CN109553162B - Stainless steel-based nano-array beta-PbO with ordered porous ZnO as template2Method for preparing electrode - Google Patents
Stainless steel-based nano-array beta-PbO with ordered porous ZnO as template2Method for preparing electrode Download PDFInfo
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Abstract
The invention discloses a stainless steel-based nano-array beta-PbO taking ordered porous ZnO as a template2A preparation method of an electrode, belonging to PbO2The technical field of electrode materials. The method adopts a liquid surface assembly method to prepare a single-layer polystyrene microsphere template on a stainless steel substrate; preparing an ordered ZnO nano material by adopting a low-temperature hydrothermal method; removing PS microspheres by using organic solvent, and using H3BO3The solution is used for carrying out through hole treatment on the holes left after the PS microspheres are removed to obtain an ordered porous ZnO nano template; adopting an anodic oxidation method to prepare the nano beta-PbO through electrodeposition in the pores of the ordered porous ZnO nano template2Particles of using H3BO3Removing ZnO nano template from the solution, and electrodepositing nano beta-PbO again2Preparation of stainless steel-based nano-array beta-PbO with remarkably increased specific surface area by using particles2And an electrode. The electrode has larger specific surface area, electrocatalytic activity and better corrosion resistance.
Description
Technical Field
The invention relates to a stainless steel-based nano-array beta-PbO taking ordered porous ZnO as a template2Of electrodesThe preparation method belongs to the metal oxide PbO2The technical field of electrodes.
Background
With the continuous development of national economy, the problem of environmental pollution at the cost of environmental destruction is further highlighted, and the problem of environmental pollution caused by the problem is more serious. Such as the problem of uncontrolled discharge of industrial waste water without treatment, the waste water contains many refractory organic substances, such as various pesticides, dyes, aromatic compounds, etc., which cannot be desorbed and absorbed by the natural world and remain in various waters and soils. The traditional methods for degrading organic wastewater mainly comprise a physical method, a chemical method and a biological method, but the methods always have the problems of complex process, low efficiency, high cost, easy secondary pollution and the like.
In order to degrade toxic and harmful aromatic substances in industrial wastewater, remarkably improve the degradation efficiency and reduce the energy consumption, the electrochemical treatment technology has obvious advantages in the aspects of catalytic activity, convenience, high efficiency, low energy consumption and the like, the principle is that an external power supply is utilized to directly degrade organic matters in an electrochemical reactor, or strong oxidative free radicals are generated through redox reactions on electrodes to indirectly degrade the organic matters, so that the research and development of novel inert anode materials with high catalytic activity and stability are imperative.
The electrodes used for degrading aromatic substances in organic wastewater at the present stage comprise a metal electrode, a non-metal compound electrode, a metal oxide electrode and the like, wherein the metal oxide electrode is mostly researched by PbO2The electrode, in which Pb is in its highest oxidation state and has strong oxidizing property, high oxygen evolution potential and good catalytic performance, still has many problems, such as easy detachment of the surface active layer, low stability and catalytic activity, and PbO after use2The electrodes may exhibit voids and structural defects.
Disclosure of Invention
Aiming at the metal oxide PbO in the prior art2The invention provides stainless steel taking ordered porous ZnO as a template, and solves the problems that an active layer on the surface of an electrode is easy to fall off and the stability and the catalytic activity are still lowBase nanoarray beta-PbO2The preparation method of the electrode is characterized in that ordered rugged PbO is formed on the surface of the substrate2The nano array obviously increases the specific surface area, the number of active sites and the catalytic activity. The electrode has higher oxygen evolution overpotential, electrocatalytic activity and higher corrosion resistance.
Stainless steel-based nano-array beta-PbO with ordered porous ZnO as template2The preparation method of the electrode comprises the following specific steps:
(1) the method comprises the following steps of (1) self-assembling a single-layer polystyrene microsphere template on a stainless steel plate substrate by using a stainless steel plate as the substrate and adopting a liquid surface assembly method to obtain the stainless steel base/single-layer polystyrene microsphere template;
(2) placing the stainless steel plate/single-layer polystyrene microsphere template in the step (1) in a precursor solution, and preparing an ordered nano ZnO template by adopting a low-temperature hydrothermal method to obtain a stainless steel base/single-layer polystyrene microsphere/ordered nano ZnO template; wherein the precursor solution is ZnCl2A sodium citrate aqueous solution, wherein the pH value of the precursor solution is 10-11;
(3) adopting an organic solvent to dissolve and remove the single-layer polystyrene microspheres in the stainless steel base/single-layer polystyrene microspheres/ordered nano ZnO template in the step (2), and adopting H3BO3The solution is used for carrying out through hole treatment on the holes left after the single-layer polystyrene microspheres are removed to obtain a stainless steel base/porous nano ZnO template; wherein the organic solvent is toluene, dichloromethane, tetrahydrofuran or acetone;
(4) taking the stainless steel base/porous nano ZnO template in the step (3) as an anode and a stainless steel plate as a cathode, and in electroplating solution, electrodepositing nano beta-PbO in the holes of the stainless steel base/porous nano ZnO template by adopting an anodic oxidation method2Obtaining the stainless steel base/porous nano ZnO/nano array beta-PbO2；
(5) Stainless steel base/porous nano ZnO/nano beta-PbO2Is arranged at H3BO3Soaking in solution to remove the ordered porous ZnO template to obtain the stainless steel base/nano array beta-PbO2；
(6) With stainless steel of step (5)Steel-based/nano-array beta-PbO2Taking the stainless steel plate as the cathode, and in the electroplating solution, adopting the anodic oxidation method again to perform the beta-PbO on the stainless steel base/nano array2The lattice structure of the nano beta-PbO is electrodeposited2To obtain the stainless steel-based nano-array beta-PbO2And an electrode.
The stainless steel plate in the step (1) is an activated stainless steel plate subjected to pretreatment, wherein the pretreatment comprises the steps of polishing the stainless steel plate to remove surface burrs and oxide films, removing oil, washing and drying; then, activating in a hydrochloric acid solution for 5-10 min, washing with water, and drying to obtain an activated stainless steel plate;
the specific method for self-assembling the monolayer polystyrene microsphere template on the stainless steel plate substrate by adopting the liquid surface assembly method in the step (1) is that monodisperse polystyrene microsphere stock solution is added into absolute ethyl alcohol and is subjected to ultrasonic treatment for 1-5 min to obtain a polystyrene/absolute ethyl alcohol mixed solution, the polystyrene/absolute ethyl alcohol mixed solution is dripped into deionized water to be kept stand at the temperature of 20-30 ℃ to generate a monolayer polystyrene microsphere film, the stainless steel substrate is inserted into the deionized water at an angle of more than 45 degrees, and the monolayer polystyrene microsphere template is taken out and dried after the stainless steel substrate is uniformly paved with the monolayer polystyrene microspheres; wherein the concentration of the monodisperse polystyrene microsphere stock solution is 25-50 g/L, and the particle size of the monodisperse polystyrene microsphere is 5-10 μm; the volume ratio of the monodisperse polystyrene microsphere stock solution to the absolute ethyl alcohol is 4 (3-2);
ZnCl in the precursor solution in the step (2)2The concentration is 0.1-0.3 mol/L, and the concentration of sodium citrate is 0.2-0.8 g/L;
the step (2) of preparing the ordered nano ZnO template by adopting a low-temperature hydrothermal method to obtain the stainless steel-based/single-layer polystyrene microsphere/ordered nano ZnO template comprises the specific steps of placing the stainless steel-based/single-layer polystyrene microsphere template in a precursor solution, carrying out constant-temperature hydrothermal reaction for 1-5 h at the temperature of 80-100 ℃, taking out, cooling, washing and drying to obtain the stainless steel-based/single-layer polystyrene microsphere/ordered nano ZnO template;
said H3BO3The concentration of the solution is 0.05-0.50 mol/L；
The electroplating solution is Pb (NO)3)2-NaF-Cu(NO3)2Electroplating solution, wherein the pH value of the electroplating solution is 2-3;
pb (NO) in the plating solution3)2190.0-210.0 g/L NaF concentration 0.5-0.8 g/L Cu (NO)3)2 The concentration is 15.0-30.0 g/L;
the temperature of the anodic oxidation method in the step (4) is 30-60 ℃, and the direct current density is 10-15 mA/cm2The direct current deposition time is 20-30 min;
the temperature of the anodic oxidation method in the step (6) is 30-60 ℃, and the direct current density is 10-15 mA/cm2The direct current deposition time is 10-30 min;
the stainless steel-based nano-array beta-PbO of the invention2The electrode can be used as an electrode for degrading aromatic substances in industrial organic wastewater.
The invention has the beneficial effects that:
(1) the surface of the coating of the nano array electrode material of the invention presents a regular convex lattice structure, the specific surface area is obviously increased, and the electrocatalytic activity of the electrode material can be obviously improved so as to solve the problem of common plane beta-PbO2The specific surface area of the electrode is small, the electrocatalytic activity is low and the like;
(2) the nano array electrode material takes a stainless steel plate as a substrate, has low price and is easy to obtain, and the stainless steel substrate and the beta-PbO2The plating layer has the advantages of excellent binding force, small internal stress and the like;
(3) the nano array electrode material takes the ordered porous ZnO film material as the template, and compared with other templates, the ZnO template has simple preparation process and low price of raw materials, and is suitable for large-scale use;
(4) the ordered porous ZnO template of the nano array electrode material adopts H3BO3The solution is subjected to through-hole and dissolution, and can utilize H3BO3The weak acidity of the solution effectively controls the through holes and the dissolving process of the solution to form an ordered porous ZnO template so as to facilitate the subsequent beta-PbO2Dot matrixForming a structure;
(5) the electrode coating of the nano-array electrode material has fine crystal grains and better corrosion resistance, and can better prevent the substrate from being damaged and prolong the service life of the electrode material;
(6) when the nano array electrode material is used for degrading aromatic substances in organic wastewater, the electrode material has excellent electrocatalytic performance, and has the advantages of high degradation efficiency, excellent corrosion resistance, low energy consumption and the like.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a stainless steel based nanoarray of β -PbO prepared in example 12SEM images of the electrodes;
FIG. 3 is a stainless steel based nanoarray of β -PbO prepared in example 22SEM images of the electrodes;
FIG. 4 is a stainless steel based nanoarray of β -PbO prepared in example 32SEM images of the electrodes;
FIG. 5 is a stainless steel based nanoarray of β -PbO prepared in example 42SEM images of the electrodes;
FIG. 6 is a stainless steel based nanoarray of β -PbO prepared in example 52SEM images of the electrodes;
FIG. 7 is a stainless steel base plane of beta-PbO2Electrode and stainless steel base nano array beta-PbO2A graph of the removal rate of electrode-degraded phenol as a function of time;
FIG. 8 is a stainless steel based nanoarray of β -PbO prepared under different example conditions2The removal rate of electrode-degraded phenol as a function of time.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
The stainless steel-based nano array beta-PbO of the embodiment of the invention2Electrocatalytic performance study of the electrodes: with the example stainless steel-based nanoarrays beta-PbO2The electrode is an anode, the stainless steel plate with the same area is a cathode, a direct current power supply supplies power, a two-electrode system is adopted, andsimulating industrial wastewater by using phenol as a target pollutant, and performing electrocatalytic degradation on the phenol to serve as an experimental group; using a generally planar beta-PbO2Stainless steel-based nanoarrays of electrodes and examples beta-PbO2The electrodes are respectively used as anodes, and the other conditions are unchanged, so that phenol is subjected to electrocatalytic degradation; the volume of the phenol solution was 1000mL, the concentration was 100mg/L, and the current density was 30mA/cm2。
Example 1: as shown in figure 1, a stainless steel-based nano-array beta-PbO taking ordered porous ZnO as a template2The preparation method of the electrode comprises the following specific steps:
(1) the method comprises the following steps of (1) self-assembling a single-layer polystyrene microsphere template on a stainless steel plate substrate by using a stainless steel plate as the substrate and adopting a liquid surface assembly method to obtain the stainless steel base/single-layer polystyrene microsphere template; the stainless steel plate is an activated stainless steel plate subjected to pretreatment, wherein the pretreatment comprises the steps of polishing the stainless steel plate to remove surface burrs and an oxidation film, removing oil, washing with water and drying; then placing the stainless steel plate in a hydrochloric acid solution for activation for 5min, washing and drying to obtain an activated stainless steel plate;
the specific method for self-assembling the monolayer polystyrene microsphere template on the stainless steel plate substrate by adopting the liquid surface assembly method comprises the steps of adding a monodisperse polystyrene microsphere stock solution into absolute ethyl alcohol, carrying out ultrasonic treatment for 3min to obtain a polystyrene/absolute ethyl alcohol mixed solution, dripping the polystyrene/absolute ethyl alcohol mixed solution into deionized water at the temperature of 25 ℃, standing to generate a monolayer polystyrene microsphere film, inserting the stainless steel substrate into the deionized water at an angle of more than 45 degrees, taking out the stainless steel substrate after the monolayer polystyrene microspheres are uniformly fully paved with the stainless steel substrate, and drying to obtain the stainless steel substrate/monolayer polystyrene microsphere template; wherein the concentration of the monodisperse polystyrene microsphere stock solution is 25g/L, and the particle size of the monodisperse polystyrene microsphere is 8 μm; the volume ratio of the monodisperse polystyrene microsphere stock solution to the absolute ethyl alcohol is 4: 3;
(2) placing the stainless steel plate/single-layer polystyrene microsphere template in the step (1) in a precursor solution, and preparing an ordered nano ZnO template by adopting a low-temperature hydrothermal method to obtain a stainless steel base/single-layer polystyrene microsphere/ordered nano ZnO template; wherein the precursor solution is ZnCl2-an aqueous solution of sodium citrate, the pH value of the precursor solution being 10.5; ZnCl in precursor solution2The concentration is 0.20mol/L, and the concentration of sodium citrate is 0.5 g/L;
preparing an ordered nano ZnO template by adopting a low-temperature hydrothermal method to obtain a stainless steel base/single-layer polystyrene microsphere/ordered nano ZnO template, which comprises the specific steps of placing a stainless steel plate/single-layer polystyrene microsphere template in a precursor solution, carrying out constant-temperature hydrothermal reaction for 2.0h at the temperature of 95 ℃, taking out, cooling, washing and drying to obtain the stainless steel base/single-layer polystyrene microsphere/ordered nano ZnO template;
(3) dissolving and removing the single-layer polystyrene microspheres in the stainless steel base/single-layer polystyrene microspheres/ordered nano ZnO template in the step (2) by adopting an organic solvent (toluene is used as the organic solvent), and adopting H3BO3The solution is used for carrying out through hole treatment on the holes left after the single-layer polystyrene microspheres are removed to obtain a stainless steel base/porous nano ZnO template; wherein H3BO3The concentration of the solution is 0.30 mol/L;
(4) taking the stainless steel base/porous nano ZnO template in the step (3) as an anode and a stainless steel plate as a cathode, and in electroplating solution, electrodepositing nano beta-PbO in the holes of the stainless steel base/porous nano ZnO template by adopting an anodic oxidation method2Obtaining the stainless steel base/porous nano ZnO/nano array beta-PbO2(ii) a Wherein the electroplating solution is Pb (NO)3)2-NaF-Cu(NO3)2The pH value of the electroplating solution is 2.5; pb (NO) in electroplating bath3)2The concentration is 190.0g/L, the NaF concentration is 0.5g/L, and Cu (NO)3)2 The concentration is 15.0 g/L; the temperature of the anodic oxidation method is 40 ℃, and the direct current density is 12.5mA/cm2The direct current deposition time is 20 min;
(5) stainless steel base/porous nano ZnO/nano beta-PbO2Is arranged at H3BO3Soaking in solution to remove the ordered porous ZnO template to obtain the stainless steel base/nano array beta-PbO2(ii) a Wherein H3BO3The concentration of the solution is 0.35 mol/L;
(6) with the stainless steel base/nano of the step (5)Rice array beta-PbO2Is used as an anode, a stainless steel plate is used as a cathode, and in the electroplating solution, the anode oxidation method is adopted to carry out the beta-PbO on the stainless steel base/nano array2In the pores of the porous body is electrodeposited with nano beta-PbO2To obtain the stainless steel-based nano-array beta-PbO2An electrode; wherein the electroplating solution is Pb (NO)3)2-NaF-Cu(NO3)2The pH value of the electroplating solution is 2.5; pb (NO) in electroplating bath3)2The concentration is 190.0g/L, the NaF concentration is 0.5g/L, and Cu (NO)3)2 The concentration is 15.0g/L, the temperature of the anodic oxidation method is 40 ℃, and the direct current density is 12.5mA/cm2The DC deposition time is 20 min.
The stainless steel-based nanoarrays of beta-PbO were prepared by the present example2SEM image of electrode (see FIG. 2), stainless steel-based nanoarray of beta-PbO2The electrode material has obvious regular raised lattice structure and common plane beta-PbO2Compared with the electrode material, the raised lattice structure increases the number of electrocatalytic active sites, effectively increases the specific surface area of electrocatalytic reaction, and thus improves the electrocatalytic performance.
Example 2: as shown in figure 1, a stainless steel-based nano-array beta-PbO taking ordered porous ZnO as a template2The preparation method of the electrode comprises the following specific steps:
(1) the method comprises the following steps of (1) self-assembling a single-layer polystyrene microsphere template on a stainless steel plate substrate by using a stainless steel plate as the substrate and adopting a liquid surface assembly method to obtain the stainless steel base/single-layer polystyrene microsphere template; the stainless steel plate is an activated stainless steel plate subjected to pretreatment, wherein the pretreatment comprises the steps of polishing the stainless steel plate to remove surface burrs and an oxidation film, removing oil, washing with water and drying; then placing the stainless steel plate in a hydrochloric acid solution for activation for 5min, washing and drying to obtain an activated stainless steel plate;
the specific method for self-assembling the monolayer polystyrene microsphere template on the stainless steel plate substrate by adopting the liquid surface assembly method comprises the steps of adding a monodisperse polystyrene microsphere stock solution into absolute ethyl alcohol, carrying out ultrasonic treatment for 3min to obtain a polystyrene/absolute ethyl alcohol mixed solution, dripping the polystyrene/absolute ethyl alcohol mixed solution into deionized water at the temperature of 25 ℃, standing to generate a monolayer polystyrene microsphere film, inserting the stainless steel substrate into the deionized water at an angle of more than 45 degrees, taking out the stainless steel substrate after the monolayer polystyrene microspheres are uniformly fully paved with the stainless steel substrate, and drying to obtain the stainless steel substrate/monolayer polystyrene microsphere template; wherein the concentration of the monodisperse polystyrene microsphere stock solution is 25g/L, and the particle size of the monodisperse polystyrene microsphere is 8 μm; the volume ratio of the monodisperse polystyrene microsphere stock solution to the absolute ethyl alcohol is 4: 3;
(2) placing the stainless steel plate/single-layer polystyrene microsphere template in the step (1) in a precursor solution, and preparing an ordered nano ZnO template by adopting a low-temperature hydrothermal method to obtain a stainless steel base/single-layer polystyrene microsphere/ordered nano ZnO template; wherein the precursor solution is ZnCl2-an aqueous solution of sodium citrate, the pH value of the precursor solution being 10.5; ZnCl in precursor solution2The concentration is 0.2 mol/L, and the concentration of the sodium citrate is 0.20 g/L;
preparing an ordered nano ZnO template by adopting a low-temperature hydrothermal method to obtain a stainless steel base/single-layer polystyrene microsphere/ordered nano ZnO template, which comprises the specific steps of placing a stainless steel plate/single-layer polystyrene microsphere template in a precursor solution, carrying out constant-temperature hydrothermal reaction for 2 hours at the temperature of 90 ℃, taking out, cooling, washing and drying to obtain the stainless steel base/single-layer polystyrene microsphere/ordered nano ZnO template;
(3) dissolving and removing the single-layer polystyrene microspheres in the stainless steel base/single-layer polystyrene microspheres/ordered nano ZnO template in the step (2) by adopting an organic solvent (toluene is used as the organic solvent), and adopting H3BO3The solution is used for carrying out through hole treatment on the holes left after the single-layer polystyrene microspheres are removed to obtain a stainless steel base/porous nano ZnO template; wherein H3BO3The concentration of the solution is 0.10 mol/L;
(4) taking the stainless steel base/porous nano ZnO template in the step (3) as an anode and a stainless steel plate as a cathode, and in electroplating solution, electrodepositing nano beta-PbO in the holes of the stainless steel base/porous nano ZnO template by adopting an anodic oxidation method2Obtaining the stainless steel base/porous nano ZnO/nano array beta-PbO2(ii) a Wherein the electroplating solution is Pb (NO)3)2-NaF-Cu(NO3)2The pH value of the electroplating solution is 2; pb (NO) in electroplating bath3)2The concentration is 190.0g/L, the NaF concentration is 0.5g/L, and Cu (NO)3)2 The concentration is 15.0 g/L; the temperature of the anodic oxidation method is 40 ℃, and the direct current density is 10mA/cm2The direct current deposition time is 30 min;
(5) stainless steel base/porous nano ZnO/nano beta-PbO2Is arranged at H3BO3Soaking in solution to remove the ordered porous ZnO template to obtain the stainless steel base/nano array beta-PbO2(ii) a Wherein H3BO3The concentration of the solution is 0.25 mol/L;
(6) with the stainless steel base/nano array beta-PbO of the step (5)2Taking the stainless steel plate as the cathode, and in the electroplating solution, adopting the anodic oxidation method again to perform the beta-PbO on the stainless steel base/nano array2The lattice structure of the nano beta-PbO is electrodeposited2To obtain the stainless steel-based nano-array beta-PbO2An electrode; wherein the electroplating solution is Pb (NO)3)2-NaF-Cu(NO3)2The pH value of the electroplating solution is 2; pb (NO) in electroplating bath3)2The concentration is 190.0g/L, the NaF concentration is 0.5g/L, and Cu (NO)3)2 The concentration is 15.0g/L, the temperature of the anodic oxidation method is 40 ℃, and the direct current density is 10mA/cm2The DC deposition time is 20 min.
By stainless steel based nanoarrays of beta-PbO2SEM picture of electrode (see FIG. 3) shows that the stainless steel-based nanoarray prepared by this example is beta-PbO2The electrode material had more regular convex granular structure than example 1, but the surface grains were reduced and the regular lattice structure was reduced; but its catalytic active surface area is in common plane with beta-PbO2Compared with the electrode material, the electrode material is still increased, and the specific surface area of the electrocatalytic reaction is effectively increased, so that the electrocatalytic performance is improved.
Example 3: as shown in figure 1, a stainless steel-based nano-array beta-PbO taking ordered porous ZnO as a template2The preparation method of the electrode comprises the following specific steps:
(1) the method comprises the following steps of (1) self-assembling a single-layer polystyrene microsphere template on a stainless steel plate substrate by using a stainless steel plate as the substrate and adopting a liquid surface assembly method to obtain the stainless steel base/single-layer polystyrene microsphere template; the stainless steel plate is an activated stainless steel plate subjected to pretreatment, wherein the pretreatment comprises the steps of polishing the stainless steel plate to remove surface burrs and an oxidation film, removing oil, washing with water and drying; then placing the stainless steel plate in a hydrochloric acid solution for activation for 8 min, washing with water and drying to obtain an activated stainless steel plate;
the specific method for self-assembling the monolayer polystyrene microsphere template on the stainless steel plate substrate by adopting the liquid surface assembly method comprises the steps of adding a monodisperse polystyrene microsphere stock solution into absolute ethyl alcohol, carrying out ultrasonic treatment for 1min to obtain a polystyrene/absolute ethyl alcohol mixed solution, dripping the polystyrene/absolute ethyl alcohol mixed solution into deionized water at the temperature of 20 ℃, standing to generate a monolayer polystyrene microsphere film, inserting the stainless steel substrate into the deionized water at an angle of more than 45 degrees, taking out the stainless steel substrate after the monolayer polystyrene microspheres are uniformly fully paved with the stainless steel substrate, and drying to obtain the stainless steel substrate/monolayer polystyrene microsphere template; wherein the concentration of the monodisperse polystyrene microsphere stock solution is 30 g/L, and the particle size of the monodisperse polystyrene microsphere is 5 μm; the volume ratio of the monodisperse polystyrene microsphere stock solution to the absolute ethyl alcohol is 4: 2.5;
(2) placing the stainless steel plate/single-layer polystyrene microsphere template in the step (1) in a precursor solution, and preparing an ordered nano ZnO template by adopting a low-temperature hydrothermal method to obtain a stainless steel base/single-layer polystyrene microsphere/ordered nano ZnO template; wherein the precursor solution is ZnCl2-an aqueous solution of sodium citrate, the pH value of the precursor solution being 10.0; ZnCl in precursor solution2The concentration is 0.15 mol/L, and the concentration of the sodium citrate is 0.20 g/L;
preparing an ordered nano ZnO template by adopting a low-temperature hydrothermal method to obtain a stainless steel base/single-layer polystyrene microsphere/ordered nano ZnO template, which comprises the specific steps of placing a stainless steel plate/single-layer polystyrene microsphere template in a precursor solution, carrying out constant-temperature hydrothermal reaction for 4.5 hours at the temperature of 85 ℃, taking out, cooling, washing and drying to obtain the stainless steel base/single-layer polystyrene microsphere/ordered nano ZnO template;
(3) using an organic solvent (Dichloromethane is used as organic solvent) is dissolved and removed from the stainless steel base/single-layer polystyrene microsphere in the ordered nano ZnO template in the step (2), and H is adopted3BO3The solution is used for carrying out through hole treatment on the holes left after the single-layer polystyrene microspheres are removed to obtain a stainless steel base/porous nano ZnO template; wherein H3BO3The concentration of the solution is 0.35 mol/L;
(4) taking the stainless steel base/porous nano ZnO template in the step (3) as an anode and a stainless steel plate as a cathode, and in electroplating solution, electrodepositing nano beta-PbO in the holes of the stainless steel base/porous nano ZnO template by adopting an anodic oxidation method2Obtaining the stainless steel base/porous nano ZnO/nano array beta-PbO2(ii) a Wherein the electroplating solution is Pb (NO)3)2-NaF-Cu(NO3)2The pH value of the electroplating solution is 2.5; pb (NO) in electroplating bath3)2Concentration of 200.0 g/L, NaF concentration of 0.6 g/L, Cu (NO)3)2 The concentration is 20.0 g/L; the temperature of the anodic oxidation method is 50 ℃, and the direct current density is 10mA/cm2The direct current deposition time is 20 min;
(5) stainless steel base/porous nano ZnO/nano beta-PbO2Is arranged at H3BO3Soaking in solution to remove the ordered porous ZnO template to obtain the stainless steel base/nano array beta-PbO2(ii) a Wherein H3BO3The concentration of the solution is 0.10 mol/L;
(6) with the stainless steel base/nano array beta-PbO of the step (5)2Is used as an anode, a stainless steel plate is used as a cathode, and in the electroplating solution, the anode oxidation method is adopted to carry out the beta-PbO on the stainless steel base/nano array2In the pores of the porous body is electrodeposited with nano beta-PbO2To obtain the stainless steel-based nano-array beta-PbO2An electrode; wherein the electroplating solution is Pb (NO)3)2-NaF-Cu(NO3)2The pH value of the electroplating solution is 2.5; pb (NO) in electroplating bath3)2Concentration of 200.0 g/L, NaF concentration of 0.6 g/L, Cu (NO)3)2 The concentration is 20.0 g/L, the temperature of the anodic oxidation method is 50 ℃, and the direct current density is 10mA/cm2The DC deposition time is 10 min.
By stainless steel based nanoarrays of beta-PbO2The SEM picture (FIG. 4) of the electrode shows that the stainless steel-based nanoarray prepared by the present example is beta-PbO2Compared with the electrode material in the embodiment 1, the electrode material has a similar convex lattice structure, but the surface grains are not completely formed; but its catalytic active surface area is in common plane with beta-PbO2Compared with the electrode material, the electrode material is still increased, and the specific surface area of the electrocatalytic reaction is effectively increased, so that the electrocatalytic performance is improved.
Example 4: as shown in figure 1, a stainless steel-based nano-array beta-PbO taking ordered porous ZnO as a template2The preparation method of the electrode comprises the following specific steps:
(1) the method comprises the following steps of (1) self-assembling a single-layer polystyrene microsphere template on a stainless steel plate substrate by using a stainless steel plate as the substrate and adopting a liquid surface assembly method to obtain the stainless steel base/single-layer polystyrene microsphere template; the stainless steel plate is an activated stainless steel plate subjected to pretreatment, wherein the pretreatment comprises the steps of polishing the stainless steel plate to remove surface burrs and an oxidation film, removing oil, washing with water and drying; then placing the stainless steel plate in a hydrochloric acid solution for activation for 10min, washing with water and drying to obtain an activated stainless steel plate;
the specific method for self-assembling the monolayer polystyrene microsphere template on the stainless steel plate substrate by adopting the liquid surface assembly method comprises the steps of adding a monodisperse polystyrene microsphere stock solution into absolute ethyl alcohol, carrying out ultrasonic treatment for 5min to obtain a polystyrene/absolute ethyl alcohol mixed solution, dripping the polystyrene/absolute ethyl alcohol mixed solution into deionized water at the temperature of 30 ℃, standing to generate a monolayer polystyrene microsphere film, inserting the stainless steel substrate into the deionized water at an angle of more than 45 degrees, taking out the stainless steel substrate after the monolayer polystyrene microspheres are uniformly fully paved with the stainless steel substrate, and drying to obtain the stainless steel substrate/monolayer polystyrene microsphere template; wherein the concentration of the monodisperse polystyrene microsphere stock solution is 35g/L, and the particle size of the monodisperse polystyrene microsphere is 10 μm; the volume ratio of the monodisperse polystyrene microsphere stock solution to the absolute ethyl alcohol is 4: 2;
(2) placing the stainless steel plate/single-layer polystyrene microsphere template obtained in the step (1) in a precursor solution, and preparing the ordered nano ZnO mold by adopting a low-temperature hydrothermal methodObtaining a stainless steel base/single-layer polystyrene microsphere/ordered nano ZnO template by the plate; wherein the precursor solution is ZnCl2-an aqueous solution of sodium citrate, the pH value of the precursor solution being 11; ZnCl in precursor solution2The concentration is 0.3mol/L, and the concentration of sodium citrate is 0.8 g/L;
preparing an ordered nano ZnO template by adopting a low-temperature hydrothermal method to obtain a stainless steel base/single-layer polystyrene microsphere/ordered nano ZnO template, which comprises the specific steps of placing a stainless steel plate/single-layer polystyrene microsphere template in a precursor solution, carrying out constant-temperature hydrothermal reaction for 1h at the temperature of 100 ℃, taking out, cooling, washing and drying to obtain the stainless steel base/single-layer polystyrene microsphere/ordered nano ZnO template;
(3) dissolving and removing the single-layer polystyrene microspheres in the stainless steel base/single-layer polystyrene microspheres/ordered nano ZnO template in the step (2) by adopting an organic solvent (tetrahydrofuran), and adopting H3BO3The solution is used for carrying out through hole treatment on the holes left after the single-layer polystyrene microspheres are removed to obtain a stainless steel base/porous nano ZnO template; wherein H3BO3The concentration of the solution is 0.45 mol/L;
(4) taking the stainless steel base/porous nano ZnO template in the step (3) as an anode and a stainless steel plate as a cathode, and in electroplating solution, electrodepositing nano beta-PbO in the holes of the stainless steel base/porous nano ZnO template by adopting an anodic oxidation method2Obtaining the stainless steel base/porous nano ZnO/nano array beta-PbO2(ii) a Wherein the electroplating solution is Pb (NO)3)2-NaF-Cu(NO3)2The pH value of the electroplating solution is 3; pb (NO) in electroplating bath3)2190.0g/L concentration, 0.5g/L concentration of NaF, Cu (NO)3)2 The concentration is 15.0 g/L; the temperature of the anodic oxidation method is 60 ℃, and the direct current density is 15mA/cm2The direct current deposition time is 20 min;
(5) stainless steel base/porous nano ZnO/nano beta-PbO2Is arranged at H3BO3Soaking in solution to remove the ordered porous ZnO template to obtain the stainless steel base/nano array beta-PbO2(ii) a Wherein H3BO3The concentration of the solution is0.45 mol/L；
(6) With the stainless steel base/nano array beta-PbO of the step (5)2Is used as an anode, a stainless steel plate is used as a cathode, and in the electroplating solution, the anode oxidation method is adopted to carry out the beta-PbO on the stainless steel base/nano array2In the pores of the porous body is electrodeposited with nano beta-PbO2To obtain the stainless steel-based nano-array beta-PbO2An electrode; wherein the electroplating solution is Pb (NO)3)2-NaF-Cu(NO3)2The pH value of the electroplating solution is 3; pb (NO) in electroplating bath3)2The concentration is 190.0g/L, the NaF concentration is 0.5g/L, and Cu (NO)3)2 The concentration is 15.0g/L, the temperature of the anodic oxidation method is 60 ℃, and the direct current density is 15mA/cm2The DC deposition time was 30 min.
By stainless steel based nanoarrays of beta-PbO2SEM picture of electrode (see FIG. 5) shows that the stainless steel-based nanoarrays prepared by this example are beta-PbO2The electrode material had a similar regular convex granular structure compared to example 1, but the surface granular particle size was significantly increased. But its catalytic active surface area is in common plane with beta-PbO2Compared with the electrode material, the electrode material is still increased, and the specific surface area of the electrocatalytic reaction is effectively increased, so that the electrocatalytic performance is also improved.
Example 5: as shown in figure 1, a stainless steel-based nano-array beta-PbO taking ordered porous ZnO as a template2The preparation method of the electrode comprises the following specific steps:
(1) the method comprises the following steps of (1) self-assembling a single-layer polystyrene microsphere template on a stainless steel plate substrate by using a stainless steel plate as the substrate and adopting a liquid surface assembly method to obtain the stainless steel base/single-layer polystyrene microsphere template; the stainless steel plate is an activated stainless steel plate subjected to pretreatment, wherein the pretreatment comprises the steps of polishing the stainless steel plate to remove surface burrs and an oxidation film, removing oil, washing with water and drying; then placing the stainless steel plate in a hydrochloric acid solution for activation for 5min, washing and drying to obtain an activated stainless steel plate;
the specific method for self-assembling the monolayer polystyrene microsphere template on the stainless steel plate substrate by adopting the liquid surface assembly method comprises the steps of adding a monodisperse polystyrene microsphere stock solution into absolute ethyl alcohol, carrying out ultrasonic treatment for 3min to obtain a polystyrene/absolute ethyl alcohol mixed solution, dripping the polystyrene/absolute ethyl alcohol mixed solution into deionized water at the temperature of 25 ℃, standing to generate a monolayer polystyrene microsphere film, inserting the stainless steel substrate into the deionized water at an angle of more than 45 degrees, taking out the stainless steel substrate after the monolayer polystyrene microspheres are uniformly fully paved with the stainless steel substrate, and drying to obtain the stainless steel substrate/monolayer polystyrene microsphere template; wherein the concentration of the monodisperse polystyrene microsphere stock solution is 50 g/L, and the particle size of the monodisperse polystyrene microsphere is 8 μm; the volume ratio of the monodisperse polystyrene microsphere stock solution to the absolute ethyl alcohol is 4: 3;
(2) placing the stainless steel plate/single-layer polystyrene microsphere template in the step (1) in a precursor solution, and preparing an ordered nano ZnO template by adopting a low-temperature hydrothermal method to obtain a stainless steel base/single-layer polystyrene microsphere/ordered nano ZnO template; wherein the precursor solution is ZnCl2-an aqueous solution of sodium citrate, the pH value of the precursor solution being 10.5; ZnCl in precursor solution2The concentration is 0.20mol/L, and the concentration of sodium citrate is 0.5 g/L;
preparing an ordered nano ZnO template by adopting a low-temperature hydrothermal method to obtain a stainless steel base/single-layer polystyrene microsphere/ordered nano ZnO template, which comprises the specific steps of placing a stainless steel plate/single-layer polystyrene microsphere template in a precursor solution, carrying out constant-temperature hydrothermal reaction for 2.0h at the temperature of 90 ℃, taking out, cooling, washing and drying to obtain the stainless steel base/single-layer polystyrene microsphere/ordered nano ZnO template;
(3) dissolving and removing the stainless steel base/single-layer polystyrene microspheres in the ordered nano ZnO template in the step (2) by adopting an organic solvent (acetone is used as the organic solvent), and adopting H3BO3The solution is used for carrying out through hole treatment on the holes left after the single-layer polystyrene microspheres are removed to obtain a stainless steel base/porous nano ZnO template; wherein H3BO3The concentration of the solution is 0.08 mol/L;
(4) taking the stainless steel base/porous nano ZnO template in the step (3) as an anode and the stainless steel plate as a cathode, and in electroplating solution, electrodepositing nano ZnO in the holes of the stainless steel base/porous nano ZnO template by adopting an anodic oxidation methodβ-PbO2Obtaining the stainless steel base/porous nano ZnO/nano array beta-PbO2(ii) a Wherein the electroplating solution is Pb (NO)3)2-NaF-Cu(NO3)2The pH value of the electroplating solution is 2; pb (NO) in electroplating bath3)2The concentration is 210.0 g/L, the NaF concentration is 0.8g/L, and Cu (NO)3)2 The concentration is 30.0 g/L; the temperature of the anodic oxidation method is 50 ℃, and the direct current density is 10mA/cm2The direct current deposition time is 30 min;
(5) stainless steel base/porous nano ZnO/nano beta-PbO2Is arranged at H3BO3Soaking in solution to remove the ordered porous ZnO template to obtain the stainless steel base/nano array beta-PbO2(ii) a Wherein H3BO3The concentration of the solution is 0.25 mol/L;
(6) with the stainless steel base/nano array beta-PbO of the step (5)2Is used as an anode, a stainless steel plate is used as a cathode, and in the electroplating solution, the anode oxidation method is adopted to carry out the beta-PbO on the stainless steel base/nano array2In the pores of the porous body is electrodeposited with nano beta-PbO2To obtain the stainless steel-based nano-array beta-PbO2An electrode; wherein the electroplating solution is Pb (NO)3)2-NaF-Cu(NO3)2The pH value of the electroplating solution is 2; pb (NO) in electroplating bath3)2The concentration is 210.0 g/L, the NaF concentration is 0.8g/L, and Cu (NO)3)2 The concentration is 30.0 g/L, the temperature of the anodic oxidation method is 50 ℃, and the direct current density is 10mA/cm2The DC deposition time is 20 min.
By stainless steel based nanoarrays of beta-PbO2SEM picture of electrode (see FIG. 6) shows that the stainless steel-based nanoarrays prepared by this example are beta-PbO2The electrode material had a similar regular convex granular structure compared to examples 2 and 4, but the structure was dendritic. But its catalytic active surface area is in common plane with beta-PbO2Compared with the electrode material, the electrode material is still increased, and the specific surface area of the electrocatalytic reaction is effectively increased, so that the electrocatalytic performance is improved;
this example stainless Steel base plane beta-PbO2Electrode and stainless steel base nano arrayβ-PbO2FIG. 7 shows the time-dependent change of the removal rate of phenol degraded by the electrode, and after 90min of degradation, the stainless steel-based nanoarray of this example, β -PbO, was obtained2The removal rate of the electrode to phenol is as high as 80-85%; and a common plane beta-PbO2The removal rate of the electrode to phenol was 65%; common plane beta-PbO2The catalytic efficiency of the electrode is obviously lower than that of the electrode material of the embodiment, and the electrode of the embodiment has larger electrocatalytic active surface area;
stainless steel-based nanoarrays beta-PbO prepared under different example conditions2The graph of the removal rate of the electrode-degraded phenol along with the time is shown in FIG. 8, and it can be seen from FIG. 8 that the stainless steel-based nanoarrays beta-PbO with similar morphology can be prepared under the conditions of proper polystyrene microsphere particle size, proper temperature, proper electrodeposition time, current density and the like2An electrode material; factors such as different electrodeposition time and current density influence the morphology, and too short time can cause beta-PbO2The lattice structure is not formed, the regularity of the lattice structure is lost due to too long time, but the lattice structure has better catalysis effect, and the beta-PbO prepared under different conditions of examples2Electrode material with catalytic activity of beta-PbO in a relatively flat surface2The electrodes are greatly improved.
Claims (10)
1. Stainless steel-based nano-array beta-PbO with ordered porous ZnO as template2The preparation method of the electrode is characterized by comprising the following specific steps:
(1) the method comprises the following steps of (1) self-assembling a single-layer polystyrene microsphere template on a stainless steel plate substrate by using a stainless steel plate as the substrate and adopting a liquid surface assembly method to obtain the stainless steel base/single-layer polystyrene microsphere template;
(2) placing the stainless steel-based/single-layer polystyrene microsphere template in the step (1) in a precursor solution, and preparing an ordered nano ZnO template by adopting a low-temperature hydrothermal method to obtain the stainless steel-based/single-layer polystyrene microsphere/ordered nano ZnO template; wherein the precursor solution is ZnCl2A sodium citrate aqueous solution, wherein the pH value of the precursor solution is 10-11;
(3) removing by dissolving with organic solventStep (2) is to adopt H in the stainless steel base/single-layer polystyrene microsphere in the ordered nano ZnO template3BO3The solution is used for carrying out through hole treatment on the holes left after the single-layer polystyrene microspheres are removed to obtain a stainless steel base/porous nano ZnO template; wherein the organic solvent is toluene, dichloromethane, tetrahydrofuran or acetone; h3BO3The concentration of the solution is 0.05-0.50 mol/L;
(4) taking the stainless steel base/porous nano ZnO template in the step (3) as an anode and a stainless steel plate as a cathode, and in electroplating solution, electrodepositing nano beta-PbO in the holes of the stainless steel base/porous nano ZnO template by adopting an anodic oxidation method2Obtaining the stainless steel base/porous nano ZnO/nano array beta-PbO2；
(5) Stainless steel base/porous nano ZnO/nano beta-PbO2Is arranged at H3BO3Soaking in solution to remove the ordered porous ZnO template to obtain the stainless steel base/nano array beta-PbO2；
(6) With the stainless steel base/nano array beta-PbO of the step (5)2Taking the stainless steel plate as the cathode, and in the electroplating solution, adopting the anodic oxidation method again to perform the beta-PbO on the stainless steel base/nano array2The lattice structure of the nano beta-PbO is electrodeposited2To obtain the stainless steel-based nano-array beta-PbO2And an electrode.
2. The stainless steel-based nanoarray β -PbO as templated by ordered porous ZnO as claimed in claim 12The preparation method of the electrode is characterized in that: the stainless steel plate in the step (1) is an activated stainless steel plate for pretreatment, wherein the pretreatment comprises the steps of mechanically polishing the stainless steel plate to remove surface burrs and oxide films, removing oil, washing and drying; and then, activating in a hydrochloric acid solution for 5-10 min, washing with water, and drying to obtain the activated stainless steel plate.
3. The stainless steel-based nanoarray β -PbO as templated by ordered porous ZnO as claimed in claim 12The preparation method of the electrode is characterized in that: step (1) adopts a liquid surface assembly method to assemble on a stainless steel plate substrateAdding a monodisperse polystyrene microsphere stock solution into absolute ethyl alcohol, performing ultrasonic treatment for 1-5 min to obtain a polystyrene/absolute ethyl alcohol mixed solution, dropwise adding the polystyrene/absolute ethyl alcohol mixed solution into deionized water at the temperature of 20-30 ℃, standing to generate a single-layer polystyrene microsphere film, inserting a stainless steel substrate into the deionized water at an angle of more than 45 degrees, taking out the single-layer polystyrene microsphere film after the stainless steel substrate is uniformly paved with the single-layer polystyrene microspheres, and drying to obtain the stainless steel-based/single-layer polystyrene microsphere template; wherein the concentration of the monodisperse polystyrene microsphere stock solution is 25-50 g/L, and the particle size of the monodisperse polystyrene microsphere is 5-10 μm; the volume ratio of the monodisperse polystyrene microsphere stock solution to the absolute ethyl alcohol is 4 (3-2).
4. The stainless steel-based nanoarray β -PbO as templated by ordered porous ZnO as claimed in claim 12The preparation method of the electrode is characterized in that: ZnCl in the precursor solution in the step (2)2The concentration is 0.1-0.3 mol/L, and the concentration of sodium citrate is 0.2-0.8 g/L.
5. The stainless steel-based nanoarray β -PbO as templated by ordered porous ZnO as claimed in claim 12The preparation method of the electrode is characterized in that: the step (2) of preparing the ordered nano ZnO template by adopting a low-temperature hydrothermal method to obtain the stainless steel-based/single-layer polystyrene microsphere/ordered nano ZnO template comprises the specific steps of placing the stainless steel-based/single-layer polystyrene microsphere template in a precursor solution, carrying out constant-temperature hydrothermal reaction for 1-5 h at the temperature of 80-100 ℃, taking out, cooling, washing and drying to obtain the stainless steel-based/single-layer polystyrene microsphere/ordered nano ZnO template.
6. The stainless steel-based nanoarray β -PbO as templated by ordered porous ZnO as claimed in claim 12The preparation method of the electrode is characterized in that: the electroplating solution is Pb (NO)3)2-NaF-Cu(NO3)2The pH value of the electroplating solution is 2-3.
7. The stainless steel-based nanoarray β -PbO as templated by ordered porous ZnO as claimed in claim 12The preparation method of the electrode is characterized in that: pb (NO) in electroplating bath3)2190.0-210.0 g/L NaF concentration 0.5-0.8 g/L Cu (NO)3)2 The concentration is 15.0-30.0 g/L.
8. The stainless steel-based nanoarray β -PbO as templated by ordered porous ZnO as claimed in claim 12The preparation method of the electrode is characterized in that: the temperature of the anodic oxidation method in the step (4) is 30-60 ℃, and the direct current density is 10-15 mA/cm2The time of direct current deposition is 20-30 min.
9. The stainless steel-based nanoarray β -PbO as templated by ordered porous ZnO as claimed in claim 12The preparation method of the electrode is characterized in that: the temperature of the anodic oxidation method in the step (6) is 30-60 ℃, and the direct current density is 10-15 mA/cm2The time of direct current deposition is 10-30 min.
10. The stainless steel-based nanoarray beta-PbO with ordered porous ZnO as template according to any one of claims 1 to 92The electrode prepared by the preparation method of the electrode is applied to the degradation of aromatic substances in industrial organic wastewater.
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