CN109534463A - A kind of preparation method and applications of the amorphous state combination electrode for electro-catalysis dechlorination - Google Patents
A kind of preparation method and applications of the amorphous state combination electrode for electro-catalysis dechlorination Download PDFInfo
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- CN109534463A CN109534463A CN201811408881.5A CN201811408881A CN109534463A CN 109534463 A CN109534463 A CN 109534463A CN 201811408881 A CN201811408881 A CN 201811408881A CN 109534463 A CN109534463 A CN 109534463A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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Abstract
The present invention relates to a kind of preparation method and applications of amorphous state combination electrode for electro-catalysis dechlorination, belong to technical field of electrochemical water treatment, purpose is that electrode catalyst load capacity of the solution for electro-catalysis reduction dechlorination is big, and electrode stability is low, problem at high cost.Preparation method, comprising the following steps: substrate pretreated；In three-electrode electro Chemical system, pretreated matrix is as working electrode, NaSO4For electrolyte, precious metal salt and the base metal salt containing N, B or P is reaction solution, and under ultrasonic wave auxiliary, galvanostatic conditions prepare amorphous state noble metal combination electrode.The method that electro-catalysis reduction dechlorination handles chlorinatedorganic in water: using above-mentioned amorphous state combination electrode as working electrode, Pt piece is used as to electrode, and saturated calomel electrode is reference electrode, and in constant voltage mode, anodolyte uses H2SO4Solution, catholyte use NaSO4.Present invention preparation amorphous state combination electrode is conductive good, and catalytic activity is high, and at low cost, stability is good.
Description
Technical field
The invention belongs to technical field of electrochemical water treatment, and in particular to a kind of amorphous state for electro-catalysis dechlorination is compound
The preparation method and applications of electrode.
Background technique
The chlorinatedorganic overwhelming majority is all toxic, and stable structure, long half time, is difficult to drop in the natural environment
Solution, detoxification and the committed step for destroying decomposition are dechlorinations.Electro-catalysis reduction dechlorination is a kind of cleaner efficient processing method.
For the electrode of electro-catalysis reduction dechlorination, mainly by crystalline state precious metals pd load with different matrix on, as Pd/ activated carbon electrodes,
Pd/Ti electrode, Pd/ polypyrrole/Ni electrode etc., but there are the big (2mg/cm of catalyst loadings2,Electrochemical
Society, 150 (2) D17-D24 (2003), Electrochimica Acta 69 (2012) 389-396), electrode stability
Low, at high cost problem, it is difficult to widely be promoted.Therefore, the electrode of research and development high catalytic activity and stability is needed at present.
Summary of the invention
Big for the existing electrode catalyst load capacity for electro-catalysis reduction dechlorination, electrode stability is low, at high cost,
Be difficult to the problem of being widely applied, the present invention provide a kind of amorphous state combination electrode for electro-catalysis dechlorination preparation method and
Method for handling chlorinatedorganic in water, conductive good using this method preparation amorphous state combination electrode, catalysis is lived
Property high, at low cost, the good advantage of stability.
In order to achieve the above objectives, the invention adopts the following technical scheme:
One aspect of the present invention provides a kind of preparation method of amorphous state combination electrode for electro-catalysis dechlorination, including following
Step:
(1) substrate pretreated: metal electrode substrate surface is cleaned, is purified；
(2) preparation of amorphous state combination electrode: in three-electrode electro Chemical system, Pt is saturated calomel as working electrode
Electrode is as reference electrode, and step (1) pretreated matrix is as working electrode, NaSO4For electrolyte, precious metal salt and containing N,
The base metal salt of B or P is reaction solution, and under ultrasonic wave auxiliary, galvanostatic conditions prepare amorphous state noble metal compound electric
Pole.
Further, step (1) the metal electrode substrate is nickel foam, titanium net or copper mesh.
Further, step (1) described matrix is pretreated method particularly includes: under ultrasonic oscillation, first uses salt acidleach
Ultrasonic vibration cleaning is steeped, then is cleaned by ultrasonic with dehydrated alcohol, is finally dried for standby.
Further, the concentration of hydrochloric acid is 0.5mol/L.
Further, step (2) precious metal salt is AgCl2、RuCl2、PdCl2。
Further, the base metal salt containing N, B or P described in step (2) is pyrroles, boric acid or sodium thiosulfate.
Further, the concentration of step (2) described precious metal salt is 1~3mmol L-1, the concentration of base metal salt is
0.05~0.2mol L-1, NaSO4Electrolyte concentration is 0.05~0.1mol L-1。
Further, the density of step (2) described constant current is 0.1~0.3mA/cm2。
The present invention also provides the methods of chlorinatedorganic in a kind of electro-catalysis reduction dechlorination processing water, include the following steps:
Using amorphous state combination electrode obtained above as working electrode, Pt piece is used as to electrode, and saturated calomel electrode is reference electrode,
In H-type reactor, electroreduction dechlorination handles Polychlorinated organic under constant voltage mode, and anodolyte uses H2SO4Solution,
Catholyte uses NaSO4。
Further, noble-metal-supported amount is 0.05~0.1mg/cm on the working electrode2。
Further, the anodolyte H2SO4Concentration is 0.1~0.3mol/L；The catholyte NaSO4It is dense
Degree is 0.05~0.1mol/L；The constant voltage range is -0.8~-1.2V.
With crystalline phases ratio, the structure of the longrange disorder shortrange order of amorphous state itself, surface defect is more, it is easier to which exposure is high
The active site of density, catalytic activity are better than traditional catalyst, have many reports in the field of chemical synthesis, and electroreduction dechlorination
Field does not have been reported that.The present invention use electrochemical process, the disastrously miscellaneous base metal B in carried noble metal on net metal matrix, P or
S etc. obtains amorphous state composite noble metal catalyst, and amorphous state combination electrode obtained handles water in electro-catalysis as working electrode
When middle Polychlorinated organic, catalytic activity and stability with higher.
Detailed description of the invention
Fig. 1 is the preparation facilities schematic diagram of 1 amorphous state combination electrode of embodiment；1, anode chamber in figure；2, cathode chamber；3, right
Electrode Pt；4, working electrode；5, cation-exchange membrane；6, potentiostat；7, magnetic rotor.
Fig. 2 is that the SEM of 1 Amorphous Ru-N/ foam nickel electrode of embodiment schemes；
Fig. 3 is embodiment 1EDX constituent analysis figure, and Ru load capacity is 0.063mg/cm2；
Fig. 4 is 1 selective electron diffraction figure (SADE) of embodiment；
Fig. 5 is that 1 Amorphous Ru-N/ foam nickel electrode of embodiment, crystalline state Ru/ foam nickel electrode access times and PCP degrade
Rate relational graph；
Fig. 6 is that the SEM of 2 amorphous state Pd-B/ foam nickel electrode of embodiment schemes；
Fig. 7 is embodiment 2EDX constituent analysis figure；
Fig. 8 is the X-ray diffractogram of 2 amorphous state Pd-B/ foam nickel electrode of embodiment；
Fig. 9 is 2 selective electron diffraction figure (SADE) of embodiment
Figure 10 is 2 amorphous state combination electrode B content of embodiment and PCP degradation rate relational graph；
Figure 11 is 2 amorphous state combination electrode access times of embodiment and PCP degradation rate relational graph.
Specific embodiment
Combined with specific embodiments below and attached drawing is described in further details the present invention.
Embodiment 1
One, the preparation of amorphous state combination electrode
Foam Ni (20mm × 25mm) is put into ultrasonic vibration 5min in the hydrochloric acid of 0.5mol/L and removes impurity, distilled water flushing
Be put into ultrasound 10min in dehydrated alcohol after clean, after flushing with distilled water it is 3 times ultrasonic after dry.Weigh the RuCl of 0.20g3Powder
Constant volume is made into 500ml volumetric flask containing N-RuCl after completely dissolution with 10mL pyrroles at end3Mixed electrolytic solution solution.Pretreated bubble
Foam Ni electrode is cathode, and platinized platinum is anode, N-RuCl3Solution is electrolyte, current density 0.2mA/cm2, electro-deposition 40min,
Then Amorphous Ru-N/ foam nickel electrode is made in electrochemical deposition.As shown in Figure 1, the preparation facilities of amorphous state combination electrode is illustrated
Figure.
Fig. 2 is that the SEM of Amorphous Ru-N/ foam nickel electrode schemes；Fig. 3 is EDX constituent analysis figure, and Ru load capacity is
0.063mg/cm2；Fig. 4 is selective electron diffraction figure (SADE).
Two, electro-catalysis reduction dechlorination
Using Amorphous Ru-N/ nickel foam obtained above as working electrode, platinized platinum is used as to electrode, saturated calomel electrode
As reference electrode, yin, yang pole room is separated with cation-exchange membrane, and anodolyte uses 0.1mol/L H2SO4Solution, cathode
Add 0.05mol/L NaSO4, lead to the waste water that constant voltage -1.2V electroreduction dechlorination processing contains pentachlorophenol (PCP), concentration for the treatment of is
50mg/L, 80mL, processing time are 2h.
Using the identical crystalline state Ru/ foam nickel electrode of catalyst loadings as working electrode, it is de- to carry out above-mentioned electro-catalysis reduction
The performance of Amorphous Ru-N/ nickel foam and crystalline state Ru/ foam nickel electrode in dechlorination processing is compared in chlorine operation.
As shown in figure 5, compared with crystalline state Ru/ foam nickel electrode, Amorphous Ru-N/ foam nickel electrode catalytic activity and stabilization
Property significantly improves.The degradation rate of PCP is respectively 83.3% He in crystalline state Ru/ nickel foam and Amorphous Ru-N/ foam nickel electrode
94.3%.From the point of view of electrode reuse, PCP removal rate is significantly reduced on crystalline state Ru/ foam nickel electrode, and amorphous state Ru-N/
Nickel foam can be used as working electrode Reusability, when using the 8th time, the removal rate of waste water pentachlorophenol still reach 90% with
On, it was demonstrated that electrode catalyst activity is high, and stability is good.
Embodiment 2
One, the preparation of amorphous state combination electrode
Nickel foam (20mm × 25mm) is sequentially placed into the sulfuric acid and sodium hydroxide solution of 0.5mol/L and impregnates ultrasound shake
5min removal impurity is swung, ultrasound 10min in dehydrated alcohol is put into after distilled water flushing is clean, with distilled water ultrasound 3 times after flushing
After dry.Weigh 0.1gPdCl2Powder is soluble in water, and a small amount of hydrochloric acid, which is added, makes PdCl2It is completely dissolved, it is anhydrous to add 3.551g
Sodium sulphate and 2-5g boric acid, constant volume to 500ml is made into the different mixed solution of boron content after completely dissolution.By pretreated foam
For nickel as cathode, platinized platinum is anode, PdCl2B solution is electrolyte, current density 0.2mA/cm2, electro-deposition 40min is then electric
Pd-B/ nickel foam amorphous state combination electrode is made in chemical deposition.
Fig. 6 is that the SEM of amorphous state Pd-B/ foam nickel electrode schemes；Fig. 7 is EDX constituent analysis figure, and Pd load capacity is
0.15mg/cm2；Fig. 8 is the X-ray diffractogram of amorphous state Pd-B/ foam nickel electrode.Fig. 9 is selective electron diffraction figure (SADE).
Two, electro-catalysis reduction dechlorination
Using amorphous state Pd-B/ nickel foam obtained above as working electrode, platinized platinum is used as to electrode, saturated calomel electrode
As reference electrode, yin, yang pole room is separated with cation-exchange membrane, and anodolyte uses 0.1mol/L H2SO4Solution, cathode
Add 0.05mol/LNaSO4With, lead to constant voltage -1.2V electroreduction handle the waste water containing PCP, PCP concentration be 50mg/L.
As shown in Figure 10, under the premise for the treatment of capacity is certain, amorphous state Pd-B/ nickel foam has preferable catalytic activity,
The B content (mass percent in Pd-B) loaded on electrode has an impact to the removal rate of PCP, and B content is in the range of 0-30%
When, B content increases, and PCP removal rate improves, and B content is more than the removal rate reduction of PCP after 30%, model of the B content in 20-30%
In enclosing, PCP removal rate reaches 90% or more.
As shown in figure 11, amorphous state Pd-B/ nickel foam can be used as working electrode Reusability, it was demonstrated that the stabilization of the electrode
Property is good.
Embodiment described above is only that preferred embodiments of the present invention will be described, not to the scope of the present invention
It is defined, without departing from the spirit of the design of the present invention, those of ordinary skill in the art are to technical solution of the present invention
The various changes and improvements made should all be fallen into the protection scope that claims of the present invention determines.
Claims (10)
1. a kind of preparation method of the amorphous state combination electrode for electro-catalysis dechlorination, which comprises the following steps:
(1) substrate pretreated: metal electrode substrate surface is cleaned, is purified；
(2) preparation of amorphous state combination electrode: in three-electrode electro Chemical system, Pt is as working electrode, saturated calomel electrode
As reference electrode, step (1) pretreated matrix is as working electrode, NaSO4For electrolyte, precious metal salt and containing N, B or
The base metal salt of person P is reaction solution, and under ultrasonic wave auxiliary, galvanostatic conditions prepare amorphous state noble metal combination electrode.
2. preparation method according to claim 1, which is characterized in that step (1) the metal electrode substrate be nickel foam,
Titanium net or copper mesh.
3. preparation method according to claim 1, which is characterized in that the pretreated specific method of step (1) described matrix
Are as follows: under ultrasonic oscillation, is first cleaned with salt acid soak ultrasonic vibration, then be cleaned by ultrasonic with dehydrated alcohol, be finally dried for standby.
4. preparation method according to claim 1, which is characterized in that step (2) precious metal salt is AgCl2、RuCl2、
PdCl2。
5. preparation method according to claim 1, which is characterized in that the base metal containing N, B or P described in step (2)
Salt is pyrroles, boric acid or sodium thiosulfate.
6. preparation method according to claim 1, which is characterized in that the concentration of step (2) described precious metal salt be 1~
3mmol L-1, the concentration of base metal salt is 0.05~0.2mol L-1, NaSO4Electrolyte concentration is 0.05~0.1mol L-1。
7. preparation method according to claim 1, which is characterized in that the density of step (2) described constant current be 0.1~
0.3mA/cm2。
8. a kind of method of chlorinatedorganic in electro-catalysis reduction dechlorination processing water, which comprises the steps of: with power
Benefit require 1 made from amorphous state combination electrode be working electrode, Pt piece be used as to electrode, saturated calomel electrode is reference electrode,
In H-type reactor, electroreduction dechlorination handles Polychlorinated organic under constant voltage mode, and anodolyte uses H2SO4 is molten
Liquid, catholyte use Na2SO4。
9. the method for chlorinatedorganic in dechlorination treatment water according to claim 8, which is characterized in that the working electrode
Upper noble-metal-supported amount is 0.05~0.1mg/cm2。
10. the method for chlorinatedorganic in dechlorination treatment water according to claim 8, which is characterized in that the anode electricity
Solve matter H2SO4Concentration is 0.1~0.3mol/L；The catholyte NaSO4Concentration is 0.05~0.1mol/L；The permanent electricity
Pressure range is -0.8~-1.2V.
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| CN117282431A (en) * | 2023-09-22 | 2023-12-26 | 上海园林绿化建设有限公司 | Amorphous Co-Ni-Fe hydrodechlorination catalyst and preparation method and application thereof |
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