Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the titanium-based tin antimony oxide electrode modified by the titanium dioxide mesh structure and the preparation method thereof, wherein the titanium-based tin antimony oxide electrode has strong stability, a catalyst layer is not easy to fall off, the corrosion of a titanium substrate is effectively prevented, and the service life of the electrode is prolonged.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a titanium-based tin antimony oxide electrode modified by a titanium dioxide mesh structure comprises a titanium substrate and a catalyst layer, and is characterized in that: the titanium substrate is subjected to hydro-thermal synthesis reaction, the middle layer of a titanium dioxide net structure is formed on the surface of the titanium substrate, and then a surface tin antimony oxide coating is formed on the middle layer of the net structure by a pulse electrodeposition method and a temperature programmed annealing activation method, wherein the surface tin antimony oxide coating is a tin antimony oxide catalyst layer.
And the surface of the middle layer of the titanium dioxide net structure is composed of meshes with the average diameter of 5 mu m, filamentous fibers are fully distributed in the meshes, and the average width of each filamentous fiber is less than 100 nm.
A preparation method of a titanium-based tin antimony oxide electrode modified by a titanium dioxide net structure is characterized by comprising the following steps: the method comprises the following steps:
(1) pretreatment of the titanium substrate: firstly, polishing the surface of a titanium substrate by using sand paper to remove oxidized titanium dioxide on the surface; then, washing the titanium matrix with alkali by using a sodium hydroxide solution at high temperature to remove oil; then, acid etching is carried out on the titanium matrix by oxalic acid solution at high temperature; finally, repeatedly washing the treated substrate by using deionized water and absolute ethyl alcohol in sequence, and storing in the absolute ethyl alcohol;
(2) synthesizing a titanium dioxide network structure by a hydrothermal method: preparing a precursor solution by using 0.007-0.035 mol of sodium hydroxide, 2-6 mL of absolute ethyl alcohol and 29-33 mL of deionized water by a hydrothermal method, placing the precursor solution and the pretreated titanium matrix in a 50mL polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction for 8-20 h at the temperature of 180-240 ℃, taking out the titanium matrix after cooling along with a furnace, soaking the titanium matrix in 0.05-0.5 mol/L of hydrochloric acid for 4-10 h, repeatedly washing with deionized water, drying, and carrying out temperature programming annealing and activating treatment to obtain a titanium dioxide mesh structure;
(3) hydrogenation treatment of a titanium dioxide net structure: preparing a sodium sulfate solution with the mass fraction of 2-10% by adopting a cathodic electro-reduction method, taking a common nickel plate as an anode and a titanium dioxide net structure as a cathode, and selecting the current density of 5-30 mA/cm2The reduction time is 10-30 min;
(4) preparing a surface tin antimony oxide coating by a pulse electrodeposition method: preparing a deposition solution by using 20-40 g/L of tin dichloride, 2-6 g/L of antimony trichloride, 5-10 g/L of tartaric acid and 80-140 g/L of sodium pyrophosphate by adopting a pulse electrodeposition method, and selecting a forward pulse current density of 5-30 mA/cm2The negative pulse current density is 1-5 mA/cm2And the deposition time is 30-120 min, after the deposition is finished, deionized water is used for repeatedly washing and drying, and temperature programming annealing activation treatment is carried out to obtain the final electrode.
Moreover, the chemical reagents used in the steps (1), (2), (3) and (4) are all of analytical grade and are not subjected to any treatment before use.
The invention has the advantages and positive effects that:
1. according to the titanium-based tin antimony oxide electrode modified by the titanium dioxide mesh structure and the preparation method thereof, the titanium dioxide mesh structure is introduced between the metal titanium substrate and the surface catalyst layer, so that the binding force between the catalyst layer and the titanium substrate is enhanced, the catalyst layer is prevented from falling off, the service life of the electrode is prolonged, and the stability of the electrode is enhanced; due to the introduction of the titanium dioxide network structure, the particles of the tin antimony oxide catalyst layer are refined, the specific surface area of the catalyst layer is improved, and the electrocatalytic performance is improved, so that the degradation efficiency is effectively improved when the organic dye wastewater is degraded; the titanium dioxide network structure provides a path for the transmission of electrons, thereby reducing the impedance of the electrode, so that the cell voltage is reduced when the organic dye wastewater is degraded. Meanwhile, when the organic dye wastewater is degraded to the same degree, the time required by the titanium dioxide net structure modified tin antimony oxide electrode is shorter, so that the energy consumption of the electrode is lower.
2. The titanium-based tin antimony oxide electrode modified by the titanium dioxide mesh structure and the preparation method thereof have the advantages of scientific and reasonable design, strong stability, difficult shedding of the catalyst layer, effective prevention of corrosion of the titanium substrate, prolonged service life of the electrode, strong electrocatalysis capability, low energy consumption of the electrode and the like, and are highly innovative.
Detailed Description
The embodiments of the invention are described in further detail below with reference to the following figures:
example 1
A titanium-based tin antimony oxide electrode modified by a titanium dioxide net structure comprises a titanium substrate and a catalyst layer, and is characterized in that: the titanium substrate is subjected to hydro-thermal synthesis reaction, the middle layer of a titanium dioxide net structure is formed on the surface of the titanium substrate, and then a surface tin antimony oxide coating is formed on the middle layer of the net structure by a pulse electrodeposition method and a temperature programmed annealing activation method, wherein the surface tin antimony oxide coating is a tin antimony oxide catalyst layer.
The surface of the middle layer of the titanium dioxide net structure is composed of meshes with the average diameter of 5 mu m, filiform fibers are fully distributed in the meshes, and the average width of each filiform fiber is less than 100 nm.
A preparation method of a titanium-based tin antimony oxide electrode modified by a titanium dioxide net structure is characterized by comprising the following steps: the method comprises the following steps:
(1) pretreatment of metallic titanium substrates
Cutting a metal titanium plate into 2 multiplied by 2cm, then polishing the surface of the metal titanium plate by adopting 240-mesh abrasive paper, removing a titanium dioxide oxide film on the surface, soaking the polished titanium plate in a sodium hydroxide solution with the mass fraction of 5%, carrying out water bath treatment at 90 ℃ for 1h, then placing the titanium plate in oxalic acid with the mass fraction of 10%, carrying out water bath treatment at 99 ℃ for 2h, finally repeatedly washing by deionized water, and placing the titanium plate in absolute ethyl alcohol for preservation;
(2) hydrothermal synthesis of titanium dioxide network structure
Preparing a precursor solution by using 0.018mol of sodium hydroxide, 4mL of anhydrous ethanol and 31mL of deionized water by a hydrothermal method, putting the precursor solution and a pretreated titanium substrate into a 50mL polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 220 ℃ for 16h, taking out the titanium substrate after cooling along with a furnace, soaking the titanium substrate in 0.1mol/L hydrochloric acid for 6h, repeatedly washing with deionized water, drying, putting the dried electrode into a muffle furnace, heating at the heating rate of 4 ℃/min, keeping the temperature at 500 ℃ for 2h, and taking out after naturally cooling to obtain a titanium dioxide mesh structure;
(3) hydrogenation treatment of titanium dioxide network structure
Preparing a sodium sulfate solution with the mass fraction of 5 percent by adopting a cathodic electro-reduction method, taking a common nickel plate as an anode and a titanium dioxide net structure as a cathode, and selecting the current density of 20mA/cm2The reduction time is 20 min;
(4) preparation of surface tin antimony oxide coating by pulse electrodeposition
Adopting pulse electrodeposition method, preparing deposition solution by using 30g/L of tin dichloride, 4.5g/L of antimony trichloride, 7g/L of tartaric acid and 115g/L of sodium pyrophosphate, and selecting forward pulse current density as 20mA/cm2The negative pulse current density is 2.5mA/cm2And the deposition time is 90min, after the deposition is finished, deionized water is used for repeatedly washing and drying, the dried electrode is placed in a muffle furnace, the temperature is raised at the rate of 1 ℃/min, the temperature is kept at 500 ℃ for 2h, and the electrode is taken out after natural cooling to obtain the final electrode.
And (4) subsequent testing:
(1) titanium dioxide net structure and apparent morphology of tin antimony oxide electrode modified by titanium dioxide net structure
Observing the titanium dioxide network structure and the morphology of the tin antimony oxide electrode modified by the titanium dioxide network structure by using an S-4800 type scanning electron microscope to obtain Scanning Electron Microscope (SEM) photos as shown in figures 1 and 2;
(2) stability test of titanium dioxide mesh structure modified tin antimony oxide electrode
Adopts a two-electrode system, the prepared electrode is an anode, a common metal titanium plate is a cathode, and the electrolyte adopts 0.5mol/L sulfuric acid solution at 1A/cm2The stability of the electrode was tested at the current density of (3), and the test results are shown in fig. 3;
(3) test of catalytic performance of titanium dioxide mesh structure modified tin antimony oxide electrode
Adopting a three-electrode system, taking the prepared electrode as an anode, taking two common metal titanium plates as cathodes, and adopting 1g/L acid red and 0.1mol/L sodium sulfate solution as electrolyte at 50mA/cm2The degradation experiment of the organic dye wastewater is carried out under the current density of (1), the catalytic performance of the electrode is tested, and the test result is shown in figure 4;
(4) energy consumption of titanium dioxide net structure modified tin antimony oxide electrode
First, the degradation reaction rate (c) is calculated by equation 10Initial concentration of acid Red solution, ctConcentration of acid red solution at time t, k is degradation reaction rate). Then, the energy consumption required by the electrode in the degradation process is calculated according to the formula 2 (E is the energy consumption of the electrode, S is the working area of the electrode, i is the current density, U is the voltage of the degradation tank, and t is the degradation time), and the result is shown in fig. 5.
Example 2
Step (1) was the same as step (1) in example 1;
(2) hydrothermal synthesis of titanium dioxide network structure
Preparing a precursor solution by using 0.025mol of sodium hydroxide, 6mL of absolute ethyl alcohol and 29mL of deionized water by adopting a hydrothermal method, putting the precursor solution and the pretreated titanium substrate into a 50mL polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at the temperature of 200 ℃ for 14h, and taking out the titanium substrate after cooling along with a furnace; soaking the mixture in 0.1mol/L hydrochloric acid for 9 hours, and then repeatedly washing the mixture with deionized water and drying the washed mixture; placing the dried electrode in a muffle furnace, heating at a heating rate of 10 ℃/min, preserving heat at 400 ℃ for 3h, and taking out after natural cooling to obtain a titanium dioxide mesh structure;
(3) hydrogenation treatment of titanium dioxide network structure
By cathodic electroreductionThe method comprises the steps of preparing a sodium sulfate solution with the mass fraction of 8%, using a common nickel plate as an anode, and using a titanium dioxide net structure as a cathode. The selected current density was 30mA/cm2The reduction time is 30 min;
(4) preparation of surface tin antimony oxide coating by pulse electrodeposition
Adopting pulse electrodeposition method, preparing deposition solution by using 35g/L of tin dichloride, 5g/L of antimony trichloride, 6g/L of tartaric acid and 100g/L of sodium pyrophosphate, and selecting forward pulse current density of 15mA/cm2The negative pulse current density is 2.5mA/cm2The deposition time was 60 min. And after the deposition is finished, repeatedly washing the electrode by using deionized water, drying the electrode, putting the dried electrode into a muffle furnace, heating the electrode at the heating rate of 1 ℃/min, preserving the temperature for 2 hours at 500 ℃, and taking the electrode out after natural cooling to obtain the final electrode.
Comparative example
The comparative electrode also adopts a pulse electrodeposition method to prepare a surface tin antimony oxide coating, and is different from the electrode of the above example in that the comparative electrode directly deposits the surface coating on the pretreated metal titanium plate without adding a titanium dioxide network structure.
Step (1) the pretreatment process of the titanium plate is the same as that of step (1) in example 1;
(2) preparation of surface tin antimony oxide coating by pulse electrodeposition
Preparing a deposition solution by adopting a pulse electrodeposition method and using 25g/L of tin dichloride, 3.5g/L of antimony trichloride, 8g/L of tartaric acid and 120g/L of sodium pyrophosphate, and selecting a forward pulse current density of 25mA/cm2The negative pulse current density is 2.5mA/cm2The deposition time was 90 min. And after the deposition is finished, repeatedly washing with deionized water and drying, placing the dried electrode in a muffle furnace, heating at the heating rate of 1 ℃/min, keeping the temperature at 500 ℃ for 2h, and taking out after natural cooling to obtain the final titanium-based tin antimony oxide electrode.
Through comparison, the following results are found: compared with the common metal titanium plate in the comparative example, the titanium dioxide net structure can provide more growth sites for the tin antimony oxide coating in the deposition process of the surface tin antimony oxide coating, so that the nucleation speed of tin dioxide particles is increased, the size of the tin dioxide particles is reduced, and the surface layer particles are more densely distributed. The binding force between the catalyst layer and the titanium substrate is enhanced, thereby prolonging the service life of the electrode and enhancing the stability of the electrode. In addition, the particle size of the surface tin antimony oxide coating is reduced, so that the specific surface area of the surface layer is increased, and the electrocatalytic activity of the electrode is favorably improved.
The applicant also applies a titanium-based tin antimony oxide electrode modified by a titanium dioxide nanotube before the application, and the titanium-based tin antimony oxide electrode is oxidized for 2-3.5 hours by applying 30-50V voltage to the solution which is prepared from 2.5-5% by mass of ammonium fluoride, 1-5% by volume of ultrapure water and 95-99% by volume of ethylene glycol.
The contrast shows that the medicine required by the preparation of the titanium dioxide network structure only needs trace sodium hydroxide, and the solvent is mainly deionized water; the titanium dioxide nanotubes require more ammonium fluoride (2 times the price of sodium hydroxide) and nearly 99% ethylene glycol, which increases the cost of producing titanium dioxide nanotubes.
In addition, in terms of comparison of electrode performance: the titanium dioxide net structure and the titanium dioxide nanotubes are added into the electrode, and the main purpose is to prolong the service life of the electrode and improve the stability of the electrode. The comparison shows that the service life of the electrode added with the titanium dioxide nanotube can be improved by 6.5 times to the maximum. The service life of the electrode added with the titanium dioxide net structure can be prolonged by more than 11 times. In addition, after the titanium dioxide network structure is prepared, the titanium dioxide network structure is subjected to hydrogenation reaction in a sodium sulfate solution, so that the conductivity of the electrode is improved, the cell voltage in the degradation process is reduced, and the energy consumption required by degradation is reduced.
Although the embodiments of the present invention and the accompanying drawings are disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the disclosure of the embodiments and the accompanying drawings.