CN113061955A - Preparation method of conductive polyaniline modified electrode - Google Patents
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Abstract
The invention discloses a preparation method of a conductive polyaniline modified electrode, belonging to the technical field of electrode materials and utilizing an electrochemical deposition methodPreparation of titanium dioxide nanotubes (TiO)2NTs) and conductive Polyaniline (PANI) and doping modified Carbon Nanotubes (CNTs) on the surface layer to prepare Ti/TiO2NTs/PANI/PbO2A CNTs electrode, a composite intermediate layer which can reduce corrosion rate, prolong electrode service life and improve electrode activity, CNTs surface doping which can improve electrode active surface area and catalytic activity, and Ti/PbO2Compared with the electrode, the hydroxyl radical generating capacity is increased by 46.50%, and the accelerated life of the electrode is increased by 230%.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a preparation method of a conductive polyaniline modified electrode.
Background
The electrocatalytic oxidation is called as an environment-friendly pollution treatment technology, and electrons are used as a catalyst, so that the organic pollutant-containing wastewater can be effectively treated at normal temperature and normal pressure. With the progress of energy saving and consumption reduction technology of enterprises, the electric power generated by waste heat power generation enables the electrocatalytic oxidation pollution treatment technology to be industrialized continuously. The most key technology in electrocatalytic oxidation is the preparation and application of high-performance anode materials. In many studies at home and abroad, Ti/PbO2The anode material is considered to have the most development potential due to the advantages of good catalytic activity, high oxygen evolution potential, good chemical stability, low price and the like. But Ti matrix and PbO2The internal stress between the coatings is large, and the coatings are cracked due to stress in the use process. The problem of electrode corrosion is always a difficult problem in engineering application, the introduction of an intermediate layer into an electrochemical oxidation electrode is an effective method for improving corrosion resistance, and the conventional intermediate layer has SnO2-Sb2Ox、SnO2-RuO2、IrO2-Ta2O5And the intermediate layers are all prepared by a thermal decomposition method, so that the preparation process is complicated, cracks are easily generated, and the electrodes are unstable.
Polyaniline is widely applied to the aspects of conductive composite materials, metal anticorrosive materials and the like as a conductive polymer, has the characteristics of large specific surface area, stable chemical properties and easiness in film preparation, and can be directly used for preparing a conductive polyaniline intermediate layer by an electrochemical deposition method. Paper "polyaniline interlayer modified Ti/PbO2Preparation of electrode and degradation performance thereof' two-step electrodeposition method is adopted to successfully prepare Ti/PANI/PbO2Electrodes and for methyl orange degradation; in patent CN 105185601A, CN 110112012A, for the preparation of electrode material of double electric layer super capacitor, a two-step oxidation method is adopted to prepare polyaniline-titanium dioxide nanotube composite electrode, the electrode has only two layers, and has no surface active layer, and cannot be used for catalytic degradation of organic matter in water treatment. For increasing PbO2The electrode activity can be modified by doping certain active substances when the surface active layer is electrodeposited. Patent CN 111254435A discloses a Ti/Sb-SnO2/PVDF-CNTPbO2Electrode and preparation method thereof, wherein the intermediate layer is Sb-SnO2The surface layer is PVDF and Carbon Nano Tube (CNT) doped PbO2. At present, the electrodeposition method is not used for preparing titanium-based layers and TiO2NTs/PANI intermediate layer, PbO2-reports of CNTs active layer.
Disclosure of Invention
Aiming at the requirement of industrial wastewater treatment, the invention prepares titanium-based and TiO by using a simple electrodeposition process2NTs/PANI intermediate layer, PbO2The electrode of the CNTs active layer has the comprehensive advantages of long service life and high electrocatalytic activity, and the invention comprises the following contents:
the invention aims to provide a preparation method of a conductive polyaniline modified electrode, which has the technical points that: the method comprises the following steps:
step one, TiO2Preparation of NTs intermediate layer: pretreating a titanium plate, and then taking the pretreated titanium plate as an anode, a stainless steel sheet as a cathode and adding NH4F, carrying out electrochemical oxidation treatment in an ethylene glycol solution of deionized water, calcining the titanium plate subjected to electrochemical treatment in a muffle furnace at 500 ℃ for 2h, naturally cooling, then placing the titanium plate in a 0.5mol/L sodium sulfate solution, carrying out reduction reaction for 15-20s by taking the titanium plate subjected to electrochemical treatment as a cathode and a stainless steel sheet as an anode to obtain TiO2An NTs intermediate layer;
step two, preparing the PANI intermediate layer: with the TiO prepared in step one2Depositing NTs intermediate layer as anode and stainless steel sheet as cathode in aniline sulfuric acid solution at constant voltage of 4-6V for 4-8min2Plating a PANI intermediate layer on the surface of NTs;
step three, PbO2Preparing a surface layer, and preparing the TiO plated with the PANI intermediate layer in the second step2NTs as anode, stainless steel sheet as cathode, and 10-20mA/cm at 50-60 deg.C2Current density in the presence of Pb (NO)3)2NaF and HNO3Electroplating in the electroplating solution for 60-90min to obtain Ti/TiO2NTs/PANI/PbO2An electrode;
step four, Ti/TiO in the step three2NTs/PANI/PbO2The electrode is an anode and is made of stainless steelThe sheet is cathode with electrode spacing of 2-3cm, temperature controlled at 50-60 deg.C, and current density of 10-20mA/cm2In the presence of Pb (NO)3)2、NaF、HNO3Electroplating the modified CNTs and sodium dodecyl benzene sulfonate in electroplating solution for 90-150min to prepare Ti/TiO2NTs/PANI/PbO2-a CNTs electrode.
The preparation method of the conductive polyaniline modified electrode comprises the following steps: selecting a titanium plate with the purity of more than 99 percent, polishing the titanium plate by using 320-mesh, 600-mesh and 1000-mesh sand paper in sequence, and washing the titanium plate by using deionized water; then putting the titanium plate into 10 wt% sodium hydroxide solution, heating for 2h at the temperature of 85 ℃ to remove oil stains on the surface; and finally, putting the titanium plate into 10 wt% oxalic acid solution, etching for 2 hours at the temperature of 80-90 ℃, cleaning and putting the titanium plate into absolute ethyl alcohol solution for later use.
In the first step of the preparation method of the conductive polyaniline modified electrode of the invention, NH is adopted4The concentration of F is 0.3-1.0 wt%, and the concentration of water is 2-5 vol%.
The preparation method of the conductive polyaniline modified electrode comprises the following first anodizing treatment conditions in the first step: the voltage is set to be 50-100V, and the reaction time is 1-6 h.
In the second step of the preparation method of the conductive polyaniline modified electrode, the aniline sulfuric acid solution comprises aniline with the degree of 0.1-0.2mol/L and sulfuric acid with the degree of 0.5-1.0 mol/L.
The preparation method of the conductive polyaniline modified electrode comprises the third step of the preparation method, Pb (NO) in the electroplating solution3)2The concentration of (A) is 0.3-0.6mol/L, NaF and the concentration of (B) is 0.01-0.02mol/L, HNO3The concentration of (A) is 0.1-0.3 mol/L.
The preparation method of the conductive polyaniline modified electrode comprises the following steps: placing the multi-wall carbon nanotube powder in a mixed acid of concentrated sulfuric acid and concentrated nitric acid at a ratio of 3:1 at 105 ℃ for heating and refluxing for 30min, repeatedly washing to be neutral after cooling, adding pure water for ultrasonic treatment for 2h, repeatedly washing until the conductivity is below 10 mu S/cm, finally vacuum drying at 75 ℃ for 12h, and grinding into powder for later use.
The preparation method of the conductive polyaniline modified electrode comprises the fourth step of the preparation method, Pb (NO) in the electroplating solution3)2The concentration of (A) is 0.3-0.6mol/L, NaF and the concentration of (B) is 0.01-0.02mol/L, HNO3The concentration of the modified CNTs is 0.1-0.3mol/L, the concentration of the modified CNTs is 5-10g/L, and the concentration of the sodium dodecyl benzene sulfonate is 0.1-0.2 g/L.
The embodiment of the invention adopts at least one technical scheme which can achieve the following beneficial effects:
the preparation method of the conductive polyaniline modified electrode utilizes TiO2The composite intermediate layer of NTs and PANI not only improves the corrosion resistance of the electrode, but also improves the activity of the electrode. With Ti/PbO2Compared with the prior art, the corrosion voltage is improved by nearly 7 times, the corrosion current is reduced to 1/4000, the accelerated life of the electrode is increased by 230%, and the generation capacity of hydroxyl radicals is increased by 46.50%.
Drawings
FIG. 1 is a drawing ofTi/PbO2And Ti/TiO2NTs/PANI/PbO2-CNTs electrode accelerated life test pattern;
FIG. 2 shows Ti/PbO2And Ti/TiO2NTs/PANI/PbO2-a plot of the ac impedance of the different electrodes of the CNTs;
FIG. 3 shows Ti/TiO2NTs/PANI/PbO2SEM image of intermediate layer of-CNTs electrode-Ti/TiO2NTs (left), Ti/TiO2NTs/PANI (right);
FIG. 4 shows Ti/TiO2NTs/PANI/PbO2SEM picture of-CNTs electrode surface layer-Ti/TiO2NTs/PANI/PbO2(left), Ti/TiO2NTs/PANI/PbO2CNTs (right).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the specific embodiments of the present invention and the accompanying drawings. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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.
Example 1
(1) Pretreatment of a titanium plate: selecting a pure titanium metal plate as a Ti sheet, wherein the purity is more than 99%; sequentially polishing the Ti sheet by using 320-mesh, 600-mesh and 1000-mesh sand paper, and washing with deionized water; then, putting the Ti sheet into 10 wt% sodium hydroxide solution, and heating at 85 ℃ for 2h to remove oil stains on the surface; and finally, putting the Ti sheet into 10 wt% oxalic acid solution, etching for 2h in a slightly boiling state, cleaning, and putting into absolute ethyl alcohol solution for later use.
(2)TiO2Preparation of NTs intermediate layer: taking a pretreated Ti sheet as an anode, a stainless steel sheet as a cathode, NH in a glycol solution4F with the concentration of 0.3 percent and water with the concentration of 3vol percent are taken as electrolyte and oxidized for 5 hours under the voltage of 60V; then calcined in a muffle furnace at 450 ℃ for 2 hours. After natural cooling, use Ti/TiO2NTs is used as a cathode, a stainless steel sheet is used as an anode, and reduction is carried out for 15s in 0.5mol/L sodium sulfate solution.
(3) Preparation of PANI interlayer: preparing polyaniline by a potentiostatic method, preparing aniline sulfuric acid solution according to aniline concentration of 0.1mol/L and sulfuric acid concentration of 0.5mol/L, and performing ultrasonic treatment for 20 min. With Ti/TiO2The NTs sheet is used as anode, the stainless steel sheet is used as cathode, and the deposition is carried out in aniline sulfuric acid solution at constant voltage of 5V for 15 min.
(4)PbO2Preparation of the surface layer: Ti/TiO prepared as described above2The NTs/PANI electrode is used as an anode, the stainless steel sheet is used as a cathode, the temperature is controlled to be 60 ℃, and the current density is 20mA/cm2At 0.5mol/L Pb (NO)3)2、0.01mol/L NaF、0.1mol/L HNO3Electroplating in the electroplating solution for 90min to prepare Ti/TiO2NTs/PANI/PbO2And an electrode.
(5) Modification of CNTs: placing the multi-wall carbon nanotube powder in a mixed acid of concentrated sulfuric acid and concentrated nitric acid at a ratio of 3:1 at 105 ℃ for heating and refluxing for 30min, repeatedly washing to be neutral after cooling, adding pure water for ultrasonic treatment for 2h, repeatedly washing until the conductivity is below 10 mu S/cm, finally vacuum drying at 75 ℃ for 12h, and grinding into powder for later use.
(6) CNTs doped PbO2Surface ofPreparation of the layer: Ti/TiO prepared as described above2NTs/PANI electrode as anode, stainless steel sheet as cathode, electrode spacing of 2cm, temperature controlled at 60 deg.C, and current density of 20mA/cm2At 0.5mol/L Pb (NO)3)2、0.01mol/L NaF、0.1mol/L HNO35g/L modified CNTs and 0.1g/L (sodium dodecyl benzene sulfonate) electroplating solution for 100min to prepare Ti/TiO2NTs/PANI/PbO2-a CNTs electrode.
Example 2
(1) Pretreatment of a titanium plate: selecting a pure titanium metal plate as a Ti sheet, wherein the purity is more than 99%; sequentially polishing the Ti sheet by using 320-mesh, 600-mesh and 1000-mesh sand paper, and washing with deionized water; then, putting the Ti sheet into 10 wt% sodium hydroxide solution, and heating at 85 ℃ for 2h to remove oil stains on the surface; and finally, putting the Ti sheet into 10 wt% oxalic acid solution, etching for 2h in a slightly boiling state, cleaning, and putting into absolute ethyl alcohol solution for later use.
(2)TiO2Preparation of NTs intermediate layer: taking a pretreated Ti sheet as an anode, a stainless steel sheet as a cathode, NH in a glycol solution4F with the concentration of 0.4 wt% and water with the concentration of 3 vol% are used as electrolyte, and oxidation reaction is carried out for 4h under the voltage of 70V; then calcined in a muffle furnace at 450 ℃ for 2 hours. After natural cooling, use Ti/TiO2NTs is used as a cathode, a stainless steel sheet is used as an anode, and reduction is carried out for 15s in 0.5mol/L sodium sulfate solution.
(3) Preparation of PANI interlayer: preparing polyaniline by a potentiostatic method, preparing aniline sulfuric acid solution according to aniline concentration of 0.15mol/L and sulfuric acid concentration of 0.75mol/L, and performing ultrasonic treatment for 20 min. With Ti/TiO2And (3) depositing the NTs sheet serving as an anode and the stainless steel sheet serving as a cathode in an aniline sulfuric acid solution at a constant voltage of 5V for 10min.
(4)PbO2Preparation of the surface layer: Ti/TiO prepared as described above2The NTs/PANI electrode is used as an anode, the stainless steel sheet is used as a cathode, the temperature is controlled to be 55 ℃, and the current density is 15mA/cm2At 0.6mol/L Pb (NO)3)2、0.015mol/L NaF、0.2mol/L HNO3Electroplating in electroplating solution for 75min to prepare Ti/TiO2NTs/PANI/PbO2And an electrode.
(5) Modification of CNTs: placing the multi-wall carbon nanotube powder in a mixed acid of concentrated sulfuric acid and concentrated nitric acid at a ratio of 3:1 at 105 ℃ for heating and refluxing for 30min, repeatedly washing to be neutral after cooling, adding pure water for ultrasonic treatment for 2h, repeatedly washing until the conductivity is below 10 mu S/cm, finally vacuum drying at 75 ℃ for 12h, and grinding into powder for later use.
(6) CNTs doped PbO2Preparation of the surface layer: Ti/TiO prepared as described above2NTs/PANI electrode as anode, stainless steel sheet as cathode, electrode spacing of 3cm, temperature controlled at 55 deg.C, and current density of 15mA/cm2At 0.6mol/L Pb (NO)3)2、0.015mol/L NaF、0.2mol/L HNO38g/L modified CNTs and 0.15g/L (sodium dodecyl benzene sulfonate) electroplating solution for 120min to prepare Ti/TiO2NTs/PANI/PbO2-a CNTs electrode.
Examples of the experiments
Prepared in example 1Ti/TiO2NTs/PANI/PbO2-CNTs composite electrode with conventional Ti/PbO2Comparative experiments were carried out, fig. 1 is an accelerated life test chart of an electrode, fig. 2 is an AC impedance chart of two different electrodes, fig. 3 is a Ti/TiO2NTs/PANI/PbO2SEM image of intermediate layer of-CNTs electrode-Ti/TiO2NTs (left), Ti/TiO2NTs/PANI (right); FIG. 4 shows Ti/TiO2NTs/PANI/PbO2SEM picture of-CNTs electrode surface layer-Ti/TiO2NTs/PANI/PbO2(left), Ti/TiO2NTs/PANI/PbO2CNTs (right), table 1 free radical production for different electrodes.
TABLE 1. radical production at different electrodes
From the above figures, TiO can be seen2NTs has high specific surface area, unique nano structure, physical and chemical properties and stability, is a good metal electrode base material and can make up for the defect of internal stress. Polyaniline is used as a conductive polymer, has large specific surface area and stable chemical property, and is easy to prepare a membraneThe method has the characteristics of wide application in the aspects of conductive composite materials, metal anticorrosive materials and the like, and can directly prepare the conductive polyaniline intermediate layer by an electrochemical deposition method. In practical application, the catalytic activity of the electrode can be further improved by surface doping, the carbon nano tube has high hardness, wear resistance, corrosion resistance and good electric and thermal conductivity, and the performance of the electrode can be further improved by surface doping. The invention is realized by matching the traditional Ti/PbO2And (3) modifying the electrode, introducing a novel composite middle layer to improve the corrosion resistance and activity of the material, and carrying out surface doping by using the modified carbon nano tube to improve the electrocatalytic activity of the electrode. The service life and the catalytic activity of the electrode are improved through a technical approach of compounding the intermediate layer and compounding the surface activity. The above description is only an example of the present invention, and is not intended to limit the present invention. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (8)
1. A preparation method of a conductive polyaniline modified electrode is characterized by comprising the following steps: the method comprises the following steps:
step one, TiO2Preparation of NTs intermediate layer: pretreating a titanium plate, and then taking the pretreated titanium plate as an anode, a stainless steel sheet as a cathode and adding NH4F, carrying out electrochemical oxidation treatment in an ethylene glycol solution of deionized water, calcining the titanium plate subjected to electrochemical treatment in a muffle furnace at 500 ℃ for 2h, naturally cooling, then placing the titanium plate in a 0.5mol/L sodium sulfate solution, carrying out reduction reaction for 15-20s by taking the titanium plate subjected to electrochemical treatment as a cathode and a stainless steel sheet as an anode to obtain TiO2An NTs intermediate layer;
step two, preparing the PANI intermediate layer: with the TiO prepared in step one2Depositing NTs intermediate layer as anode and stainless steel sheet as cathode in aniline sulfuric acid solution at constant voltage of 4-6V for 4-8min2Plating a PANI intermediate layer on the surface of NTs;
step three, PbO2Preparation of the surface layer, preparation of the plating in step twoTiO with PANI interlayer2NTs as anode, stainless steel sheet as cathode, and 10-20mA/cm at 50-60 deg.C2Current density in the presence of Pb (NO)3)2NaF and HNO3Electroplating in the electroplating solution for 60-90min to obtain Ti/TiO2NTs/PANI/PbO2An electrode;
step four, Ti/TiO in the step three2NTs/PANI/PbO2The electrode is anode, the stainless steel sheet is cathode, the distance between the electrodes is 2-3cm, the temperature is controlled at 50-60 deg.C, and the current density is 10-20mA/cm2In the presence of Pb (NO)3)2、NaF、HNO3Electroplating the modified CNTs and sodium dodecyl benzene sulfonate in electroplating solution for 90-150min to prepare Ti/TiO2NTs/PANI/PbO2-a CNTs electrode.
2. The method of claim 1, wherein the method comprises the following steps: the method for pretreating the titanium plate in the first step comprises the following steps: selecting a titanium plate with the purity of more than 99 percent, polishing the titanium plate by using 320-mesh, 600-mesh and 1000-mesh sand paper in sequence, and washing the titanium plate by using deionized water; then putting the titanium plate into 10 wt% sodium hydroxide solution, heating for 2h at the temperature of 85 ℃ to remove oil stains on the surface; and finally, putting the titanium plate into 10 wt% oxalic acid solution, etching for 2 hours at the temperature of 80-90 ℃, cleaning and putting the titanium plate into absolute ethyl alcohol solution for later use.
3. The method of claim 1, wherein the method comprises the following steps: NH in step one4The concentration of F is 0.3-1.0 wt%, and the concentration of water is 2-5 vol%.
4. The method of claim 1, wherein the method comprises the following steps: the conditions of the first anodic oxidation treatment in the first step are as follows: the voltage is set to be 50-100V, and the reaction time is 1-6 h.
5. The method of claim 1, wherein the method comprises the following steps: in the second step, the aniline sulfuric acid solution comprises aniline with the concentration of 0.1-0.2mol/L and sulfuric acid with the concentration of 0.5-1.0 mol/L.
6. The method of claim 1, wherein the method comprises the following steps: pb (NO) in the electroplating solution in the third step3)2The concentration of (A) is 0.3-0.6mol/L, NaF and the concentration of (B) is 0.01-0.02mol/L, HNO3The concentration of (A) is 0.1-0.3 mol/L.
7. The method of claim 1, wherein the method comprises the following steps: the preparation method of the modified CNTs in the fourth step comprises the following steps: placing the multi-wall carbon nanotube powder in a mixed acid of concentrated sulfuric acid and concentrated nitric acid at a ratio of 3:1 at 105 ℃ for heating and refluxing for 30min, repeatedly washing to be neutral after cooling, adding pure water for ultrasonic treatment for 2h, repeatedly washing until the conductivity is below 10 mu S/cm, finally vacuum drying at 75 ℃ for 12h, and grinding into powder for later use.
8. The method of claim 1, wherein the method comprises the following steps: pb (NO) in the electroplating solution in the fourth step3)2The concentration of (A) is 0.3-0.6mol/L, NaF and the concentration of (B) is 0.01-0.02mol/L, HNO3The concentration of the modified CNTs is 0.1-0.3mol/L, the concentration of the modified CNTs is 5-10g/L, and the concentration of the sodium dodecyl benzene sulfonate is 0.1-0.2 g/L.
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