CN101648736A - Method for removing chlorine in chlorinated organic pollutant through electrochemistry method - Google Patents
Method for removing chlorine in chlorinated organic pollutant through electrochemistry method Download PDFInfo
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- CN101648736A CN101648736A CN200910018601A CN200910018601A CN101648736A CN 101648736 A CN101648736 A CN 101648736A CN 200910018601 A CN200910018601 A CN 200910018601A CN 200910018601 A CN200910018601 A CN 200910018601A CN 101648736 A CN101648736 A CN 101648736A
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Abstract
The invention discloses a method for removing chlorine in chlorinated organic pollutant through electrochemistry method, and the method comprises the following steps: using a three-electrode system which adopts glassy carbon electrode modified with core-shell nanoscale bimetallic Fe/Pd catalyst as working electrode to perform cyclic voltammetry sweep in a mixed solution of H2SO4 solution and CCl4and determine the range of hydrogen region; and (2) electrolyzing for a period of time in the mixed solution of H2SO4 solution and CCl4 under the constant potential according to the determined range of hydrogen region. The method uses couple corrosion between Pd and Fe so as to accelerate the adsorption of hydrogen on Pd, the method is applicable to the fast chlorine-removing of chlorinated organic material at room temperature and normal pressure under the strong acid condition and the dechlorination efficiency is high.
Description
Technical field
The present invention relates to the method for a kind of organochlorine, refer more particularly to a kind of method of utilizing core-shell type nano Fe/Pd catalyzer to removing chlorine in chlorinated organic pollutant through electrochemistry, belong to the processing technology field of water pollutant for the pollutent dechlorination.
Background technology
Organochlorine is an organic pollutant common in the environment water for thing (as tetracol phenixin etc.).Its improvement method generally can be divided into the physics method, biological process, chemical method (being divided into chemical oxidization method and chemical reduction method).Physics method cost is higher, general just with pollutent from a phase transition to another phase, pollutent is not thoroughly degraded; The research of biodegradation technique is of long duration, but because the existence of chlorine element in the organism biological degradability is reduced greatly, and the corresponding microbial species of occurring in nature also seldom, thereby degradation effect is not good.The maximum zeroth order iron powder reduction method of research exists the accumulation of chloro by product and the existence of surface passivation layer that its reactive behavior is reduced at present.And organochlorine is for the degraded of thing at Fe, and pH has harsh requirement to external world: pH is low excessively, quickens the dissolving of iron; PH is too high, easily makes the Fe passivation.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, and a kind of method of removing chlorine in chlorinated organic pollutant through electrochemistry is provided.
The technical scheme that the present invention takes is:
A kind of method of removing chlorine in chlorinated organic pollutant through electrochemistry may further comprise the steps:
(1) will be with the three-electrode system of core-shell type nano bimetal Fe/Pd catalyzer modified glassy carbon, respectively at H as working electrode
2SO
4Solution, H
2SO
4Solution and CCl
4Mixing solutions in carry out cyclic voltammetry scan, determine hydrogen district scope;
(2) according to determined hydrogen district scope, at H
2SO
4Solution and CCl
4Mixing solutions in, electrolysis certain hour under constant potential.
The method of above-mentioned removing chlorine in chlorinated organic pollutant through electrochemistry, the three-electrode system described in the step (1) is a counter electrode with the Pt sheet, saturated calomel electrode is as reference electrode; Described H
2SO
4The concentration of solution is 0.5mol dm
-3, described H
2SO
4Solution and CCl
4Mixing solutions in H
2SO
4Concentration be 0.5mol dm
-3, CCl
4Concentration be 30mg dm
-3The scanning potential region of described cyclic voltammetry scan is-0.2V～+ 1.0V, sweep velocity is 50mV s
-1, cycle index is 3 circles; Described hydrogen district scope is-0.2V～0.05V.
H described in the step (2)
2SO
4Solution and CCl
4Mixing solutions in H
2SO
4Concentration be 0.5mol dm
-3, CCl
4Concentration be 30mg dm
-3Described electrolysis constant potential is-0.05V～-0.2V, the described potentiostatic deposition time is 15～30min.
Electrolysis constant potential described in the step (2) is preferred-0.2V, and the potentiostatic deposition time is preferably 30min.
The dechlorination efficiency of the method for removing chlorine in chlorinated organic pollutant through electrochemistry of the present invention sees Table 1.
Table 1
| Electrolytic potential/V | Dechlorination efficiency/% | |
| ??1 | Be untreated | |
| ??2 | ??-0.05 | ??52.1 |
| ??3 | ??-0.08 | ??91.3 |
| ??4 | ??-0.1 | ??59.4 |
| ??5 | ??-0.15 | ??39.0 |
| ??6 | ??-0.2 | ??97.4 |
Method of the present invention is compared for the thing dechlorination method with existing organochlorine and is had the following advantages:
(1) this method is based on the suction hydrogen character of Pd, in strongly acidic solution, makes the surface of hydrogen adsorption at Pd under the constant potential, thereby makes organochlorine for thing hydrogenation dechlorination.
(2) this method is utilized the galvanic corrosion between Pd and the Fe, can quicken the absorption of hydrogen on Pd.
(3) this method is applicable under the normal temperature and pressure, and organochlorine is for the quick dechlorination of thing under the strong acidic condition, and dechlorination efficiency height, reductive agent are the active hydrogen of Pd absorption.
Description of drawings
Fig. 1 (a) is the SEM photo of prepared Fe film;
Fig. 1 (b) is the SEM photo that the cubes configuration of prepared Fe film amplifies;
The SEM photo of the core-shell type nano bimetal Fe/Pd catalyzer that Fig. 2 (a) makes for the present invention;
The EDS photo of the core-shell type nano bimetal Fe/Pd catalyzer that Fig. 2 (b) makes for the present invention;
Fig. 3 is that bimetal Fe/Pd film is at 0.5mol dm
-3H
2SO
4, H
2SO
4Solution and CCl
4Mixing solutions (0.5moldm
-3H
2SO
4, 30mg dm
-3CCl
4) in cyclic voltammetry curve.
Embodiment
Embodiment 1
Preparation with core-shell type nano bimetal Fe/Pd catalyzer modified glassy carbon:
Earlier glass-carbon electrode is polished with the 3500# abrasive paper for metallograph, use the aluminum oxide powder polishing paper minute surface of 0.5 μ m again.Before the experiment beginning, glass-carbon electrode is earlier at HNO
3Solution (HNO
3: H
2O volume ratio 1: 1) ultrasonic 5min rinses well with ultrapure water again in.Electrochemistry experiment all carries out in the electrolyzer of traditional three-electrode system: clean glass-carbon electrode is as working electrode, and the Pt sheet is a counter electrode, and saturated calomel electrode is as reference electrode.
With NaCl and FeCl
2Mixing solutions make deposit fluid, wherein the concentration of NaCl is 0.25mol dm
-3, FeCl
2Concentration be 10mmol dm
-3, controlled temperature is 30 ℃, by applying two successive potential pulse: deposit 1s at negative nucleation current potential-1.15V, deposit 1000s at the nucleus growth current potential-1.05V of calibration, a large amount of Fe is deposited on the surface of glass-carbon electrode.By in-1.15V deposition 1s nucleation, then make and nucleus growth can form cubic Fe nanometer aggregate in-1.05V continuous sweep.Its SEM photo as shown in Figure 1.
The glass-carbon electrode that deposits Fe is immersed in 25 μ L 10mmol dm
-3Precious metal ion (H
2PdCl
4) solution in 30min, make Fe part be replaced, thereby prepare with core-shell type nano bimetal Fe/Pd catalyzer modified glassy carbon by Pd.The SEM of core-shell type nano bimetal Fe/Pd catalyzer and EDS photo are respectively as Fig. 2 (a) with (b).
Embodiment 2
The method of removing chlorine in chlorinated organic pollutant through electrochemistry:
The core-shell type nano bimetal Fe/Pd catalyzer modified glassy carbon that will make with embodiment 1 is counter electrode as working electrode with the Pt sheet, and saturated calomel electrode is as the three-electrode system of reference electrode, respectively at 0.5mol dm
-3H
2SO
4Solution, H
2SO
4Solution and CCl
4Mixing solutions (0.5mol dm
-3H
2SO
4, 30mg dm
-3CCl
4) in carry out cyclic voltammetry scan, scanning potential region be-0.2V～+ 1.0V, sweep velocity is 50mV s
-1, cycle index is 3 circles, determines that hydrogen district scope is-0.2V～0.05V; According to determined hydrogen district scope, at 0.5mol dm
-3H
2SO
4Solution, H
2SO
4Solution and CCl
4Mixing solutions (0.5mol dm
-3H
2SO
4, 30mg dm
-3CCl
4), respectively-0.05V ,-0.08V ,-0.1V ,-0.15V ,-0.2V under potentiostatic deposition 30min, electrolysis temperature is 30 ℃.Dechlorination efficiency is as shown in table 1.
Add H by contrast
2SO
4Solution, H
2SO
4Solution and CCl
4Cyclic voltammetry curve in the mixing solutions finds to add CCl
4After, because CCl
4Molecule has occupied the avtive spot of hydrogen adsorption in the absorption of electrode surface, thereby makes and disappearing than the hydrogen adsorption of positive potential and oxidation peak, and reduces than the formation peak and the desorption peaks of the hydrogen of negative potential, as shown in Figure 3.
Claims (4)
1, a kind of method of removing chlorine in chlorinated organic pollutant through electrochemistry is characterized in that, may further comprise the steps:
(1) will be with the three-electrode system of core-shell type nano bimetal Fe/Pd catalyzer modified glassy carbon, respectively at H as working electrode
2SO
4Solution, H
2SO
4Solution and CCl
4Mixing solutions in carry out cyclic voltammetry scan, determine hydrogen district scope;
(2) according to determined hydrogen district scope, at H
2SO
4Solution and CCl
4Mixing solutions in, electrolysis certain hour under constant potential.
According to the method for the described a kind of removing chlorine in chlorinated organic pollutant through electrochemistry of claim 1, it is characterized in that 2, the three-electrode system described in the step (1) is a counter electrode with the Pt sheet, saturated calomel electrode is as reference electrode; Described H
2SO
4The concentration of solution is 0.5mol dm
-3, described H
2SO
4Solution and CCl
4Mixing solutions in H
2SO
4Concentration be 0.5mol dm
-3, CCl
4Concentration be 30mg dm
-3The scanning potential region of described cyclic voltammetry scan is-0.2V～+ 1.0V, sweep velocity is 50mVs
-1, cycle index is 3 circles; Described hydrogen district scope is-0.2V～0.05V.
3, according to the method for the described a kind of removing chlorine in chlorinated organic pollutant through electrochemistry of claim 1, it is characterized in that the H described in the step (2)
2SO
4Solution and CCl
4Mixing solutions in H
2SO
4Concentration be 0.5mol dm
-3, CCl
4Concentration be 30mgdm
-3Described electrolysis constant potential is-0.05V～-0.2V, the described potentiostatic deposition time is 15～30min.
4, according to the method for the described a kind of removing chlorine in chlorinated organic pollutant through electrochemistry of claim 3, it is characterized in that, electrolysis constant potential described in the step (2) is preferred-0.2V, the potentiostatic deposition time is preferably 30min.
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|---|---|---|---|
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|---|---|---|---|
| CN200910018601A CN101648736A (en) | 2009-09-02 | 2009-09-02 | Method for removing chlorine in chlorinated organic pollutant through electrochemistry method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101810921A (en) * | 2010-04-27 | 2010-08-25 | 江苏大学 | Method for electrochemical reduction degradation of dichloro-diphenyl-trichloroethane |
| CN102206786A (en) * | 2011-05-16 | 2011-10-05 | 清华大学 | High-efficiency alloy material for reducing halogenated organics in water and ball-milling preparation method thereof |
| CN103086494A (en) * | 2012-12-30 | 2013-05-08 | 浙江工业大学 | Method for performing catalytic dechlorination treatment on chlorine wastewater by utilizing palladium/iron particles |
| CN104129834A (en) * | 2014-07-16 | 2014-11-05 | 国家电网公司 | Molten salt electrochemical polychlorinated biphenyl treatment method |
| CN104129835A (en) * | 2014-07-16 | 2014-11-05 | 武汉大学 | Method for treating chlorination aromatic hydrocarbon by means of molten salt electrochemistry |
| CN115645814A (en) * | 2022-10-27 | 2023-01-31 | 浙江工业大学 | Ultralow-load palladium nanocrystal modified electrode, preparation method thereof and application thereof in electrochemical dechlorination |
-
2009
- 2009-09-02 CN CN200910018601A patent/CN101648736A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101810921A (en) * | 2010-04-27 | 2010-08-25 | 江苏大学 | Method for electrochemical reduction degradation of dichloro-diphenyl-trichloroethane |
| CN102206786A (en) * | 2011-05-16 | 2011-10-05 | 清华大学 | High-efficiency alloy material for reducing halogenated organics in water and ball-milling preparation method thereof |
| CN103086494A (en) * | 2012-12-30 | 2013-05-08 | 浙江工业大学 | Method for performing catalytic dechlorination treatment on chlorine wastewater by utilizing palladium/iron particles |
| CN103086494B (en) * | 2012-12-30 | 2014-06-04 | 浙江工业大学 | Method for performing catalytic dechlorination treatment on chlorine wastewater by utilizing palladium/iron particles |
| CN104129834A (en) * | 2014-07-16 | 2014-11-05 | 国家电网公司 | Molten salt electrochemical polychlorinated biphenyl treatment method |
| CN104129835A (en) * | 2014-07-16 | 2014-11-05 | 武汉大学 | Method for treating chlorination aromatic hydrocarbon by means of molten salt electrochemistry |
| CN104129835B (en) * | 2014-07-16 | 2015-11-04 | 武汉大学 | A kind of method of molten salt electrochemistry process chlorination aromatic hydrocarbon |
| CN115645814A (en) * | 2022-10-27 | 2023-01-31 | 浙江工业大学 | Ultralow-load palladium nanocrystal modified electrode, preparation method thereof and application thereof in electrochemical dechlorination |
| CN115645814B (en) * | 2022-10-27 | 2024-04-05 | 浙江工业大学 | Ultralow-load palladium nanocrystal modified electrode, preparation method thereof and application thereof in electrochemical dechlorination |
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Open date: 20100217 |