CN113562815A - Preparation method of composite coating DSA electrode for water treatment and prepared composite coating DSA electrode - Google Patents
Preparation method of composite coating DSA electrode for water treatment and prepared composite coating DSA electrode Download PDFInfo
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Classifications
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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
-
- 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
Abstract
The invention discloses a preparation method of a composite coating DSA electrode for water treatment, which comprises the following steps: preprocessing a DSA base material; preparing a Sn-Sb base layer; carrying out electrodeposition treatment on the DSA base material by using the Sn-Sb subbase layer electrodeposition solution to obtain an initial product; alpha-PbO2Preparing the intermediate layer; by alpha-PbO2Carrying out electrodeposition treatment on the initial product by using the interlayer electrodeposition solution to obtain an intermediate product; beta-PbO2Preparing a catalytic layer; by beta-PbO2And (4) carrying out electrodeposition treatment on the intermediate product by using the electrodeposition liquid of the catalyst layer to obtain the composite coating DSA electrode. The invention also provides the composite coating DSA electrode prepared by the preparation method. According to the invention, an electrodeposition and nanoparticle fusion technology is adopted to prepare the high-efficiency and long-life composite coating DSA electrode, the high-efficiency and long-life composite coating DSA electrode has good stability under an enhanced degradation test, and the enhanced degradation result of the DSA electrode can be comparable to that of a noble metal coating; in addition, the deposition solution adopts the aqueous solution of each medicament in the preparation process, replaces the traditional method of generating a large amount of waste gas by coating organic solvent, and is from the sourceVOCs production is eliminated.
Description
Technical Field
The invention relates to the field of environmental catalysis and water pollution treatment, in particular to a preparation method of a composite coating DSA electrode for water treatment and the prepared composite coating DSA electrode.
Background
With the continuous development of the industry in China, more and more organic wastewater is generated; it has the characteristics of high concentration of pollution factors, strong toxicity, complex components and poor biodegradability. The traditional wastewater treatment technology is mostly the combination of a simple physical and chemical method and a biochemical method, but the long-term and complex characteristics of the industrial wastewater make the industrial wastewater increasingly difficult to meet the requirement of standard discharge. The advanced oxidation technology is mainly characterized in that hydroxyl free radicals (. OH) with strong oxidation capacity are generated, and under the conditions of catalyst, electricity, sound, illumination, high temperature, high pressure and the like, macromolecular refractory organic matters are mineralized into low-toxicity or non-toxic micromolecular substances. Depending on the manner of generating radicals and the reaction conditions, they can be classified into photocatalysis, catalytic wet oxidation, sonochemical oxidation, ozone oxidation, electrochemical oxidation, fenton oxidation, and the like. In the field of industrial wastewater treatment, the electrocatalytic oxidation technology has the advantages of environmental protection, no need of adding medicaments, controllable process, simple operation and the like, so that the electrocatalytic oxidation technology becomes an advanced oxidation technology which is popular with the public, has potential and hopes.
The core element of electrocatalytic oxidation is an electrocatalytic electrode material, so that a catalytic electrode material with good performance becomes a main reason for restricting the development of the technology. Chinese patent publication No. CN109292918A reports "a method for preparing a DSA electrode", which uses a noble metal loading method, and physical methods such as spin coating or dipping to coat and sinter and form the electrode; the electrode has the advantages of high manufacturing cost, poor bonding force of electrode base materials, long and complex manufacturing process flow, and volatile organic solvent which is adopted seriously pollutes the environment and the working environment of workers. Chinese patent with publication number CN106542613A reports "a sewage treatment electrocatalytic anode material and a preparation method thereof", which adopts a process method that a biomass carbonized material is doped with catalytic powder and is bonded by conductive adhesive; although the cost of the carrier material is low, the catalyst is easy to oxidize and has unstable structure when being used as a catalytic anode, so that a catalytic electrode structure system is broken down, and the service time is short; in addition, the electrode is not acid and alkali resistant, and the application range is limited.
Disclosure of Invention
The invention aims to solve the technical problems that the conventional DSA electrode has short service life, waste gas is easily generated in the preparation process, and the traditional electrode material is high in price.
The invention solves the technical problems through the following technical means:
a preparation method of a composite coating DSA electrode for water treatment comprises the following steps:
(1) preprocessing a DSA base material;
(2) preparation of Sn-Sb underlayer: firstly, preparing Sn-Sb base layer electrodeposition liquid, wherein the base layer electrodeposition liquid mainly comprises the following components: SnCl40.05-0.5mol/l、TiO20.05-0.2g/l of nano particles, 0.1-0.5mol/l of citric acid, 1-50ml/l of HCl and 0.005-0.05mol/l of antimonate, and sequentially dissolving, ultrasonically treating, heating in a water bath, stirring and aging the deposition solution for later use;
(3) transferring the prepared underlayer electrodeposition solution into an electrodeposition reactor, and performing electrodeposition treatment on the DSA substrate pretreated in the step (1) in the underlayer electrodeposition solution at the water bath stirring temperature of 40 ℃ and the deposition current density of 0.5-1.0A/dm2The deposition time is 0.5-1.0h, the deposited polar plate is washed by deionized water and then dried in an oven at the temperature of 80-100 ℃, and the dried polar plate is placed in a muffle furnace to be fired for 1.0h at the temperature of 500-;
(4)α-PbO2preparation of the intermediate layer: firstly, preparing an intermediate layer deposition solution, wherein the intermediate layer deposition solution mainly comprises the following components: NaOH35mol/l, 1-10ml/l of PTFE emulsion, 0.1-0.5mol/l of PbO0.1-0.5 g/l of nano graphite powder, and sequentially dissolving, ultrasonically treating, heating in a water bath, stirring and aging the deposition solution for later use;
(5) transferring the prepared intermediate layer deposition solution into an electrodeposition reactor, and performing electrodeposition treatment on the initial product prepared by sintering in the step (3) in the intermediate layer deposition solution, wherein the water bath temperature is 40 ℃, and the deposition current density is 0.3-0.5A/dm2The deposition time is 1.0-5.0 h; washing the deposited polar plate with deionized water, and drying in an oven at 80-100 deg.C to obtain intermediate productPreparing a product;
(6)β-PbO2preparation of the catalytic layer: firstly, preparing a catalyst layer deposition solution, wherein the catalyst layer deposition solution mainly comprises the following components: pb (NO)3)340-220g/l, 0.001-0.002mol/l of rare earth element, 1-5ml/l of PTFE emulsion and HNO30.1-0.5mol/l and 0.1-0.5mol/l of citric acid, and sequentially dissolving, ultrasonically treating, heating and stirring in a water bath, and aging the deposition solution for later use;
(7) transferring the prepared catalyst layer deposition solution into an electro-deposition reactor, and carrying out electro-deposition treatment on the intermediate product prepared in the step (5) in the catalyst layer deposition solution, wherein the water bath temperature is 40 ℃, and the deposition current density is 1.0-5.0A/dm2The deposition time is 1.0-2.0 h; and washing the deposited polar plate with deionized water, and drying in an oven at 80-100 ℃ to obtain the composite coating electrocatalysis electrode material.
The invention adopts the technology of electrodepositing and fusing nano particles to prepare the high-efficiency and long-life composite coating DSA electrode, and the prepared electrode is prepared in 4mol/l sulfuric acid solution and 100A/cm2The stability under the strengthening degradation test of the polar distance of 1cm is good, and the strengthening degradation result can be compared with that of a noble metal coating; in the preparation process, the deposition solution adopts aqueous solutions of various medicaments, replaces the traditional method of generating a large amount of waste gas by coating organic solvents, and eliminates the generation of VOCs from the source.
Preferably, the titanium substrate pretreatment comprises the following steps:
(a) polishing the DSA substrate by using abrasive paper with the roughness of 100-1000 meshes to form a certain rough surface on the surface, washing the surface by using deionized water, then performing ultrasonic treatment for 30min, and airing for later use;
(b) boiling the polished DSA substrate in an alkali solution with the concentration of 40% for 1-2h, performing deoiling treatment, washing, and airing for later use;
(c) and (3) steaming the DSA substrate subjected to alkali washing in an acid solution with the concentration of 40% for 1-2h, performing etching treatment, washing, and airing for later use.
Preferably, the DSA substrate in step (a) comprises a titanium plate or other DSA valve type metal.
Preferably, the alkali solution in step (b) comprises NaOH or KOH.
Preferably, the acid solution in step (c) comprises oxalic acid, hydrochloric acid, sulfuric acid or nitric acid.
Preferably, the antimony salt in step (2) comprises SbCl3Or Sb2O3。
Preferably, in the steps (2), (4) and (6), the ultrasonic temperature is 30 ℃ and the time is 30min, the water bath heating and stirring temperature is 30 ℃, the time is 30-60min, and the aging time is 12-24 h.
Preferably, the solid content of the PTFE emulsion in the step (4) and the step (6) is 60%.
Preferably, the rare earth element in step (6) includes one or more of La, Ce, Co and Nd.
The invention also provides a composite coating DSA electrode prepared by the preparation method, and the composite coating DSA electrode comprises a DSA base material, a Sn-Sb underlayer and alpha-PbO which are sequentially coated from inside to outside2Intermediate layer and beta-PbO2And a catalytic layer.
The invention has the following beneficial effects:
1. the invention adopts the technology of electrodepositing and fusing nano particles to prepare the high-efficiency and long-life composite coating DSA electrode, and the prepared electrode is prepared in 4mol/l sulfuric acid solution and 1A/cm2The stability under the strengthening degradation test of the polar distance of 1cm is good, and the strengthening degradation result can be compared with that of a noble metal coating; in the preparation process, the deposition solution adopts aqueous solutions of various medicaments, replaces the traditional method of generating a large amount of waste gas by coating organic solvents, and eliminates the generation of VOCs from the source.
2. The invention is a green electrode preparation process with low raw material cost, short process flow and no pollution in the manufacturing process, and solves the problems of high price and difficult obtainment of noble metal oxide coating electrodes.
3. The composite coating metal oxide electrode prepared by the invention has the characteristics of high degradation efficiency and good activity, and can quickly reduce organic matters in wastewater and improve the biodegradability of the wastewater.
Drawings
FIG. 1 is a process flow diagram of a method of making a composite coated DSA electrode for water treatment according to the present invention;
fig. 2 is a schematic structural view of a composite coated DSA electrode prepared in example 1 of the present invention;
fig. 3 is a pictorial view of a composite coated DSA electrode prepared in example 1 of the present invention;
FIG. 4 is a graph illustrating the enhanced lifetime of a composite coated DSA electrode prepared in example 1 of the present invention;
FIG. 5 is a graph of enhanced lifetime of a commercial Ru-Ir-Ta ternary electrode of comparative example 1 in accordance with the present invention;
FIG. 6 is a morphology electron microscope image of a composite coating DSA electrode prepared in example 1 of the present invention;
fig. 7 is a graph showing the treatment effect and biochemical effect of the composite coating DSA electrode prepared in example 1 of the present invention.
The reference numbers illustrate:
1. a DSA substrate; 2. a Sn-Sb underlayer; 3. alpha-PbO2An intermediate layer; 4. beta-PbO2Catalytic layer
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
A preparation method of a composite coating DSA electrode for water treatment comprises the following steps:
(1) pretreatment of DSA substrate 1: polishing a titanium plate by using abrasive paper with the roughness of 100 meshes to form a certain rough surface on the surface of the titanium plate, washing the titanium plate by using deionized water, then performing ultrasonic treatment for 30min, and airing for later use; boiling the polished DSA substrate in a 40% NaOH solution for 1.5h, performing deoiling treatment, washing, and airing for later use; boiling the DSA substrate subjected to alkali washing in an oxalic acid solution with the concentration of 40% for 1.5h, carrying out etching treatment, washing, and airing for later use;
(2) preparation of the Sn-Sb underlayer 2: firstly, preparing Sn-Sb base layer electrodeposition liquid, wherein the base layer electrodeposition liquid mainly comprises the following components: SnCl40.2mol/l, 0.2mol/l citric acid, 10ml/l HCl, TiO2Nanoparticles 0.2g/l, SbCl30.03mol/l, dissolving the deposition solution in sequence, performing ultrasonic treatment at 30 ℃ for 30min, heating and stirring in water bath at 30 ℃ for 30min, and aging for 12h for later use;
(3) transferring the prepared underlayer electrodeposition solution into an electrodeposition reactor, and performing electrodeposition treatment on the DSA substrate pretreated in the step (1) in the underlayer electrodeposition solution at the water bath stirring temperature of 40 ℃ and the deposition current density of 1.0A/dm2The deposition time is 0.5h, the deposited polar plate is washed by deionized water and then dried in an oven at 80 ℃, and the dried polar plate is put into a muffle furnace to be fired for 1.0h at 500 ℃ to prepare an initial product;
(4)α-PbO2preparation of intermediate layer 3: firstly, preparing an intermediate layer deposition solution, wherein the intermediate layer deposition solution mainly comprises the following components: dissolving deposition liquid sequentially by NaOH3mol/l, PbO0.2mol/l, PTFE emulsion with solid content of 60% 10ml/l and nano graphite powder 0.2g/l, performing ultrasonic treatment at 30 ℃ for 30min, heating and stirring in water bath at 30 ℃ for 30min, and aging for 12h for later use;
(5) transferring the prepared intermediate layer deposition solution into an electrodeposition reactor, and performing electrodeposition treatment on the initial product prepared by sintering in the step (3) in the intermediate layer deposition solution, wherein the water bath temperature is 40 ℃, and the deposition current density is 0.5A/dm2The deposition time is 2.0 h; washing the deposited polar plate with deionized water, and drying in an oven at 80 ℃ to obtain an intermediate product;
(6)β-PbO2preparation of catalytic layer 4: firstly, preparing a catalyst layer deposition solution mainly containingComprises the following components: pb (NO)3)3160g/l of PTFE emulsion with solid content of 60 percent, 5ml/l of rare earth elements (La, Ce and Co)0.002mol/l and HNO30.13mol/l and 0.13mol/l of citric acid, dissolving the deposition solution in sequence, performing ultrasonic treatment at 30 ℃ for 30min, heating and stirring in a water bath at 30 ℃ for 30min, and aging for 12h for later use;
(7) transferring the prepared catalytic layer deposition solution into an electro-deposition reactor, and carrying out electro-deposition treatment on the intermediate product prepared in the step (5) in the catalytic layer deposition solution, wherein the water bath temperature is 40 ℃, and the deposition current density is 3.0A/dm2The deposition time is 2.0 h; and washing the deposited polar plate with deionized water, and drying in an oven at 80 ℃ to obtain the composite coating electrocatalysis electrode material.
The schematic structural diagram and the physical diagram of the composite coating DSA electrode prepared in the embodiment are respectively shown in FIG. 2 and FIG. 3, and the composite coating DSA electrode prepared in the invention comprises a DSA base material, a Sn-Sb underlayer and alpha-PbO which are sequentially coated from inside to outside2Intermediate layer and beta-PbO2And a catalytic layer.
Example 2
A preparation method of a composite coating DSA electrode for water treatment comprises the following steps:
(1) pretreatment of DSA substrate 1: polishing a titanium plate by using sand paper with the roughness of 500 meshes to form a certain rough surface on the surface of the titanium plate, washing the titanium plate by using deionized water, then performing ultrasonic treatment for 30min, and airing for later use; boiling the polished DSA substrate in a 40% NaOH solution for 1h, performing deoiling treatment, washing, and airing for later use; boiling the DSA substrate subjected to alkali washing in an oxalic acid solution with the concentration of 40% for 1h, carrying out etching treatment, washing, and airing for later use;
(2) preparation of the Sn-Sb underlayer 2: firstly, preparing Sn-Sb base layer electrodeposition liquid, wherein the base layer electrodeposition liquid mainly comprises the following components: SnCl40.05mol/l, citric acid 0.1mol/l, HCl1ml/l, TiO20.05g/l of nanoparticles, Sb2O30.005mol/l, dissolving the deposition solution in sequence, performing ultrasonic treatment at 30 ℃ for 30min, heating and stirring in water bath at 30 ℃ for 30min, and aging for 12h for later use;
(3) a substrate to be arrangedTransferring the layer electrodeposition solution to an electrodeposition reactor, and performing electrodeposition treatment on the DSA substrate pretreated in the step (1) in the subbase layer electrodeposition solution at the water bath stirring temperature of 40 ℃ and the deposition current density of 0.5A/dm2The deposition time is 0.5h, the deposited polar plate is washed by deionized water and then dried in a drying oven at the temperature of 90 ℃, and the dried polar plate is put into a muffle furnace to be fired for 1.0h at the temperature of 550 ℃ to obtain an initial product;
(4)α-PbO2preparation of intermediate layer 3: firstly, preparing an intermediate layer deposition solution, wherein the intermediate layer deposition solution mainly comprises the following components: dissolving the deposition solution by 4mol/l of NaOH, 0.1mol/l of PbO0, 1ml/l of PTFE emulsion with solid content of 60% and 0.1g/l of nano graphite powder in sequence, performing ultrasonic treatment at 30 ℃ for 30min, heating and stirring in a water bath at 30 ℃ for 30min, and aging for 12h for later use;
(5) transferring the prepared intermediate layer deposition solution into an electrodeposition reactor, and performing electrodeposition treatment on the initial product prepared by sintering in the step (3) in the intermediate layer deposition solution, wherein the water bath temperature is 40 ℃, and the deposition current density is 0.3A/dm2The deposition time is 1.0 h; washing the deposited polar plate with deionized water, and drying in a drying oven at 90 ℃ to obtain an intermediate product;
(6)β-PbO2preparation of catalytic layer 4: firstly, preparing a catalyst layer deposition solution, wherein the catalyst layer deposition solution mainly comprises the following components: pb (NO)3)340g/l of PTFE emulsion with solid content of 60%, 1ml/l of rare earth elements (La, Ce and Co)0.002mol/l and HNO30.1mol/l and 0.1mol/l of citric acid, dissolving the deposition solution in sequence, performing ultrasonic treatment at 30 ℃ for 30min, heating and stirring in a water bath at 30 ℃ for 30min, and aging for 12h for later use;
(7) transferring the prepared catalytic layer deposition solution into an electro-deposition reactor, and carrying out electro-deposition treatment on the intermediate product prepared in the step (5) in the catalytic layer deposition solution, wherein the water bath temperature is 40 ℃, and the deposition current density is 1.0A/dm2The deposition time is 1.0 h; and washing the deposited polar plate with deionized water, and drying in an oven at 90 ℃ to obtain the composite coating electrocatalysis electrode material.
Example 3
A preparation method of a composite coating DSA electrode for water treatment comprises the following steps:
(1) pretreatment of DSA substrate 1: polishing a titanium plate by using sand paper with the roughness of 1000 meshes to form a certain rough surface on the surface of the titanium plate, washing the titanium plate by using deionized water, then performing ultrasonic treatment for 30min, and airing for later use; boiling the polished DSA substrate in a 40% NaOH solution for 2h, performing deoiling treatment, washing, and airing for later use; boiling the DSA substrate subjected to alkali washing in an oxalic acid solution with the concentration of 40% for 2 hours, carrying out etching treatment, washing, and airing for later use;
(2) preparation of the Sn-Sb underlayer 2: firstly, preparing Sn-Sb base layer electrodeposition liquid, wherein the base layer electrodeposition liquid mainly comprises the following components: SnCl40.5mol/l, 0.5mol/l citric acid, 50ml/l HCl, TiO2Nanoparticles 0.2g/l, SbCl30.05mol/l, dissolving the deposition solution in sequence, performing ultrasonic treatment at 30 ℃ for 30min, heating and stirring in water bath at 30 ℃ for 30min, and aging for 12h for later use;
(3) transferring the prepared underlayer electrodeposition solution into an electrodeposition reactor, and performing electrodeposition treatment on the DSA substrate pretreated in the step (1) in the underlayer electrodeposition solution at the water bath stirring temperature of 40 ℃ and the deposition current density of 1.0A/dm2The deposition time is 1.0h, the deposited polar plate is washed by deionized water and then dried in a drying oven at 100 ℃, and the dried polar plate is put into a muffle furnace to be fired for 1.0h at 600 ℃ to prepare an initial product;
(4)α-PbO2preparation of intermediate layer 3: firstly, preparing an intermediate layer deposition solution, wherein the intermediate layer deposition solution mainly comprises the following components: dissolving a deposition solution in sequence by using 5mol/l of NaOH, 0.5mol/l of PbO0.5mol/l of nano graphite powder and 10ml/l of PTFE emulsion with the solid content of 60%, performing ultrasonic treatment at 30 ℃ for 30min, heating and stirring in a water bath at 30 ℃ for 30min, and aging for 12h for later use;
(5) transferring the prepared intermediate layer deposition solution into an electrodeposition reactor, and performing electrodeposition treatment on the initial product prepared by sintering in the step (3) in the intermediate layer deposition solution, wherein the water bath temperature is 40 ℃, and the deposition current density is 0.5A/dm2The deposition time is 5.0 h; washing the deposited polar plate with deionized water, and drying in a 100 ℃ drying oven to obtain an intermediate product;
(6)β-PbO2preparation of catalytic layer 4: firstly, preparing a catalyst layer deposition solution, wherein the catalyst layer deposition solution mainly comprises the following components: pb (NO)3)3220g/l of PTFE emulsion with solid content of 60 percent, 5ml/l of rare earth elements (La, Ce and Co)0.002mol/l and HNO30.5mol/l and 0.5mol/l of citric acid, dissolving the deposition solution in sequence, performing ultrasonic treatment at 30 ℃ for 30min, heating and stirring in a water bath at 30 ℃ for 30min, and aging for 12h for later use;
(7) transferring the prepared catalytic layer deposition solution into an electro-deposition reactor, and carrying out electro-deposition treatment on the intermediate product prepared in the step (5) in the catalytic layer deposition solution, wherein the water bath temperature is 40 ℃, and the deposition current density is 5.0A/dm2The deposition time is 2.0 h; and washing the deposited polar plate with deionized water, and drying in an oven at 100 ℃ to obtain the composite coating electrocatalysis electrode material.
Comparative example 1
This comparative example was prepared by purchasing a commercial Ru-Ir-Ta ternary electrode on the market.
Performance test
The composite coating DSA electrode prepared in the example 1 is compared with a certain commercial Ru-Ir-Ta ternary electrode purchased in the market in an enhanced deterioration experiment, wherein the deterioration condition is as follows: 40 ℃ 100A/dm2，4mol/LH2SO4The results are shown in FIGS. 4 and 5, and it can be seen that the composite coating DSA electrode prepared in example 1 is dissolved in 4mol/l sulfuric acid solution at 100A/cm2And the electrode distance is 1cm, and the stability is good under the strengthening degradation test, and the strengthening degradation result of the coating can be compared with that of a noble metal coating.
The composite coating DSA electrode prepared in the embodiment 1 is subjected to morphology electron microscope analysis, treatment effect and biodegradability effect analysis, a morphology electron microscope image is shown in FIG. 6, and a treatment effect and biodegradability effect image is shown in FIG. 7.
In conclusion, the invention adopts the technology of electrodepositing and fusing nano particles to prepare the high-efficiency and long-life composite coating DSA electrode, and the prepared electrode is prepared in 4mol/l sulfuric acid solution and 1A/cm2The stability under the strengthening degradation test of the polar distance of 1cm is good, and the strengthening degradation result can be compared with that of a noble metal coating; in the preparation process, the deposition solution adopts aqueous solutions of various medicaments, replaces the traditional method of generating a large amount of waste gas by coating organic solvents, and eliminates the generation of VOCs from the source.
The invention is a green electrode preparation process with low raw material cost, short process flow and no pollution in the manufacturing process, solves the problems of high price and difficult obtainment of noble metal oxide coating electrodes, and the prepared composite coating metal oxide electrode has the characteristics of high degradation efficiency and good activity, can quickly reduce organic matters in wastewater and improve the biodegradability of the wastewater.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a composite coating DSA electrode for water treatment is characterized by comprising the following steps:
(1) preprocessing a DSA base material;
(2) preparation of Sn-Sb underlayer: firstly, preparing Sn-Sb base layer electrodeposition liquid, wherein the base layer electrodeposition liquid mainly comprises the following components: SnCl40.05-0.5mol/l、TiO20.05-0.2g/l of nano particles, 0.1-0.5mol/l of citric acid, 1-50ml/l of HCl and 0.005-0.05mol/l of antimonate, and sequentially dissolving, ultrasonically treating, heating in a water bath, stirring and aging the deposition solution for later use;
(3) transferring the prepared underlayer electrodeposition solution into an electrodeposition reactor, and performing electrodeposition treatment on the DSA substrate pretreated in the step (1) in the underlayer electrodeposition solution at the water bath stirring temperature of 40 ℃ and the deposition current density of 0.5-1.0A/dm2The deposition time is 0.5 to 1.0 hour,washing the deposited polar plate with deionized water, drying in an oven at 80-100 ℃, and firing the dried polar plate in a muffle furnace at 500-600 ℃ for 1.0h to obtain an initial product;
(4)α-PbO2preparation of the intermediate layer: firstly, preparing an intermediate layer deposition solution, wherein the intermediate layer deposition solution mainly comprises the following components: dissolving, ultrasonically treating, heating and stirring in a water bath, and aging a deposition solution sequentially by using 3-5mol/l of NaOH, 1-10ml/l of PTFE emulsion, 0.1-0.5mol/l of PbO0.1-0.5mol/l of nano graphite powder for later use;
(5) transferring the prepared intermediate layer deposition solution into an electrodeposition reactor, and performing electrodeposition treatment on the initial product prepared by sintering in the step (3) in the intermediate layer deposition solution, wherein the water bath temperature is 40 ℃, and the deposition current density is 0.3-0.5A/dm2The deposition time is 1.0-5.0 h; washing the deposited polar plate with deionized water, and drying in an oven at 80-100 ℃ to obtain an intermediate product;
(6)β-PbO2preparation of the catalytic layer: firstly, preparing a catalyst layer deposition solution, wherein the catalyst layer deposition solution mainly comprises the following components: pb (NO)3)340-220g/l, 0.001-0.002mol/l of rare earth element, 1-5ml/l of PTFE emulsion and HNO30.1-0.5mol/l and 0.1-0.5mol/l of citric acid, and sequentially dissolving, ultrasonically treating, heating and stirring in a water bath, and aging the deposition solution for later use;
(7) transferring the prepared catalyst layer deposition solution into an electro-deposition reactor, and carrying out electro-deposition treatment on the intermediate product prepared in the step (5) in the catalyst layer deposition solution, wherein the water bath temperature is 40 ℃, and the deposition current density is 1.0-5.0A/dm2The deposition time is 1.0-2.0 h; and washing the deposited polar plate with deionized water, and drying in an oven at 80-100 ℃ to obtain the composite coating electrocatalysis electrode material.
2. The preparation method of the DSA electrode for the water treatment composite coating according to claim 1, wherein the pretreatment of the titanium substrate comprises the following steps:
(a) polishing the DSA substrate by using abrasive paper with the roughness of 100-1000 meshes to form a certain rough surface on the surface, washing the surface by using deionized water, then performing ultrasonic treatment for 30min, and airing for later use;
(b) boiling the polished DSA substrate in an alkali solution with the concentration of 40% for 1-2h, performing deoiling treatment, washing, and airing for later use;
(c) and (3) steaming the DSA substrate subjected to alkali washing in an acid solution with the concentration of 40% for 1-2h, performing etching treatment, washing, and airing for later use.
3. The preparation method of a composite coated DSA electrode for water treatment according to claim 2, wherein the composite coated DSA electrode comprises: the DSA substrate in step (a) comprises a titanium plate or other DSA valve type metal.
4. The preparation method of a composite coated DSA electrode for water treatment according to claim 2, wherein the composite coated DSA electrode comprises: the alkali solution in the step (b) comprises NaOH or KOH.
5. The preparation method of a composite coated DSA electrode for water treatment according to claim 2, wherein the composite coated DSA electrode comprises: the acid solution in the step (c) comprises oxalic acid, hydrochloric acid, sulfuric acid or nitric acid.
6. The preparation method of a composite coated DSA electrode for water treatment according to claim 1, wherein the composite coated DSA electrode comprises: the antimony salt in the step (2) comprises SbCl3Or Sb2O3。
7. The preparation method of a composite coated DSA electrode for water treatment according to claim 1, wherein the composite coated DSA electrode comprises: in the steps (2), (4) and (6), the ultrasonic temperature is 30 ℃, the ultrasonic time is 30min, the water bath heating and stirring temperature is 30 ℃, the ultrasonic time is 30-60min, and the aging time is 12-24 h.
8. The preparation method of a composite coated DSA electrode for water treatment according to claim 1, wherein the composite coated DSA electrode comprises: the solid content of the PTFE emulsion in the step (4) and the step (6) is 60 percent.
9. The preparation method of a composite coated DSA electrode for water treatment according to claim 1, wherein the composite coated DSA electrode comprises: in the step (6), the rare earth elements comprise one or more of La, Ce, Co and Nd.
10. A composite coated DSA electrode made by the method of any of claims 1-9 for the preparation of a composite coated DSA electrode for water treatment, wherein: the composite coating DSA electrode comprises a DSA base material, a Sn-Sb underlayer and alpha-PbO which are sequentially coated from inside to outside2Intermediate layer and beta-PbO2And a catalytic layer.
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