CN113562819A - DSA electrode and manufacturing method thereof - Google Patents
DSA electrode and manufacturing method thereof Download PDFInfo
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- CN113562819A CN113562819A CN202110863903.2A CN202110863903A CN113562819A CN 113562819 A CN113562819 A CN 113562819A CN 202110863903 A CN202110863903 A CN 202110863903A CN 113562819 A CN113562819 A CN 113562819A
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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
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
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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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
Abstract
The invention relates to a DSA electrode and a manufacturing method thereof, the DSA electrode comprises a metal matrix and a surface active layer coating coated on the surface of the metal matrix, and the material of the surface active layer coating is SiO2·Ta2O5. The manufacturing method specifically comprises the following steps: (a) treating the substrate: pretreating a metal raw material to obtain a metal matrix with a uniform and flat surface and a pitted surface; (b) preparation of surface active layer coating: and uniformly coating an organic solution containing Si element and Ta element on the surface of the metal matrix, drying, calcining, repeating coating, drying and calcining for several times, and forming a surface active layer coating which is tightly combined with the metal matrix on the surface of the metal matrix to obtain the DSA electrode. Compared with the prior art, the invention can prolong the service life of the DSA electrode, increase the surface cracks of the electrode, increase the surface area, improve the activity and improve the use efficiency after the DSA electrode has the surface active layer.
Description
Technical Field
The invention relates to the technical field of electrolysis, in particular to a DSA electrode and a manufacturing method thereof.
Background
The electric flocculation treatment technology is a green process and has unique advantages in the aspect of water treatment. The core of the electric flocculation technology is the preparation of electrodes. In consideration of the fact that noble metals generally have good catalytic activity, high stability, good conductivity, strong corrosion resistance and the like, noble metals are generally selected to manufacture electrodes required by the electroflocculation technology.
Titanium-based coated electrodes are a main form of metal oxide electrodes, and the application of catalytic coatings on the surface of a titanium metal substrate has become a huge industrial system, and the electrodes are generally called DSA electrodes. The DSA electrode not only overcomes the defects of the traditional graphite electrode, platinum electrode, lead-based alloy electrode, lead dioxide electrode and the like, but also can design the composition and structure of the electrocatalytic material according to the requirements of electrode reaction, effectively induces or controls surface side reactions, develops to the present, and is widely applied to the fields of sewage treatment, cathode protection, organic synthesis, metallurgy and the like. However, when the DSA electrode is applied to electrochemical water treatment, the electrode plate is greatly corroded in the treatment process, the service life is short, the electrode plate needs to be replaced frequently, and the operation cost is high.
Patent CN102560561A discloses a DSA electrode and a manufacturing method thereof. The DSA electrode consists of a metal matrix, a middle protective layer and a surface active coating; the metal matrix is selected from one of metal Ti, metal Ta or a metal composite material with a Ta-coated surface; the middle protective layer is composed of a multi-component compound composed of platinum group metal oxide and other metal oxide; the surface active coating consists of IrO2·Ta2O5And (4) forming. The manufacturing method of the DSA electrode comprises the steps of processing a matrix, preparing an intermediate protective layer and preparing a surface active coating. The invention only improves the problems of anode passivation and coating shedding of the DSA electrode in the using process, and can not improve the electrochemical performance of the electrode, but improves the oxygen evolution potential of the DSA electrode, and improves the electrocatalytic activity and performance.
Patent CN103147093A provides a method for preparing a long-life DSA electrode, which uses metal titanium or titanium alloy as a substrate, and carries out certain surface treatment to the substrate, and the substrate is used as a cathode and contains Sn4+、Sb3+The solution is electroplated for a certain time at constant current to obtain a compact electroplating intermediate layer, and finally, an active layer is uniformly coated on the surface of the compact electroplating intermediate layer. The surface active layer may be SnO2、PbO2、RuO2、IrO2、Sb2O5、Ta2O5、Cr2O3And one or more of the metal oxides. The surface active layer can be produced by a dipping method, a sol-gel method, a spraying method, an electrodeposition method, a vapor deposition method, a sputtering method, or the like. The intermediate protective layer in CN103147093A is prepared by electrodeposition, which is complicated in process and difficult to prepare electrode with large area, and the voltage and current are adjusted during electrodeposition and the deposition time is controlled. When the generation speed of crystal nucleus and the growth speed of crystal grain are controlled by adjusting voltage and current, if the growth speed of crystal grain is greater than the generation speed of crystal nucleus, the crystal grain grows and becomes coarse, so that the electrocatalytic activity of the electrode is reduced; on the other hand, if the electrodeposition time is too short, the plating layer is too thin, and the purpose of improving the electrode life is not achieved. Moreover, the patent only changes the service life of the electrode and does not have the efficacy of improving the performance of the electrode. The invention adopts simple process equipment, and improves the electrocatalytic activity of the DSA electrode in application.
Disclosure of Invention
The invention aims to provide a DSA electrode and a manufacturing method thereof.
The purpose of the invention is realized by the following technical scheme:
the DSA electrode comprises a metal matrix and a surface active layer coating coated on the surface of the metal matrix, wherein the material of the surface active layer coating is SiO2·Ta2O5。
The metal matrix is made of Ti.
The surface active layer is composed of a multi-component compound composed of platinum group metal oxides and other metal compounds.
A manufacturing method of the DSA electrode specifically comprises the following steps:
(a) treatment of the metal substrate: pretreating a metal raw material to obtain a metal matrix with a uniform and flat surface and a pitted surface;
(b) preparation of surface active layer coating: and (b) uniformly coating an organic solution containing Si and Ta on the surface of the metal matrix obtained in the step (a), drying, calcining, repeating coating, drying and calcining for several times, and forming a surface active layer coating tightly combined with the metal matrix on the surface of the metal matrix to obtain the DSA electrode.
In the step (a), the pretreatment process specifically comprises: the metal raw material is sequentially subjected to polishing to remove an oxidation film, alkali washing to remove oil, acid washing and water washing.
In the step (a), the alkali washing process specifically comprises the following steps: and (3) putting the metal substrate polished to be silvery white and metallic luster into NaOH with the mass percentage of 5-20%, and carrying out ultrasonic cleaning for 50-70 min.
Preferably, the alkali washing process specifically comprises the following steps: and (3) putting the metal matrix polished to be silvery white and metallic luster into NaOH with the mass percentage of 10%, and ultrasonically cleaning for 60 min.
In the step (a), the acid washing process specifically comprises the following steps: and putting the metal matrix into 10 mass percent oxalic acid solution, and soaking and boiling for 90-110 min at a constant temperature of 85-95 ℃. The pickling function is as follows: the DSA electrode matrix is etched through the low-concentration oxalic acid, so that the surface of the matrix presents a uniform and flat crack structure, and the surface area of the matrix is increased.
Preferably, the pickling process specifically comprises: and putting the metal matrix into oxalic acid solution with the mass percentage of 10%, and soaking and boiling the metal matrix at the constant temperature of 90 ℃ for 100 min.
In the step (a), the water washing process specifically comprises the following steps: taking the pickled metal substrate out of the oxalic acid solution, repeatedly washing the metal substrate with water until the pH of the washing water is 7-8, and then putting the metal substrate into the solution (CH)2OH)2And (4) storing.
In step (b), taking C in proportion8H20O4Si and TaCl5Dissolved in an organic solvent to prepare an organic solution containing an element Si and an element Ta.
In the step (b), the organic solvent consists of C with the volume ratio of 1:13H8O and C2H5And OH is mixed.
In the step (b), in the organic solution containing the Si element and the Ta element, the molar ratio of Si to Ta is 1:1, and the concentration of total ions is 0.2 mol/L.
In the step (b), the coating weight of each coating is 60-200 mL/m2。
In the step (b), the drying process specifically comprises: and (3) drying the coated metal matrix in a 75-85 ℃ drying oven for 5-15 min to volatilize the liquid on the surface of the metal matrix.
Preferably, the drying process specifically comprises: and (3) drying the coated metal matrix in an oven at 80 ℃ for 5-15 min to volatilize the liquid on the surface of the metal matrix.
In the step (b), the calcination process specifically comprises: and (3) placing the dried metal matrix into a muffle furnace, slowly heating to 400-500 ℃, and calcining for 6.5-9.5 min at 400-500 ℃.
Preferably, the calcination process specifically comprises: the dried metal matrix was placed in a muffle furnace and slowly heated to 450 ℃ and then calcined at 450 ℃ for 8 min.
In the step (b), the total times of coating, drying and calcining is 11-15 times, and after the final drying is finished, the coating, drying and calcining are heated in a muffle furnace for high-temperature tempering for 0.8-1.2 h.
Preferably, the total times of coating, drying and calcining is 11-15 times, and the coating, drying and calcining are heated in a muffle furnace for high-temperature tempering for 1 hour after the final drying is finished. High temperature tempering can improve the stability of the surface active layer and keep the stability of the performance of the surface active layer.
The invention adopts a method of sintering a layer of metal oxide on the surface of a metal matrix as a surface active layer, thereby improving the problem of short service life of the electrode.
The invention has the beneficial effects that: the DSA electrode has the advantages that the surface of the DSA electrode is coated with the metal oxide layer, the metal oxide layer has high corrosion resistance, and the service life of the DSA electrode is prolonged after the metal oxide layer is protected; after the DSA electrode is provided with the surface active layer coating, a crack mud structure can be formed, cracks are increased, the surface area of the electrode is increased, the activity is improved, the catalytic efficiency of the electrode is improved, and the service efficiency is improved.
Drawings
Fig. 1 is a schematic cross-sectional view of a DSA electrode;
fig. 2 is a polarization graph of the DSA electrode prepared in example 1 in a mixed solution of glucose and sodium chloride;
FIG. 3 is a schematic electron microscope view of the DSA electrode prepared in example 1;
fig. 4 is an EDS energy spectrum of the DSA electrode prepared in example 1;
FIG. 5 is a spectrum of the total number of distributions associated with FIG. 4.
In the figure: 1-a metal matrix; 2-surface active coating.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A DSA electrode comprises a metal substrate and a surface active layer coating coated on the surface of the metal substrate, wherein the material of the surface active layer coating is SiO2·Ta2O5The material of the metal matrix is Ti.
A manufacturing method of the DSA electrode specifically comprises the following steps:
(a) treatment of the metal substrate: taking a metal raw material for pretreatment to obtain a metal matrix with a uniform and flat surface and a pitted surface, wherein the pretreatment process specifically comprises the following steps: the metal raw material is sequentially polished, washed with alkali to remove oil, washed with acid and washed with water, wherein the alkali washing process specifically comprises the following steps: putting a metal substrate polished to be silvery white and metallic luster into NaOH with the mass percentage of 5-20%, and ultrasonically cleaning for 50-70 min, wherein the acid cleaning process specifically comprises the following steps: putting the metal matrix into 10 mass percent oxalic acid solution, and soaking and boiling the metal matrix for 90-110 min at a constant temperature of 85-95 ℃, wherein the water washing process specifically comprises the following steps: taking the pickled metal substrate out of the oxalic acid solution, repeatedly washing the metal substrate with water until the pH of the washing water is 7-8, and then putting the metal substrate into the solution (CH)2OH)2Preserving;
(b) preparation of surface active layer coating: taking C in proportion8H20O4Si and TaCl5Dissolving in organic solvent to obtain organic solution containing Si and Ta elements, uniformly coating the organic solution containing Si and Ta elements on the surface of the metal substrate obtained in the step (a), and dryingAnd (3) performing post-calcination, repeating coating-drying-calcination for a plurality of times, and forming a surface active layer coating which is tightly combined with the metal matrix on the surface of the metal matrix to obtain the DSA electrode, wherein the organic solvent is C with the volume ratio of 1:13H8O and C2H5OH is mixed, the molar ratio of Si to Ta in the organic solution containing Si element and Ta element is 1:1, the concentration of total ions is 0.2mol/L, and the drying process specifically comprises the following steps: placing the coated metal matrix in a 75-85 ℃ oven for drying for 5-15 min to volatilize the liquid on the surface of the metal matrix, wherein the calcining process specifically comprises the following steps: and (2) placing the dried metal matrix into a muffle furnace, slowly heating to 400-500 ℃, then calcining for 6.5-9.5 min at 400-500 ℃, wherein the total times of coating, drying and calcining are 11-15 times, and after the final drying, heating and tempering for 0.8-1.2 h at high temperature in the muffle furnace.
Example 1
As shown in figure 1, the DSA electrode comprises a metal substrate 2 and a surface active coating 1 coated on the surface of the metal substrate 2, wherein the material of the surface active coating 1 is SiO2·Ta2O5The electrode can be protected, the corrosion resistance of the electrode is improved, and the metal matrix 2 is made of Ti.
A manufacturing method of a DSA electrode specifically comprises the following steps:
a titanium plate raw material with the length of 200mm, the width of 200mm and the thickness of 1mm is selected and processed into a square (with the thickness unchanged) with the length and the width of 50 mm. Polishing the surface of a titanium plate raw material by using abrasive paper, removing an oxide film on the surface, then putting the titanium plate raw material into 10% NaOH solution, cleaning the titanium plate raw material for 60min by using an ultrasonic cleaning machine, putting the titanium substrate subjected to alkali cleaning into 10% oxalic acid solution by mass percent, soaking and boiling the titanium substrate at the constant temperature of 90 ℃ for 100min to ensure that the surface of the titanium substrate is a uniform and flat pitted surface, then repeatedly washing the titanium substrate by using deionized water until the PH of the washing water is 7-8, and then putting the titanium substrate into a Container (CH)2OH)2And (4) storing.
(II) preparing a mixed organic solution containing a Si compound and a Ta compound. 0.01mol of C8H20O4Si and 0.01mol TaCl5Dissolved in C with a volume ratio of 1:13H8O and C2H5OH is mixed into the obtained mixed liquid, and the molar ratio of Si to Ta is controlled to be 1:1, and the total ion concentration is controlled to be 0.2 mol/L.
(III) uniformly coating the surface of the treated titanium substrate with a mixed organic solution containing a Si compound and a Ta compound, wherein the coating amount per coating is 150mL/m2And putting the coated titanium substrate into an oven at 80 ℃ for drying for 8min to dry the surface of the titanium substrate, then putting the titanium substrate into a muffle furnace for heating to 450 ℃, then calcining for 8min at 450 ℃, repeating the coating, drying and calcining for 13 times, and finally tempering for 1h at high temperature in the muffle furnace at 450 ℃ to finish the manufacture of the DSA electrode.
As shown in FIG. 2, the DSA electrode prepared in this example was tested, and the electrode was placed in a mixed solution of 9g/L glucose solution and 2g/L sodium chloride solution at a mixing ratio of 1:1, and a polarization curve graph was obtained with platinum as a reference electrode, and it can be seen that the modified electrode has a higher oxygen evolution potential of 3.03V, which increases the degradation efficiency, and a series of experiments have shown that the DSA electrode applied to the landfill leachate in the electrocoagulation treatment had an original total phosphorus content of about 36.35mg/L, a total phosphorus content of 1.17mg/L, and a total phosphorus removal efficiency of 96.78% at the highest.
As shown in fig. 3, the DSA electrode prepared in this example has a surface morphology of "cracked mud" after being enlarged 2000 times under an electron microscope, the specific surface area is increased, and the catalytic activity of the electrode is improved.
As shown in fig. 4 and 5, the EDS spectra of the DSA electrode prepared in this example showed Ta and Si elements at the highest peak, and a small amount of Ta element was also contained at the other peaks, and fig. 5 shows that the Ta content exceeded 50%, the Si content exceeded 10%, and the O content exceeded 20%, indicating that the surface active layer was mainly composed of Ta oxide and Si oxide. And a small amount of Cl and Ca elements are also contained, wherein the Cl element is derived from Ta used as a coating raw material2Cl, and Ca element is derived from the matrix containing a small amount of Ca element.
Comparative example 1
Titanium-based Ce-doped SnO2-RuO2DSA electrode with oxygen evolution potential of about2.5V. The DSA electrode has the oxygen evolution potential of 3.03V, and the oxygen uptake potential is improved to effectively inhibit oxygen evolution side reaction, which means that the higher the current efficiency of anodic oxidation is, the higher the degradation efficiency of pollutants is.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The DSA electrode is characterized by comprising a metal matrix and a surface active layer coating coated on the surface of the metal matrix, wherein the material of the surface active layer coating is SiO2·Ta2O5。
2. The DSA electrode of claim 1 wherein the metal matrix is Ti.
3. A method of manufacturing a DSA electrode according to claim 1 or 2, comprising in particular the steps of:
(a) treatment of the metal substrate: pretreating a metal raw material to obtain a metal matrix with a uniform and flat surface and a pitted surface;
(b) preparation of surface active layer coating: and (b) uniformly coating an organic solution containing Si and Ta on the surface of the metal matrix obtained in the step (a), drying, calcining, repeating coating, drying and calcining for several times, and forming a surface active layer coating tightly combined with the metal matrix on the surface of the metal matrix to obtain the DSA electrode.
4. The method of claim 3, wherein in step (a), the pre-treatment process comprises: the metal raw material is sequentially polished, washed with alkali to remove oil, washed with acid and washed with water.
5. The method for manufacturing a DSA electrode according to claim 4, wherein in step (a), the alkaline cleaning process specifically comprises: putting the metal substrate polished to be silvery white and metallic luster into NaOH with the mass percentage of 5-20%, and ultrasonically cleaning for 50-70 min;
in the step (a), the acid washing process specifically comprises the following steps: putting the metal matrix into 10 mass percent oxalic acid solution, and soaking and boiling the metal matrix for 90-110 min at the constant temperature of 85-95 ℃;
in the step (a), the water washing process specifically comprises the following steps: taking the pickled metal substrate out of the oxalic acid solution, repeatedly washing the metal substrate with water until the pH of the washing water is 7-8, and then putting the metal substrate into the solution (CH)2OH)2And (4) storing.
6. A method of making a DSA electrode as claimed in claim 3 wherein in step (b) C is scaled8H20O4Si and TaCl5Dissolved in an organic solvent to prepare an organic solution containing an element Si and an element Ta.
7. The method of claim 6, wherein in step (b), the organic solvent is selected from C with a volume ratio of 1:13H8O and C2H5OH is mixed;
in the step (b), in the organic solution containing the Si element and the Ta element, the molar ratio of Si to Ta is 1:1, and the concentration of total ions is 0.2 mol/L.
8. The method of claim 3, wherein in step (b), the drying process is specifically as follows: and (3) drying the coated metal matrix in a 75-85 ℃ drying oven for 5-15 min to volatilize the liquid on the surface of the metal matrix.
9. The method of claim 3, wherein in step (b), the calcination process comprises: and (3) placing the dried metal matrix into a muffle furnace, slowly heating to 400-500 ℃, and calcining for 6.5-9.5 min at 400-500 ℃.
10. The method for manufacturing a DSA electrode according to claim 3, wherein in step (b), the total number of coating, drying and calcining is 11-15, and after the final drying, the DSA electrode is heated in a muffle furnace for high temperature tempering for 0.8-1.2 h.
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| CN1888141A (en) * | 2006-05-24 | 2007-01-03 | 中国船舶重工集团公司第七二五研究所 | Sea water pollution resisting oxide anode and its prepn |
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| CN1888141A (en) * | 2006-05-24 | 2007-01-03 | 中国船舶重工集团公司第七二五研究所 | Sea water pollution resisting oxide anode and its prepn |
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