CN103739043A - Particle electrode for photocatalytic three-dimensional electrode/electro-Fenton system and preparation method thereof - Google Patents
Particle electrode for photocatalytic three-dimensional electrode/electro-Fenton system and preparation method thereof Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 18
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 65
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
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- 238000009835 boiling Methods 0.000 claims description 10
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- 229910052799 carbon Inorganic materials 0.000 claims description 10
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
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- 239000010953 base metal Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000002525 ultrasonication Methods 0.000 claims 1
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 9
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Abstract
The invention discloses a particle electrode for a photocatalytic three-dimensional electrode/electro-Fenton system and a preparation method thereof. The particle electrode is prepared from activated-carbon loaded bimetallic codoping P25. The preparation method comprises the following steps: preprocessing activated carbon to obtain ultrasonic-nitric acid modified activated carbon; preparing bimetallic codoping P25, and then loading the ultrasonic-nitric acid modified activated carbon and the bimetallic codoping P25 to obtain the particle electrode used for the visible-light photocatalytic three-dimensional electrode/electro-Fenton system. The preparation method is simple, and the obtained particle electrode has a visible-light photoelectrocatalytic effect and can rapidly and efficiently degrade organic pollutants. The particle electrode can obtain an obvious visible-light photocatalysis and three-dimensional electrode/electro-Fenton synergetic treatment effect at the visible-light photocatalytic three-dimensional electrode/electro-Fenton system.
Description
Technical field
The invention belongs to water treatment and water pollution control field, relate to the fast degradation technology of hardly degraded organic substance in waste water, refer more particularly to a kind of granule electrode and preparation method of photochemical catalysis three-dimensional electrode/electro-Fenton system.
Background technology
The combination of photochemical catalysis and electrocatalysis technology is the study hotspot of processing at present Persistent organic pollutants thing, the combination of the two, both solved that catalyzer in photochemical catalysis difficultly separates, the easily problem of compound, practical application of electron hole, solved again the limitation that in electrocatalysis, energy current efficiency is low, energy consumption is high, being combined in multinomial research of the two is proved to be and has associated treatment effect.
Three-diemsnional electrode is that particle filled composite electrode forms third electrode between traditional two-dimensional electrode electrolytic bath electrode plate, compared with two-dimensional electrode, three-diemsnional electrode greatly improved reactor specific surface area and current efficiency, improved the mass-transfer efficiency between electrode, thereby raising degradation efficiency is than more preferably electrocatalytic oxidation method of two-dimensional electrode.Three-dimensional electrode/electro-Fenton technology is on three-diemsnional electrode basis, by carbonaceous cathodes surface aeration and additional Fe
2+, can in system, form Fenton's reaction, accelerate rate of contaminant degradation with three-diemsnional electrode electrocatalysis synergy; The combination of photochemical catalysis simultaneously and Fenton technology is also the method for efficient degradation organic pollutant, the Synergistic degradation effect of the two is also proved to be, but photochemical catalysis and three-dimensional electrode/electro-Fenton treating processes is collaborative, and especially visible light catalytic three-dimensional electrode/electro-Fenton process there is not yet realization.
By the combination of three-diemsnional electrode electrocatalysis technology and photocatalysis technology, its key is to develop new granule electrode, this granule electrode not only will have electrocatalysis function, and will have photocatalysis performance, can realize the collaborative of electrocatalysis and photocatalytic effect in system.For the research of using three-dimensional electrodes system granule electrode PhotoelectrocatalytiPerformance Performance, mostly concentrate on ultraviolet catalytic at present, do not there is visible ray PhotoelectrocatalytiPerformance Performance.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide one to there is visible ray PhotoelectrocatalytiPerformance Performance, and the granule electrode that can realize the photochemical catalysis three-dimensional electrode/electro-Fenton system of the synergistic effect of visible light photocatalysis and three-dimensional electrode/electro-Fenton process, another object of the present invention is to provide the preparation method that above-mentioned granule electrode is provided.
For achieving the above object, technical scheme of the present invention is as follows:
A granule electrode for photochemical catalysis three-dimensional electrode/electro-Fenton system, this granule electrode is mixed altogether P25 by activated carbon supported bimetal and is formed;
Above-described gac is granulated active carbon or columnar activated carbon.
The particle diameter of above-described granulated active carbon is 3～5mm; The diameter of described columnar activated carbon is 3～5mm, and length-to-diameter ratio is 1～5:1.
Above-described bimetal is that two kinds in base metal Fe, Co, Ni, Al, Cu, Sn, Zn, Mn are mixed altogether.
Above-described bimetal is preferably that Fe-Ni mixes altogether or Fe-Co mixes altogether.
A preparation method for the granule electrode of photochemical catalysis three-dimensional electrode/electro-Fenton system, the method comprises the following steps:
(1) pre-treatment of gac: the gac that washes away most of Heisui River is soaked in dilute acid soln, is washed till neutrality after boiling 30min, then in dilute alkaline soln, be washed till neutrality, the gac that obtains cleaning up after boiling 30min; By supersound process 2 times of clean gac, each 0.5～1h, then dry 10～12h at 105～120 ℃, obtains supersonic modifying gac; Supersonic modifying gac is impregnated into and in salpeter solution, carries out the oxidation modification that duration is 1～2h, and then scalping is filtered, and is washed till neutrality with deionized water, and at 105～120 ℃, dry 10～12h, obtains ultrasonic-Nitric Acid Modified gac;
(2) bimetal is mixed the preparation of P25 altogether: get P25 and carry out after vigorous stirring mixing, with ultrasonic dispersion 30min, add successively two kinds of metal nitrates, magnetic agitation 30min, after ultrasonic lower load 1～2h, through 0.45um filtering with microporous membrane, at 105～120 ℃, dry 10～12h, then grinds, finally, at 350～450 ℃ of calcining 2～4h, obtain bimetal and mix altogether P25;
(3) preparation of granule electrode: bimetal prepared by step (2) is mixed altogether P25 and is dispersed in deionized water, after vigorous stirring is disperseed, by the bimetal after disperseing mix altogether P25 and step (1) ultrasonic-Nitric Acid Modified gac and by the mass ratio of 0.2～2:100 dip loading 2～4h under ultrasound environments, after scalping filtration, with deionized water, rinse well, dry 10～12h at 105～120 ℃, at 350～450 ℃ of calcining 2～4h, obtain activated carbon supported bimetallic-modified P25 granule electrode, for the granule electrode of visible light photocatalysis three-dimensional electrode/electro-Fenton system.
Diluted acid described in above step (1) is sulfuric acid, and concentration is 0.01～0.05mol/L; Described diluted alkaline is sodium hydroxide, and concentration is 0.01～0.05mol/L; The concentration of described nitric acid is 3～10mol/L.
Ultrasonic power described in above step (1) and step (2) is 75～105W, and frequency is 20～40kHZ; Load ultrasonic power described in step (3) is 60～75W, and frequency is 20kHZ.
P25 described in above step (2) is the P25 after activation; Activation temperature is 300～400 ℃, and soak time is 2～4h.
Two kinds of metal nitrate mol ratios that add in above step (2) are 1:1; Two kinds of metal nitrate total amounts that add and the mol ratio of P25 are 0.4～10:100.
Above-described metal nitrate is analytical pure nitrate reagent.
With respect to prior art, beneficial effect of the present invention is as follows:
1, the present invention adopts diluted acid and diluted alkaline respectively gac to be cleaned, and has removed solid impurity and the greasy dirt in gac, has improved activated carbon surface adsorption activity, has improved granule electrode to being adsorbed on the degradation capability of surface organic matter.
2, the present invention adopts and ultrasonic gac is carried out to modification, can effectively improve gac aperture, and central hole structure is increased, and is conducive to the area load of catalyzer, reduces because catalyst cupport causes space and stops up, and has improved the adsorptive power of loading type granule electrode.
3, common gac belongs to non-polar adsorbent, the present invention adopts nitric acid to carry out modification to activated carbon surface, changes activated carbon surface oxygen-containing functional group, makes activated carbon surface have certain polarity, increase the absorption of granule electrode to water Semi-polarity pollutent, increased TIO simultaneously
2in the tack of activated carbon surface.
4, in visible ray three-dimensional electrode/electro-Fenton system, effectively to reduce electron-hole compound for the granule electrode in the present invention, improve visible ray photoelectrocatalysis efficiency, rapidly and efficiently degradable organic pollutant, and can obtain obvious visible light photocatalysis and three-dimensional electrode/electro-Fenton associated treatment effect.
5, the present invention, as the granule electrode for visible light catalytic three-dimensional electrode/electro-Fenton system, has visible ray PhotoelectrocatalytiPerformance Performance, also can use in general three dimensional electrode photo electrocatalysis system, has equally associated treatment effect; In preparation process to gac after ultrasonic-Nitric Acid Modified, granule electrode all has absorption to polarity and nonpolar organic pollutants, is applicable to process various Persistent organic pollutants, has the advantages such as use range is wide, energy consumption is low, easy to maintenance, social benefit is remarkable, has a extensive future.
Accompanying drawing explanation
Fig. 1 is visible light catalytic three-dimensional electrode/electro-Fenton reaction unit schematic diagram
Accompanying drawing sign: 1-visible light source, 2-glass electrolyzer, 3-positive plate, 4-negative plate, 5-insulating barrier, the activated carbon supported granule electrode of 6-, 7-micropore aeration pipe, 8-aerator, 9-D.C. regulated power supply, 10-camera bellows.
Fig. 2 is the electrocatalysis of granule electrode prepared of common gac and the present invention and the contrast effect figure of two kinds of reaction process of visible ray photoelectrocatalysis;
Accompanying drawing sign: the common activated carbon particles electrode photo electrocatalysis of a-effect, the common activated carbon grain sub-electrode of b-electrocatalysis effect, activated carbon supported Fe-Ni prepared by c-embodiment 1 mixes P25 granule electrode electrocatalysis effect altogether, and activated carbon supported Fe-Ni prepared by d-embodiment 1 mixes P25 granule electrode photoelectrocatalysis effect altogether.
Fig. 3 is the design sketch of visible light photocatalysis, three-diemsnional electrode electricity Fenton and the degraded of three kinds of processes of visible light catalytic three-dimensional electrode/electro-Fenton to 20mg/L rhodamine B.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1:
The granule electrode of the photochemical catalysis three-dimensional electrode/electro-Fenton system of the present embodiment, is 3～5mm by particle diameter, and the columnar activated carbon load bimetal Fe-Ni that length-to-diameter ratio is 1:1 mixes P25 composition altogether.
Its preparation method is:
(1) pre-treatment of gac: the gac that washes away most of Heisui River is soaked in the sulphuric acid soln that volumetric concentration is 0.01mol/L, after boiling 30min, be washed till neutrality, then in the sodium hydroxide solution that is 0.01mol/L in volumetric concentration, after boiling 30min, be washed till neutrality, the gac that obtains cleaning up; By clean gac, at power, be 75W, in the ultrasonic environment that frequency is 20kHZ, process 2 times, each 0.5h, then dry 12h at 105 ℃, obtains supersonic modifying gac; Supersonic modifying gac is impregnated in the salpeter solution that volumetric concentration is 5mol/L and carries out the oxidation modification that duration is 2h, then filter, then with deionized water, be washed till neutrality, at 105 ℃, dry 12h, obtains ultrasonic-Nitric Acid Modified gac;
(2) Fe-Ni mixes the preparation of P25 altogether: the overactivation temperature of learning from else's experience is 400 ℃, soak time is that the P25 after 2h activation carries out after vigorous stirring mixing, at power, be 105W, frequency is to disperse 30min in the ultrasound environments of 40kHZ, add successively and analyze pure Fe nitrate reagent and analyze pure metal Ni nitrate reagent, two kinds of metal nitrate mol ratios are 1:1, the mol ratio of the analysis pure Fe nitrate reagent adding and analysis pure metal Ni nitrate reagent total amount and P25 is 1:100, magnetic agitation 30min, at power, be 75W, frequency is through 0.45um filtering with microporous membrane after the ultrasonic environment doping 2h of 40kHZ, dry 12h at 120 ℃, then grind, finally at 450 ℃ of calcining 2h, obtain bimetal Fe-Ni and mix altogether P25,
(3) preparation of granule electrode: Fe-Ni prepared by step (2) mixes altogether P25 and is dispersed in deionized water, after vigorous stirring is disperseed, by the Fe-Ni after disperseing mix altogether P25 and step (1) ultrasonic-Nitric Acid Modified gac and be that 75W frequency is dip loading 2h under the ultrasound environments of 20kHZ at power by the mass ratio of 1:100, after scalping filtration, with deionized water, rinse well, dry 12h at 120 ℃, at 450 ℃ of calcining 2h, obtained for visible light photocatalysis three-dimensional electrode/electro-Fenton system, there is the activated carbon supported Fe-Ni modification P25 granule electrode of visible ray PhotoelectrocatalytiPerformance Performance.
Embodiment 2:
Contrast the activated carbon supported Fe-Ni that common activated carbon grain sub-electrode and embodiment 1 make and mix altogether P25 granule electrode, whether the granule electrode of investigating preparation has visible ray PhotoelectrocatalytiPerformance Performance.
Get 40g granule electrode and in rhodamine B solution, carry out saturated adsorption experiment, until be issued to adsorption equilibrium in 20mg/L concentration.The granule electrode adsorbing after saturated is filled in the visible light catalytic three-dimensional electrode/electro-Fenton reactor shown in Fig. 1, and positive plate is titanium plate, and negative plate is graphite cake.Adding concentration is that the rhodamine B solution 400ml of 20mg/L carries out contaminant degradation experiment.Control voltage of supply 30V, aeration rate 1.5L/min, anhydrous sodium sulphate dosage 5g/L, pH value of solution is 3.
For getting rid of the impact of electric Fenton, investigate the visible ray PhotoelectrocatalytiPerformance Performance of granule electrode, in experimentation, do not add Fe
2+, two kinds of reaction process of the electrocatalysis of the granule electrode to common gac and preparation and visible ray photoelectrocatalysis contrast.Result as shown in Figure 2 and Table 1.
The different granule electrode electrocatalysis of table 1 and light-catalysed effect comparison table
The 60min clearance of curve a and b is respectively 64.17% and 60.52%, illustrates that gac is as granule electrode, and the photoelectrocatalysis effect under visible ray is little, and visible ray does not almost have katalysis to three dimensional electrode photo electrocatalysis system.The removal effect of the 60min of correlation curve b and c can be found out (b:60.52%, c:71.88%), and the granule electrode of preparing for the present invention is not in the situation that there is no additional light source, and its electrocatalysis characteristic is better than common gac.Correlation curve a and d removal effect can be found out (a:64.17%, d:88.41%), and granule electrode prepared by the present invention, compared with common gac, has good PhotoelectrocatalytiPerformance Performance under visible ray.Correlation curve c and d effect can find out that ((c:71.88%, d:88.41%), the existence of visible ray can obviously improve the removal speed of pollutent, proves that this granule electrode has visible ray PhotoelectrocatalytiPerformance Performance.
Embodiment 3:
Adopt the activated carbon supported Fe-Ni preparing in embodiment 1 to mix altogether P25 granule electrode and carry out saturated adsorption processing, until no longer absorption under the rhodamine B solution of 20mg/L, after saturated processing, be filled in the visible light catalytic three-dimensional electrode/electro-Fenton reactor shown in Fig. 1, this device positive plate is titanium plate, and negative plate is graphite cake.Control voltage of supply 30V, aeration rate 1.5L/min, anhydrous sodium sulphate dosage 5g/L, pH value of solution is 3, Fe
2+dosage 0.05mmol/L.Investigate respectively visible light photocatalysis (no power, add light source), (energising of three-diemsnional electrode electricity Fenton, do not add light source) (the energising of visible light catalytic three-dimensional electrode/electro-Fenton, add light source) three kinds of processes, contrast the degradation effect of three kinds of processes to 20mg/L rhodamine B, experimental result as shown in Figure 3.
By finding out in Fig. 3, the prepared granule electrode of the present invention has the PhotoelectrocatalytiPerformance Performance under visible ray, and has the synergy of certain visible light photocatalysis and three-dimensional electrode/electro-Fenton process.The visible light photocatalytic degradation effect of 60min is 12.22%; In three-dimensional electrode/electro-Fenton system, this granule electrode and positive plate show good electrocatalysis effect, and 60min clearance arrives 77.68%; In visible light catalytic using three-dimensional electrodes system, 60min clearance reaches 96.64%, its processing rate be greater than visible light catalytic and three-dimensional electrode/electro-Fenton process adding and, proved adding of visible ray, make three-diemsnional electrode electricity Fenton and visible light catalytic have associated treatment effect, the 60min processing rate of three-dimensional electrode/electro-Fenton process has been improved to 24.4%.
Embodiment 4:
The granule electrode of the photochemical catalysis three-dimensional electrode/electro-Fenton system of the present embodiment, mixes altogether P25 by Supported On Granular Activated Carbon bimetal Fe-Ni and forms, and wherein, the particle diameter of granulated active carbon is 3～5mm.
Its preparation method is:
(1) pre-treatment of gac: the gac that washes away most of Heisui River is soaked in the sulphuric acid soln that volumetric concentration is 0.05mol/L, after boiling 30min, be washed till neutrality, then in the sodium hydroxide solution that is 0.05mol/L in volumetric concentration, after boiling 30min, be washed till neutrality, the gac that obtains cleaning up; By clean gac, at power, be 75W, in the ultrasonic environment that frequency is 40kHZ, process 2 times, each 1h, then dry 12h at 105 ℃, obtains supersonic modifying gac; Supersonic modifying gac is impregnated in the salpeter solution that volumetric concentration is 10mol/L and carries out the oxidation modification that duration is 1h, then filter, then with deionized water, be washed till neutrality, at 105 ℃, dry 12h, obtains ultrasonic-Nitric Acid Modified gac;
(2) Fe-Ni mixes the preparation of P25 altogether: the overactivation temperature of learning from else's experience is 400 ℃, soak time is that the P25 after 4h activation carries out after vigorous stirring mixing, at power, be 90W, frequency is to disperse 30min in the ultrasonic environment of 40kHZ, add successively and analyze pure Fe nitrate reagent and analyze pure metal Ni nitrate reagent, two kinds of metal nitrate mol ratios are 1:1, the mol ratio of the analysis pure Fe nitrate reagent adding and analysis pure metal Ni nitrate reagent total amount and P25 is 10:100, magnetic agitation 30min, at power, be 75W, frequency is through 0.45um filtering with microporous membrane after the ultrasonic environment load 1.5h of 20kHZ, dry 12h at 120 ℃, then grind, finally at 350 ℃ of calcining 2h, obtain bimetal Fe-Ni and mix altogether P25,
(3) preparation of granule electrode: Fe-Ni prepared by step (2) mixes altogether P25 and is dispersed in deionized water, after vigorous stirring is disperseed, by the Fe-Ni after disperseing mix altogether P25 and step (1) ultrasonic-Nitric Acid Modified gac and be that 75W frequency is dip loading 2h under the ultrasonic environment of 20kHZ at power by the mass ratio of 0.2:100, after scalping filtration, with deionized water, rinse well, dry 12h at 120 ℃, at 350 ℃ of calcining 4h, obtained having the activated carbon supported Fe-Ni modification P25 granule electrode of visible ray PhotoelectrocatalytiPerformance Performance.
After saturated the granule electrode absorption of making, be filled in the visible light catalytic three-diemsnional electrode electro-Fenton reactor shown in Fig. 1, loading level is 100g/L, and adding concentration is that the rhodamine B solution 400ml of 20mg/L carries out contaminant degradation experiment.Control voltage of supply 30V, aeration rate 1.5L/min, anhydrous sodium sulphate dosage 5g/L, pH value of solution is 3.React visible light photocatalysis after 60min minute, three-diemsnional electrode electricity Fenton, three kinds of processes of visible light catalytic three-dimensional electrode/electro-Fenton are 9.78%, 68.87%, 98.92% to the clearance of rhodamine B.
Embodiment 5:
The granule electrode of the photochemical catalysis three-dimensional electrode/electro-Fenton system of the present embodiment, by being 3～5mm by particle diameter, the columnar activated carbon load bimetal Fe-Co that length-to-diameter ratio is 5:1 mixes P25 composition altogether
(1) pre-treatment of gac: the gac that washes away most of Heisui River is soaked in the hydrochloric acid soln that volumetric concentration is 0.01mol/L, after boiling 30min, be washed till neutrality, then in the sodium hydroxide solution that is 0.01mol/L in volumetric concentration, after boiling 30min, be washed till neutrality, the gac that obtains cleaning up; By clean gac, at power, be 105W, in the ultrasonic environment that frequency is 20kHZ, process 2 times, each 1h, then dry 10h at 120 ℃, obtains supersonic modifying gac; Supersonic modifying gac is impregnated in the salpeter solution that volumetric concentration is 3mol/L and carries out the oxidation modification that duration is 2h, then filter, then with deionized water, be washed till neutrality, at 120 ℃, dry 10h, obtains ultrasonic-Nitric Acid Modified gac;
(2) Fe-Co mixes the preparation of P25 altogether: the overactivation temperature of learning from else's experience is 400 ℃, soak time is that the P25 after 4h activation carries out after vigorous stirring mixing, at power, be 75W, frequency is to disperse 30min in the ultrasonic environment of 20kHZ, add successively and analyze pure Fe nitrate reagent and analytical pure metal Co nitrate reagent, two kinds of metal nitrate mol ratios are 1:1, the analysis pure Fe nitrate reagent adding and the mol ratio of analytical pure metal Co nitrate reagent total amount and P25 are 0.4:100, magnetic agitation 30min, at power, be 105W, frequency is through 0.45um filtering with microporous membrane after the ultrasound environments load 1h of 40kHZ, dry 10h at 105 ℃, then grind, finally at 450 ℃ of calcining 4h, obtain bimetal Fe-Co and mix altogether P25,
(3) preparation of granule electrode: Fe-Co prepared by step (2) mixes altogether P25 and is dispersed in deionized water, after vigorous stirring is disperseed, by the Fe-Co after disperseing mix altogether P25 and step (1) ultrasonic-Nitric Acid Modified gac and be that 60W frequency is dip loading 2h under the ultrasound environments of 20kHZ at power by the mass ratio of 2:100, after scalping filtration, with deionized water, rinse well, dry 10h at 105 ℃, at 400 ℃ of calcining 2h, obtained having the activated carbon supported Fe-Co modification P25 granule electrode of visible ray PhotoelectrocatalytiPerformance Performance.
After saturated the granule electrode absorption of making, be filled in the visible light catalytic three-diemsnional electrode electro-Fenton reactor shown in Fig. 1, loading level is 100g/L, and adding concentration is that the rhodamine B solution 400ml of 20mg/L carries out contaminant degradation experiment.Control voltage of supply 30V, aeration rate 1.5L/min, anhydrous sodium sulphate dosage 5g/L, pH value of solution is 3.React visible light photocatalysis after 60min minute, three-diemsnional electrode electricity Fenton, three kinds of processes of visible light catalytic three-dimensional electrode/electro-Fenton are 9.12%, 74.32%, 94.21% to the clearance of rhodamine B.
Claims (10)
1. a granule electrode for photochemical catalysis three-dimensional electrode/electro-Fenton system, is characterized in that: this granule electrode is mixed altogether P25 by activated carbon supported bimetal and formed.
2. the granule electrode of a kind of photochemical catalysis three-dimensional electrode/electro-Fenton system according to claim 1, is characterized in that: described gac is granulated active carbon or columnar activated carbon.
3. the granule electrode of a kind of photochemical catalysis three-dimensional electrode/electro-Fenton system according to claim 2, is characterized in that: the particle diameter of described granulated active carbon is 3 ~ 5mm; The diameter of described columnar activated carbon is 3 ~ 5mm, and length-to-diameter ratio is 1 ~ 5:1.
4. the granule electrode of a kind of photochemical catalysis three-dimensional electrode/electro-Fenton system according to claim 1, is characterized in that: described bimetal is that two kinds in base metal Fe, Co, Ni, Al, Cu, Sn, Zn, Mn are mixed altogether.
5. the granule electrode of a kind of photochemical catalysis three-dimensional electrode/electro-Fenton system according to claim 1, is characterized in that: described bimetal is that Fe-Ni mixes altogether or Fe-Co mixes altogether.
6. a preparation method for the granule electrode of photochemical catalysis three-dimensional electrode/electro-Fenton system, is characterized in that: the method comprises the following steps:
(1) pre-treatment of gac: the gac that washes away most of Heisui River is soaked in dilute acid soln, is washed till neutrality after boiling 30min, then in dilute alkaline soln, be washed till neutrality, the gac that obtains cleaning up after boiling 30min; By ultrasonication 2 times of clean gac, each 0.5 ~ 1h, then dry 10 ~ 12h at 105 ~ 120 ℃, obtains supersonic modifying gac; Supersonic modifying gac is impregnated in salpeter solution and carries out the oxidation modification that duration is 1 ~ 2h, then filter, then with deionized water, be washed till neutrality, at 105 ~ 120 ℃, dry 10 ~ 12h, obtains ultrasonic-Nitric Acid Modified gac;
(2) bimetal is mixed the preparation of P25 altogether: get P25 and carry out after vigorous stirring mixing, disperse 30min by ultrasonic wave, add successively two kinds of metal nitrates, magnetic agitation 30min, under ultrasonic wave after load 1 ~ 2h through 0.45um filtering with microporous membrane, at 105 ~ 120 ℃, dry 10 ~ 12h, then grinds, finally, at 350 ~ 450 ℃ of calcining 2 ~ 4h, obtain bimetal and mix altogether P25;
(3) preparation of granule electrode: bimetal prepared by step (2) is mixed altogether P25 and is dispersed in deionized water, after vigorous stirring is disperseed, by the bimetal after disperseing mix altogether P25 and step (1) ultrasonic-Nitric Acid Modified gac and by the mass ratio of 0.2 ~ 2:100 dip loading 2 ~ 4h under ultrasonic environment, after scalping filtration, with deionized water, rinse well, dry 10 ~ 12h at 105 ~ 120 ℃, at 350 ~ 450 ℃ of calcining 2 ~ 4h, obtain activated carbon supported bimetallic-modified P25 granule electrode, for the granule electrode of visible light photocatalysis three-dimensional electrode/electro-Fenton system.
7. the preparation method of the granule electrode of a kind of photochemical catalysis three-dimensional electrode/electro-Fenton system according to claim 6, is characterized in that: the diluted acid described in step (1) is that volumetric concentration is sulfuric acid or the hydrochloric acid of 0.01 ~ 0.05mol/L; Described diluted alkaline is that sodium hydroxide volumetric concentration is 0.01 ~ 0.05 mol/L; The volumetric concentration of described nitric acid is 3 ~ 10mol/L.
8. the preparation method of the granule electrode of a kind of photochemical catalysis three-dimensional electrode/electro-Fenton system according to claim 6, is characterized in that: the hyperacoustic power described in step (1) and step (2) is 75 ~ 105W, and frequency is 20 ~ 40kHZ; Hyperacoustic power described in step (3) is 60 ~ 75W, and frequency is 20kHZ.
9. the preparation method of the granule electrode of a kind of photochemical catalysis three-dimensional electrode/electro-Fenton system according to claim 6, is characterized in that: the P25 described in step (2) is the P25 after activation; Activation temperature is 400 ℃, and soak time is 2 ~ 4 h.
10. the preparation method of the granule electrode of a kind of photochemical catalysis three-dimensional electrode/electro-Fenton system according to claim 6, is characterized in that: the mol ratio of two kinds of metal nitrates described in step (2) is: 1:1; The total amount of two kinds of metal nitrates and the mol ratio of P25 that add are: 0.4 ~ 10:100.
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