CN104961199A - 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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- CN104961199A CN104961199A CN201510353990.1A CN201510353990A CN104961199A CN 104961199 A CN104961199 A CN 104961199A CN 201510353990 A CN201510353990 A CN 201510353990A CN 104961199 A CN104961199 A CN 104961199A
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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, be specifically related to a kind of preparation method of Pd-Fe/ nickel foam three dimensional particles electrode.
Background technology
Microbiotic be a class for the people that stops and treat microbial infection disease with and veterinary drug, have purposes widely in human and animal's disease treatment field and culture fishery.At present, people have detected hundreds of microbiotic in the water resourcess such as river, lake, underground water, because microbiotic has difficult degradation, toxicity high, and traditional water technology is poor to microbiotic removal effect, trace even traces of antibiotic all may cause the resistance of bacterium, causes a significant threat human health and the ecosystem.Therefore, be necessary to study the treatment technology of such material.
Fenton method is a kind of traditional water technology, carries out deep oxidation by the organism in the OH radical pair waste water that collaborative generation oxidation capacity is extremely strong, reaches general biological process and to be beyond one's reach removal effect.But Fenton method usually has and needs to add a large amount of added regents, transport and preserve H
2o
2there is potential risk, produce iron containing sludge, the problem that Simultaneous Stabilization is poor, based on the deficiency of above-mentioned Fenton method, Chinese scholars research supplements and improves the method for Fenton method, has occurred that light helps the emerging technologies such as Fenton method, ultrasonic wave Fenton method and Electro-Fenton process.
Wherein Fenton technology utilizes electrochemical action to produce Fe in system
2+and (or) H
2o
2, thus generation Fenton reacts the method be oxidized organism, has without the need to adding H compared with traditional F enton method
2o
2, simultaneously due to Fe
2+the generation of mud can be decreased at cathode regenerative.But because there is dosage, transport, the storage of difficult control molysite and using H in traditional Electro-Fenton process
2o
2have potential danger, the catalytic efficiency of Fenton relies on H to a great extent simultaneously
2o
2production rate, want to produce H efficiently
2o
2just must use costliness and be not very stable gas diffusion electrode.At present based on Pd catalytic electrolysis aquatic products thing H
2and O
2fabricated in situ H
2o
2novel electric Fenton technology, effectively overcome synthesis H
2o
2anticathode material according to patience.But the recyclability of Pd catalyst fines is poor, in treating processes, additional divalent iron salt adds Operating Complexity, and these two factors all can increase processing cost, are unfavorable for industrial application.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, there is provided a kind of as heterogeneous Fenton catalyzer and simultaneously can as the granule electrode of three-diemsnional electrode, make it have that pollutants removal rate is high, catalytic activity advantages of higher, another object of the present invention is to provide the preparation method of above-mentioned granule electrode.
Technical scheme of the present invention is as follows:
A preparation method for Pd-Fe/ nickel foam three dimensional particles electrode, the method to be applicable to particle foam nickel as carrier prepares palladium, iron double metal loading type granule electrode, comprises granule electrode pre-treatment, dipping, calcining, dipping reduction Four processes:
(1) granule electrode pre-treatment: first, is placed in acetone ultrasonic vibration 10 ~ 20min by the nickel foam granule electrode cut out, to remove the organism on surface; Subsequently, pretreated nickel foam granule electrode is put into the H of 0.5-2mol/L
2sO
4or HNO
3middle acid treatment 2-5min, to remove the zone of oxidation on surface; Nickel foam granule electrode taking-up ultrapure water after peracid treatment is washed till neutrality, dries at 100-110 DEG C;
(2) flood: the nickel foam granule electrode that step (1) processed is put into divalent iron salt steeping fluid, by pH regulator to 2.5-3.5, carry out vibration dipping absorption 2-4h, the nickel foam granule electrode after the absorption of vibration dipping is taken out, dry 3-5h at 80-100 DEG C;
(3) calcine: the granule electrode prepared through step (2) is placed in retort furnace, is warming up to 300-500 DEG C with constant temperature rise rate, calcining at constant temperature can obtain Fe/ nickel foam granule electrode;
(4) dipping reduction: palladium is dissolved in the mixed impregnant liquor of hydrochloric acid and ethanol, the Fe/ nickel foam granule electrode obtained after calcination processing is added in above-mentioned mixed impregnant liquor, regulate pH to neutral, stir that to add 15-25mL concentration after 20-40min be that 3-5h is reduced in water bath with thermostatic control that 0.5-1.5mol/L sodium formiate is placed in 60-80 DEG C, until the color of mixed impregnant liquor becomes colourless by initial black, put into 70-90 DEG C of vacuum drying oven after cleaning 3-4 time with ultrapure water to dry, obtain Pd-Fe/ nickel foam granule electrode.
In step (1) described in aforesaid method, the particle diameter of the described nickel foam granule electrode cut out is 5mm × 5mm, and granule electrode loading level is 12.5-25g/L.
In step (2) described in aforesaid method, described divalent iron salt is ferrous sulfate or Iron nitrate, and its active ingredient Fe content is the 5-20wt% of nickel foam granule electrode quality.
In step (3) described in aforesaid method, the temperature rise rate of described retort furnace is 5 DEG C/min; The described calcining at constant temperature time is 120-240min.
In step (4) described in aforesaid method, active ingredient Pd content is the 0.5-2wt% of nickel foam granule electrode quality.
In step (4) described in aforesaid method, Pd-Fe/ nickel foam granule electrode will have Pd, Fe active constituent loading of catalysis in nickel foam surface or nickel foam endoporus, avoid the loss of Pd and Fe active ingredient, the work-ing life of extending catalyst, reduce processing cost.
The present invention also the claimed Pd-Fe/ nickel foam granule electrode that is prepared from according to aforesaid method and this granule electrode in the application of 3 D electrode reactor process antibiotic waste water.
By adopting, the present invention has that specific surface area is large, the nickel foam of 3 D stereo network structure is carrier, loaded to by Pd and Fe bimetallic catalyst in nickel foam surface or nickel foam endoporus, this loading type granule electrode can provide Fe for reaction
2+while can also catalytic electrolysis water product generate H
2o
2, solving traditional electrical Fenton needs additional molysite to occur the problems such as dosage wayward and troublesome poeration, Pd catalyzer difficulty reclaims, current efficiency is low, to the good degrading effect of antibiotic waste water, can reuse.Specifically, the present invention possesses following beneficial effect relative to prior art:
1. prepare a kind of as heterogeneous Fenton catalyzer and simultaneously as the three dimensional particles electrode of loading type with dipping, calcining and immersion reduction method, the granule electrode porous of preparation, specific surface area is large, absorption property is very strong, conductivity and catalytic performance good, it is a kind of novel granule electrode, considerably increase the reaction area of electrode, improve the speed of response of electrode, antibiotic waste water of degrading efficiently;
The H that 2.Pd-Fe/ nickel foam three dimensional particles electrode energy situ catalytic brine electrolysis generates
2and O
2produce H
2o
2and Fe
2+, solve traditional electrical Fenton need additional molysite to occur dosage wayward and troublesome poeration, Pd catalyzer difficulty reclaims, high in cost of production problem;
3.Pd-Fe/ nickel foam granule electrode will have Pd and the Fe active constituent loading of catalysis in nickel foam surface or nickel foam endoporus, substantially increase the specific surface of catalyzer, it also avoid the loss of Pd, Fe active ingredient simultaneously, extend the work-ing life of granule electrode, can reuse;
4. preparation method of the present invention is simple, is easy to promote on a large scale.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the nickel foam granule electrode only obtained through step (1) pre-treatment in embodiment 1.
Fig. 2 is the SEM figure of the Fe/ nickel foam three dimensional particles electrode only obtained through step (1)-(3) in embodiment 1.
Fig. 3 is the SEM figure of the Pd-Fe/ nickel foam three dimensional particles electrode obtained through step (1)-(4) in embodiment 1.
Fig. 4 is that the EDS of Pd-Fe/ nickel foam three dimensional particles electrode in embodiment 1 can spectrogram.
Embodiment
The present invention adopts novel three-dimensional electrode/electro-Fenton method, and by Based on Three-dimensional Electrode Method and Electro-Fenton process coupling, can carry out anode and granule electrode direct oxidation simultaneously, anode produces OH indirect oxidation, granule electrode produces H
2o
2, and and Fe
2+there is Fenton reaction in ion, is a kind of comprehensively multiple electrochemical oxidation technology acting on one.Compared with traditional Fenton technology, it has face body than increasing, and spacing of particle is little, and material mass transfer effect is greatly improved, current efficiency advantages of higher.
Below in conjunction with the drawings and specific embodiments, technical scheme of the present invention and beneficial effect are described further.The granule electrode loading level of the nickel foam substrate described in embodiment 1-5 is 12.5-25g/L.
Embodiment 1:
(1) granule electrode pre-treatment: first, being cut out by nickel foam substrate material to particle diameter is 5mm × 5mm, and the nickel foam granule electrode cut out is placed in acetone ultrasonic vibration 10min, to remove the organism on surface; Subsequently, pretreated nickel foam granule electrode is put into the H of 2mol/L
2sO
4middle acid treatment 2min, to remove the zone of oxidation on surface; Nickel foam taking-up ultrapure water after peracid treatment is washed till neutrality, dries at 105 DEG C; The electrode pattern obtained as shown in Figure 1;
(2) flood: get 10g nickel foam granule electrode and put into FeSO
4in steeping fluid, wherein the mass ratio of Fe load quality and nickel foam granule electrode is 20wt%, by pH regulator to 3, carries out vibration dipping absorption 4h, is taken out by the nickel foam granule electrode after the absorption of vibration dipping, dry 4h at 80 DEG C;
(3) calcine: the granule electrode prepared through above-mentioned steeping process is placed in retort furnace, heat up with the temperature rise rate that 5 DEG C/min is constant, under 300 DEG C of conditions, calcining at constant temperature 180min, can obtain Fe/ nickel foam granule electrode; Obtained electrode pattern as shown in Figure 2.
(4) dipping reduction: get 0.1063g (0.5wt%Pd) palladium and be dissolved in the mixed impregnant liquor be made up of 100mL dehydrated alcohol and 3mL 1mol/L hydrochloric acid soln under 60 DEG C of water bath condition, after solution cooling, 10g Fe/ nickel foam granule electrode is put into and its pH is adjusted to neutrality, stir and to add water bath with thermostatic control that 20mL 1mol/L sodium formiate is placed in 70 DEG C after 30min and reduce 4h, until the color of steeping fluid becomes colourless by initial black, put into 80 DEG C of vacuum drying ovens after cleaning 3-4 time with ultrapure water to dry, obtain Pd-Fe/ nickel foam granule electrode.Obtained electrode pattern as shown in Figure 3.
Be respectively anode and negative electrode with Pt sheet, stainless steel plate, by the add-on of 15g/L, the Pd-Fe/ nickel foam granule electrode prepared in above-described embodiment throwing be filled in reactor, obtained 3 D electrode reactor.Preadsorption test is carried out to get rid of adsorbing impact before electrolysis.Test is 3 at pH, and voltage is 10V, ionogen Na
2sO
4concentration is 5g/L, and aeration rate is under 1L/min condition, and energising degraded 400mL concentration is 50mg/L dimetridazole solution 60min.Degradation time and clearance be the results are shown in table 1, the clearance of 93.62% after processing 60min as shown in Table 1, can be reached.
The Pd-Fe/ nickel foam granule electrode of table 1 embodiment 1 gained is to the clearance result of 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 pre-treatment: first, being cut out by nickel foam substrate material to particle diameter is 5mm × 5mm, and the nickel foam granule electrode cut out is placed in acetone ultrasonic vibration 15min, to remove the organism on surface; Subsequently, pretreated nickel foam granule electrode is put into the HNO of 0.5mol/L
3middle acid treatment 5min, to remove the zone of oxidation on surface; Nickel foam taking-up ultrapure water after peracid treatment is washed till neutrality, dries at 100 DEG C;
(2) flood: get 10g nickel foam granule electrode and put into Fe (NO
3)
2in steeping fluid, the mass ratio of Fe load quality and nickel foam granule electrode is 15wt%, by pH regulator to 2.5, carries out vibration dipping absorption 3h, is taken out by the nickel foam granule electrode after the absorption of vibration dipping, dry 3h at 100 DEG C;
(3) calcine: the granule electrode prepared through above-mentioned steeping process is placed in retort furnace, heat up with the temperature rise rate that 5 DEG C/min is constant, under 500 DEG C of conditions, calcining at constant temperature 120min, can obtain Fe/ nickel foam granule electrode;
(4) dipping reduction: get 0.3189g (1.5wt%Pd) palladium and be dissolved in the mixed impregnant liquor be made up of 100mL dehydrated alcohol and 3mL 1mol/L hydrochloric acid soln under 60 DEG C of water bath condition, after solution cooling, 10g Fe/ nickel foam granule electrode is put into and its pH is adjusted to neutrality, stir and to add water bath with thermostatic control that 20mL 1mol/L sodium formiate is placed in 80 DEG C after 20min and reduce 3h, until the color of steeping fluid becomes colourless by initial black, put into 70 DEG C of vacuum drying ovens after cleaning 3-4 time with ultrapure water to dry, obtain Pd-Fe/ nickel foam granule electrode.
Be respectively anode and negative electrode with Pt sheet, stainless steel plate, by the add-on of 20g/L, the Pd-Fe/ nickel foam granule electrode prepared in above-described embodiment throwing be filled in reactor, obtained 3 D electrode reactor.Preadsorption test is carried out to get rid of adsorbing impact before electrolysis.Test is 3 at pH, and voltage is 10V, ionogen Na
2sO
4concentration is 5g/L, and aeration rate is under the condition of 1L/min, and energising degraded 400mL concentration is 50mg/L dimetridazole solution 60min.Degradation time and clearance be the results are shown in table 2, the clearance of 95.13% after processing 60min as shown in Table 2, can be reached.
The Pd-Fe/ nickel foam granule electrode of table 2 embodiment 2 gained is to the clearance result of 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 pre-treatment: first, being cut out by nickel foam substrate material to particle diameter is 5mm × 5mm, and the nickel foam granule electrode cut out is placed in acetone ultrasonic vibration 20min, to remove the organism on surface; Subsequently, pretreated nickel foam granule electrode is put into the H of 0.5mol/L
2sO
4middle acid treatment 5min, to remove the zone of oxidation on surface; Nickel foam taking-up ultrapure water after peracid treatment is washed till neutrality, dries at 110 DEG C;
(2) flood: get 10g nickel foam granule electrode and put into FeSO
4in steeping fluid, the mass ratio of Fe load quality and nickel foam granule electrode is 10wt%, by pH regulator to 3.5, carries out vibration dipping absorption 4h, is taken out by the nickel foam granule electrode after the absorption of vibration dipping, dry 4h at 100 DEG C;
(3) calcine: the granule electrode prepared through above-mentioned steeping process is placed in retort furnace, heat up with the temperature rise rate that 5 DEG C/min is constant, under 400 DEG C of conditions, calcining at constant temperature 180min, can obtain Fe/ nickel foam granule electrode;
(4) dipping reduction: get 0.2126g (1wt%Pd) palladium and be dissolved in the mixed impregnant liquor be made up of 100mL dehydrated alcohol and 3mL 1mol/L hydrochloric acid soln under 60 DEG C of water bath condition, after solution cooling, 10g Fe/ nickel foam granule electrode is put into and its pH is adjusted to neutrality, stir and to add water bath with thermostatic control that 20mL 1mol/L sodium formiate is placed in 60 DEG C after 40min and reduce 5h, until the color of steeping fluid becomes colourless by initial black, put into 90 DEG C of vacuum drying ovens after cleaning 3-4 time with ultrapure water to dry, obtain Pd-Fe/ nickel foam granule electrode.
Be respectively anode and negative electrode with Pt sheet, stainless steel plate, by the add-on of 12.5g/L, the Pd-Fe/ nickel foam granule electrode prepared in above-described embodiment throwing be filled in reactor, obtained 3 D electrode reactor.Preadsorption test is carried out to get rid of adsorbing impact before electrolysis.Test is 3 at pH, and voltage is 10V, ionogen Na
2sO
4concentration is 5g/L, and aeration rate is under the condition of 1L/min, and energising degraded 400mL concentration is 50mg/L dimetridazole solution 60min.Degradation time and clearance be the results are shown in table 3, the clearance of 92.51% after processing 60min as shown in Table 3, can be reached.
The Pd-Fe/ nickel foam granule electrode of table 3 embodiment 3 gained is to the clearance result of 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 pre-treatment: first, being cut out by nickel foam substrate material to particle diameter is 5mm × 5mm, and the nickel foam granule electrode cut out is placed in acetone ultrasonic vibration 20min, to remove the organism on surface; Subsequently, pretreated nickel foam granule electrode is put into the HNO of 1mol/L
3middle acid treatment 3min, to remove the zone of oxidation on surface; Nickel foam taking-up ultrapure water after peracid treatment is washed till neutrality, dries at 105 DEG C;
(2) flood: get 10g nickel foam granule electrode and put into FeSO
4in steeping fluid, the mass ratio of Fe load quality and nickel foam granule electrode is 5wt%, by pH regulator to 3, carries out vibration dipping absorption 2h, is taken out by the nickel foam granule electrode after the absorption of vibration dipping, dry 4h at 100 DEG C;
(3) calcine: the granule electrode prepared through above-mentioned steeping process is placed in retort furnace, heat up with the temperature rise rate that 5 DEG C/min is constant, under 300 DEG C of conditions, calcining at constant temperature 240min, can obtain Fe/ nickel foam granule electrode;
(4) dipping reduction: get 0.3189g (2wt%Pd) palladium and be dissolved in the mixed impregnant liquor be made up of 100mL dehydrated alcohol and 3mL 1mol/L hydrochloric acid soln under 60 DEG C of water bath condition, after solution cooling, 10g Fe/ nickel foam granule electrode is put into and its pH is adjusted to neutrality, stir and to add water bath with thermostatic control that 20mL 1mol/L sodium formiate is placed in 70 DEG C after 30min and reduce 4h, until the color of steeping fluid becomes colourless by initial black, put into 80 DEG C of vacuum drying ovens after cleaning 3-4 time with ultrapure water to dry, obtain Pd-Fe/ nickel foam granule electrode.
Be respectively anode and negative electrode with Pt sheet, stainless steel plate, by the add-on of 25g/L, the Pd-Fe/ nickel foam granule electrode prepared in above-described embodiment throwing be filled in reactor, obtained 3 D electrode reactor.Preadsorption test is carried out to get rid of adsorbing impact before electrolysis.Test is 3 at pH, and voltage is 10V, ionogen Na
2sO
4concentration is 5g/L, and aeration rate is under the condition of 1L/min, and energising degraded 400mL concentration is 50mg/L dimetridazole solution 60min.Degradation time and clearance be the results are shown in table 4, the clearance of 96.85% after processing 60min as shown in Table 4, can be reached.
The Pd-Fe/ nickel foam granule electrode of table 4 embodiment 4 gained is to the clearance result of 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 pre-treatment: first, being cut out by nickel foam substrate material to particle diameter is 5mm × 5mm, and the nickel foam granule electrode cut out is placed in acetone ultrasonic vibration 10min, to remove the organism on surface; Subsequently, pretreated nickel foam granule electrode is put into the H of 2mol/L
2sO
4middle acid treatment 3min, to remove the zone of oxidation on surface; Nickel foam taking-up ultrapure water after peracid treatment is washed till neutrality, dries at 105 DEG C;
(2) flood: get 10g nickel foam granule electrode and put into FeSO
4in steeping fluid, the mass ratio of Fe load quality and nickel foam granule electrode is 10wt%, by pH regulator to 3, carries out vibration dipping absorption 4h, is taken out by the nickel foam granule electrode after the absorption of vibration dipping, dry 5h at 80 DEG C;
(3) calcine: the granule electrode prepared through above-mentioned steeping process is placed in retort furnace, heat up with the temperature rise rate that 5 DEG C/min is constant, under 300 DEG C of conditions, calcining at constant temperature 180min, can obtain Fe/ nickel foam granule electrode;
(4) dipping reduction: get 0.1063g (0.5wt%Pd) palladium and be dissolved in the mixed impregnant liquor be made up of 100mL dehydrated alcohol and 3mL 1mol/L hydrochloric acid soln under 60 DEG C of water bath condition, after solution cooling, 10g Fe/ nickel foam granule electrode is put into and its pH is adjusted to neutrality, stir and to add water bath with thermostatic control that 20mL 1mol/L sodium formiate is placed in 70 DEG C after 30min and reduce 4h, until the color of steeping fluid becomes colourless by initial black, put into 80 DEG C of vacuum drying ovens after cleaning 3-4 time with ultrapure water to dry, obtain Pd-Fe/ nickel foam granule electrode.
Be respectively anode and negative electrode with Pt sheet, stainless steel plate, by the add-on of 12.5g/L, the Pd-Fe/ nickel foam granule electrode prepared in above-described embodiment throwing be filled in reactor, obtained 3 D electrode reactor.Preadsorption test is carried out to get rid of adsorbing impact before electrolysis.Test is 3 at pH, and voltage is 10V, ionogen Na
2sO
4concentration is 5g/L, and aeration rate is under the condition of 1L/min, and energising degraded 400mL concentration is 50mg/L dimetridazole solution 60min.Degradation time and clearance be the results are shown in table 5, the clearance of 91.86% after processing 60min as shown in Table 5, can be reached.
The Pd-Fe/ nickel foam granule electrode of table 5 embodiment 5 gained is to the clearance result of 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 pre-treatment: first, being cut out by nickel foam substrate material to particle diameter is 5mm × 5mm, and the nickel foam granule electrode cut out is placed in acetone ultrasonic vibration 10min, to remove surface organic matter; Subsequently, pretreated nickel foam granule electrode is put into the H of 1mol/L
2sO
4middle acid treatment 5min, to remove the zone of oxidation on surface; Nickel foam taking-up ultrapure water after peracid treatment is washed till neutrality, dries at 110 DEG C;
(2) flood: get 10g nickel foam granule electrode and put into FeSO
4in steeping fluid, the mass ratio of Fe load quality and nickel foam granule electrode is 10wt%, by pH regulator to 3, carries out vibration dipping absorption 4h, is taken out by the nickel foam granule electrode after the absorption of vibration dipping, dry 5h at 80 DEG C;
(3) calcine: the granule electrode prepared through above-mentioned steeping process is placed in retort furnace, heat up with the temperature rise rate that 5 DEG C/min is constant, under 600 DEG C of conditions, calcining at constant temperature 120min, can obtain Fe/ nickel foam granule electrode;
(4) dipping reduction: get 1.063g (5wt%Pd) palladium and be dissolved in the mixed impregnant liquor be made up of 100mL dehydrated alcohol and 3mL 1mol/L hydrochloric acid soln under 60 DEG C of water bath condition, after solution cooling, 10g Fe/ nickel foam granule electrode is put into and its pH is adjusted to neutrality, stir and to add water bath with thermostatic control that 25mL 0.5mol/L sodium formiate is placed in 70 DEG C after 30min and reduce 4h, until the color of steeping fluid becomes colourless by initial black, put into 90 DEG C of vacuum drying ovens after cleaning 3-4 time with ultrapure water to dry, obtain Pd-Fe/ nickel foam granule electrode.
Be respectively anode and negative electrode with Pt sheet, stainless steel plate, by the add-on of 20g/L, the Pd-Fe/ nickel foam granule electrode prepared in above-described embodiment throwing be filled in reactor, obtained 3 D electrode reactor.Preadsorption test is carried out to get rid of adsorbing impact before electrolysis.Test is 3 at pH, and voltage is 10V, ionogen Na
2sO
4concentration is 5g/L, and aeration rate is under the condition of 1L/min, and energising degraded 400mL concentration is 50mg/L dimetridazole solution 60min.Degradation time and clearance be the results are shown in table 6, is the clearance of 74.05% after processing 60min as shown in Table 6.
The Pd-Fe/ nickel foam granule electrode of table 6 embodiment 6 gained is to the clearance result of 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 pre-treatment: first, being cut out by nickel foam substrate material to particle diameter is 5mm × 5mm, and the nickel foam granule electrode cut out is placed in acetone ultrasonic vibration 10min, to remove surface organic matter; Subsequently, pretreated nickel foam granule electrode is put into the H of 1mol/L
2sO
4middle acid treatment 3min, to remove the zone of oxidation on surface; Nickel foam taking-up ultrapure water after peracid treatment is washed till neutrality, dries at 100 DEG C;
(2) flood: get 10g nickel foam granule electrode and put into FeSO
4in steeping fluid, the mass ratio of Fe load quality and nickel foam granule electrode is 25wt%, by pH regulator to 3, carries out vibration dipping absorption 4h, is taken out by the nickel foam granule electrode after the absorption of vibration dipping, dry 3h at 100 DEG C;
(3) calcine: the granule electrode prepared through above-mentioned steeping process is placed in retort furnace, heat up with the temperature rise rate that 5 DEG C/min is constant, under 300 DEG C of conditions, calcining at constant temperature 180min, can obtain Fe/ nickel foam granule electrode;
(4) dipping reduction: get 1.063g (5wt%Pd) palladium and be dissolved in the mixed impregnant liquor be made up of 100mL dehydrated alcohol and 3mL 1mol/L hydrochloric acid soln under 60 DEG C of water bath condition, after solution cooling, 10g Fe/ nickel foam granule electrode is put into and its pH is adjusted to neutrality, stir and to add water bath with thermostatic control that 20mL 1mol/L sodium formiate is placed in 70 DEG C after 30min and reduce 4h, until the color of steeping fluid becomes colourless by initial black, put into 90 DEG C of vacuum drying ovens after cleaning 3-4 time with ultrapure water to dry, obtain Pd-Fe/ nickel foam granule electrode.
Be respectively anode and negative electrode with Pt sheet, stainless steel plate, by the add-on of 12.5g/L, the Pd-Fe/ nickel foam granule electrode prepared in above-described embodiment throwing be filled in reactor, obtained 3 D electrode reactor.Preadsorption test is carried out to get rid of adsorbing impact before electrolysis.Test is 3 at pH, and voltage is 10V, ionogen Na
2sO
4concentration is 5g/L, and aeration rate is under the condition of 1L/min, and energising degraded 400mL concentration is 50mg/L dimetridazole solution 60min.Degradation time and clearance be the results are shown in table 7, is the clearance of 65.28% after processing 60min as shown in Table 7.
The Pd-Fe/ nickel foam granule electrode of table 7 embodiment 7 gained is to the clearance result of dimetridazole
| Time/min | 10 | 20 | 30 | 40 | 50 | 60 |
| Clearance/% | 35.29 | 49.75 | 57.30 | 61.97 | 63.25 | 65.28 |
Embodiment 8:
Prepare pretreated nickel foam, Fe/ nickel foam and Pd/ nickel foam granule electrode granule electrode in contrast, the Pd-Fe/ nickel foam granule electrode of preparation and contrast granule electrode are carried out electrolytic experiment, and the Pd-Fe/ nickel foam granule electrode investigating preparation has higher electro catalytic activity.
Its preparation method is:
(1) granule electrode pre-treatment: first, being cut out by nickel foam substrate material to particle diameter is 5mm × 5mm, and the nickel foam granule electrode cut out is placed in acetone ultrasonic vibration 10min, to remove the organism on surface; Subsequently, pretreated nickel foam granule electrode is put into the H of 2mol/L
2sO
4middle acid treatment 3min, to remove the zone of oxidation on surface; Nickel foam taking-up ultrapure water after peracid treatment is washed till neutrality, dries at 100 DEG C, obtain pretreated nickel foam;
(2) flood: get 10g nickel foam granule electrode and put into FeSO
4in steeping fluid, the mass ratio of Fe load quality and nickel foam granule electrode is 10wt%, by pH regulator to 3, carries out vibration dipping absorption 3h, is taken out by the nickel foam granule electrode after the absorption of vibration dipping, dry 4h at 100 DEG C;
(3) calcine: the granule electrode prepared through above-mentioned steeping process is placed in retort furnace, heat up with the temperature rise rate that 5 DEG C/min is constant, under 300 DEG C of conditions, calcining at constant temperature 180min, can obtain Fe/ nickel foam granule electrode;
(4) dipping reduction: get 0.1063g (0.5wt%Pd) palladium and be dissolved in the mixed impregnant liquor be made up of 100mL dehydrated alcohol and 3mL 1mol/L hydrochloric acid soln under 60 DEG C of water bath condition, after solution cooling, 10g Fe/ nickel foam granule electrode is put into and its pH is adjusted to neutrality, stir and to add water bath with thermostatic control that 20mL 1mol/L sodium formiate is placed in 70 DEG C after 30min and reduce 4h, until the color of steeping fluid becomes colourless by initial black, put into 80 DEG C of vacuum drying ovens after cleaning 3-4 time with ultrapure water to dry, obtain Pd-Fe/ nickel foam granule electrode.
Anode and negative electrode is respectively, by the add-on of 20g/L by the pre-treatment nickel foam of preparation in above-described embodiment 8, Fe/ nickel foam, Pd/ nickel foam, Pd-Fe/ nickel foam granule electrode and Pd/ nickel foam granule electrode and additional 0.2mmol/L FeSO with Pt sheet, stainless steel plate
4be filled in reactor, obtained 3 D electrode reactor.Preadsorption test is carried out to get rid of adsorbing impact before electrolysis.Test is 3 at pH, and voltage is 10V, ionogen Na
2sO
4concentration is 5g/L, and aeration rate is under the condition of 1L/min, and energising degraded 400mL concentration is 50mg/L dimetridazole solution 60min.Different granule electrode be the results are shown in table 8 when 60min to dimetridazole clearance.
In table 8 embodiment 8, the granule electrode of preparation is to the clearance result of dimetridazole
| Granule electrode | Nickel foam | Fe/ nickel foam | Pd/ nickel foam | Pd-Fe/ nickel foam | Pd/ nickel foam+0.2mmol/LFeSO 4 |
| Clearance % | 34.90 | 35.88 | 37.25 | 95.88 | 71.85 |
As can be seen from Table 8, the Pd-Fe/ nickel foam granule electrode prepared of the present invention to the clearance of dimetridazole higher than pretreated nickel foam, Fe/ nickel foam, Pd/ nickel foam granule electrode and Pd/ nickel foam granule electrode and 0.2mmol/L FeSO
4the electrocatalysis efficiency of system.
Embodiment 9:
The stability test of Pd-Fe/ nickel foam granule electrode:
Be respectively anode and negative electrode with Pt sheet, stainless steel plate, Pd-Fe/ nickel foam granule electrode embodiment 2 prepared by the add-on of 20g/L is filled in reactor, obtained 3 D electrode reactor.Preadsorption test is carried out to get rid of adsorbing impact before electrolysis.Test is 3 at pH, and voltage is 10V, ionogen Na
2sO
4concentration is 5g/L, aeration rate is under the condition of 1L/min, and energising degraded 400mL concentration is after 50mg/L dimetridazole solution 60min, and solution is carried out simple filtration, after the granule electrode milli-Q water after separation, oven dry, carry out Electrocatalysis Degradation test under the same conditions.Continuous repetition five times, records dimetridazole degradation rate and is followed successively by: 95.13%, 94.67%, 93.65%, 91.51%, 90.13%.This shows, after Pd-Fe/ nickel foam granule electrode prepared by the present invention recycles for five times, the clearance of dimetridazole all maintains more than 90%, illustrates that Pd-Fe/ nickel foam granule electrode stability is higher, has good repeat performance.
Claims (7)
1. a preparation method for Pd-Fe/ nickel foam three dimensional particles electrode, is characterized in that, comprise granule electrode pre-treatment, dipping, calcining and dipping reduction Four processes, concrete steps are as follows:
(1) granule electrode pre-treatment: first, is placed in acetone ultrasonic vibration 10 ~ 20min by the nickel foam granule electrode cut out, to remove the organism on surface; Subsequently, pretreated nickel foam granule electrode is put into the H of 0.5-2mol/L
2sO
4or HNO
3middle acid treatment 2-5min, to remove the zone of oxidation on surface; Nickel foam granule electrode taking-up ultrapure water after peracid treatment is washed till neutrality, dries at 100-110 DEG C;
(2) flood: the nickel foam granule electrode that step (1) processed is put into divalent iron salt steeping fluid, by pH regulator to 2.5-3.5, carry out vibration dipping absorption 2-4h, the nickel foam granule electrode after the absorption of vibration dipping is taken out, dry 3-5h at 80-100 DEG C;
(3) calcine: the granule electrode prepared through step (2) is placed in retort furnace, is warming up to 300-500 DEG C with constant temperature rise rate, calcining at constant temperature can obtain Fe/ nickel foam granule electrode;
(4) dipping reduction: palladium is dissolved in the mixed impregnant liquor of hydrochloric acid and ethanol, the Fe/ nickel foam granule electrode obtained after calcination processing is added in above-mentioned mixed impregnant liquor, regulate pH to neutral, stir that to add 15-25mL concentration after 20-40min be that 3-5h is reduced in water bath with thermostatic control that 0.5-1.5mol/L sodium formiate is placed in 60-80 DEG C, until the color of mixed impregnant liquor becomes colourless by initial black, put into 70-90 DEG C of vacuum drying oven after cleaning 3-4 time with ultrapure water to dry, obtain Pd-Fe/ nickel foam granule electrode.
2. the preparation method of Pd-Fe/ nickel foam three dimensional particles electrode according to claim 1, is characterized in that, the particle diameter of the described nickel foam granule electrode cut out is 5mm × 5mm, and granule electrode loading level is 12.5-25g/L.
3. the preparation method of Pd-Fe/ nickel foam three dimensional particles electrode according to claim 1, it is characterized in that, described divalent iron salt is ferrous sulfate or Iron nitrate, and its active ingredient Fe content is the 5-20wt% of nickel foam granule electrode quality.
4. the preparation method of Pd-Fe/ nickel foam three dimensional particles electrode according to claim 1, is characterized in that, the temperature rise rate of described retort furnace is 5 DEG C/min; The described calcining at constant temperature time is 120-240min.
5. the preparation method of Pd-Fe/ nickel foam three dimensional particles electrode according to claim 1, is characterized in that, in described palladium, active ingredient Pd content is the 0.5-2wt% of nickel foam granule electrode quality; Described Pd-Fe/ nickel foam granule electrode will have Pd and the Fe active constituent loading of catalysis in nickel foam surface or nickel foam endoporus.
6. the Pd-Fe/ nickel foam three dimensional particles electrode that the preparation method according to any one of claim 1-5 is prepared from.
7. Pd-Fe/ nickel foam three dimensional particles electrode according to claim 6 is in the application of 3 D electrode reactor process antibiotic waste water.
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