Preparation method of titanium dioxide nanotube doped cobalt-tungsten alloy electrodeposition coating
Technical Field
The invention relates to the technical field of electrical elements, in particular to a preparation method of a titanium dioxide nanotube doped cobalt-tungsten alloy electrodeposition coating.
Background
The hydrogen production by water electrolysis is an important means for realizing the industrial and cheap hydrogen preparation, but the technology has the biggest problems of large electric energy consumption, higher production cost and large electric energy consumption due to overhigh hydrogen evolution overpotential of an electrolysis electrode, so the research on reducing the hydrogen evolution overpotential to reduce the electrolysis energy consumption is particularly important. The prior electrode material for water electrolysis has the defects of high price, small specific surface, low electrocatalytic activity and the like, so that the hydrogen evolution potential of the electrolysis electrode is too high, the energy consumption is too high, and the development of the hydrogen production technology by the water electrolysis method is seriously restricted. The influence of the electrode material, especially the cathode material, on the hydrogen evolution performance is particularly important. The electrocatalytic hydrogen evolution active electrode widely used at present comprises: (1) an iron-based alloy hydrogen evolution electrode; (2) a nickel-based alloy hydrogen evolution electrode; (3) the noble metal modifies the hydrogen evolution electrode. In addition, other hydrogen evolving electrodes are: a rare earth element modified hydrogen evolution electrode, a high polymer modified hydrogen evolution electrode and the like. These materials are used to reduce hydrogen evolution overpotential and improve catalytic performance.
Although the hydrogen evolution materials reduce hydrogen evolution overpotential to a certain extent, the materials are expensive, and the hydrogen evolution performance is still not ideal, so that the hydrogen evolution materials have certain limitations from large-scale industrial application. Therefore, the need for an electrode material which is cheap and easy to obtain and has excellent electrocatalytic performance is urgent.
Disclosure of Invention
The invention provides a preparation method of a titanium dioxide nanotube-doped cobalt-tungsten alloy electrodeposition coating aiming at the problems, so as to solve one or more technical problems in the prior art and provide at least one beneficial choice or creation condition.
The development of nanotechnology provides a new development opportunity for the technical upgrade of traditional materials, and the nanoparticles can be used for improving the quality of the materials and the specific surface area of the materials due to the characteristics of high specific surface area, easiness in preparation and the like, so that the traditional materials have excellent catalytic performance, and the invention provides the following technical scheme:
a preparation method of a titanium dioxide nanotube doped cobalt-tungsten alloy electrodeposition coating comprises the following steps:
a. preparing a mixed solution from cobalt sulfate, sodium tungstate, sodium sulfate, citric acid, boric acid, a titanium dioxide nanotube and a surfactant, and adjusting the pH value to 4-8 by using ammonia water;
b. and performing electrodeposition on the prepared mixed solution on a copper substrate by adopting a three-electrode system to obtain the titanium dioxide nanotube doped cobalt-tungsten alloy electrodeposition coating.
Further, the concentration of the cobalt sulfate is 0.05-0.2M; the concentration of the sodium tungstate is 0.05-0.25M; the concentration of the sodium sulfate is 0.1-0.4M; the concentration of the citric acid is 0.1-0.5M; the concentration of the boric acid is 0.1-0.2M; the concentration of the titanium dioxide nanotube is 0.01-0.1M; the concentration of the surfactant is 0.01-0.1 g/l.
Further, the ammonia water concentration is 1M.
Further, the mixed solution in the step a is prepared at room temperature.
Further, the electrodeposition process in the step b is carried out under the condition of water bath at 45 ℃.
Further, the electrodeposition parameters are: current density 100mA/cm2The plating time was 1800 s.
Compared with the prior art, the invention has the advantages that:
1. the most common electroplating method in the industry is adopted, which is beneficial to industrial production;
2. the material preparation condition requirement is low, and the operation is easy;
3. the raw materials are low in price and easy to obtain;
4. the electrode material has excellent hydrogen evolution catalytic performance, and hydrogen evolution test is carried out in 1M NaOH solution at 25mA/cm2The hydrogen evolution overpotential is less than 0.4V at the current density of (1).
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples, but the present invention is not limited to these examples.
Example 1
In this embodiment, an electrolyte is first prepared: a mixed solution of 0.08M cobalt sulfate, 0.09M sodium tungstate, 0.15M sodium sulfate, 0.15M citric acid, 0.13M boric acid, 0.01M titanium dioxide nanotubes, and 0.1g/l surfactant was prepared at room temperature, and the pH was adjusted to 4 with 1M aqueous ammonia. The prepared solution is put in a water bath at 45 ℃ and a three-electrode system is adopted at 1 multiplied by 1cm2The copper substrate was subjected to electrodeposition with a current density of 100mA/cm2The plating time was 1800 s.
The obtained electrode is used as a cathode to carry out cyclic voltammetry in a 1M NaOH solution, the test temperature is 25 ℃, and the current density is 25mA/cm2When the voltage is high, the overpotential is only 0.38V.
Example 2
In this embodiment, an electrolyte is first prepared: a mixed solution of 0.08M cobalt sulfate, 0.09M sodium tungstate, 0.15M sodium sulfate, 0.15M citric acid, 0.13M boric acid, 0.05M titanium dioxide nanotubes, and 0.1g/l surfactant was prepared at room temperature, and the pH was adjusted to 4 with 1M aqueous ammonia. The prepared solution is put in a water bath at 45 ℃ and a three-electrode system is adopted at 1 multiplied by 1cm2The copper substrate was subjected to electrodeposition with a current density of 100mA/cm2The plating time was 1800 s.
The obtained electrode was used as a cathode and dissolved in 1M NaOHPerforming cyclic voltammetry in liquid at 25 deg.C and current density of 25mA/cm2When the voltage is high, the overpotential is only 0.34V.
Example 3
In this embodiment, an electrolyte is first prepared: a mixed solution of 0.06M cobalt sulfate, 0.25M sodium tungstate, 0.15M sodium sulfate, 0.15M citric acid, 0.13M boric acid, 0.08M titanium dioxide nanotubes and 0.1g/l surfactant was prepared at room temperature, and the pH was adjusted to 4 with 1M ammonia water. The prepared solution is put in a water bath at 45 ℃ and a three-electrode system is adopted at 1 multiplied by 1cm2The copper substrate was subjected to electrodeposition with a current density of 100mA/cm2The plating time was 1800 s.
The obtained electrode is used as a cathode to carry out cyclic voltammetry in a 1M NaOH solution, the test temperature is 25 ℃, and the current density is 25mA/cm2Its overpotential is only 0.3V.
Example 4
In this embodiment, an electrolyte is first prepared: a mixed solution of 0.1M cobalt sulfate, 0.2M sodium tungstate, 0.15M sodium sulfate, 0.1M citric acid, 0.15M boric acid, 0.08M titanium dioxide nanotubes, and 0.1g/l surfactant was prepared at room temperature, and the pH was adjusted to 6 with 1M ammonia water. The prepared solution is put in a water bath at 45 ℃ and a three-electrode system is adopted at 1 multiplied by 1cm2The copper substrate was subjected to electrodeposition with a current density of 100mA/cm2The plating time was 1800 s.
The obtained electrode is used as a cathode to carry out cyclic voltammetry in a 1M NaOH solution, the test temperature is 25 ℃, and the current density is 25mA/cm2When the voltage is high, the overpotential is only 0.36V.
The preferred embodiments of the present invention have been described in detail, but the present invention is not limited to the details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, which fall within the protective scope of the present invention.