CN103739043B - A kind of granule electrode of photochemical catalysis three-dimensional electrode/electro-Fenton system and preparation method - Google Patents
A kind of granule electrode of photochemical catalysis three-dimensional electrode/electro-Fenton system and preparation method Download PDFInfo
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
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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 present invention discloses a kind of granule electrode and preparation method of photochemical catalysis three-dimensional electrode/electro-Fenton system, and this granule electrode is mixed P25 altogether by activated carbon supported bimetal and formed; First its preparation method is the pre-treatment of gac, obtains ultrasonic-Nitric Acid Modified gac; Then carry out the preparation that P25 mixed altogether by bimetal, then ultrasonic-Nitric Acid Modified gac and bimetal are mixed P25 altogether and carry out load, obtain the granule electrode for visible light photocatalysis three-dimensional electrode/electro-Fenton system.Preparation method of the present invention is simple, and the granule electrode obtained has visible ray photoelectrocatalysis effect, can fast and efficient degradation organic pollutant; And obvious visible light photocatalysis and three-dimensional electrode/electro-Fenton associated treatment effect can be obtained in visible light catalytic three-dimensional electrode/electro-Fenton system.
Description
Technical field
The invention belongs to water treatment and field of water pollution control, 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 processing Persistent organic pollutants thing at present, the combination of the two, both the problem of the difficult separation of catalyzer in photochemical catalysis, the easy compound in electron hole, practical application had been solved, solving again in electrocatalysis can current efficiency is low, energy consumption is high limitation, the two be combined in multinomial research to be proved to be and have 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 substantially increases the specific surface area of reactor and current efficiency, improve mass-transfer efficiency between electrode, thus raising degradation efficiency, be than two-dimensional electrode more preferably electrocatalytic oxidation method.Three-dimensional electrode/electro-Fenton technology is on three-diemsnional electrode basis, by carbonaceous cathodes surface aeration and additional Fe
2+, Fenton's reaction can be formed in system, act synergistically with three-diemsnional electrode electrocatalysis and accelerate rate of contaminant degradation; 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 systems in which.At present for the research of using three-dimensional electrodes system granule electrode PhotoelectrocatalytiPerformance Performance, mostly concentrate on ultraviolet catalytic, 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, one is provided to have visible ray PhotoelectrocatalytiPerformance Performance, and can realize the granule electrode of 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 providing above-mentioned granule electrode.
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 P25 altogether 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 Fe-Ni and 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: be soaked in dilute acid soln by the gac washing away most of Heisui River, is washed till neutrality after boiling 30min, then in dilute alkaline soln, is washed till neutrality after boiling 30min, obtains the gac cleaned up; By clean gac supersound process 2 times, each 0.5 ~ 1h, then dry 10 ~ 12h at 105 ~ 120 DEG C, obtains supersonic modifying gac; Be impregnated into by supersonic modifying gac in salpeter solution and carry out the oxidation modification that duration is 1 ~ 2h, then scalping is filtered, and is washed till neutrality with deionized water, and at 105 ~ 120 DEG C, dry 10 ~ 12h, obtains ultrasonic-Nitric Acid Modified gac;
(2) preparation of P25 mixed altogether by bimetal: get after P25 carries out vigorous stirring mixing, use ultrasonic disperse 30min, add two kinds of metal nitrates successively, magnetic agitation 30min, through 0.45um filtering with microporous membrane after ultrasonic lower load 1 ~ 2h, at 105 ~ 120 DEG C, dry 10 ~ 12h, then grinds, finally at 350 ~ 450 DEG C of calcining 2 ~ 4h, namely obtain bimetal and mix P25 altogether;
(3) preparation of granule electrode: bimetal prepared by step (2) is mixed altogether P25 dispersion in deionized water, after vigorous stirring dispersion, bimetal after dispersion is mixed altogether P25 and step (1) ultrasonic-Nitric Acid Modified gac and the mass ratio dip loading 2 ~ 4h under ultrasound environments by 0.2 ~ 2:100, scalping is clean with deionized water rinsing after filtering, dry 10 ~ 12h at 105 ~ 120 DEG C, at 350 ~ 450 DEG C of calcining 2 ~ 4h, obtain activated carbon supported bimetallic-modified P25 granule electrode, namely 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.
Above step (1) and the ultrasonic power described in step (2) are 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 DEG C, and soak time is 2 ~ 4h.
The two kinds of metal nitrate mol ratios added in above step (2) are 1:1; The two kinds of metal nitrate total amounts added and the mol ratio of P25 are 0.4 ~ 10:100.
Above-described metal nitrate is analytical pure nitrate reagent.
Relative to prior art, beneficial effect of the present invention is as follows:
1, the present invention adopts diluted acid and diluted alkaline to clean gac respectively, eliminates the solid impurity in gac and greasy dirt, improves activated carbon surface adsorption activity, improves granule electrode to the degradation capability being adsorbed on surface organic matter.
2, the present invention adopts and ultrasonicly carries out modification to gac, effectively can improve activated carbon pore size, central hole structure is increased, be conducive to the area load of catalyzer, reduce because catalyst cupport causes space to block, improve the adsorptive power of loading type granule electrode.
3, normal activated carbon 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, add the absorption of granule electrode to water Semi-polarity pollutent, add TIO simultaneously
2in the tack of activated carbon surface.
4, the granule electrode in the present invention can effectively reduce electron-hole compound in visible ray three-dimensional electrode/electro-Fenton system, improve visible ray photoelectrocatalysis efficiency, rapidly and efficiently degradable organic pollutant, and obvious visible light photocatalysis and three-dimensional electrode/electro-Fenton associated treatment effect can be obtained.
5, the present invention is as the granule electrode for visible light catalytic three-dimensional electrode/electro-Fenton system, has visible ray PhotoelectrocatalytiPerformance Performance, also can be used in general three dimensional electrode photo electrocatalysis system, have associated treatment effect equally; 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 identifies: 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 contrast effect figure of the electrocatalysis of granule electrode prepared by normal activated carbon and the present invention and two kinds of reaction process of visible ray photoelectrocatalysis;
Accompanying drawing identifies: a-normal activated carbon granule electrode photoelectrocatalysis effect, b-normal activated carbon granule electrode 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 that visible light photocatalysis, three-diemsnional electrode electricity Fenton and visible light catalytic three-dimensional electrode/electro-Fenton three kinds of processes are to the design sketch of the degraded of 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 length-to-diameter ratio is that the columnar activated carbon supported bi-metallic Fe-Ni of 1:1 mixes P25 composition altogether.
Its preparation method is:
(1) pre-treatment of gac: the gac washing away most of Heisui River being soaked in volumetric concentration is in the sulphuric acid soln of 0.01mol/L, neutrality is washed till after boiling 30min, then be in the sodium hydroxide solution of 0.01mol/L in volumetric concentration, be washed till neutrality after boiling 30min, obtain the gac cleaned up; Be 75W by clean gac at power, frequency is process 2 times in the ultrasonic environment of 20kHZ, each 0.5h, and then dry 12h at 105 DEG C, obtains supersonic modifying gac; Supersonic modifying gac being impregnated into volumetric concentration is carry out the oxidation modification that duration is 2h in the salpeter solution of 5mol/L, then filters, is then washed till neutrality with deionized water, dry 12h at 105 DEG C, obtain ultrasonic-Nitric Acid Modified gac;
(2) Fe-Ni mixes the preparation of P25 altogether: overactivation temperature of learning from else's experience is 400 DEG C, soak time is after the P25 after 2h activation carries out vigorous stirring mixing, be 105W at power, frequency is disperse 30min in the ultrasound environments of 40kHZ, add successively and analyze pure Fe nitrate reagent and analytical pure W metal nitrate reagent, two kinds of metal nitrate mol ratios are 1:1, the analysis pure Fe nitrate reagent added and the mol ratio of analytical pure W metal nitrate reagent total amount and P25 are 1:100, magnetic agitation 30min, be 75W at power, frequency is through 0.45um filtering with microporous membrane after the ultrasonic environment doping 2h of 40kHZ, dry 12h at 120 DEG C, then grind, finally at 450 DEG C of calcining 2h, namely obtain bimetal Fe-Ni and mix P25 altogether,
(3) preparation of granule electrode: Fe-Ni prepared by step (2) is mixed altogether P25 dispersion in deionized water, after vigorous stirring dispersion, Fe-Ni after dispersion is mixed altogether P25 and step (1) ultrasonic-Nitric Acid Modified gac and dip loading 2h under be 75W frequency being the ultrasound environments of 20kHZ by the mass ratio of 1:100 at power, scalping is clean with deionized water rinsing after filtering, dry 12h at 120 DEG C, at 450 DEG C of calcining 2h, namely obtain 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:
The activated carbon supported Fe-Ni that contrast normal activated carbon granule electrode and embodiment 1 obtain mixes P25 granule electrode altogether, and whether the granule electrode investigating preparation has visible ray PhotoelectrocatalytiPerformance Performance.
Get 40g granule electrode and carry out saturated adsorption experiment in rhodamine B solution, until be issued to adsorption equilibrium in 20mg/L concentration.Adsorb saturated after granule electrode be filled in the visible light catalytic three-dimensional electrode/electro-Fenton reactor shown in Fig. 1, 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, investigating the visible ray PhotoelectrocatalytiPerformance Performance of granule electrode, in experimentation, not adding Fe
2+, the electrocatalysis of granule electrode of normal activated carbon and preparation and two kinds of reaction process of visible ray photoelectrocatalysis are contrasted.Result as shown in Figure 2 and Table 1.
Table 1 different granule electrode electrocatalysis 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 photoelectrocatalysis effect is under visible light 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 prepared for the present invention is not when having additional light source, and its electrocatalysis characteristic is better than normal activated carbon.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 normal activated carbon, has good PhotoelectrocatalytiPerformance Performance under visible light.Correlation curve c and d effect can be found out, and ((c:71.88%, d:88.41%), the existence of visible ray can significantly 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 of preparation in embodiment 1 to mix P25 granule electrode altogether and carry out saturated adsorption process, until no longer adsorb under the rhodamine B solution of 20mg/L, be filled in the visible light catalytic three-dimensional electrode/electro-Fenton reactor shown in Fig. 1 after saturated process, 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 visible light photocatalysis (no power respectively, add light source), three-diemsnional electrode electricity Fenton (energising, do not add light source) (the energising of visible light catalytic three-dimensional electrode/electro-Fenton, add light source) three kinds of processes, contrast three kinds of processes to the degradation effect of 20mg/L rhodamine B, experimental result as shown in Figure 3.
As can be seen from Fig. 3, the granule electrode prepared by 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 adding of visible light catalytic and three-dimensional electrode/electro-Fenton process and, demonstrate 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 is improve 24.4%.
Embodiment 4:
The granule electrode of the photochemical catalysis three-dimensional electrode/electro-Fenton system of the present embodiment, mixes P25 altogether 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 washing away most of Heisui River being soaked in volumetric concentration is in the sulphuric acid soln of 0.05mol/L, neutrality is washed till after boiling 30min, then be in the sodium hydroxide solution of 0.05mol/L in volumetric concentration, be washed till neutrality after boiling 30min, obtain the gac cleaned up; Be 75W by clean gac at power, frequency is process 2 times in the ultrasonic environment of 40kHZ, each 1h, and then dry 12h at 105 DEG C, obtains supersonic modifying gac; Supersonic modifying gac being impregnated into volumetric concentration is carry out the oxidation modification that duration is 1h in the salpeter solution of 10mol/L, then filters, is then washed till neutrality with deionized water, dry 12h at 105 DEG C, obtain ultrasonic-Nitric Acid Modified gac;
(2) Fe-Ni mixes the preparation of P25 altogether: overactivation temperature of learning from else's experience is 400 DEG C, soak time is after the P25 after 4h activation carries out vigorous stirring mixing, be 90W at power, frequency is disperse 30min in the ultrasonic environment of 40kHZ, add successively and analyze pure Fe nitrate reagent and analytical pure W metal nitrate reagent, two kinds of metal nitrate mol ratios are 1:1, the analysis pure Fe nitrate reagent added and the mol ratio of analytical pure W metal nitrate reagent total amount and P25 are 10:100, magnetic agitation 30min, be 75W at power, frequency is through 0.45um filtering with microporous membrane after the ultrasonic environment load 1.5h of 20kHZ, dry 12h at 120 DEG C, then grind, finally at 350 DEG C of calcining 2h, namely obtain bimetal Fe-Ni and mix P25 altogether,
(3) preparation of granule electrode: Fe-Ni prepared by step (2) is mixed altogether P25 dispersion in deionized water, after vigorous stirring dispersion, Fe-Ni after dispersion is mixed altogether P25 and step (1) ultrasonic-Nitric Acid Modified gac and dip loading 2h under be 75W frequency being the ultrasonic environment of 20kHZ by the mass ratio of 0.2:100 at power, scalping is clean with deionized water rinsing after filtering, dry 12h at 120 DEG C, at 350 DEG C of calcining 4h, namely obtain the activated carbon supported Fe-Ni modification P25 granule electrode with visible ray PhotoelectrocatalytiPerformance Performance.
Be filled in the visible light catalytic three-diemsnional electrode electro-Fenton reactor shown in Fig. 1 after saturated for the granule electrode made absorption, 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, visible light catalytic three-dimensional electrode/electro-Fenton three kinds of processes 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, length-to-diameter ratio is that the columnar activated carbon supported bi-metallic Fe-Co of 5:1 mixes P25 composition altogether
(1) pre-treatment of gac: the gac washing away most of Heisui River being soaked in volumetric concentration is in the hydrochloric acid soln of 0.01mol/L, neutrality is washed till after boiling 30min, then be in the sodium hydroxide solution of 0.01mol/L in volumetric concentration, be washed till neutrality after boiling 30min, obtain the gac cleaned up; Be 105W by clean gac at power, frequency is process 2 times in the ultrasonic environment of 20kHZ, each 1h, and then dry 10h at 120 DEG C, obtains supersonic modifying gac; Supersonic modifying gac being impregnated into volumetric concentration is carry out the oxidation modification that duration is 2h in the salpeter solution of 3mol/L, then filters, is then washed till neutrality with deionized water, dry 10h at 120 DEG C, obtain ultrasonic-Nitric Acid Modified gac;
(2) Fe-Co mixes the preparation of P25 altogether: overactivation temperature of learning from else's experience is 400 DEG C, soak time is after the P25 after 4h activation carries out vigorous stirring mixing, be 75W at power, frequency is 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 added and the mol ratio of analytical pure metal Co nitrate reagent total amount and P25 are 0.4:100, magnetic agitation 30min, be 105W at power, frequency is through 0.45um filtering with microporous membrane after the ultrasound environments load 1h of 40kHZ, dry 10h at 105 DEG C, then grind, finally at 450 DEG C of calcining 4h, namely obtain bimetal Fe-Co and mix P25 altogether,
(3) preparation of granule electrode: Fe-Co prepared by step (2) is mixed altogether P25 dispersion in deionized water, after vigorous stirring dispersion, Fe-Co after dispersion is mixed altogether P25 and step (1) ultrasonic-Nitric Acid Modified gac and dip loading 2h under be 60W frequency being the ultrasound environments of 20kHZ by the mass ratio of 2:100 at power, scalping is clean with deionized water rinsing after filtering, dry 10h at 105 DEG C, at 400 DEG C of calcining 2h, namely obtain the activated carbon supported Fe-Co modification P25 granule electrode with visible ray PhotoelectrocatalytiPerformance Performance.
Be filled in the visible light catalytic three-diemsnional electrode electro-Fenton reactor shown in Fig. 1 after saturated for the granule electrode made absorption, 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, visible light catalytic three-dimensional electrode/electro-Fenton three kinds of processes are 9.12%, 74.32%, 94.21% to the clearance of rhodamine B.
Claims (7)
1. a granule electrode for photochemical catalysis three-dimensional electrode/electro-Fenton system, is characterized in that: this granule electrode is mixed P25 altogether by activated carbon supported bimetal and formed;
Described gac is granulated active carbon or columnar activated carbon;
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;
Described bimetal is that two kinds in base metal Fe, Co, Ni, Al, Cu, Sn, Zn, Mn are mixed altogether.
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 bimetal is that Fe-Ni mixes altogether or Fe-Co mixes altogether.
3. 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: be soaked in dilute acid soln by the gac washing away most of Heisui River, is washed till neutrality after boiling 30min, then in dilute alkaline soln, is washed till neutrality after boiling 30min, obtains the gac cleaned up; By clean gac ultrasonication 2 times, each 0.5 ~ 1h, then dry 10 ~ 12h at 105 ~ 120 DEG C, obtains supersonic modifying gac; Be impregnated into by supersonic modifying gac in salpeter solution and carry out the oxidation modification that duration is 1 ~ 2h, then filter, be then washed till neutrality with deionized water, at 105 ~ 120 DEG C, dry 10 ~ 12h, obtains ultrasonic-Nitric Acid Modified gac;
(2) preparation of P25 mixed altogether by bimetal: get after P25 carries out vigorous stirring mixing, 30min is disperseed by ultrasonic wave, add two kinds of metal nitrates successively, magnetic agitation 30min, under ultrasonic wave after load 1 ~ 2h through 0.45um filtering with microporous membrane, at 105 ~ 120 DEG C, dry 10 ~ 12h, then grinds, finally at 350 ~ 450 DEG C of calcining 2 ~ 4h, namely obtain bimetal and mix P25 altogether;
(3) preparation of granule electrode: bimetal prepared by step (2) is mixed altogether P25 dispersion in deionized water, after vigorous stirring dispersion, bimetal after dispersion is mixed altogether P25 and step (1) ultrasonic-Nitric Acid Modified gac and the mass ratio dip loading 2 ~ 4h under ultrasonic environment by 0.2 ~ 2:100, scalping is clean with deionized water rinsing after filtering, dry 10 ~ 12h at 105 ~ 120 DEG C, at 350 ~ 450 DEG C of calcining 2 ~ 4h, obtain activated carbon supported bimetallic-modified P25 granule electrode, namely for the granule electrode of visible light photocatalysis three-dimensional electrode/electro-Fenton system.
4. the preparation method of the granule electrode of a kind of photochemical catalysis three-dimensional electrode/electro-Fenton system according to claim 3, is characterized in that: sulfuric acid or the hydrochloric acid of to be volumetric concentration the be 0.01 ~ 0.05mol/L of the diluted acid described in step (1); Described diluted alkaline is sodium hydroxide volumetric concentration is 0.01 ~ 0.05 mol/L; The volumetric concentration of described nitric acid is 3 ~ 10mol/L.
5. the preparation method of the granule electrode of a kind of photochemical catalysis three-dimensional electrode/electro-Fenton system according to claim 3, is characterized in that: step (1) and the hyperacoustic power described in step (2) are 75 ~ 105W, and frequency is 20 ~ 40kHZ; Hyperacoustic power described in step (3) is 60 ~ 75W, and frequency is 20kHz.
6. the preparation method of the granule electrode of a kind of photochemical catalysis three-dimensional electrode/electro-Fenton system according to claim 3, is characterized in that: the P25 described in step (2) is the P25 after activation; Activation temperature is 400 DEG C, and soak time is 2 ~ 4 h.
7. the preparation method of the granule electrode of a kind of photochemical catalysis three-dimensional electrode/electro-Fenton system according to claim 3, is characterized in that: the mol ratio of two kinds of metal nitrates described in step (2) is: 1:1; The total amount of the two kinds of metal nitrates added and the mol ratio of P25 are: 0.4 ~ 10:100.
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