CN108914122B - Preparation method of titanium-based lead dioxide anode - Google Patents
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Abstract
A preparation method of a titanium-based lead dioxide anode comprises the following steps: pretreating the titanium-based matrix; dissolving tin tetrachloride and antimony trichloride in isopropanol containing hydrochloric acid, coating the solution on the surface of a titanium plate substrate, drying and roasting to obtain an electrode with a tin-antimony oxide bottom layer; taking an electrode with a tin-antimony oxide bottom layer as an anode and a titanium plate as a cathode, and electrodepositing alpha-PbO in a sodium hydroxide plating solution dissolved with PbO2An intermediate layer; taking a titanium plate as an anode and a titanium plate as a cathode, and electrodepositing to prepare the modified beta-PbO containing cerium dioxide, bait and fluorine2And obtaining the titanium-based lead dioxide anode. The surface of the polar plate prepared by the preparation method is uniform and compact, and the service life is long; the electrochemical oxidation performance is high; the treatment cost is low.
Description
Technical Field
The invention relates to the technical field of industrial wastewater electrocatalytic oxidation treatment, in particular to a preparation method of a cerium dioxide and bait co-doped titanium-based lead dioxide anode in an electrocatalytic oxidation process.
Background
With the rapid development of modern industry, the global economy is dramatically increased, which brings convenience to people's life and simultaneously produces a great amount of industrial wastewater containing toxic, harmful and difficultly-degradable pollutants, and if the industrial wastewater directly enters a water body without being treated, the industrial wastewater can cause serious pollution and damage to the environment, thereby further harming human health. Therefore, the treatment of industrial wastewater is urgent and not negligible.
The traditional treatment methods of industrial wastewater comprise biochemical methods, physical methods, chemical methods and the like, which have the defects of harsh reaction conditions, secondary pollution and the like, and the purpose of degrading pollutants is difficult to achieve really. The electrocatalytic oxidation method is an advanced oxidation method suitable for treating refractory pollutants based on the traditional oxidation method, and has the advantages of high efficiency, mild treatment conditions, good environmental compatibility and the like.
Lead dioxide has the advantages of high oxygen evolution potential, good stability, good conductivity, corrosion resistance, low price and the like, and has been applied to industrial production as an anode. With the continuous and intensive research on lead dioxide electrodes, titanium-based lead dioxide electrodes are widely used to solve the problems of large electrode distortion, machining and the like of the lead dioxide electrodes without matrixes.
The titanium-based lead dioxide electrode has the advantages of good conductivity, easy processing, titanium material thermal expansion coefficient close to that of lead dioxide and the like, but has the defects of low current efficiency and short service life of easy passivation of a coating in the use process. Therefore, improvement of electrode performance by incorporating a small amount of additives into the plating solution has been widely studied.
The related patent CN 102280626A discloses a composite lead dioxide electrode plate and a manufacturing method thereof, wherein the method comprises a titanium substrate, a transition layer and alpha-PbO in sequence2Intermediate layer, beta-PbO2The active layer, but only the transition layer playing the role of passivation prevention is added with elements such as Pt, Ta, Ir and the like, and the active layer playing the key role of the performance of the polar plate is not improved, so that the prepared polar plate beta-PbO2The active layer is not ideal in terms of electrode density, conductivity and catalytic performance.
The related patent CN 103014800A discloses a method for preparing a cerium-doped graphite-based lead dioxide catalytic electrode, which takes graphite as a substrate, and alpha-PbO is sequentially plated on the surface of the graphite substrate2Intermediate layer and cerium-doped beta-PbO2Active layer, but this method uses Ce3+As dopant, in comparison with CeO2，Ce3+Doped prepared beta-PbO2The active layer has a rough surface and large grain pores, so that the active layer has defects in corrosion resistance and service life.
Disclosure of Invention
The invention aims to provide a preparation method of a cerium-doped and erbium-modified titanium-based lead dioxide anode, and the lead dioxide polar plate prepared by the method has the advantages of high oxidation activity, strong conductivity, long electrode service life and the like, and can effectively remove organic pollutants which are difficult to degrade in industrial wastewater. The adopted technical method comprises the following steps: a preparation method of a titanium-based lead dioxide anode is characterized by comprising the following steps: the method comprises the following steps:
1) pretreating the titanium-based matrix to remove impurities on the surface of the matrix and obtain a surface with good treatment performance;
2) dissolving stannic chloride and antimony trichloride in isopropanol containing hydrochloric acid, coating the isopropanol on the surface of a titanium plate substrate, drying at 120 ℃ for 10-15min, roasting for 5-20min, repeating for 8-10 times, and roasting for 1.0-2.0h to obtain an electrode with a stannum-antimony oxide bottom layer;
3) taking an electrode with a tin-antimony oxide bottom layer as an anode and a titanium plate as a cathode, and electrodepositing alpha-PbO in a sodium hydroxide plating solution dissolved with PbO2An intermediate layer;
4) taking the titanium plate prepared in the step (3) as an anode and the titanium plate as a cathode, and in the acidic fluorine-containing lead solution doped with cerium dioxide and nitric acid bait, the acidic fluorine-containing lead plating solution containing cerium dioxide and nitric acid bait has the composition of Pb (NO)3)2、HNO3、NaF、CeO2And Er (NO)3)3Electrodepositing to obtain modified beta-PbO containing cerium dioxide, bait and fluorine2And obtaining the titanium-based lead dioxide anode.
In order to obtain the grey pitted surface, the pretreatment of the titanium-based substrate in the step 1) of the method comprises grinding, decontamination and acid etching treatment.
The suitable calcination temperature in step 2) of the present invention is 500 ℃.
Dissolving stannic chloride and antimony trichloride in the step 2) into a solution prepared from isopropanol containing hydrochloric acid, wherein the stannic chloride and antimony trichloride coating solution comprise 500mmol/L SnCl4·5H2O, 60mmol/L SbCl3The volume ratio of the isopropanol to the concentrated hydrochloric acid is 20:1-20: 10.
The composition of the PbO sodium hydroxide plating solution in the step 3) is 0.10mol/LPbO and 140g/L sodium hydroxide.
Electrodeposition of alpha-PbO in step 3)2The deposition time of the intermediate layer is 0.5-1.0h, the deposition temperature is 35-45 ℃, and the current density of the electrodeposition is 20mA/cm2The stirring speed is about 300-500 rpm in the electrodeposition process, and the distance between the polar plates is 1.5-5 cm.
The composition of the acid fluorine-containing lead plating solution in the step 4) is 0.5mol/L Pb (NO)3)20.15mol/L of HNO30.012mol/L NaF, 1.8g/L CeO2And Er (NO3) 0.05g/L3。
The modified beta-PbO containing cerium dioxide, bait and fluorine is prepared by the electrodeposition in the step 4)2The electro-deposition time of the active layer is 1.0-2.0h, the deposition temperature is 35-5045 ℃, and the electro-deposition current density is 35-45mA/cm2The stirring speed is about 300-500 rpm in the electrodeposition process, and the distance between the polar plates is 1.5-5 cm.
The invention has the beneficial effects that:
1) the prepared pole plate has uniform and compact surface and long service life. The doping of cerium dioxide and erbium can prevent the continuous growth of lead dioxide crystal and refine crystal grains, thereby improving the service life of the electrode.
2) The electrochemical oxidation performance is high. The doping of cerium dioxide and erbium can increase the active sites on the surface of the electrode, thereby increasing the electrochemical oxidative degradation capability of the electrode.
3) Low treatment cost and easy popularization and application. The lead dioxide anode prepared by the method has strong conductivity, high removal efficiency of COD and the like, and mild reaction conditions, thereby greatly reducing the operation cost of electricity charge, medicaments and the like.
Detailed Description
The following describes a specific embodiment of the present invention.
The invention discloses a preparation method of a titanium-based lead dioxide anode, which comprises the following steps:
1) the method comprises the following steps of pretreating a titanium-based substrate to remove impurities on the surface of the substrate and obtain a surface with good treatment performance, wherein the pretreatment of the surface comprises polishing, decontamination and acid etching, and pitted surface can be obtained by acid etching.
2) Dissolving stannic chloride and antimony trichloride in isopropanol containing hydrochloric acid, coating the isopropanol on the surface of a titanium plate substrate, drying at 120 ℃ for 10-15min, roasting for 5-20min, repeating for 8-10 times, and roasting for 1.0-2.0h to obtain an electrode with a stannum-antimony oxide bottom layer, wherein the stannic chloride and antimony trichloride are dissolved in a solution prepared from isopropanol containing hydrochloric acid, and the composition of the stannic chloride and antimony trichloride coating solution is 500mmol/L SnCl4·5H2O, 60mmol/L SbCl3The volume ratio of the isopropanol to the concentrated hydrochloric acid is 20:1-20: 10. Step (ii) of2) The medium firing temperature is preferably 500 ℃.
3) Taking an electrode with a tin-antimony oxide bottom layer as an anode and a titanium plate as a cathode, and electrodepositing alpha-PbO in a sodium hydroxide plating solution dissolved with PbO2The middle layer and the PbO sodium hydroxide plating solution consist of 0.10mol/LPbO and 140g/L sodium hydroxide. Electrodeposition of alpha-PbO2The deposition time of the intermediate layer is 0.5-1.0h, the deposition temperature is 35-45 ℃, and the current density of the electrodeposition is 20mA/cm2The stirring speed is about 300-500 rpm in the electrodeposition process, and the distance between the polar plates is 1.5-5 cm.
4) Taking the titanium plate prepared in the step (3) as an anode and the titanium plate as a cathode, and in the acidic fluorine-containing lead solution doped with cerium dioxide and nitric acid bait, the acidic fluorine-containing lead plating solution containing cerium dioxide and nitric acid bait has the composition of Pb (NO)3)2、HNO3、NaF、CeO2And Er (NO)3)3Electrodepositing to obtain modified beta-PbO containing cerium dioxide, bait and fluorine2And obtaining the titanium-based lead dioxide anode. The composition of the acid fluorine-containing lead plating solution is 0.5mol/L Pb (NO)3)20.15mol/L of HNO30.012mol/L NaF, 1.8g/L CeO2And Er (NO) 0.05g/L3)3. Electrodepositing to obtain modified beta-PbO containing cerium dioxide, bait and fluorine2The electro-deposition time of the active layer is 1.0-2.0h, the deposition temperature is 35-50 ℃, and the electro-deposition current density is 35-45mA/cm2The stirring speed is about 300-500 rpm in the electrodeposition process, and the distance between the polar plates is 1.5-5 cm.
Example 1:
a ceric oxide and bait doped co-modified titanium-based lead dioxide anode is prepared by the following steps: polishing a 10 x 10cm x 3mm titanium screen plate by using abrasive paper, washing with clear water, heating to remove oil for 2 hours at 80 ℃ in a 40% sodium hydroxide solution, washing with the clear water, heating to boil for 2-3 hours in a 10% oxalic acid solution until a grey pitted surface appears on the surface of the screen plate, and washing with the clear water.
Dissolving stannic chloride and antimony trichloride in isopropanol containing hydrochloric acid, coating on the surface of titanium plate substrate, oven drying at 120 deg.C for 10min, calcining at 500 deg.C for 5min, repeating for 10 times, and calcining at 500 deg.C for 1.0hTo obtain an electrode with a tin-antimony oxide bottom layer, and the SnCl of which the composition of the coating liquid of tin tetrachloride and antimony trichloride is 500mmol/L4·5H2O, 60mmol/L SbCl3100mL of isopropanol and 15mL of concentrated hydrochloric acid.
Taking an electrode with a tin-antimony oxide bottom layer as an anode and a titanium plate as a cathode, and electrodepositing alpha-PbO in a sodium hydroxide plating solution dissolved with PbO2The middle layer consists of 0.10mol/LPbO and 140g/L sodium hydroxide in PbO sodium hydroxide plating solution, the deposition time is 1.0h, the deposition temperature is 45 ℃, and the current density of electrodeposition is 20mA/cm2The stirring speed is about 400 revolutions per minute during the electrodeposition process, and the distance between the polar plates is 4 cm.
Taking the titanium plate prepared in the above step as an anode and the titanium plate as a cathode, and in the acidic fluorine-containing lead solution doped with cerium dioxide and nitric acid bait, the composition of the acidic fluorine-containing lead plating solution containing cerium dioxide and nitric acid bait is 0.5mol/L of Pb (NO)3)20.15mol/L of HNO30.012mol/L NaF, 1.8g/L CeO2And Er (NO) 0.05g/L3)3Electrodepositing to obtain modified beta-PbO containing cerium dioxide, bait and fluorine2The active layer has an electrodeposition time of 2.0h, a deposition temperature of 45 ℃ and an electrodeposition current density of 35-45mA/cm2The stirring speed is about 400 revolutions per minute during the electrodeposition process, and the distance between the polar plates is 4 cm. Thus obtaining the titanium-based lead dioxide anode which is doped with cerium dioxide and is decorated by bait.
The electrode plate is used as an anode, a stainless steel plate is used as a cathode, reverse osmosis concentrated water of a certain plant is treated, and the area of the anode and the area of the cathode are both 100cm2The interpolar distance was 3cm, and the input current intensity was 2.0A. The initial COD concentration of the reverse osmosis concentrated water is 2000mg/L, the volume is 1.0L, the initial pH6.8, the reaction is carried out for 2 hours, and the removal rate of COD reaches 77%.
Example 2:
a ceric oxide and bait doped co-modified titanium-based lead dioxide anode is prepared by the following steps: polishing a 50 x 20cm x 3mm titanium screen plate by using abrasive paper, washing with clear water, heating to remove oil for 2 hours at 80 ℃ in a 40% sodium hydroxide solution, washing with the clear water, heating to boil for 2-3 hours in a 10% oxalic acid solution until a grey ramie surface appears on the surface of the screen plate, and washing with the clear water.
Dissolving stannic chloride and antimony trichloride in isopropanol containing hydrochloric acid, coating on the surface of a titanium plate substrate, drying at 120 ℃ for 15min, roasting at 500 ℃ for 15min, repeating for 10 times, and roasting at 500 ℃ for 1.2h to obtain an electrode with a stannum-antimony oxide bottom layer, wherein the stannic chloride and antimony trichloride coating solution is SnCl with the composition of 500mmol/L4·5H2O, 60mmol/L SbCl3100mL of isopropanol and 50mL of concentrated hydrochloric acid.
Taking an electrode with a tin-antimony oxide bottom layer as an anode and a titanium plate as a cathode, and electrodepositing alpha-PbO in a sodium hydroxide plating solution dissolved with PbO2The middle layer consists of 0.10mol/LPbO and 140g/L sodium hydroxide in PbO sodium hydroxide plating solution, the deposition time is 1.0h, the deposition temperature is 35 ℃, and the current density of electrodeposition is 20mA/cm2The stirring speed is about 400 revolutions per minute during the electrodeposition process, and the distance between the polar plates is 1.5 cm.
Taking the titanium plate prepared in the above step as an anode and the titanium plate as a cathode, and in the acidic fluorine-containing lead solution doped with cerium dioxide and nitric acid bait, the composition of the acidic fluorine-containing lead plating solution containing cerium dioxide and nitric acid bait is 0.5mol/L of Pb (NO)3)20.15mol/L of HNO30.012mol/L NaF, 1.8g/L CeO2And Er (NO) 0.05g/L3)3Electrodepositing to obtain modified beta-PbO containing cerium dioxide, bait and fluorine2The active layer has an electrodeposition time of 2.0h, a deposition temperature of 45 ℃ and an electrodeposition current density of 35-45mA/cm2And stirring at the speed of about 400 revolutions per minute in the electrodeposition process, wherein the distance between the polar plates is 4cm, thus obtaining the titanium-based lead dioxide anode which is co-modified by doping cerium dioxide and bait.
The electrode plate is used as an anode, a stainless steel plate is used as a cathode, reverse osmosis concentrated water of a certain plant is treated, and the area of the anode and the area of the cathode are both 100cm2The inter-polar distance was 4cm, and the input current intensity was 2.0A. The initial COD concentration of the reverse osmosis concentrated water is 2200mg/L, the volume is 1.0L, the initial pH is 6.6, the reaction is carried out for 2 hours, and the removal rate of COD reaches 73 percent.
Example 3:
a ceric oxide and bait doped co-modified titanium-based lead dioxide anode is prepared by the following steps: polishing a 50 x 20cm x 3mm titanium screen plate by using abrasive paper, washing with clear water, heating to remove oil for 2 hours at 80 ℃ in a 40% sodium hydroxide solution, washing with the clear water, heating to boil for 2-3 hours in a 10% oxalic acid solution until a grey ramie surface appears on the surface of the screen plate, and washing with the clear water.
Dissolving stannic chloride and antimony trichloride in isopropanol containing hydrochloric acid, coating on the surface of a titanium plate substrate, drying at 120 ℃ for 10min, roasting at 500 ℃ for 20min, repeating for 10 times, and roasting at 500 ℃ for 2h to obtain an electrode with a stannic-antimony oxide bottom layer, wherein the stannic chloride and antimony trichloride coating solution comprises 500mmol/L SnCl4·5H2O, 60mmol/L SbCl3100mL of isopropanol and 5mL of concentrated hydrochloric acid.
Taking an electrode with a tin-antimony oxide bottom layer as an anode and a titanium plate as a cathode, and electrodepositing alpha-PbO in a sodium hydroxide plating solution dissolved with PbO2The middle layer consists of 0.10mol/LPbO and 140g/L sodium hydroxide in PbO sodium hydroxide plating solution, the deposition time is 1.0h, the deposition temperature is 35 ℃, and the current density of electrodeposition is 20mA/cm2The stirring speed is about 400 revolutions per minute during the electrodeposition process, and the distance between the polar plates is 1.5 cm.
Taking the titanium plate prepared in the above step as an anode and the titanium plate as a cathode, and in the acidic fluorine-containing lead solution doped with cerium dioxide and nitric acid bait, the composition of the acidic fluorine-containing lead plating solution containing cerium dioxide and nitric acid bait is 0.5mol/L of Pb (NO)3)20.15mol/L of HNO30.012mol/L NaF, 1.8g/L CeO2And Er (NO) 0.05g/L3)3Electrodepositing to obtain modified beta-PbO containing cerium dioxide, bait and fluorine2The active layer has an electrodeposition time of 1.5h, a deposition temperature of 50 ℃ and an electrodeposition current density of 35-45mA/cm2Stirring at the speed of about 500 revolutions per minute in the electrodeposition process, and obtaining the titanium-based lead dioxide anode which is co-modified by doping cerium dioxide and bait, wherein the distance between the polar plates is 4 cm.
The electrode plate is used as an anode, a stainless steel plate is used as a cathode, reverse osmosis concentrated water of a certain plant is treated, and the area of the anode and the area of the cathode are both 100cm2The inter-polar distance was 4cm, and the input current intensity was 2.0A.The initial COD concentration of the reverse osmosis concentrated water is 2200mg/L, the volume is 1.0L, the initial pH is 6.6, the reaction is carried out for 2 hours, and the removal rate of COD reaches 70%.
Claims (5)
1. A preparation method of a titanium-based lead dioxide anode is characterized by comprising the following steps: the method comprises the following steps: 1) Pretreating the titanium-based matrix to remove impurities on the surface of the matrix and obtain a surface with good treatment performance;
2) dissolving stannic chloride and antimony trichloride in isopropanol containing hydrochloric acid to obtain coating solution, wherein the composition of the stannic chloride and antimony trichloride coating solution is 500mmol/L SnCl4·5H2O, 60mmol/L SbCl3The volume ratio of the isopropanol to the concentrated hydrochloric acid is 20:1-20: 10; coating the coating liquid on the surface of a titanium plate substrate, drying at 120 ℃ for 10-15min, roasting for 5-20min, repeating for 8-10 times, and finally roasting for 1.0-2.0h to obtain an electrode with a tin-antimony oxide bottom layer;
3) taking an electrode with a tin-antimony oxide bottom layer as an anode and a titanium plate as a cathode, and electrodepositing alpha-PbO in a sodium hydroxide plating solution dissolved with PbO2An intermediate layer;
electrodeposition of alpha-PbO in step 3)2The deposition time of the intermediate layer is 0.5-1.0h, the deposition temperature is 35-45 ℃, and the current density of the electrodeposition is 20mA/cm2Stirring at the speed of 300-;
4) taking the titanium plate prepared in the step (3) as an anode and the titanium plate as a cathode, and in the acidic fluorine-containing lead solution doped with cerium dioxide and nitric acid bait, the composition of the acidic fluorine-containing lead plating solution containing the cerium dioxide and the nitric acid bait is 0.5mol/L of Pb (NO)3)20.15mol/L of HNO30.012mol/L NaF, 1.8g/L CeO2And Er (NO) 0.05g/L3)3Electrodepositing to obtain modified beta-PbO containing cerium dioxide, bait and fluorine2The active layer is used for obtaining the titanium-based lead dioxide anode;
in the step 4), the modified beta-PbO containing cerium dioxide, bait and fluorine is prepared by electrodeposition2The electro-deposition time of the active layer is 1.0-2.0h, the deposition temperature is 35-50 ℃, and the electro-deposition current density is 35-45mA/cm2The stirring speed is 500 rpm at 300-.
2. The method of claim 1, wherein: the pretreatment of the titanium-based substrate in step 1) comprises grinding and decontamination.
3. The method of claim 2, wherein: the pretreatment further comprises an acid etching treatment.
4. The method of claim 1, wherein: the roasting temperature in the step 2) is 500 ℃.
5. The method of claim 1, wherein: the composition of the PbO sodium hydroxide plating solution in the step 3) is 0.10mol/LPbO and 140g/L sodium hydroxide.
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| CN110255677A (en) * | 2019-07-08 | 2019-09-20 | 西安泰金工业电化学技术有限公司 | Multicomponent is co-doped with modified ti-supported lead dioxide electric pole and preparation method thereof |
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