CN109534463B - Preparation method and application of amorphous composite electrode for electro-catalytic dechlorination - Google Patents

Preparation method and application of amorphous composite electrode for electro-catalytic dechlorination Download PDF

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CN109534463B
CN109534463B CN201811408881.5A CN201811408881A CN109534463B CN 109534463 B CN109534463 B CN 109534463B CN 201811408881 A CN201811408881 A CN 201811408881A CN 109534463 B CN109534463 B CN 109534463B
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electrode
dechlorination
noble metal
amorphous
amorphous composite
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CN109534463A (en
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崔春月
王婧
郑庆柱
辛言君
马东
张雪
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Qingdao Agricultural University
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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
    • 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 invention relates to a preparation method and application of an amorphous composite electrode for electrocatalytic dechlorination, belonging to the electrochemical water treatment technologyThe method aims to solve the problems of large loading capacity of an electrode catalyst for electro-catalytic reduction dechlorination, low stability of an electrode and high cost. The preparation method comprises the following steps: pretreating a substrate; in a three-electrode electrochemical system, the pretreated substrate is used as a working electrode, NaSO4The amorphous noble metal composite electrode is prepared by taking noble metal salt and non-noble metal salt containing N, B or P as reaction liquid under the constant current condition under the assistance of ultrasonic waves. The method for treating chlorinated organic matters in water by electrocatalysis reduction dechlorination comprises the following steps: taking the amorphous composite electrode as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode, and adopting H as an anode electrolyte in a constant voltage mode2SO4The solution and the cathode electrolyte adopt NaSO4. The amorphous composite electrode prepared by the invention has the advantages of good conductivity, high catalytic activity, low cost and good stability.

Description

Preparation method and application of amorphous composite electrode for electro-catalytic dechlorination
Technical Field
The invention belongs to the technical field of electrochemical water treatment, and particularly relates to a preparation method and application of an amorphous composite electrode for electrocatalytic dechlorination.
Background
Most chlorinated organic compounds are toxic, stable in structure, long in half-life period and difficult to degrade in natural environment, and dechlorination is a key step for detoxification and destruction and decomposition. The electrocatalysis reduction dechlorination is a cleaner and more efficient treatment method. The electrode for electro-catalytic reduction dechlorination is mainly characterized in that crystalline noble metal Pd is loaded on different matrixes, such as Pd/activated carbon electrode, Pd/Ti electrode, Pd/polypyrrole/Ni electrode and the like, but the loading amount of the catalyst is large (2 mg/cm)2Electrochemical Society,150(2) D17-D24(2003), Electrochimica Acta 69(2012) 389-396), low stability of the electrode, high cost, and difficult to be widely popularized. Therefore, there is a need to develop an electrode having high catalytic activity and stability.
Disclosure of Invention
Aiming at the problems of large loading capacity, low electrode stability, high cost and difficult wide application of the existing electrode catalyst for electrocatalytic reduction dechlorination, the invention provides a preparation method of an amorphous composite electrode for electrocatalytic dechlorination and a method for treating chlorinated organic compounds in water.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of an amorphous composite electrode for electrocatalytic dechlorination, which comprises the following steps:
(1) matrix pretreatment: cleaning and purifying the surface of the metal electrode substrate;
(2) preparing an amorphous composite electrode: in a three-electrode electrochemical system, Pt is used as a working electrode, a saturated calomel electrode is used as a reference electrode, the substrate pretreated in the step (1) is used as the working electrode, and NaSO4The amorphous noble metal composite electrode is prepared by taking noble metal salt and non-noble metal salt containing N, B or P as reaction liquid under the constant current condition under the assistance of ultrasonic waves.
Further, the metal electrode substrate in the step (1) is a foamed nickel, titanium mesh or copper mesh.
Further, the specific method for pretreating the substrate in the step (1) comprises the following steps: under the ultrasonic oscillation, soaking the mixture by hydrochloric acid, carrying out ultrasonic oscillation cleaning, then carrying out ultrasonic cleaning by absolute ethyl alcohol, and finally drying the mixture for later use.
Further, the concentration of the hydrochloric acid is 0.5 mol/L.
Further, the noble metal salt in the step (2) is AgCl2、RuCl2、PdCl2。
Further, the non-noble metal salt containing N, B or P in the step (2) is pyrrole, boric acid or sodium thiosulfate.
Further, the concentration of the noble metal salt in the step (2) is 1-3 mmol L-1The concentration of non-noble metal salt is 0.05～0.2mol L-1，NaSO4The electrolyte concentration is 0.05-0.1 mol L-1。
Further, the density of the constant current in the step (2) is 0.1-0.3 mA/cm2。
The invention also provides a method for treating chlorinated organic compounds in water through electrocatalytic reduction and dechlorination, which comprises the following steps: taking the prepared amorphous composite electrode as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode, carrying out electro-reduction dechlorination on polychlorinated organic matters in an H-shaped reactor in a constant voltage mode, and adopting H as an anode electrolyte2SO4The solution and the cathode electrolyte adopt NaSO4。
Furthermore, the loading amount of the noble metal on the working electrode is 0.05-0.1 mg/cm2。
Further, the anolyte H2SO4The concentration is 0.1-0.3 mol/L; the cathode electrolyte NaSO4The concentration is 0.05-0.1 mol/L; the constant voltage range is-0.8 to-1.2V.
Compared with the crystalline state, the long-range disorder short-range ordered structure of the amorphous state has more surface defects, is easier to expose high-density active sites, has catalytic activity superior to that of the traditional catalyst, and has a lot of reports in the field of chemical synthesis, but has no report in the field of electro-reduction dechlorination. The invention adopts an electrochemical method, when the reticular metal matrix is loaded with noble metal, non-noble metals B, P or S and the like are doped to obtain the amorphous composite noble metal catalyst, and the prepared amorphous composite electrode has higher catalytic activity and stability when being used as a working electrode for electro-catalytically treating polychlorinated organic matters in water.
Drawings
FIG. 1 is a schematic view of an apparatus for preparing an amorphous composite electrode according to example 1; in figure 1, an anode chamber; 2. a cathode chamber; 3. a counter electrode Pt; 4. a working electrode; 5. a cation exchange membrane; 6. a potentiostat; 7. a magnetic rotor.
FIG. 2 is an SEM image of an amorphous Ru-N/nickel foam electrode of example 1;
FIG. 3 is the EDX composition analysis chart of example 1, with Ru loading of 0.063mg/cm2；
FIG. 4 is a selected area electron diffraction pattern (SADE) of example 1;
FIG. 5 is a graph showing the relationship between the number of times of use of the amorphous Ru-N/nickel foam electrode and the number of times of use of the crystalline Ru/nickel foam electrode and the degradation rate of PCP in example 1;
FIG. 6 is an SEM image of an amorphous Pd-B/nickel foam electrode of example 2;
FIG. 7 is the EDX composition analysis chart of example 2;
FIG. 8 is an X-ray diffraction pattern of the amorphous Pd-B/nickel foam electrode of example 2;
FIG. 9 is the selected area electron diffraction pattern (SADE) of example 2
FIG. 10 is a graph showing the relationship between the content of amorphous composite electrode B and the degradation rate of PCP in example 2;
FIG. 11 is a graph showing the relationship between the number of times the amorphous composite electrode is used and the degradation rate of PCP in example 2.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments and the accompanying drawings.
Example 1
Preparation of amorphous composite electrode
Putting foamed Ni (20mm multiplied by 25mm) into 0.5mol/L hydrochloric acid, ultrasonically vibrating for 5min to remove impurities, washing with distilled water, ultrasonically vibrating in absolute ethyl alcohol for 10min, ultrasonically vibrating with distilled water for 3 times, and drying. 0.20g of RuCl was weighed3The powder and 10mL of pyrrole are fully dissolved and then the volume is determined to be 500mL, and the volumetric flask is prepared to contain N-RuCl3The electrolyte solution is mixed. The pretreated foam Ni electrode is used as a cathode, a platinum sheet is used as an anode, and N-RuCl3The solution is electrolyte, and the current density is 0.2mA/cm2And performing electro-deposition for 40min to obtain the amorphous Ru-N/foamed nickel electrode by electro-chemical deposition. As shown in fig. 1, the device for preparing the amorphous composite electrode is schematically illustrated.
FIG. 2 is an SEM image of an amorphous Ru-N/nickel foam electrode; FIG. 3 is an EDX composition analysis chart showing that the Ru loading is 0.063mg/cm2(ii) a FIG. 4 is a selected area electron diffraction pattern (SADE).
Secondly, dechlorination by electrocatalysis reduction
The amorphous Ru-N/foamed nickel prepared by the method is used asWorking electrode, platinum sheet as counter electrode, saturated calomel electrode as reference electrode, cathode and anode chambers separated by cation exchange membrane, and anode electrolyte of 0.1mol/L H2SO4Adding 0.05mol/L NaSO into the solution at the cathode4And carrying out electro-reduction dechlorination on wastewater containing pentachlorophenol (PCP) by constant voltage of-1.2V, wherein the treatment concentration is 50mg/L and 80mL, and the treatment time is 2 h.
The electrocatalytic reduction dechlorination operation is carried out by taking the crystalline Ru/foamed nickel electrode with the same catalyst loading capacity as a working electrode, and the performances of the amorphous Ru-N/foamed nickel electrode and the crystalline Ru/foamed nickel electrode in dechlorination treatment are compared.
As shown in FIG. 5, the catalytic activity and stability of the amorphous Ru-N/nickel foam electrode are significantly improved compared to the crystalline Ru/nickel foam electrode. The degradation rates of PCP on crystalline Ru/nickel foam and amorphous Ru-N/nickel foam electrodes were 83.3% and 94.3%, respectively. From the view of electrode repeated use, the removal rate of PCP on the crystalline Ru/foam nickel electrode is obviously reduced, while the amorphous Ru-N/foam nickel can be used as a working electrode repeatedly, and when the electrode is used for the 8 th time, the removal rate of the pentachlorophenol in the wastewater still reaches over 90 percent, so that the electrode is proved to have high catalytic activity and good stability.
Example 2
Preparation of amorphous composite electrode
Sequentially putting foamed nickel (20mm multiplied by 25mm) into 0.5mol/L sulfuric acid and sodium hydroxide solution for soaking and ultrasonic oscillation for 5min to remove impurities, washing the foamed nickel with distilled water, putting the foamed nickel into absolute ethyl alcohol for ultrasonic oscillation for 10min, washing the foamed nickel with distilled water for 3 times, and drying the foamed nickel. Weighing 0.1g of PdCl2Dissolving the powder in water, adding a small amount of hydrochloric acid to make PdCl2And (3) completely dissolving, then adding 3.551g of anhydrous sodium sulfate and 2-5g of boric acid, fully dissolving, and metering to 500ml to prepare mixed solutions with different boron contents. Taking pretreated foamed nickel as a cathode, a platinum sheet as an anode and PdCl2The solution B is electrolyte with current density of 0.2mA/cm2And performing electro-deposition for 40min to obtain the Pd-B/foamed nickel amorphous composite electrode by electro-chemical deposition.
FIG. 6 is an SEM image of an amorphous Pd-B/nickel foam electrode; FIG. 7 is an EDX composition analysis chart showing a Pd loading amount of 0.15mg/cm2(ii) a FIG. 8 is an X-ray diffraction pattern of an amorphous Pd-B/nickel foam electrode. FIG. 9 is a selected area electron diffraction pattern (SADE).
Secondly, dechlorination by electrocatalysis reduction
The amorphous Pd-B/foamed nickel prepared by the method is used as a working electrode, a platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a cathode chamber and an anode chamber are separated by a cation exchange membrane, and an anode electrolyte adopts 0.1mol/L H2SO4Adding 0.05mol/LNaSO into the solution and the cathode4And carrying out electro-reduction treatment on the wastewater containing the PCP by constant voltage of-1.2V, wherein the concentration of the PCP is 50 mg/L.
As shown in fig. 10, under the premise of a certain treatment capacity, the amorphous Pd-B/nickel foam has a good catalytic activity, the content of B (mass percentage in Pd-B) loaded on the electrode has an effect on the removal rate of PCP, when the content of B is in the range of 0-30%, the content of B increases, the removal rate of PCP increases, when the content of B exceeds 30%, the removal rate of PCP decreases, when the content of B is in the range of 20-30%, the removal rate of PCP reaches above 90%.
As shown in fig. 11, the amorphous Pd-B/nickel foam can be used repeatedly as a working electrode, which proves its good stability.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.

Claims (6)

1. The preparation method of the amorphous composite electrode for electrocatalytic dechlorination is characterized by comprising the following steps of:
(1) matrix pretreatment: cleaning and purifying the surface of the metal electrode substrate;
(2) preparing an amorphous composite electrode: in a three-electrode electrochemical system, Pt is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the substrate pretreated in the step (1) is used as a working electrode, and NaSO4Is electrolyte, noble metal salt PdCl2And pyridinePyrrole is a reaction liquid or a noble metal salt PdCl2And boric acid as reaction solution, the NaSO4The electrolyte concentration is 0.05-0.1 mol L-1The concentration of the noble metal salt is 1-3 mmol L-1The concentration of the pyrrole and the boric acid is 0.05-0.2 mol L-1Under the assistance of ultrasonic wave, the density of constant current is 0.1-0.3 mA/cm2Preparing the amorphous noble metal composite electrode.
2. The method according to claim 1, wherein the metal electrode substrate in step (1) is a foamed nickel, titanium mesh or copper mesh.
3. The preparation method according to claim 1, wherein the specific method for pretreating the substrate in the step (1) is as follows: under the ultrasonic oscillation, soaking the mixture by hydrochloric acid, carrying out ultrasonic oscillation cleaning, then carrying out ultrasonic cleaning by absolute ethyl alcohol, and finally drying the mixture for later use.
4. A method for treating chlorinated organic matters in water through electrocatalytic reduction and dechlorination is characterized by comprising the following steps: taking the amorphous composite electrode prepared in claim 1 as a working electrode, a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode, carrying out electro-reduction dechlorination on polychlorinated organic matters in an H-shaped reactor in a constant voltage mode, and adopting H as an anode electrolyte2SO4 solution, and Na as cathode electrolyte2SO4。
5. The method of dechlorination of chlorinated organic compounds in water according to claim 4, wherein the loading amount of noble metal on the working electrode is 0.05-0.1 mg/cm2。
6. The method of dechlorination of chlorinated organics in water of claim 5, wherein the anolyte H is2SO4The concentration is 0.1-0.3 mol/L; the cathode electrolyte NaSO4The concentration is 0.05-0.1 mol/L; the constant voltage range is-0.8 to-1.2V.
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