CN104961199B - Preparation method of Pd-Fe/foamed nickel three-dimensional particle electrodes - Google Patents
Preparation method of Pd-Fe/foamed nickel three-dimensional particle electrodes Download PDFInfo
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Abstract
The invention relates to a preparation method of Pd-Fe/foamed nickel three-dimensional particle electrodes. The foamed nickel three-dimensional particle electrodes are preprocessed and then placed into ferrous salt maceration extract, pH is adjusted to 2.5-3.5, vibration adsorption is conducted for 2-4 h, and then the foamed nickel three-dimensional particle electrodes are taken out to be dried; the temperature is raised to 300-500 DEG C, and constant-temperature calcining is conducted; palladium acetate is dissolved in hydrochloric acid and ethyl alcohol mixed maceration extract, the calcinated particle electrodes are added into the mixed maceration extract, pH is adjusted to be neutral, a sodium formate solution is added into the mixed maceration extract in a stirred mode, the mixture is placed in 60-80 DEG C constant-temperature bath to be subjected to reduction for 3-5 h until the color of the mixed maceration extract becomes colorless from the initial black, the particle electrodes are washed through ultrapure water for 3-4 times and then placed in a 70-90 DEG C vacuum drying box to be dried, the obtained Pd-Fe/foamed nickel particle electrodes can serve as a heterogeneous Fenton catalyst but also can serve as particle electrodes of three-dimensional electrodes, and the Pd-Fe/foamed nickel three-dimensional particle electrodes have the advantages of being high in pollutant removal rate and catalytic activity.
Description
Technical field
The invention belongs to environmental protection and treatment field, and in particular to a kind of system of Pd-Fe/ nickel foams three dimensional particles electrode
Preparation Method.
Background technology
Antibiotic is that a class is used to preventing and treating the human and veterinary medicine of microbial infection disease, in the mankind and dynamic
Thing disease treatment field and culture fishery have extensive purposes.At present, people provide in water such as river, lake, underground water
Hundreds of antibiotic is had been detected by source, there is difficult degradation because of antibiotic, the features such as toxicity is high, and traditional water treatment technology
Poor to antibiotic removal effect, micro or even traces of antibiotic may all cause the drug resistance of bacterium, to human health and life
State system is caused a significant threat.Therefore, it is necessary to study the treatment technology of such material.
Fenton methods are a kind of traditional water technologies, and by collaboration the extremely strong OH free radicals pair of oxidability are produced
Organic matter in waste water carries out deep oxidation, reaches general bioanalysis and is beyond one's reach removal effect.But Fenton methods are usual
With needing to add substantial amounts of added regent, transport and storage H2O2There is potential risk, produce iron containing sludge, Simultaneous Stabilization
Poor problem, based on the method that the deficiency of above-mentioned Fenton methods, Chinese scholars research are supplemented and improve Fenton methods, occurs
Light helps the emerging technologies such as Fenton methods, ultrasonic wave Fenton methods and Electro-Fenton process.
Wherein Fenton technology is that Fe is produced in system using electrochemical action2+And (or) H2O2, so as to occur
The method that Fenton reactions are aoxidized to organic matter, having compared with traditional Fenton methods need not add H2O2, simultaneously because
Fe2+The yield of sludge can be reduced in cathode regenerative.But because there is adding for difficult control molysite in traditional Electro-Fenton process
Measure, transport, store and use H2O2There is potential danger, while the catalytic efficiency of Fenton relies heavily on H2O2's
Generation rate, wants efficiently to produce H2O2Expensive and not very stable gas-diffusion electrode must just be used.It is currently based on Pd
Catalytic electrolysis aquatic products H2And O2Fabricated in situ H2O2New Fenton technology, effectively overcome synthesis H2O2To cathode material
Accordance with tolerance.But, the recyclability of Pd catalyst fineses is poor, and additional divalent iron salt increased complex operation in processing procedure
Property, the two factors can all increase processing cost, be unfavorable for commercial Application.
The content of the invention
The technical problem to be solved is for above-mentioned the deficiencies in the prior art, there is provided one kind is used as heterogeneous
Fenton catalyst and it is also capable as the granule electrode of three-diemsnional electrode so as to pollutants removal rate is high, catalysis activity is high
The advantages of, it is a further object of the present invention to provide the preparation method of above-mentioned granule electrode.
Technical scheme is as follows：
A kind of preparation method of Pd-Fe/ nickel foams three dimensional particles electrode, the method is applied to particle foam nickel as carrier
Prepare palladium, iron double metal support type granule electrode, including granule electrode pretreatment, dipping, calcining, dipping reduction Four processes：
(1) granule electrode pretreatment：First, by the nickel foam granule electrode cut out be placed in ultrasonic vibration 10 in acetone～
20min, to remove the organic matter on surface；Subsequently, the nickel foam granule electrode of pretreatment is put into into the H of 0.5-2mol/L2SO4Or
HNO3Middle acid treatment 2-5min, to remove the oxide layer on surface；Nickel foam granule electrode after acid treatment is taken out and uses super
Pure water is washed till neutrality, dries at 100-110 DEG C；
(2) impregnate：The nickel foam granule electrode that step (1) was processed is put in divalent iron salt maceration extract, pH is adjusted
To 2.5-3.5, vibration dipping absorption 2-4h is carried out, the nickel foam granule electrode after vibration dipping absorption is taken out, in 80-100
3-5h is dried at DEG C；
(3) calcine：Granule electrode prepared by Jing steps (2) is placed in Muffle furnace, is warming up to constant heating rate
300-500 DEG C, calcining at constant temperature is obtained Fe/ nickel foam granule electrodes；
(4) dipping reduction：Palladium is dissolved in the mixed impregnant liquor of hydrochloric acid and ethanol, will be obtained Jing after calcination processing
Fe/ nickel foams granule electrode add in above-mentioned mixed impregnant liquor, adjust pH to neutrality, add 15- after stirring 20-40min
25mL concentration is placed in 60-80 DEG C of water bath with thermostatic control for 0.5-1.5mol/L sodium formates and reduces 3-5h, until mixed impregnant liquor
Color becomes colourless by initial black, is put into after cleaning 3-4 time with ultra-pure water in 70-90 DEG C of vacuum drying chamber and dries, and obtains
Pd-Fe/ nickel foam granule electrodes.
In step (1) described in said method, the particle diameter of the described nickel foam granule electrode cut out is 5mm × 5mm,
Granule electrode loading is 12.5-25g/L.
In step (2) described in said method, described divalent iron salt is ferrous sulfate or ferrous nitrate, its active component
Fe contents are the 5-20wt% of nickel foam granule electrode quality.
In step (3) described in said method, the heating rate of described Muffle furnace is 5 DEG C/min；Described constant temperature is forged
The burning time is 120-240min.
In step (4) described in said method, active component Pd content is the 0.5- of nickel foam granule electrode quality
2wt%.
In step (4) described in said method, Pd-Fe/ nickel foams granule electrode is active by Pd, Fe with catalysis
Component is carried in foam nickel surface or nickel foam endoporus, it is to avoid the loss of Pd and Fe active components, extends the use of catalyst
In the life-span, reduce processing cost.
The present invention is also claimed the Pd-Fe/ nickel foams granule electrode and the particle being prepared from according to said method
Electrode processes the application of antibiotic waste water in 3 D electrode reactor.
The present invention by adopt with specific surface area greatly, the nickel foam of 3 D stereo network structure for carrier, by Pd and Fe
Bimetallic catalyst is loaded in foam nickel surface or nickel foam endoporus, and the support type granule electrode can provide Fe for reaction2+'s
Simultaneously can also the product of catalytic electrolysis water generate H2O2, solve traditional Fenton and need additional molysite dosage occur and be difficult
Control and troublesome poeration, Pd catalyst it is difficult reclaim, the low problem of current efficiency, good degrading effect to antibiotic waste water, can
Recycling.Specifically, the present invention possesses following beneficial effect relative to prior art：
1. prepared with dipping, calcining and immersion reduction method a kind of as heterogeneous Fenton catalyst and while as load
The three dimensional particles electrode of type, the granule electrode porous of preparation, specific surface area is big, absorption property very strong, electric conductivity and catalytic
Can be good, it is a kind of new granule electrode, the response area of electrode is considerably increased, improve the reaction speed of electrode, energy
Efficiently degrade antibiotic waste water；
2.Pd-Fe/ nickel foam three dimensional particles electrode energy situ catalytic is electrolysed the H of water generating2And O2Produce H2O2And Fe2+, solution
Traditional Fenton of having determined needs additional molysite wayward dosage and the difficult recovery of troublesome poeration, Pd catalyst, cost occur
High the problems such as；
Pd and Fe active components with catalysis are carried on foam nickel surface by 3.Pd-Fe/ nickel foams granule electrode
Or in nickel foam endoporus, the specific surface of catalyst is substantially increased, while it also avoid the loss of Pd, Fe active component, extend
The service life of granule electrode, repeats and utilizes；
4. the preparation method of the present invention is simple, it is easy to promote on a large scale.
Description of the drawings
Fig. 1 is the SEM figures of the nickel foam granule electrode that Jing steps (1) pretreatment is obtained in embodiment 1.
Fig. 2 is the SEM figures of the Fe/ nickel foam three dimensional particles electrodes that Jing steps (1)-(3) obtains in embodiment 1.
Fig. 3 is the SEM figures of the Pd-Fe/ nickel foam three dimensional particles electrodes that Jing steps (1)-(4) obtain in embodiment 1.
Fig. 4 is the EDS energy spectrum diagrams of Pd-Fe/ nickel foam three dimensional particles electrodes in embodiment 1.
Specific embodiment
The present invention adopts new three-dimensional electrode/electro-Fenton method, Based on Three-dimensional Electrode Method and Electro-Fenton process is coupled, Ke Yitong
Shi Jinhang anodes and granule electrode direct oxidation, anode produce OH indirect oxidations, and granule electrode produces H2O2, and and Fe2+From
There is Fenton reactions in son, be a kind of various electrochemical oxidation technologies for acting on one of synthesis.With traditional Fenton skill
Art is compared, and it has face body than increase, and interparticle distance is little, and material mass transfer effect is greatly improved, the advantages of current efficiency is high.
Below in conjunction with the accompanying drawings technical scheme and beneficial effect are described further with specific embodiment.Implement
The granule electrode loading of the nickel foam substrate described in example 1-5 is 12.5-25g/L.
Embodiment 1：
(1) granule electrode pretreatment：First, it is 5mm × 5mm nickel foam substrate material to be cut out to particle diameter, will be cut out
Nickel foam granule electrode be placed in ultrasonic vibration 10min in acetone, to remove the organic matter on surface；Subsequently, by the bubble of pretreatment
Foam nickel shot sub-electrode is put into the H of 2mol/L2SO4Middle acid treatment 2min, to remove the oxide layer on surface；By after acid treatment
Nickel foam is taken out and is washed to neutrality with ultrapure, is dried at 105 DEG C；The electrode pattern for obtaining is as shown in Figure 1；
(2) impregnate：Take 10g nickel foam granule electrodes and be put into FeSO4In maceration extract, wherein Fe load qualities and foam nickel shot
The mass ratio of sub-electrode is 20wt%, and pH is adjusted to 3, carries out vibration dipping absorption 4h, by the foam after vibration dipping absorption
Nickel shot sub-electrode takes out, and at 80 DEG C 4h is dried；
(3) calcine：Granule electrode prepared by the above-mentioned dipping process of Jing is placed in Muffle furnace, with the liter that 5 DEG C/min is constant
Warm ramp, under the conditions of 300 DEG C, calcining at constant temperature 180min, you can obtain Fe/ nickel foam granule electrodes；Obtained electrode shape
Looks are as shown in Figure 2.
(4) dipping reduction：Take 0.1063g (0.5wt%Pd) palladiums be dissolved under 60 DEG C of water bath conditions by 100mL without
In the mixed impregnant liquor of water-ethanol and 3mL 1mol/L hydrochloric acid solutions composition, by 10g Fe/ foam nickel particles after solution cooling
Electrode is put into and its pH is adjusted to into neutrality, adds 20mL 1mol/L sodium formates to be placed in 70 DEG C of water bath with thermostatic control after stirring 30min
Reduction 4h, until the color of maceration extract becomes colourless by initial black, is put into 80 DEG C of vacuum and does after cleaning 3-4 time with ultra-pure water
Dry in dry case, obtain Pd-Fe/ nickel foam granule electrodes.Obtained electrode pattern is as shown in Figure 3.
Anode and negative electrode are respectively with Pt pieces, corrosion resistant plate, by 15g/L addition by above-described embodiment prepare
Pd-Fe/ nickel foams granule electrode is thrown and is filled in reactor, and 3 D electrode reactor is obtained.The attached examination of pre-suction is carried out before electrolysis
Test to exclude adsorbing impact.Test is 3 in pH, and voltage is 10V, electrolyte Na2SO4Concentration is 5g/L, and aeration rate is
Under the conditions of 1L/min, the degraded 400mL concentration that is powered is 50mg/L dimetridazole solution 60min.By degradation time and the knot of clearance
Fruit is listed in table 1, and the clearance after 60min up to 93.62% is processed as shown in Table 1.
Clearance result of the Pd-Fe/ nickel foams granule electrode of the gained of 1 embodiment of table 1 to dimetridazole
| Time/min | 10 | 20 | 30 | 40 | 50 | 60 |
| Clearance/% | 48.55 | 76.13 | 82.23 | 90.93 | 92.28 | 93.62 |
Embodiment 2：
(1) granule electrode pretreatment：First, it is 5mm × 5mm nickel foam substrate material to be cut out to particle diameter, will be cut out
Nickel foam granule electrode be placed in ultrasonic vibration 15min in acetone, to remove the organic matter on surface；Subsequently, by the bubble of pretreatment
Foam nickel shot sub-electrode is put into the HNO of 0.5mol/L3Middle acid treatment 5min, to remove the oxide layer on surface；Will be after acid treatment
Nickel foam take out be washed to neutrality with ultrapure, at 100 DEG C dry；
(2) impregnate：Take 10g nickel foam granule electrodes and be put into Fe (NO3)2In maceration extract, Fe load qualities and foam nickel particles
The mass ratio of electrode is 15wt%, and pH is adjusted to 2.5, carries out vibration dipping absorption 3h, by the foam after vibration dipping absorption
Nickel shot sub-electrode takes out, and at 100 DEG C 3h is dried；
(3) calcine：Granule electrode prepared by the above-mentioned dipping process of Jing is placed in Muffle furnace, with the liter that 5 DEG C/min is constant
Warm ramp, under the conditions of 500 DEG C, calcining at constant temperature 120min, you can obtain Fe/ nickel foam granule electrodes；
(4) dipping reduction：Take 0.3189g (1.5wt%Pd) palladiums be dissolved under 60 DEG C of water bath conditions by 100mL without
In the mixed impregnant liquor of water-ethanol and 3mL 1mol/L hydrochloric acid solutions composition, by 10g Fe/ foam nickel particles after solution cooling
Electrode is put into and its pH is adjusted to into neutrality, adds 20mL 1mol/L sodium formates to be placed in 80 DEG C of water bath with thermostatic control after stirring 20min
Reduction 3h, until the color of maceration extract becomes colourless by initial black, is put into 70 DEG C of vacuum and does after cleaning 3-4 time with ultra-pure water
Dry in dry case, obtain Pd-Fe/ nickel foam granule electrodes.
Anode and negative electrode are respectively with Pt pieces, corrosion resistant plate, by 20g/L addition by above-described embodiment prepare
Pd-Fe/ nickel foams granule electrode is thrown and is filled in reactor, and 3 D electrode reactor is obtained.The attached examination of pre-suction is carried out before electrolysis
Test to exclude adsorbing impact.Test is 3 in pH, and voltage is 10V, electrolyte Na2SO4Concentration is 5g/L, and aeration rate is
Under conditions of 1L/min, the degraded 400mL concentration that is powered is 50mg/L dimetridazole solution 60min.By degradation time and clearance
As a result table 2 is listed in, the clearance after 60min up to 95.13% is processed as shown in Table 2.
Clearance result of the Pd-Fe/ nickel foams granule electrode of the gained of 2 embodiment of table 2 to dimetridazole
| Time/min | 10 | 20 | 30 | 40 | 50 | 60 |
| Clearance/% | 53.01 | 82.49 | 90.34 | 93.61 | 94.72 | 95.13 |
Embodiment 3：
(1) granule electrode pretreatment：First, it is 5mm × 5mm nickel foam substrate material to be cut out to particle diameter, will be cut out
Nickel foam granule electrode be placed in ultrasonic vibration 20min in acetone, to remove the organic matter on surface；Subsequently, by the bubble of pretreatment
Foam nickel shot sub-electrode is put into the H of 0.5mol/L2SO4Middle acid treatment 5min, to remove the oxide layer on surface；Will be after acid treatment
Nickel foam take out be washed to neutrality with ultrapure, at 110 DEG C dry；
(2) impregnate：Take 10g nickel foam granule electrodes and be put into FeSO4In maceration extract, Fe load qualities are electric with foam nickel particles
The mass ratio of pole is 10wt%, and pH is adjusted to 3.5, carries out vibration dipping absorption 4h, by the nickel foam after vibration dipping absorption
Granule electrode takes out, and at 100 DEG C 4h is dried；
(3) calcine：Granule electrode prepared by the above-mentioned dipping process of Jing is placed in Muffle furnace, with the liter that 5 DEG C/min is constant
Warm ramp, under the conditions of 400 DEG C, calcining at constant temperature 180min, you can obtain Fe/ nickel foam granule electrodes；
(4) dipping reduction：Take 0.2126g (1wt%Pd) palladiums be dissolved under 60 DEG C of water bath conditions it is anhydrous by 100mL
In the mixed impregnant liquor of ethanol and 3mL 1mol/L hydrochloric acid solutions composition, by 10g Fe/ foams nickel particles electricity after solution cooling
Pole is put into and its pH is adjusted to into neutrality, adds 20mL 1mol/L sodium formates to be placed in 60 DEG C of water bath with thermostatic control also after stirring 40min
Former 5h, until the color of maceration extract becomes colourless by initial black, is put into 90 DEG C of vacuum drying after cleaning 3-4 time with ultra-pure water
Dry in case, obtain Pd-Fe/ nickel foam granule electrodes.
Anode and negative electrode are respectively with Pt pieces, corrosion resistant plate, by 12.5g/L addition by above-described embodiment prepare
Pd-Fe/ nickel foams granule electrode is thrown and is filled in reactor, and 3 D electrode reactor is obtained.The attached examination of pre-suction is carried out before electrolysis
Test to exclude adsorbing impact.Test is 3 in pH, and voltage is 10V, electrolyte Na2SO4Concentration is 5g/L, and aeration rate is
Under conditions of 1L/min, the degraded 400mL concentration that is powered is 50mg/L dimetridazole solution 60min.By degradation time and clearance
As a result table 3 is listed in, the clearance after 60min up to 92.51% is processed as shown in Table 3.
Clearance result of the Pd-Fe/ nickel foams granule electrode of the gained of 3 embodiment of table 3 to dimetridazole
| Time/min | 10 | 20 | 30 | 40 | 50 | 60 |
| Clearance/% | 53.86 | 72.71 | 83.10 | 88.75 | 90.74 | 92.51 |
Embodiment 4：
(1) granule electrode pretreatment：First, it is 5mm × 5mm nickel foam substrate material to be cut out to particle diameter, will be cut out
Nickel foam granule electrode be placed in ultrasonic vibration 20min in acetone, to remove the organic matter on surface；Subsequently, by the bubble of pretreatment
Foam nickel shot sub-electrode is put into the HNO of 1mol/L3Middle acid treatment 3min, to remove the oxide layer on surface；By after acid treatment
Nickel foam is taken out and is washed to neutrality with ultrapure, is dried at 105 DEG C；
(2) impregnate：Take 10g nickel foam granule electrodes and be put into FeSO4In maceration extract, Fe load qualities are electric with foam nickel particles
The mass ratio of pole is 5wt%, and pH is adjusted to 3, carries out vibration dipping absorption 2h, by the foam nickel particles after vibration dipping absorption
Electrode takes out, and at 100 DEG C 4h is dried；
(3) calcine：Granule electrode prepared by the above-mentioned dipping process of Jing is placed in Muffle furnace, with the liter that 5 DEG C/min is constant
Warm ramp, under the conditions of 300 DEG C, calcining at constant temperature 240min, you can obtain Fe/ nickel foam granule electrodes；
(4) dipping reduction：Take 0.3189g (2wt%Pd) palladiums be dissolved under 60 DEG C of water bath conditions it is anhydrous by 100mL
In the mixed impregnant liquor of ethanol and 3mL 1mol/L hydrochloric acid solutions composition, by 10g Fe/ foams nickel particles electricity after solution cooling
Pole is put into and its pH is adjusted to into neutrality, adds 20mL 1mol/L sodium formates to be placed in 70 DEG C of water bath with thermostatic control also after stirring 30min
Former 4h, until the color of maceration extract becomes colourless by initial black, is put into 80 DEG C of vacuum drying after cleaning 3-4 time with ultra-pure water
Dry in case, obtain Pd-Fe/ nickel foam granule electrodes.
Anode and negative electrode are respectively with Pt pieces, corrosion resistant plate, by 25g/L addition by above-described embodiment prepare
Pd-Fe/ nickel foams granule electrode is thrown and is filled in reactor, and 3 D electrode reactor is obtained.The attached examination of pre-suction is carried out before electrolysis
Test to exclude adsorbing impact.Test is 3 in pH, and voltage is 10V, electrolyte Na2SO4Concentration is 5g/L, and aeration rate is
Under conditions of 1L/min, the degraded 400mL concentration that is powered is 50mg/L dimetridazole solution 60min.By degradation time and clearance
As a result table 4 is listed in, the clearance after 60min up to 96.85% is processed as shown in Table 4.
Clearance result of the Pd-Fe/ nickel foams granule electrode of the gained of 4 embodiment of table 4 to dimetridazole
| Time/min | 10 | 20 | 30 | 40 | 50 | 60 |
| Clearance/% | 56.51 | 87.49 | 91.26 | 94.61 | 95.04 | 96.85 |
Embodiment 5：
(1) granule electrode pretreatment：First, it is 5mm × 5mm nickel foam substrate material to be cut out to particle diameter, will be cut out
Nickel foam granule electrode be placed in ultrasonic vibration 10min in acetone, to remove the organic matter on surface；Subsequently, by the bubble of pretreatment
Foam nickel shot sub-electrode is put into the H of 2mol/L2SO4Middle acid treatment 3min, to remove the oxide layer on surface；By after acid treatment
Nickel foam is taken out and is washed to neutrality with ultrapure, is dried at 105 DEG C；
(2) impregnate：Take 10g nickel foam granule electrodes and be put into FeSO4In maceration extract, Fe load qualities are electric with foam nickel particles
The mass ratio of pole is 10wt%, and pH is adjusted to 3, carries out vibration dipping absorption 4h, by the foam nickel shot after vibration dipping absorption
Sub-electrode takes out, and at 80 DEG C 5h is dried；
(3) calcine：Granule electrode prepared by the above-mentioned dipping process of Jing is placed in Muffle furnace, with the liter that 5 DEG C/min is constant
Warm ramp, under the conditions of 300 DEG C, calcining at constant temperature 180min, you can obtain Fe/ nickel foam granule electrodes；
(4) dipping reduction：Take 0.1063g (0.5wt%Pd) palladiums be dissolved under 60 DEG C of water bath conditions by 100mL without
In the mixed impregnant liquor of water-ethanol and 3mL 1mol/L hydrochloric acid solutions composition, by 10g Fe/ foam nickel particles after solution cooling
Electrode is put into and its pH is adjusted to into neutrality, adds 20mL 1mol/L sodium formates to be placed in 70 DEG C of water bath with thermostatic control after stirring 30min
Reduction 4h, until the color of maceration extract becomes colourless by initial black, is put into 80 DEG C of vacuum and does after cleaning 3-4 time with ultra-pure water
Dry in dry case, obtain Pd-Fe/ nickel foam granule electrodes.
Anode and negative electrode are respectively with Pt pieces, corrosion resistant plate, by 12.5g/L addition by above-described embodiment prepare
Pd-Fe/ nickel foams granule electrode is thrown and is filled in reactor, and 3 D electrode reactor is obtained.The attached examination of pre-suction is carried out before electrolysis
Test to exclude adsorbing impact.Test is 3 in pH, and voltage is 10V, electrolyte Na2SO4Concentration is 5g/L, and aeration rate is
Under conditions of 1L/min, the degraded 400mL concentration that is powered is 50mg/L dimetridazole solution 60min.By degradation time and clearance
As a result table 5 is listed in, the clearance after 60min up to 91.86% is processed as shown in Table 5.
Clearance result of the Pd-Fe/ nickel foams granule electrode of the gained of 5 embodiment of table 5 to dimetridazole
| Time/min | 10 | 20 | 30 | 40 | 50 | 60 |
| Clearance/% | 51.36 | 70.33 | 81.65 | 87.79 | 89.18 | 91.86 |
Embodiment 6：
(1) granule electrode pretreatment：First, it is 5mm × 5mm nickel foam substrate material to be cut out to particle diameter, will be cut out
Nickel foam granule electrode be placed in ultrasonic vibration 10min in acetone, to remove surface organic matter；Subsequently, by the foam of pretreatment
Nickel shot sub-electrode is put into the H of 1mol/L2SO4Middle acid treatment 5min, to remove the oxide layer on surface；By the bubble after acid treatment
Foam nickel takes out and is washed to neutrality with ultrapure, dries at 110 DEG C；
(2) impregnate：Take 10g nickel foam granule electrodes and be put into FeSO4In maceration extract, Fe load qualities are electric with foam nickel particles
The mass ratio of pole is 10wt%, and pH is adjusted to 3, carries out vibration dipping absorption 4h, by the foam nickel shot after vibration dipping absorption
Sub-electrode takes out, and at 80 DEG C 5h is dried；
(3) calcine：Granule electrode prepared by the above-mentioned dipping process of Jing is placed in Muffle furnace, with the liter that 5 DEG C/min is constant
Warm ramp, under the conditions of 600 DEG C, calcining at constant temperature 120min, you can obtain Fe/ nickel foam granule electrodes；
(4) dipping reduction：Take 1.063g (5wt%Pd) palladiums be dissolved under 60 DEG C of water bath conditions it is anhydrous by 100mL
In the mixed impregnant liquor of ethanol and 3mL 1mol/L hydrochloric acid solutions composition, by 10g Fe/ foams nickel particles electricity after solution cooling
Pole is put into and its pH is adjusted to into neutrality, adds 25mL 0.5mol/L sodium formates to be placed in 70 DEG C of water bath with thermostatic control after stirring 30min
Reduction 4h, until the color of maceration extract becomes colourless by initial black, is put into 90 DEG C of vacuum and does after cleaning 3-4 time with ultra-pure water
Dry in dry case, obtain Pd-Fe/ nickel foam granule electrodes.
Anode and negative electrode are respectively with Pt pieces, corrosion resistant plate, by 20g/L addition by above-described embodiment prepare
Pd-Fe/ nickel foams granule electrode is thrown and is filled in reactor, and 3 D electrode reactor is obtained.The attached examination of pre-suction is carried out before electrolysis
Test to exclude adsorbing impact.Test is 3 in pH, and voltage is 10V, electrolyte Na2SO4Concentration is 5g/L, and aeration rate is
Under conditions of 1L/min, the degraded 400mL concentration that is powered is 50mg/L dimetridazole solution 60min.By degradation time and clearance
As a result table 6 is listed in, the clearance after 60min for 74.05% is processed as shown in Table 6.
Clearance result of the Pd-Fe/ nickel foams granule electrode of the gained of 6 embodiment of table 6 to dimetridazole
| Time/min | 10 | 20 | 30 | 40 | 50 | 60 |
| Clearance/% | 46.82 | 56.73 | 65.20 | 69.31 | 72.86 | 74.05 |
Embodiment 7：
(1) granule electrode pretreatment：First, it is 5mm × 5mm nickel foam substrate material to be cut out to particle diameter, will be cut out
Nickel foam granule electrode be placed in ultrasonic vibration 10min in acetone, to remove surface organic matter；Subsequently, by the foam of pretreatment
Nickel shot sub-electrode is put into the H of 1mol/L2SO4Middle acid treatment 3min, to remove the oxide layer on surface；By the bubble after acid treatment
Foam nickel takes out and is washed to neutrality with ultrapure, dries at 100 DEG C；
(2) impregnate：Take 10g nickel foam granule electrodes and be put into FeSO4In maceration extract, Fe load qualities are electric with foam nickel particles
The mass ratio of pole is 25wt%, and pH is adjusted to 3, carries out vibration dipping absorption 4h, by the foam nickel shot after vibration dipping absorption
Sub-electrode takes out, and at 100 DEG C 3h is dried；
(3) calcine：Granule electrode prepared by the above-mentioned dipping process of Jing is placed in Muffle furnace, with the liter that 5 DEG C/min is constant
Warm ramp, under the conditions of 300 DEG C, calcining at constant temperature 180min, you can obtain Fe/ nickel foam granule electrodes；
(4) dipping reduction：Take 1.063g (5wt%Pd) palladiums be dissolved under 60 DEG C of water bath conditions it is anhydrous by 100mL
In the mixed impregnant liquor of ethanol and 3mL 1mol/L hydrochloric acid solutions composition, by 10g Fe/ foams nickel particles electricity after solution cooling
Pole is put into and its pH is adjusted to into neutrality, adds 20mL 1mol/L sodium formates to be placed in 70 DEG C of water bath with thermostatic control also after stirring 30min
Former 4h, until the color of maceration extract becomes colourless by initial black, is put into 90 DEG C of vacuum drying after cleaning 3-4 time with ultra-pure water
Dry in case, obtain Pd-Fe/ nickel foam granule electrodes.
Anode and negative electrode are respectively with Pt pieces, corrosion resistant plate, by 12.5g/L addition by above-described embodiment prepare
Pd-Fe/ nickel foams granule electrode is thrown and is filled in reactor, and 3 D electrode reactor is obtained.The attached examination of pre-suction is carried out before electrolysis
Test to exclude adsorbing impact.Test is 3 in pH, and voltage is 10V, electrolyte Na2SO4Concentration is 5g/L, and aeration rate is
Under conditions of 1L/min, the degraded 400mL concentration that is powered is 50mg/L dimetridazole solution 60min.By degradation time and clearance
As a result table 7 is listed in, the clearance after 60min for 65.28% is processed as shown in Table 7.
Clearance result of the Pd-Fe/ nickel foams granule electrode of the gained of 7 embodiment of table 7 to dimetridazole
| Time/min | 10 | 20 | 30 | 40 | 50 | 60 |
| Clearance/% | 35.29 | 49.75 | 57.30 | 61.97 | 63.25 | 65.28 |
Embodiment 8：
Nickel foam, Fe/ nickel foams and the Pd/ nickel foams granule electrode of pretreatment are prepared as control granule electrode, will be made
Standby Pd-Fe/ nickel foams granule electrode and control granule electrode carries out electrolytic experiment, investigates the Pd-Fe/ foam nickel particles for preparing
Electrode has higher electro catalytic activity.
Its preparation method is：
(1) granule electrode pretreatment：First, it is 5mm × 5mm nickel foam substrate material to be cut out to particle diameter, will be cut out
Nickel foam granule electrode be placed in ultrasonic vibration 10min in acetone, to remove the organic matter on surface；Subsequently, by the bubble of pretreatment
Foam nickel shot sub-electrode is put into the H of 2mol/L2SO4Middle acid treatment 3min, to remove the oxide layer on surface；By after acid treatment
Nickel foam is taken out and is washed to neutrality with ultrapure, is dried at 100 DEG C, obtains the nickel foam for pre-processing；
(2) impregnate：Take 10g nickel foam granule electrodes and be put into FeSO4In maceration extract, Fe load qualities are electric with foam nickel particles
The mass ratio of pole is 10wt%, and pH is adjusted to 3, carries out vibration dipping absorption 3h, by the foam nickel shot after vibration dipping absorption
Sub-electrode takes out, and at 100 DEG C 4h is dried；
(3) calcine：Granule electrode prepared by the above-mentioned dipping process of Jing is placed in Muffle furnace, with the liter that 5 DEG C/min is constant
Warm ramp, under the conditions of 300 DEG C, calcining at constant temperature 180min, you can obtain Fe/ nickel foam granule electrodes；
(4) dipping reduction：Take 0.1063g (0.5wt%Pd) palladiums be dissolved under 60 DEG C of water bath conditions by 100mL without
In the mixed impregnant liquor of water-ethanol and 3mL 1mol/L hydrochloric acid solutions composition, by 10g Fe/ foam nickel particles after solution cooling
Electrode is put into and its pH is adjusted to into neutrality, adds 20mL 1mol/L sodium formates to be placed in 70 DEG C of water bath with thermostatic control after stirring 30min
Reduction 4h, until the color of maceration extract becomes colourless by initial black, is put into 80 DEG C of vacuum and does after cleaning 3-4 time with ultra-pure water
Dry in dry case, obtain Pd-Fe/ nickel foam granule electrodes.
Anode and negative electrode are respectively with Pt pieces, corrosion resistant plate, by 20g/L addition by above-described embodiment 8 prepare
Pretreatment nickel foam, Fe/ nickel foams, Pd/ nickel foams, Pd-Fe/ nickel foams granule electrode and Pd/ nickel foams granule electrode with it is outer
Plus 0.2mmol/L FeSO4In being filled in reactor, 3 D electrode reactor is obtained.Pre-suction adhesion test is carried out before electrolysis to arrange
Except adsorbing impact.Test is 3 in pH, and voltage is 10V, electrolyte Na2SO4Concentration is 5g/L, and aeration rate is 1L/min's
Under the conditions of, the degraded 400mL concentration that is powered is 50mg/L dimetridazole solution 60min.Different granule electrodes are beautiful to enlightening in 60min
The result of azoles clearance is listed in table 8.
Clearance result of the granule electrode prepared in the embodiment 8 of table 8 to dimetridazole
| Granule electrode | Nickel foam | Fe/ nickel foams | Pd/ nickel foams | Pd-Fe/ nickel foams | Pd/ nickel foam+0.2mmol/LFeSO4 |
| Clearance % | 34.90 | 35.88 | 37.25 | 95.88 | 71.85 |
As can be seen from Table 8, the Pd-Fe/ nickel foams granule electrode that prepared by the present invention is higher than Jing to the clearance of dimetridazole
The nickel foam of pretreatment, Fe/ nickel foams, Pd/ nickel foams granule electrode and Pd/ nickel foams granule electrode and 0.2mmol/L
FeSO4The electro-catalysis efficiency of system.
Embodiment 9：
The stability test of Pd-Fe/ nickel foam granule electrodes：
Anode and negative electrode are respectively with Pt pieces, corrosion resistant plate, by the Pd-Fe/ that the addition of 20g/L prepares embodiment 2
Nickel foam granule electrode is filled in reactor, and 3 D electrode reactor is obtained.Pre-suction adhesion test is carried out before electrolysis to exclude
Adsorbing impact.Test is 3 in pH, and voltage is 10V, electrolyte Na2SO4Concentration is 5g/L, and aeration rate is the bar of 1L/min
Under part, the degraded 400mL concentration that is powered is after 50mg/L dimetridazole solution 60min, solution to be carried out into simple filtration, after separation
After granule electrode milli-Q water, drying, Electrocatalysis Degradation test is carried out under the same conditions.Continuously repeat five times, measure
Dimetridazole degradation rate is followed successively by：95.13%th, 94.67%, 93.65%, 91.51%, 90.13%.It can thus be seen that this
After the Pd-Fe/ nickel foams granule electrode of bright preparation is recycled for five times, the clearance of dimetridazole all maintains more than 90%, says
Bright Pd-Fe/ nickel foams granule electrode stability is higher, with preferable repeat performance.
Claims (6)
1. a kind of preparation method of Pd-Fe/ nickel foams three dimensional particles electrode, it is characterised in that including granule electrode pretreatment, leaching
Stain, calcining and dipping reduction Four processes, comprise the following steps that：
(1) granule electrode pretreatment：First, by the nickel foam granule electrode cut out be placed in ultrasonic vibration 10 in acetone～
20min, to remove the organic matter on surface；Subsequently, the nickel foam granule electrode of pretreatment is put into into the H of 0.5-2mol/L2SO4Or
HNO3Middle acid treatment 2-5min, to remove the oxide layer on surface；Nickel foam granule electrode after acid treatment is taken out and uses super
Pure water is washed till neutrality, dries at 100-110 DEG C；
(2) impregnate：The nickel foam granule electrode that step (1) was processed is put in divalent iron salt maceration extract, by pH adjust to
2.5-3.5, carries out vibration dipping absorption 2-4h, the nickel foam granule electrode after vibration dipping absorption is taken out, at 80-100 DEG C
Under be dried 3-5h；
(3) calcine：Granule electrode prepared by Jing steps (2) is placed in Muffle furnace, 300- is warming up to constant heating rate
500 DEG C, calcining at constant temperature is obtained Fe/ nickel foam granule electrodes；
(4) dipping reduction：Palladium is dissolved in the mixed impregnant liquor of hydrochloric acid and ethanol, by what is obtained Jing after calcination processing
Fe/ nickel foams granule electrode is added in above-mentioned mixed impregnant liquor, adjusts pH to neutrality, and after stirring 20-40min 15-25mL is added
Concentration is placed in 60-80 DEG C of water bath with thermostatic control for 0.5-1.5mol/L sodium formates and reduces 3-5h, until the color of mixed impregnant liquor
Become colourless by initial black, be put into after cleaning 3-4 time with ultra-pure water in 70-90 DEG C of vacuum drying chamber and dry, obtain Pd-
Fe/ nickel foam granule electrodes.
2. the preparation method of Pd-Fe/ nickel foams three dimensional particles electrode according to claim 1, it is characterised in that described
Divalent iron salt is ferrous sulfate or ferrous nitrate, and its active component Fe content is the 5-20wt% of nickel foam granule electrode quality.
3. the preparation method of Pd-Fe/ nickel foams three dimensional particles electrode according to claim 1, it is characterised in that described
The heating rate of Muffle furnace is 5 DEG C/min；The described calcining at constant temperature time is 120-240min.
4. the preparation method of Pd-Fe/ nickel foams three dimensional particles electrode according to claim 1, it is characterised in that described
In palladium, active component Pd content is the 0.5-2wt% of nickel foam granule electrode quality；Described Pd-Fe/ foam nickel particles
During Pd and Fe active components with catalysis are carried on foam nickel surface or nickel foam endoporus by electrode.
5. the Pd-Fe/ nickel foam three dimensional particles electrodes that the preparation method any one of claim 1-4 is prepared from.
6. the Pd-Fe/ nickel foam three dimensional particles electrodes described in claim 5 process antibiotic waste water in 3 D electrode reactor
Using.
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| CN107585834B (en) * | 2017-09-20 | 2020-05-15 | 中国地质大学（武汉） | electro-Fenton water treatment method based on iron-containing clay mineral supported palladium catalyst |
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