preferably, in step (1), calcining temperature is 400 ~ 500 DEG C; More preferably 450 DEG C.The speed heated up is 5 ~ 10 DEG C/min, rate of cooling 5 ~ 10 DEG C/min.
As preferably, when preparing Graphene electrolytic solution in step (3), voltage is 4 ~ 9V; Temperature is 80 ~ 90 DEG C; Dissolution time is 5 ~ 30min.Na when preparing Graphene electrolytic solution
2sO
4the concentration of solution is 0.1mol/L, most preferably, is 0.1mol/L and water temperature is the Na of 85 DEG C when preparing Graphene electrolytic solution in step (3) in concentration
2sO
4in electrolytic solution, 5V constant voltage 15min in addition.
NF-TiO in step (2)
2electrode is at Fe (NO
3)
3soak time in solution is 8 ~ 15min; Fe (NO
3)
3strength of solution is 0.02 ~ 0.2mol/L, is more preferably 0.02 ~ 0.08mol/L.
As preferably, in step (4), galvanic deposit number of times is 1 ~ 5 time.Be more preferably 1 ~ 3 time, most preferably be 1 time.
As preferably, in step (4), galvanic deposit voltage is 4 ~ 9V; The time of each galvanic deposit is 10 ~ 20min.Most preferably be with constant 5V voltage galvanic deposit 20min.
As preferably, in step (5), galvanic deposit voltage is 4 ~ 9V, and electrodeposition time is 1.5 ~ 2.5min.
Electrodeposition temperature is room temperature in step (5), and more preferably, step (5) is under room temperature in 1mol/L KOH electrolytic solution, in addition 5V constant voltage anodic oxidation 2min.
A kind of preferred technical scheme, Fe of the present invention
2o
3-GO/NF-TiO
2electrode is prepared by the following method:
(1) by TiO
2-NTs electrode and NH
4f solids mixing is placed in retort furnace, and calcine 2 ~ 3 hours under air atmosphere, calcining temperature is 400 ~ 500 DEG C, and washing surface impurity after cooling obtains NF-TiO after air-dry
2electrode; The NH added
4the area ratio of F quality and electrode is 0.04g ~ 0.3g:1cm
2;
(2) by described NF-TiO
2electrode is soaked in the Fe (NO of supersound process
3)
3in solution, NF-TiO
2electrode is at Fe (NO
3)
3soak time in solution is 8 ~ 15min; Fe (NO
3)
3strength of solution is 0.02 ~ 0.2mol/L;
Take Graphite Electrodes as anode, platinized platinum be negative electrode, Na
2sO
4solution is electrolytic solution, and making alive makes Graphene dissolve, and obtains Graphene electrolytic solution; When preparing Graphene electrolytic solution, 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 is air-dry makes negative electrode, anode made by Graphite Electrodes, carries out 1 ~ 5 galvanic deposit in described Graphene electrolytic solution; Galvanic deposit voltage is 4 ~ 9V; The time of each galvanic deposit is 10 ~ 20min;
(4) electrode after processing with step (3) is anode, graphite is negative electrode, KOH solution is that electrolytic solution carries out electrodeposition process, galvanic deposit voltage is 4 ~ 9V, electrodeposition time is 1.5 ~ 2.5min, temperature is 20 ~ 30 DEG C, the air-dry visible light-responded electrode namely obtaining ferric oxide, graphene oxide codoped of electrodeposition process afterwash, i.e. Fe
2o
3-GO/NF-TiO
2electrode.
Core of the present invention is the photoelectrocatalytioxidation oxidation system building visible ray-catalysis electrode-applying bias combination.Utilize Fe
2o
3-GO/NF-TiO
2combined electrode is to the response of visible ray, promote that electron-hole is separated, and the graphene oxide of area load can accelerate electron transport rate, thus effectively suppress the compound in light induced electron and hole, substantially increase efficiency Cr in water (VI) being reduced to hypotoxic Cr (III).Under the combination of above-mentioned each optimum condition, treatment effect is better.
A kind of most preferred technical scheme, described Fe
2o
3-GO/NF-TiO
2electrode is prepared by the following method:
(1) by TiO
2-NTs electrode and NH
4f solids mixing is placed in retort furnace, and calcine 2 ~ 3 hours under air atmosphere, calcining temperature is 450 DEG C, and washing surface impurity after cooling obtains NF-TiO after air-dry
2electrode; The NH added
4the area ratio of F quality and electrode is 0.2:1cm
2;
(2) by described NF-TiO
2electrode is soaked in the Fe (NO of supersound process
3)
3in solution, N, F-TiO
2electrode is at Fe (NO
3)
3soak time in solution is 10min; Fe (NO
3)
3strength of solution is 0.02 ~ 0.08mol/L;
Take Graphite Electrodes as anode, platinized platinum be negative electrode, Na
2sO
4solution is electrolytic solution, and making alive makes Graphene dissolve, and obtains Graphene electrolytic solution; When preparing Graphene electrolytic solution, voltage is 5V; Temperature is 85 DEG C; Dissolution time is 15min;
(3) by N, the F-TiO after immersion treatment in step (2)
2electrode is air-dry makes negative electrode, anode made by Graphite Electrodes, carries out 1 galvanic deposit in described Graphene electrolytic solution; Galvanic deposit voltage is 5V; The time of each galvanic deposit is 15min;
(4) electrode after processing with step (3) is anode, graphite is negative electrode, KOH solution is that electrolytic solution carries out electrodeposition process, galvanic deposit voltage is 5V, electrodeposition time 2min, temperature is 20 ~ 30 DEG C, the air-dry visible light-responded electrode namely obtaining ferric oxide, graphene oxide codoped of electrodeposition process afterwash, i.e. Fe
2o
3-GO/NF-TiO
2electrode.
The present invention also provide a kind of as described in preparation method prepare ferric oxide, graphene oxide codoped visible light-responded electrode.
Combined electrode of the present invention is under the synergy of metal oxide, graphene oxide and N, F, the response of visible ray is promoted that electron-hole is separated, and the graphene oxide of area load can accelerate electron transport rate, thus effectively suppress the compound in light induced electron and hole, therefore to detect the current density obtained large for combined electrode, hole-electron pair good separating effect, optical Response is good.Electrode stability of the present invention is good, still has higher Cr (VI) reduction efficiency after repeatedly recycling.
Present invention also offers a kind of method utilizing described visible light-responded Electrode treatment chromate waste water, comprise the steps:
Be equipped with as described in visible light-responded electrode for anode, Ti sheet is in the reactor of negative electrode, fixes the distance between two electrodes, adds the chromate waste water containing ionogen and EDTA, adjust ph, to acid, stirs in dark place, after adsorption equilibrium, voltage, opens light source, reacts in addition.
As preferably, the hexavalent chromium concentration in described chromate waste water is 8 × 10
-5mol/L.
As preferably, the hole trapping agent added in described chromate waste water is EDTA, is more 1 × 10 as preferred EDTA concentration
-3mol/L.
As preferably, described light source is the halogen lamp utilizing spectral filter elimination wavelength X <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, the distance of fixing between two electrodes is 1 ~ 2cm.
Beneficial effect of the present invention has:
(1) with low cost, preparation method is simple, green clean;
(2) light induced electron and hole good separating effect, photoelectric current is high, has very high reducing power to Cr (VI);
(3) combined electrode prepared, stable performance, can realize repeatedly utilizing.
Accompanying drawing explanation
Fig. 1-a and Fig. 1-b is Fe
2o
3/ TiO
2-NTs and Fe
2o
3-GO/NF-TiO
2pattern comparison diagram.
Fig. 2 is Fe under different voltage in the embodiment of the present invention 1
2o
3-GO/NF-TiO
2the time current curve of electrode
Fig. 3-a is Different electrodes alternating-current impedance comparison diagram under visible light illumination in the embodiment of the present invention 2.
Fig. 3-b is Fe in the embodiment of the present invention 2
2o
3-GO/NF-TiO
2the alternating-current impedance comparison diagram of combined electrode under dark and illumination condition
Fig. 4 is the Fe of different frequency of depositing in the embodiment of the present invention 3
2o
3-GO/NF-TiO
2the photoelectric current comparison diagram of electrode.
Fig. 5 is the Cr of Different electrodes under same reaction conditions (VI) reduction effect comparison diagram in the embodiment of the present invention 4.
Fig. 6 is Fe in the embodiment of the present invention 4
2o
3-GO/NF-TiO
2the optical, electrical synergy process of electrode is containing Cr (VI) waste water design sketch.
Fig. 7 is Fe in the embodiment of the present invention 4
2o
3-GO/NF-TiO
2the Cr of electrode under different voltage (VI) reduction effect contrasts.
Fig. 8 is Fe in the embodiment of the present invention 4
2o
3-GO/NF-TiO
2electrode cycle result of use figure.
Embodiment
Now in conjunction with Figure of description and specific embodiment, the present invention is further described.
Fe in the embodiment of the present invention
2o
3-GO/NF-TiO
2electrode production process is as follows:
1, pure Ti sheet (2cm × 2.5cm) is seamless to surface with sand papering, then use the ultrasonic cleaning successively of acetone, dehydrated alcohol and deionized water successively, clean to titanium plate surface.With Ti sheet for anode, Cu sheet is negative electrode, with 0.5wt%NaF and 0.5mol/L Na
2sO
4for electrolyte solution, additional 20V constant voltage, anodic oxidation 5h.Obtained sample is cleaned, air-dry, obtain TiO
2-NTs.
2, by TiO
2-NTs is placed in crucible, and crucible bottom adds the NH of a certain amount of (0.2 ~ 1.5g is preferably 1.0g)
4f solid, 450 DEG C of cycle annealing process 2h (temperature rise rate 7 DEG C/min, rate of cooling 10 DEG C/min), obtain NF-TiO
2.
3, by NF-TiO
2be immersed in the Fe (NO that strength of solution is 0.05mol/L ultrasonic 10min
3)
310min in solution, air-dry.Using platinized platinum as negative electrode, graphite, as anode, is 0.1mol/L and water temperature is the Na of 85 DEG C in concentration
2sO
4in electrolytic solution, 5V constant voltage 15min in addition, powered-down.
4, with above-mentioned obtained solution for electrolytic solution, by the NF-TiO soaked
2as negative electrode, Graphite Electrodes as anode, with constant 5V voltage galvanic deposit 20min.
5, using this electrode as anode, graphite is negative electrode, in room temperature 1mol/L KOH electrolytic solution, in addition 5V constant voltage anodic oxidation 2min, powered-down, clean air-dry after obtain Fe
2o
3-GO/NF-TiO
2.
Fe
2o
3-GO/NF-TiO
2electrode treatment chromate waste water process is as follows:
Add chromate waste water and EDTA in the reactor, adjust ph is extremely acid, with Fe
2o
3-GO/NF-TiO
2electrode is working electrode, and Ti sheet is to electrode, after dark place whip attachment balance, and in addition certain voltage, and open light source, react.And by phenylbenzene phosphinylidyne two hydrazine, the vitriol oil, strong phosphoric acid as developer, use spectrophotometry.
Embodiment 1
By Fe
2o
3-GO/NF-TiO
2electrode is placed in the Na that concentration is 0.1mol/L
2sO
4in solution, add sacrifice agent Na
2sO
3(0.1mol/L), under electrochemical workstation 3 electrode system, with Fe
2o
3-GO/NF-TiO
2-NTs electrode is working electrode, and platinized platinum is to electrode, and silver electrode is reference electrode, and xenon lamp is light source, and by the UV-light of spectral filter below elimination 420nm.
Can see from Fig. 1-a, Fig. 1-b, TiO
2-NTs is at NH
4under F modifies, there is change greatly in the pattern of high-temperature calcination rear surface, is changed into irregular by tubulose, and meanwhile change greatly occurs for light induced electron type of transmission and electrode performance.Fig. 2 establishes Fe under voltage in different electrochemical workstation
2o
3-GO/NF-TiO
2the time current curve of electrode, can obtain by Fig. 2, and it is large that this combined electrode detects the current density obtained, and hole-electron pair good separating effect, optical Response is good.Along with improving constantly of applying bias, the recombination rate of hole-electron pair declines, and photoelectric properties promote to some extent.
Embodiment 2
Under electrochemical workstation 3 electrode system, the Na of electrolytic solution to be concentration be 0.5mol/L
2sO
4solution, respectively with Fe
2o
3-GO/NF-TiO
2electrode is working electrode, and platinum electrode is to electrode, and silver electrode is reference electrode.Measure the alternating-current impedance of the combined electrode under dark place and radiation of visible light respectively.
Fig. 3-a is Different electrodes alternating-current impedance comparison diagram under visible light illumination.In the Nyquist figure of various electrode, Fe
2o
3-GO/NF-TiO
2the impedance ring radius of combined electrode is minimum, illustrates that the interfacial charge transmission resistance of this electrode is less.
Fig. 3-b is Fe
2o
3-GO/NF-TiO
2the alternating-current impedance comparison diagram of electrode under dark and illumination condition.As seen from the figure, the impedance under illumination condition of this electrode is changed radius and is reduced, and photoelectric properties are promoted.
Embodiment 3
Study different frequency of depositing to preparation Fe
2o
3-GO/NF-TiO
2the impact of combined electrode.By N, F-TiO
2be immersed in the Fe (NO of ultrasonic 10min
3)
3in solution, air-dry.Using platinized platinum as negative electrode, graphite, as anode, is 0.1mol/L and water temperature is the Na of 85 DEG C in concentration
2sO
4in electrolytic solution, 5V constant voltage 15min in addition, powered-down.With above-mentioned obtained solution for electrolytic solution, by the NF-TiO soaked
2as negative electrode, Graphite Electrodes as anode, with constant 5V voltage galvanic deposit 20min.Using this electrode as anode, graphite is negative electrode, in room temperature 1mol/L KOH electrolytic solution, and 5V constant voltage anodic oxidation 2min in addition, powered-down.Repeat above-mentioned 4,5 steps, the final Fe obtaining different frequency of depositing
2o
3-GO/NF-TiO
2combined electrode.
Fig. 4 is the Fe of different frequency of depositing
2o
3-GO/NF-TiO
2the photoelectric current comparison diagram of electrode.As seen from the figure, frequency of depositing is many, Fe
2o
3and the increase of graphene oxide-loaded amount does not promote the photoelectric properties of electrode, therefore frequency of depositing is 1 ~ 2 time is good.
Embodiment 4
Get the Cr of 50mL
6+(8 × 10
-5mol/L), Na
2sO
4(0.2mol/L), EDTA (10
-3mol/L) mixing solutions, adjust ph is to acid (pH is 3), and take catalysis electrode as anode, clean Ti sheet is negative electrode, the distance between regulating YIN and YANG pole and the distance between working electrode and light source.After dark place reactive adsorption balance, in addition 2V constant voltage open light source, reacts, reacts after 80 minutes, sample and use spectrophotometry.Change Different electrodes or regulate impressed voltage size, change light source, power supply, organism add condition etc., and other steps are the same.
Fig. 5 is the contrast of the Cr of Different electrodes under same reaction conditions (VI) reduction effect.As seen from the figure, under same reaction conditions, Fe
2o
3-GO/NF-TiO
2the clearance of electrode pair Cr (VI), up to 94%, has unusual effect compared with similar catalysis electrode.
Fig. 6 is Fe
2o
3-GO/NF-TiO
2the optical, electrical synergy process of electrode is containing Cr (VI) waste water design sketch.As seen from the figure, when reducing Cr (VI), optical, electrical existence synergy, significantly can promote reduction efficiency.Fe
2o
3-GO/NF-TiO
2combined electrode can reduce Cr (VI) simultaneously, and oxidation of organic compounds, has synergy when all heavy metals and organism exist simultaneously.
Fig. 7 is Fe
2o
3-GO/NF-TiO
2cr (VI) the reduction effect contrast of electrode under the different impressed voltage of common power.As seen from the figure, along with the raising of applying bias, Cr (VI) reduction effect promotes to some extent.
Fig. 8 is Fe
2o
3-GO/NF-TiO
2electrode cycle result of use.As seen from the figure, this electrode stability is good, and after repeatedly recycling, the clearance range of decrease of Cr (VI) is less than 5%.There is higher Cr (VI) reduction efficiency.
Embodiment 5
By TiO
2-NTs (2cm × 2.5cm) is placed in 6 crucibles, adds the NH of 0.2g, 0.5g, 0.7g, 1.0g, 1.2g, 1.5g respectively
4f solid, setting temperature rise rate is 7 DEG C/min, and annealing constant temperature 450 DEG C of 2h, lower the temperature with 10 DEG C/min, obtain the NF-TiO of different N, F doping
2.
With NF-TiO
2for substrate, by the final Fe obtaining different N, F doping of above-mentioned steps 3-5
2o
3-GO/NF-TiO
2combined electrode, and the process being applied to chromate waste water.Result of study shows: along with NH
4the increase of F content, same reaction time Cr (VI) clearance increases progressively gradually, works as NH
4f content is that 1.0g, Cr (VI) clearance is maximum, increases NH further
4f content, electrode easily peels off, instability, and Cr (VI) clearance declines on the contrary.
Embodiment 6
By TiO
2-NTs is placed in crucible, adds the NH of 1.0g
4f solid, setting temperature rise rate is 7 DEG C/min, and anneal under specified temp (350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C) constant temperature 2h, lowers the temperature, obtain the NF-TiO of specific calcining temperature with 10 DEG C/min
2.
With NF-TiO
2for substrate, by the final Fe obtaining different calcining temperature of above-mentioned steps 3-5
2o
3-GO/NF-TiO
2combined electrode, and the process being applied to chromate waste water.Result of study shows: along with the increase of calcining temperature, and same reaction time Cr (VI) clearance increases progressively gradually, catalysis electrode removal Cr (VI) efficiency the best that 450 DEG C of process obtain.
Embodiment 7
Preparing 6 parts of volumes is 100mL, and concentration is the Na of 0.1mol/L
2sO
4solution is as electrolytic solution.Be negative electrode respectively with platinized platinum, Graphite Electrodes is anode, and 5V constant voltage, dissolves 5min respectively, 10min, 15min, 20min, 25min, 30min, obtain the graphene solution of different concns gradient in addition.By TiO
2-NTs is placed in crucible, adds the NH of 1.0g
4f solid, setting temperature rise rate is 7 DEG C/min, and anneal at specified temp 450 DEG C constant temperature 2h, lowers the temperature, obtain NF-TiO with 10 DEG C/min
2.
By NF-TiO
2be immersed in the Fe (NO that strength of solution is 0.05mol/L ultrasonic 10min
3)
310min in solution, air-dry, then immerse above-mentioned graphene solution as negative electrode, Graphite Electrodes as anode, with constant 5V voltage galvanic deposit 20min.
By the final Fe obtaining different graphene-supported amount of above-mentioned steps 5
2o
3-GO/NF-TiO
2combined electrode, and the process being applied to chromate waste water.Result of study shows: the electrode that meets that the graphene solution obtained with the 15min Graphite dissolution time obtains for infiltrate has best PhotoelectrocatalytiPerformance Performance.Visible ray-electric combined action is after 80 minutes, and the clearance of Cr (VI) reaches 94%.
Claims (9)
1. a preparation method for the visible light-responded electrode of ferric oxide, graphene oxide and N, F codoped, is characterized in that, comprise the steps:
(1) by TiO
2-NTs electrode and NH
4f solids mixing is placed in retort furnace, calcines 2 ~ 3 hours under air atmosphere, and washing surface impurity after cooling obtains NF-TiO after air-dry
2electrode;
(2) by described NF-TiO
2electrode is soaked in the Fe (NO of supersound process
3)
3in solution;
(3) take Graphite Electrodes as anode, platinized platinum is negative electrode, Na
2sO
4solution is electrolytic solution, and making alive makes Graphite dissolution, controls dissolution time, obtains the Graphene electrolytic solution of different concns;
(4) by the NF-TiO after immersion treatment in step (2)
2electrode is air-dry makes negative electrode, anode made by Graphite Electrodes, in (3) gained Graphene electrolytic solution, carry out several galvanic deposit;
(5) with the electrode after step (4) process be anode, graphite is negative electrode, KOH solution is that electrolytic solution carries out electrodeposition process, clean air-dry after namely obtain the visible light-responded electrode of ferric oxide, graphene oxide and N, F codoped.
2. the preparation method of the visible light-responded electrode of ferric oxide, graphene oxide and N, F codoped according to claim 1, is characterized in that, the NH added during step (1) calcining
4the area ratio of F quality and electrode is 0.04g ~ 0.3g:1cm
2.
3. the preparation method of the visible light-responded electrode of ferric oxide, graphene oxide and N, F codoped according to claim 1, is characterized in that, in step (1), calcining temperature is 400 ~ 500 DEG C.
4. the preparation method of the visible light-responded electrode of ferric oxide, graphene oxide and N, F codoped according to claim 1, is characterized in that, when preparing Graphene electrolytic solution in step (3), voltage is 4 ~ 9V; Temperature is 80 ~ 90 DEG C; Dissolution time is 5 ~ 30min.
5. the preparation method of the visible light-responded electrode of ferric oxide, graphene oxide and N, F codoped according to claim 1, is characterized in that, in step (4), galvanic deposit number of times is 1 ~ 5 time.
6. the preparation method of the visible light-responded electrode of ferric oxide, graphene oxide and N, F codoped according to claim 1, is characterized in that, in step (4), galvanic deposit voltage is 4 ~ 9V; The time of each galvanic deposit is 10 ~ 20min.
7. the preparation method of the visible light-responded electrode of ferric oxide, graphene oxide and N, F codoped according to claim 1, is characterized in that, in step (5), galvanic deposit voltage is 4 ~ 9V, and electrodeposition time is 1.5 ~ 2.5min.
8. the visible light-responded electrode of ferric oxide, graphene oxide and N, F codoped that preparation method prepares as described in a claim as arbitrary in claim 1 ~ 7.
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:
Be equipped with visible light-responded electrode as claimed in claim 8 as anode, Ti sheet is in the reactor of negative electrode, fix the distance between two electrodes, add the chromate waste water containing ionogen and EDTA, adjust ph, to acid, stirs in dark place, after adsorption equilibrium, voltage, opens light source, reacts in addition.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104984756A (en) * | 2015-07-10 | 2015-10-21 | 浙江工商大学 | NF-Bi2O3-SBA visible light responding photocatalyst, preparation method thereof and application thereof |
| CN105420794A (en) * | 2015-11-13 | 2016-03-23 | 上海应用技术学院 | Preparation method for graphene/ferroferric oxide composite material |
| CN107081153A (en) * | 2017-06-15 | 2017-08-22 | 青岛理工大学 | The method that one kind is based on catalyst photo catalytic reduction Cr (VI) |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100035750A1 (en) * | 2008-08-05 | 2010-02-11 | National Tsing Hua University | Carbon-coated metal oxide nano-particles and method of preparing the same |
| 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 |
-
2015
- 2015-02-12 CN CN201510076147.3A patent/CN104724788B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100035750A1 (en) * | 2008-08-05 | 2010-02-11 | National Tsing Hua University | Carbon-coated metal oxide nano-particles and method of preparing the same |
| 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 |
Cited By (9)
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|---|---|---|---|---|
| CN104984756A (en) * | 2015-07-10 | 2015-10-21 | 浙江工商大学 | NF-Bi2O3-SBA visible light responding photocatalyst, preparation method thereof and application thereof |
| 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 |
| CN105420794A (en) * | 2015-11-13 | 2016-03-23 | 上海应用技术学院 | Preparation method for graphene/ferroferric oxide composite material |
| CN107081153A (en) * | 2017-06-15 | 2017-08-22 | 青岛理工大学 | The method that one kind is based on catalyst photo catalytic reduction Cr (VI) |
| 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 |
| CN114772683A (en) * | 2022-04-26 | 2022-07-22 | 南京理工大学 | Titanium-based antimony-doped tin dioxide microporous whole-body electrode applied to oily wastewater treatment and preparation method and application 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 |
| CN116161750A (en) * | 2023-01-29 | 2023-05-26 | 上海宁和环境科技发展有限公司 | Electrochemical wastewater treatment process |
| 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 |
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