CN113061955B - Preparation method of conductive polyaniline modified electrode - Google Patents
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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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 2 NTs) and conductive Polyaniline (PANI) and doping modified Carbon Nanotubes (CNTs) on the surface layer to prepare the Ti/TiO 2 NTs/PANI/PbO 2 A 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/PbO 2 Compared 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 critical technology in electrocatalytic oxidation is the preparation and application of high-performance anode materials. In a plurality of studies at home and abroad,Ti/PbO 2 the 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 PbO 2 The 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 SnO 2 -Sb 2 O x 、SnO 2 -RuO 2 、IrO 2 -Ta 2 O 5 And 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/PbO 2 Preparation of electrode and degradation performance thereof' two-step electrodeposition method is adopted to successfully prepare Ti/PANI/PbO 2 Electrodes and for methyl orange degradation; in the patent CN 105185601A and CN 110112012A, aiming at the preparation of the electrode material of the double electric layer super capacitor, a polyaniline-titanium dioxide nanotube composite electrode is prepared by a two-step oxidation method, and the electrode has only two layers and does not have a surface active layer, so the polyaniline-titanium dioxide nanotube composite electrode can not be used for catalyzing and degrading organic matters in water treatment. For increasing PbO 2 The electrode activity can be modified by doping certain active substances when the surface active layer is electrodeposited. The patent CN 111254435A discloses Ti/Sb-SnO 2 /PVDF-CNTPbO 2 An electrode and its preparation method, the intermediate layer is Sb-SnO 2 The surface layer is PVDF and Carbon Nano Tube (CNT) doped PbO 2 . At present, the electro-deposition method is not used for preparing the titanium substrate and the TiO 2 NTs/PANI intermediate layer, pbO 2 -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 process 2 NTs/PANI intermediate layer, pbO 2 Electrodes of the CNTs active layer, the electricityThe invention has the comprehensive advantages of long service life and high electrocatalytic activity, and the contents of the invention are as follows:
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, tiO 2 Preparation 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 NH 4 F, 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 500-500 ℃ 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 TiO 2 An NTs intermediate layer;
step two, preparing the PANI intermediate layer: with the TiO prepared in step one 2 Depositing NTs intermediate layer as anode and stainless steel sheet as cathode in aniline sulfuric acid solution at constant voltage of 4-6V for 4-8min 2 Plating a PANI intermediate layer on the surface of NTs;
step three, pbO 2 Preparing a surface layer, and preparing the TiO plated with the PANI intermediate layer in the second step 2 NTs as anode, stainless steel sheet as cathode, and 10-20mA/cm at 50-60 deg.C 2 Current density in the presence of Pb (NO) 3 ) 2 NaF and HNO 3 Electroplating in the electroplating solution for 60-90min to obtain Ti/TiO 2 NTs/PANI/PbO 2 An electrode;
step four, ti/TiO in the step three 2 NTs/PANI/PbO 2 The 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/cm 2 In the presence of Pb (NO) 3 ) 2 、NaF、HNO 3 Electroplating the modified CNTs and sodium dodecyl benzene sulfonate in electroplating solution for 90-150min to prepare Ti/TiO 2 NTs/PANI/PbO 2 -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 10wt% of sodium hydroxide solution, heating for 2h at 85 ℃ and temperature-degree, and removing oil stains on the surface; finally, the titanium plate was put into an oxalic acid solution 10% by weight, etched at 80 to 90 ℃ for 2 hours, washed and then put into an absolute ethanol solution for use.
In the first step of the preparation method of the conductive polyaniline modified electrode of the invention, NH is adopted 4 The concentration of F is 0.3-1.0wt%, and the concentration of water is 2-5vol%.
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 1-6h.
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 solution 3 ) 2 The concentration of (A) is 0.3-0.6mol/L, the concentration of NaF is 0.01-0.02mol/L, HNO 3 The concentration of (b) is 0.1-0.3mol/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 of 3.
The preparation method of the conductive polyaniline modified electrode comprises the fourth step of the preparation method, pb (NO) in the electroplating solution 3 ) 2 The concentration of (A) is 0.3-0.6mol/L, the concentration of NaF is 0.01-0.02mol/L, HNO 3 The 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 0.1-0.2g/L.
The embodiment of the invention adopts at least one technical scheme to achieve the following beneficial effects:
the preparation method of the conductive polyaniline modified electrode utilizes TiO 2 The 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/PbO 2 Compared with the prior art, the corrosion voltage is improved by about 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/PbO 2 And Ti/TiO 2 NTs/PANI/PbO 2 -CNTs electrode accelerated life test pattern;
FIG. 2 shows Ti/PbO 2 And Ti/TiO 2 NTs/PANI/PbO 2 -a plot of the ac impedance of the different electrodes of the CNTs;
FIG. 3 shows Ti/TiO 2 NTs/PANI/PbO 2 SEM image of intermediate layer of-CNTs electrode-Ti/TiO 2 NTs (left), ti/TiO 2 NTs/PANI (right);
FIG. 4 shows Ti/TiO 2 NTs/PANI/PbO 2 SEM picture of-CNTs electrode surface layer-Ti/TiO 2 NTs/PANI/PbO 2 (left), ti/TiO 2 NTs/PANI/PbO 2 CNTs (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 obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to 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 placing the Ti pieces in 10% by weight sodium hydroxide solution, heating at 85 deg.C for 2h to remove oil stains on the surface; finally, the Ti sheet is put into oxalic acid solution with the weight of 10 percent, etched for 2 hours in a slightly boiling state, cleaned and put into absolute ethyl alcohol solution for standby.
(2)TiO 2 Preparation of NTs intermediate layer: taking a pretreated Ti sheet as an anode, a stainless steel sheet as a cathode, NH in a glycol solution 4 F with the concentration of 0.3 percent and water with the concentration of 3vol percent are taken as electrolyte and are 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/TiO 2 NTs 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 20min. With Ti/TiO 2 The 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 15min.
(4)PbO 2 Preparation of the surface layer: ti/TiO prepared as described above 2 The 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/cm 2 At 0.5mol/L Pb (NO) 3 ) 2 、0.01mol/L NaF、0.1mol/L HNO 3 Electroplating in the electroplating solution for 90min to prepare Ti/TiO 2 NTs/PANI/PbO 2 And an electrode.
(5) CNTs modification: placing the multi-wall carbon nanotube powder in a mixed acid of concentrated sulfuric acid and concentrated nitric acid of 3.
(6) CNTs doped with PbO 2 Preparation of the surface layer: ti/TiO prepared as described above 2 NTs/PANI electrode as anode, stainless steel sheet as cathode, electrode spacing of 2cm, temperature controlled at 60 deg.C, and current density of 20mA/cm 2 At 0.5mol/L Pb (NO) 3 ) 2 、0.01mol/L NaF、0.1mol/L HNO 3 5g/L modified CNTs and 0.1g/L (sodium dodecyl benzene sulfonate) electroplating solution for 100min to prepare Ti/TiO 2 NTs/PANI/PbO 2 -a CNTs electrode.
Examples2
(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 Ti sheets by using 320-mesh, 600-mesh and 1000-mesh sand paper, and washing with deionized water; then placing the Ti pieces in 10% by weight sodium hydroxide solution, heating at 85 deg.C for 2h to remove oil stains on the surface; finally, the Ti pieces were put into an oxalic acid solution of 10% by weight, etched in a slightly boiling state for 2 hours, washed and then put into an absolute ethanol solution for use.
(2)TiO 2 Preparation of NTs intermediate layer: taking a pretreated Ti sheet as an anode, a stainless steel sheet as a cathode, NH in a glycol solution 4 F with the concentration of 0.4wt% and water with the concentration of 3vol% 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/TiO 2 NTs 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 intermediate layer: 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 20min. With Ti/TiO 2 And (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)PbO 2 Preparation of the surface layer: ti/TiO prepared as described above 2 The 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/cm 2 At 0.6mol/L Pb (NO) 3 ) 2 、0.015mol/L NaF、0.2mol/L HNO 3 Electroplating in electroplating solution for 75min to prepare Ti/TiO 2 NTs/PANI/PbO 2 And 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 of 3.
(6) CNTs doped PbO 2 Preparation of the surface layer: ti/TiO prepared as described above 2 NTs/PANI electrode as anode and stainless steel sheet as cathodeThe distance between electrodes is 3cm, the temperature is controlled to be 55 ℃, and the current density is 15mA/cm 2 At 0.6mol/L Pb (NO) 3 ) 2 、0.015mol/L NaF、0.2mol/L HNO 3 8g/L modified CNTs and 0.15g/L (sodium dodecyl benzene sulfonate) electroplating solution for 120min to prepare Ti/TiO 2 NTs/PANI/PbO 2 -CNTs electrodes.
Examples of the experiments
Prepared in example 1Ti/TiO 2 NTs/PANI/PbO 2 -CNTs composite electrode with conventional Ti/PbO 2 Comparative 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/TiO 2 NTs/PANI/PbO 2 SEM image of intermediate layer of-CNTs electrode-Ti/TiO 2 NTs (left), ti/TiO 2 NTs/PANI (right); FIG. 4 shows Ti/TiO 2 NTs/PANI/PbO 2 SEM picture of-CNTs electrode surface layer-Ti/TiO 2 NTs/PANI/PbO 2 (left), ti/TiO 2 NTs/PANI/PbO 2 CNTs (right), table 1 free radical production for different electrodes.
TABLE 1. Radical production at different electrodes
From the above figures, it can be seen that TiO 2 NTs 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 the characteristics of large specific surface area, stable chemical property and easy film preparation, has wide application in the aspects of conductive composite materials, metal anticorrosive materials and the like, and can be directly used for preparing a 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/PbO 2 Electrode modification and introduction of novel composite intermediate layer to improve corrosion resistance of materialAnd the activity is improved, and the modified carbon nano tube is used for surface doping 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, tiO 2 Preparation 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 NH 4 F, 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 450 ℃ or 500 ℃ for 2 hours, 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 TiO 2 An NTs intermediate layer;
step two, preparing the PANI intermediate layer: with the TiO prepared in step one 2 Depositing NTs intermediate layer as anode and stainless steel sheet as cathode in aniline sulfuric acid solution at constant voltage of 4-6V for 4-8min 2 Plating a PANI intermediate layer on the surface of NTs;
step three, pbO 2 Preparing a surface layer, namely preparing the TiO coated with the PANI intermediate layer in the second step 2 NTs as anode, stainless steel sheet as cathode, and 10-20mA/cm at 50-60 deg.C 2 Current density in the presence of Pb (NO) 3 ) 2 NaF and HNO 3 Electroplating in the electroplating solution for 60-90min to obtain Ti/TiO 2 NTs/PANI/PbO 2 An electrode;
step four, ti/TiO in the step three 2 NTs/PANI/PbO 2 The electrode is an anode, the stainless steel sheet is a cathode, and the electrodesAt a distance of 2-3cm, at a controlled temperature of 50-60 deg.C and a current density of 10-20mA/cm 2 In the presence of Pb (NO) 3 ) 2 、NaF、HNO 3 Electroplating the modified CNTs and sodium dodecyl benzene sulfonate in electroplating solution for 90-150min to prepare Ti/TiO 2 NTs/PANI/PbO 2 -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 10wt% sodium hydroxide solution, heating for 2h at 85 ℃, and removing oil stains on the surface; and finally, putting the titanium plate into 10wt% 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 the first step 4 The concentration of F is 0.3-1.0wt%, and the concentration of water is 2-5vol%.
4. The method for preparing a conductive polyaniline modified electrode as claimed in claim 1, wherein: 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 1-6h.
5. The method of claim 1, wherein the method comprises the following steps: and 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 step 3 ) 2 The concentration of (A) is 0.3-0.6mol/L, the concentration of NaF is 0.01-0.02mol/L, HNO 3 The concentration of (A) is 0.1-0.3mol/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 of 3.
8. The method for preparing a conductive polyaniline modified electrode as claimed in claim 1, wherein: pb (NO) in the electroplating solution in the fourth step 3 ) 2 The concentration of (A) is 0.3-0.6mol/L, the concentration of NaF is 0.01-0.02mol/L, HNO 3 The 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 0.1-0.2g/L.
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