CN110565114B - Three-dimensional porous Fe @ Fe (OH)3Preparation method of oxygen evolution anode - Google Patents
Three-dimensional porous Fe @ Fe (OH)3Preparation method of oxygen evolution anode Download PDFInfo
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Abstract
Three-dimensional porous Fe @ Fe (OH)3The invention discloses a preparation method of an oxygen evolution anode, and relates to three-dimensional porous Fe @ Fe (OH) for electrolytic oxygen evolution of an alkaline solution3A method for preparing an anode. The invention aims to solve the problem that the price of the existing catalyst for the electrolytic oxygen evolution of alkaline solution is high due to the adoption of noble metal. Three-dimensional porous Fe @ Fe (OH)3The preparation method of the oxygen evolution anode comprises the following steps: (1) breaking cell wall of Haematococcus sp; (2) preparing a composite electroplating solution; (3) preparing a composite film on the surface of the foamed nickel; (4) heat treatment of the composite film; (5) electrolytic stripping of copper; (6) hydrothermal treatment, preparing three-dimensional porous Fe @ Fe (OH) with good oxygen evolution reaction catalytic activity on the surface of the foamed nickel3The film greatly reduces the oxygen evolution overpotential of the water electrolyzed in the alkaline solution.
Description
Technical Field
The invention belongs to the field of preparation of oxygen evolution anodes, and relates to three-dimensional porous Fe @ Fe (OH) for electrolytic oxygen evolution of alkaline solution3A method for preparing an anode.
Background
With the development of industry, fossil energy such as coal, oil, and natural gas is rapidly consumed, and in the present situation, exhaustion of fossil energy will occur in the last day. At that time, most of the energy currently used by humans will be depleted. Renewable energy sources replacing fossil fuels such as gasoline and diesel oil are searched without rain, and the renewable energy sources can be used for dealing with the exhaustion of fossil energy sources in the future. Of all the new renewable energy sources, hydrogen is considered to be the most desirable. Hydrogen can be continuously produced by solar energy, and the principle is that the hydrogen is obtained by reducing water in solution at a cathode by means of photoinduced electrons generated by a solar cell. When a human needs to release the chemical energy stored in the hydrogen, the hydrogen can be released in a primary battery or an internal combustion engine in a chemical energy or thermal energy mode, and the product is water without any pollution. Therefore, the hydrogen production by water electrolysis is a global important issue for solving the energy crisis.
During the electrolysis of water, hydrogen is produced at the cathode and oxygen is evolved at the anode. In order to improve the effective conversion of electric energy into chemical energy and reduce the energy consumption in the water electrolysis process, electrodes with excellent catalytic activity for hydrogen evolution and oxygen evolution should be respectively selected at the cathode and the anode. Therefore, the selection and preparation of highly active oxygen evolution electrodes are of great importance for the electrolysis of water and for the entire energy field. At present, RuO2Is the material with the highest oxygen evolution activity, and IrO2Also has good catalytic activity. In practical application, RuO is often used for compensating the defects of monomer materials2Or IrO2The compound is prepared, so that the activity and the stability of the compound are further improved. However, ruthenium and iridium are precious metals of the platinum group, which are expensive and have limited reserves in the earth's crust, and if ruthenium and iridium are used on a large scale to prepare oxygen evolution catalysts, they are not only low in cost performance but also not in line with the strategy of sustainable development. Therefore, the development of a non-noble metal catalyst with low price and high oxygen evolution activity is significant. In the periodic table, iron and ruthenium belong to the platinum group, and the electronic arrangement of iron and ruthenium is similar, the catalytic properties are similar, and the price is the lowest among all metals. Although the iron-based oxide catalyst is unstable in an acidic solution, the iron-based oxide catalyst has exhibited good electrolytic water evolution oxygen activity in an alkaline solution. Therefore, the preparation of the economical oxygen evolution catalyst with high specific surface area and excellent catalytic activity by utilizing the iron in the same family with ruthenium is beneficial to the reduction of the cost of large-scale electrolysis of water, and has a profound influence on the sustainable development of energy.
Disclosure of Invention
The invention aims to solve the problem of high price caused by the adoption of noble metal in the existing catalyst for the electrolytic oxygen evolution of alkaline solution, and provides a method for preparing three-dimensional porous Fe @ Fe (OH) for the electrolytic oxygen evolution of alkaline solution on the surface of foamed nickel3A method of forming a film.
The invention relates to three-dimensional porous Fe @ Fe (OH)3The preparation method of the oxygen evolution anode comprises the following steps:
(1) red ball algae wall breaking: a. freeze-drying Haematococcus at-170 deg.C for 24-36 hr, taking out, and naturally thawing; b. repeating the step a 0-5 times to obtain wall-broken haematococcus;
(2) preparing a composite electroplating solution: c. weighing 0.5-8.0 g of haematococcus processed in the step (1), adding the haematococcus into 800 mL of deionized water, and carrying out ultrasonic stirring at room temperature for 10-60 minutes to obtain a solution A; d. according to the proportion that the concentration of malic acid is 5-25 g/L, the concentration of lactic acid is 5-35 mL/L, the concentration of hydrochloric acid is 1-25 mL/L, the concentration of ferrous chloride is 6-35 g/L, the concentration of thiourea is 8-30 g/L, the concentration of cuprous chloride is 1-10 g/L, and the concentration of potassium chloride is 30-100 g/L, sequentially dissolving malic acid, lactic acid, hydrochloric acid, ferrous chloride, thiourea, cuprous chloride and potassium chloride in the solution A obtained in the step c, and obtaining a solution B after the constant volume is 1L;
(3) preparing a composite film on the surface of the foamed nickel: e. d, soaking the foam nickel with clean surface into the solution B prepared in the step d to be used as a cathode, using pure iron as an anode and controlling the current density to be 0.5-8.0A/dm2Carrying out electrodeposition for 5 minutes to 2 hours under the condition of stirring, and then washing by tap water for one time and deionized water for three times to obtain an intermediate product I with the Fe-Cu-S-Haematococcus composite film;
(4) heat treatment of the composite film: f. calcining the intermediate product I obtained in the step (3) for 2-24 hours at 300-600 ℃ in a hydrogen atmosphere, then calcining for 1-6 hours at 650-1000 ℃ in an inert atmosphere, and removing haematococcus in the film to form a porous structure, so as to obtain an intermediate product II with a three-dimensional porous iron-copper sulfide film;
(5) electrolytic stripping of copper: g. immersing the intermediate product II obtained in the step (4) into copper electrolysis solution as an anode at the temperature of 35-65 ℃ and at the concentration of 0.1-3.0A/dm2Electrolyzing for 20-360 minutes at the current density to dissolve copper in the three-dimensional porous iron sulfide copper film to obtain an intermediate product III, wherein the copper electrolysis dissolution liquid consists of 10-160 g/L thiourea, 1-5 g/L ascorbic acid, 20-90 g/L sodium acetate and 20-50 mL/L glacial acetic acid;
(6) hydrothermal treatment: h. immersing the intermediate product III obtained in the step (5) into 10-65 g/L of hydroxideIn sodium solution, carrying out hydrothermal treatment for 1-24 hours at 80-160 ℃, and obtaining three-dimensional porous Fe @ Fe (OH) on the surface of the foamed nickel3A film.
The invention relates to three-dimensional porous Fe @ Fe (OH)3The preparation method of the oxygen evolution anode stabilizes Fe by adding wall-broken haematococcus into the composite electroplating solution2+And Cu+The composite film can form an iron-sulfur film with a three-dimensional porous structure after heat treatment and copper electrolytic dissolution, and sulfide is completely hydrolyzed and converted into hydroxide by subsequent hydrothermal treatment so as to form Fe @ Fe (OH) with high specific surface area3A film. Prepared three-dimensional porous Fe @ Fe (OH)3The oxygen evolution anode not only has huge catalytic area, but also Fe @ Fe (OH)3The structure can greatly reduce the over potential of oxygen, thereby improving the catalytic activity in both geometric factors and energy factors. Thus, the three-dimensional porous Fe @ Fe (OH) prepared by the present invention3The oxygen evolution anode not only avoids the use of noble metals, but also greatly reduces the oxygen evolution overpotential and the total energy consumption of the water electrolysis in the alkaline solution, and has strategic significance for the sustainable development of energy.
Drawings
FIG. 1 is a three-dimensional porous Fe @ Fe (OH) prepared in experiment one3Technical scheme of oxygen evolving anode.
FIG. 2 shows three-dimensional porous Fe @ Fe (OH) prepared in experiment one3The oxygen evolution anode is arranged in 1.0M NaOH solution, and the anode current density is 200 mA/cm2The time-potential curve measured under the conditions of (1).
Detailed Description
The first embodiment is as follows: a three-dimensional porous Fe @ Fe (OH) of the present embodiment3The preparation method of the oxygen evolution anode comprises the following steps:
(1) red ball algae wall breaking: a. freeze-drying Haematococcus at-170 deg.C for 24-36 hr, taking out, and naturally thawing; b. repeating the step a 0-5 times to obtain wall-broken haematococcus;
(2) preparing a composite electroplating solution: c. weighing 0.5-8.0 g of haematococcus processed in the step (1), adding the haematococcus into 800 mL of deionized water, and carrying out ultrasonic stirring at room temperature for 10-60 minutes to obtain a solution A; d. according to the proportion that the concentration of malic acid is 5-25 g/L, the concentration of lactic acid is 5-35 mL/L, the concentration of hydrochloric acid is 1-25 mL/L, the concentration of ferrous chloride is 6-35 g/L, the concentration of thiourea is 8-30 g/L, the concentration of cuprous chloride is 1-10 g/L, and the concentration of potassium chloride is 30-100 g/L, sequentially dissolving malic acid, lactic acid, hydrochloric acid, ferrous chloride, thiourea, cuprous chloride and potassium chloride in the solution A obtained in the step c, and obtaining a solution B after the constant volume is 1L;
(3) preparing a composite film on the surface of the foamed nickel: e. d, soaking the foam nickel with clean surface into the solution B prepared in the step d to be used as a cathode, using pure iron as an anode and controlling the current density to be 0.5-8.0A/dm2Carrying out electrodeposition for 5 minutes to 2 hours under the condition of stirring, and then washing by tap water for one time and deionized water for three times to obtain an intermediate product I with the Fe-Cu-S-Haematococcus composite film;
(4) heat treatment of the composite film: f. calcining the intermediate product I obtained in the step (3) for 2-24 hours at 300-600 ℃ in a hydrogen atmosphere, then calcining for 1-6 hours at 650-1000 ℃ in an inert atmosphere, and removing haematococcus in the film to form a porous structure, so as to obtain an intermediate product II with a three-dimensional porous iron-copper sulfide film;
(5) electrolytic stripping of copper: g. immersing the intermediate product II obtained in the step (4) into copper electrolysis solution as an anode at the temperature of 35-65 ℃ and at the concentration of 0.1-3.0A/dm2Electrolyzing for 20-360 minutes at the current density to dissolve copper in the three-dimensional porous iron sulfide copper film to obtain an intermediate product III, wherein the copper electrolysis dissolution liquid consists of 10-160 g/L thiourea, 1-5 g/L ascorbic acid, 20-90 g/L sodium acetate and 20-50 mL/L glacial acetic acid;
(6) hydrothermal treatment: h. immersing the intermediate product III obtained in the step (5) into 10-65 g/L sodium hydroxide solution, performing hydrothermal treatment for 1-24 hours at 80-160 ℃, and obtaining three-dimensional porous Fe @ Fe (OH) on the surface of the foamed nickel3A film.
A three-dimensional porous Fe @ Fe (OH) of the present embodiment3Preparation method of oxygen evolution anodeStabilizing Fe by adding wall-broken Haematococcus in composite electroplating solution2+And Cu+The composite film can form an iron-sulfur film with a three-dimensional porous structure after heat treatment and copper electrolytic dissolution, and sulfide is completely hydrolyzed and converted into hydroxide by subsequent hydrothermal treatment so as to form Fe @ Fe (OH) with high specific surface area3A film. Prepared three-dimensional porous Fe @ Fe (OH)3The oxygen evolution anode not only has huge catalytic area, but also Fe @ Fe (OH)3The structure can greatly reduce the over potential of oxygen, thereby improving the catalytic activity in both geometric factors and energy factors. Thus, the three-dimensional porous Fe @ Fe (OH) prepared in this embodiment3The oxygen evolution anode greatly reduces the oxygen evolution overpotential of the water electrolysis in the alkaline solution, and has strategic significance on the sustainable development of energy.
The second embodiment is as follows: the difference between the present embodiment and the first embodiment is that the current density used in step (3) e is 0.8-6.0A/dm2. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that the current density used in step (5) g is 0.2 to 2.5A/dm2. The other is the same as in the first or second embodiment.
The beneficial effects of the invention were verified by the following tests:
test one: three-dimensional porous Fe @ Fe (OH) of this experiment3The preparation method of the oxygen evolution anode comprises the following steps:
(1) red ball algae wall breaking: a. freeze-drying Haematococcus at-170 deg.C for 24 hr, taking out, and naturally thawing; b. repeating the step a3 times to obtain wall-broken Haematococcus;
(2) preparing a composite electroplating solution: c. weighing 3.0 g of haematococcus pluvialis treated in the step (1), adding the haematococcus pluvialis into 800 mL of deionized water, and carrying out ultrasonic stirring at room temperature for 30 minutes to obtain a solution A; d. sequentially dissolving malic acid, lactic acid, hydrochloric acid, ferrous chloride, thiourea, cuprous chloride and potassium chloride into the solution A obtained in the step c according to the proportion that the concentration of malic acid is 15 g/L, the concentration of lactic acid is 15 mL/L, the concentration of hydrochloric acid is 20 mL/L, the concentration of ferrous chloride is 9 g/L, the concentration of thiourea is 20 g/L, the concentration of cuprous chloride is 4 g/L and the concentration of potassium chloride is 50 g/L, and obtaining a solution B after the volume is up to 1L;
(3) preparing a composite film on the surface of the foamed nickel: e. d, soaking the foam nickel with clean surface into the solution B prepared in the step d to be used as a cathode, using pure iron as an anode and controlling the current density to be 3.0A/dm2Carrying out electrodeposition for 45 minutes under the condition of stirring, and then carrying out tap water cleaning and deionized water cleaning to obtain an intermediate product I with the Fe-Cu-S-Haematococcus composite film;
(4) heat treatment of the composite film: f. calcining the intermediate product I obtained in the step (3) for 2-24 hours at 450 ℃ in a hydrogen atmosphere, then calcining for 1-6 hours at 650-1000 ℃ in an inert atmosphere, and removing haematococcus in the film to form a porous structure to obtain an intermediate product II with a three-dimensional porous iron-copper sulfide film;
(5) electrolytic stripping of copper: g. immersing the intermediate product II obtained in the step (4) into copper electrolysis solution as an anode at the temperature of 35-65 ℃ and at the concentration of 0.1-3.0A/dm2Electrolyzing for 20-360 minutes at the current density to dissolve copper in the three-dimensional porous iron sulfide copper film to obtain an intermediate product III, wherein the copper electrolysis dissolution liquid consists of 10-160 g/L thiourea, 1-5 g/L ascorbic acid, 20-90 g/L sodium acetate and 20-50 mL/L glacial acetic acid;
(6) hydrothermal treatment: h. immersing the intermediate product III obtained in the step (5) into 10-65 g/L sodium hydroxide solution, performing hydrothermal treatment for 1-24 hours at 80-160 ℃, and obtaining three-dimensional porous Fe @ Fe (OH) on the surface of the foamed nickel3A film.
A three-dimensional porous Fe @ Fe (OH) of the present embodiment3The preparation method of the oxygen evolution anode stabilizes Fe by adding wall-broken haematococcus into the composite electroplating solution2+And Cu+And the composite film can be used as a pore-forming agent, the Fe-Cu-S-Haematococcus composite film can be obtained on the surface of the foamed nickel after electrodeposition, and the composite film can form a three-dimensional porous junction after heat treatment and copper electrolytic dissolutionA structured iron-sulfur film, a subsequent hydrothermal treatment to complete the hydrolytic conversion of the sulfide to hydroxide to form Fe @ Fe (OH) with a high specific surface area3A film. Prepared three-dimensional porous Fe @ Fe (OH)3The oxygen evolution anode not only has huge catalytic area, but also Fe @ Fe (OH)3The structure can greatly reduce the over potential of oxygen, thereby improving the catalytic activity in both geometric factors and energy factors. Thus, the three-dimensional porous Fe @ Fe (OH) prepared in this embodiment3The oxygen evolution anode greatly reduces the oxygen evolution overpotential of the water electrolysis in the alkaline solution, and has strategic significance on the sustainable development of energy.
This experiment produced three-dimensional porous Fe @ Fe (OH)3The technical route of the oxygen evolution anode is schematically shown in figure 1, and the wall-broken haematococcus in the composite electroplating solution can stabilize Fe2+And Cu+The nickel foam is electrodeposited in a composite electroplating solution to obtain an iron-copper-sulfur-haematococcus composite film, the composite film can form an iron-sulfur film with a three-dimensional porous structure after heat treatment and copper electrolytic dissolution, and sulfide is completely hydrolyzed and converted into hydroxide through subsequent hydrothermal treatment to form Fe @ Fe (OH) with a high specific surface area3A film.
Three-dimensional porous Fe @ Fe (OH) prepared for this experiment3The oxygen evolution anode is arranged in 1.0M NaOH solution, and the anode current density is 200 mA/cm2The time-potential curve measured under the conditions of (1) is shown in FIG. 2. As can be seen from FIG. 2, the three-dimensional porous Fe @ Fe (OH) prepared in this experiment3The oxygen evolution potential of the oxygen evolution anode in a 1.0M NaOH solution is stabilized at about 1.45V (vs RHE), and the current density of the foamed nickel at the anode is 200 mA/cm2Under the condition of (1), the oxygen evolution potential is more than 1.75V, which indicates that the prepared three-dimensional porous Fe @ Fe (OH)3The oxygen evolution anode has good catalytic oxygen evolution activity.
Three-dimensional porous Fe @ Fe (OH) prepared for this experiment3After the oxygen evolution anode is continuously electrolyzed for oxygen generation for 960 hours, the oxygen evolution potential is still lower than 1.5V, which shows that the three-dimensional porous Fe @ Fe (OH) prepared by the experiment3The oxygen evolution anode has stable performance.
Claims (3)
1. Three-dimensional porous Fe @ Fe (OH)3The preparation method of the oxygen evolution anode is characterized in that three-dimensional porous Fe @ Fe (OH)3The preparation method of the oxygen evolution anode comprises the following steps:
(1) red ball algae wall breaking: a. freeze-drying Haematococcus at-170 deg.C for 24-36 hr, taking out, and naturally thawing; b. repeating the step a for 0-5 times to obtain wall-broken haematococcus algae;
(2) preparing a composite electroplating solution: c. weighing 0.5-8.0 g of haematococcus processed in the step (1), adding the haematococcus into 800 mL of deionized water, and carrying out ultrasonic stirring at room temperature for 10-60 minutes to obtain a solution A; d. according to the proportion that the concentration of malic acid is 5-25 g/L, the concentration of lactic acid is 5-35 mL/L, the concentration of hydrochloric acid is 1-25 mL/L, the concentration of ferrous chloride is 6-35 g/L, the concentration of thiourea is 8-30 g/L, the concentration of cuprous chloride is 1-10 g/L, and the concentration of potassium chloride is 30-100 g/L, sequentially dissolving malic acid, lactic acid, hydrochloric acid, ferrous chloride, thiourea, cuprous chloride and potassium chloride in the solution A obtained in the step c, and obtaining a solution B after the constant volume is 1L;
(3) preparing a composite film on the surface of the foamed nickel: e. d, soaking the foam nickel with clean surface into the solution B prepared in the step d to be used as a cathode, using pure iron as an anode and controlling the current density to be 0.5-8.0A/dm2Carrying out electrodeposition for 5 minutes to 2 hours under the condition of stirring, and then washing by tap water for one time and deionized water for three times to obtain an intermediate product I with the Fe-Cu-S-Haematococcus composite film;
(4) heat treatment of the composite film: f. calcining the intermediate product I obtained in the step (3) for 2-24 hours at 300-600 ℃ in a hydrogen atmosphere, then calcining for 1-6 hours at 650-1000 ℃ in an inert atmosphere, and removing haematococcus in the film to form a porous structure, so as to obtain an intermediate product II with a three-dimensional porous iron-copper sulfide film;
(5) electrolytic stripping of copper: g. immersing the intermediate product II obtained in the step (4) into copper electrolysis solution as an anode at the temperature of 35-65 ℃ and at the concentration of 0.1-3.0A/dm2Electrolyzing for 20-360 minutes at the current density to dissolve copper in the three-dimensional porous iron sulfide copper film to obtain an intermediate product III, wherein the copper is electrolyzed and dissolved outThe liquid comprises 10-160 g/L thiourea, 1-5 g/L ascorbic acid, 20-90 g/L sodium acetate and 20-50 mL/L glacial acetic acid;
(6) hydrothermal treatment: h. immersing the intermediate product III obtained in the step (5) into 10-65 g/L sodium hydroxide solution, performing hydrothermal treatment for 1-24 hours at 80-160 ℃, and obtaining three-dimensional porous Fe @ Fe (OH) on the surface of the foamed nickel3A film.
2. The three-dimensional porous Fe @ Fe (OH) of claim 13The preparation method of the oxygen evolution anode is characterized in that the current density adopted in the step (3) e is 0.8-6.0A/dm2。
3. The three-dimensional porous Fe @ Fe (OH) of claim 13The preparation method of the oxygen evolution anode is characterized in that the current density adopted in the step (5) g is 0.2-2.5A/dm2。
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