CN115386910A - Preparation method and application of heterostructure manganese-cobalt-iron-phosphorus difunctional electrolytic water electrode material - Google Patents

Preparation method and application of heterostructure manganese-cobalt-iron-phosphorus difunctional electrolytic water electrode material Download PDF

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CN115386910A
CN115386910A CN202210892529.3A CN202210892529A CN115386910A CN 115386910 A CN115386910 A CN 115386910A CN 202210892529 A CN202210892529 A CN 202210892529A CN 115386910 A CN115386910 A CN 115386910A
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cobalt
iron
manganese
electrode material
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郭兴忠
王凡
邹畅
杨辉
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Zhejiang University ZJU
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Abstract

The invention discloses a preparation method and application of a heterostructure manganese-cobalt-iron-phosphorus difunctional electrolytic water electrode material, wherein the preparation method comprises the following steps: placing cobalt nitrate, ferric nitrate, ammonium fluoride and urea in deionized water, and stirring to obtain a solution; firstly growing cobalt-iron precursor nanosheets on the processed foamed nickel by a hydrothermal method, then growing manganese nanosheets on the cobalt-iron precursor by secondary hydrothermal, obtaining a shape-controllable sheet-sheet precursor material by regulating and controlling the proportion of the cobalt-iron precursor, and finally obtaining the manganese-cobalt-iron-phosphorus electrode material with a sheet-sheet heterostructure by phosphating, thereby preparing the three-dimensional self-supporting manganese-cobalt-iron-phosphorus electrode material without an adhesive, with a heterostructure and excellent performance. The manganese-doped cobalt phosphide/iron phosphide heterostructure electrode material prepared by the method has excellent bifunctional electrolytic water performance and is a potential electrocatalytic full-hydrolytic catalyst.

Description

Preparation method and application of heterostructure manganese-cobalt-iron-phosphorus difunctional electrolytic water electrode material
Technical Field
The invention relates to a three-dimensional self-supporting heterostructure manganese-cobalt-iron-phosphorus difunctional electrolytic water electrode material and a preparation method and application thereof, belonging to the technical field of electrolytic water electrode material preparation.
Background
Energy crisis and environmental problems force people to find clean and renewable alternative energy, and hydrogen has the advantages of high energy density, high energy conversion efficiency, no pollution of combustion products and the like, and is an ideal alternative energy. Compared with the traditional hydrogen production mode, the hydrogen production by water electrolysis is a simple, efficient and environment-friendly hydrogen production mode, water is decomposed into hydrogen and oxygen by using electric energy, and products are convenient to separate. Theoretically, the voltage required for electrolyzing water is 1.23V, however, the complex dynamic process in the water electrolysis process increases the actually required voltage, and therefore, it is important to find an efficient electrocatalyst to reduce the overpotential. Commercial high-efficiency electrocatalysts are generally Pt-based, ir-based and other precious metal-based electrocatalysts, however, the precious metals are expensive, and the application of the precious metals in the electrocatalysts field is limited to a great extent. Therefore, it is necessary to develop alternative catalysts, such as transition metal-based electrocatalysts, in particular transition metal phosphides, which can replace these expensive electrocatalysts.
Transition metal phosphides have unique charged characteristics (metals and phosphorus carry positive and negative charges, respectively), and are of particular interest due to the high catalytic activity resulting from their hydrogen-like catalytic mechanisms. Transition metal phosphide has good conductivity and excellent catalytic performance and is widely used as HER and OER catalysts, and cobalt phosphide, iron phosphide and the like have excellent catalytic activity due to rich content and are often used for hydrogen production by water electrolysis. Meanwhile, the excellent performance of the catalyst depends on the size and the form of the catalyst to a great extent, the specific surface area can be effectively increased by accurately controlling the structure of the electrocatalyst, and the catalytic active sites are further increased, so thatThereby improving the electrocatalytic performance. The three-dimensional heterostructure has the advantages of large specific surface area, more exposed active sites, high mass transfer speed and the like, and the electrocatalyst with the three-dimensional heterostructure is skillfully designed by a simple synthesis method, so that the catalytic performance can be effectively enhanced. Publication No. CN109876846 discloses a three-dimensional self-supporting Cu 3 The preparation method of the PNW @ CoFeP composite material comprises the steps of firstly putting cleaned copper foam into NaOH and sodium thiosulfate for oxidation treatment, then cutting a copper hydroxide nanowire array obtained through oxidation treatment into a working electrode, carrying out electrochemical deposition in a mixed solution of ferrous sulfate and cobalt nitrate to obtain a composite material of copper hydroxide nanowires, and finally carrying out phosphating treatment on the composite material of the copper hydroxide nanowires and sodium hypophosphite to obtain the Cu composite material 3 Although the PNW @ CoFeP composite material is tested for full water solubility performance without a binder, the oxygen evolution activity is poor and needs to be improved. The patent with publication number CN110404566 discloses a preparation method of a zinc-regulated morphology CoFeP hydrogen evolution electrocatalyst with carbon cloth as a substrate, the transition metal phosphide electrocatalyst is grown on the carbon cloth through the schemes of hydrothermal treatment, annealing, alkali etching, phosphorization and the like, the control of the final sample morphology is realized by regulating the proportion of a cobalt source and a zinc source, and the CoFeP/carbon cloth electrocatalyst with two shapes of a sheet shape and a rod shape is obtained.
Disclosure of Invention
The invention aims to provide a three-dimensional self-supporting heterostructure manganese-cobalt-iron-phosphorus difunctional electrolytic water electrode material and a preparation method and application thereof.
In order to solve the technical problems, the invention provides a preparation method of a heterostructure manganese-cobalt-iron-phosphorus difunctional electrolytic water electrode material (a three-dimensional self-supporting heterostructure manganese-cobalt-iron-phosphorus difunctional electrolytic water electrode material), which comprises the following steps:
s1, placing cobalt nitrate, ferric nitrate, ammonium fluoride and urea in deionized water, and stirring until the cobalt nitrate, the ferric nitrate, the ammonium fluoride and the urea are dissolved;
cobalt nitrate: iron nitrate: ammonium fluoride: urea = 0.5-1.5;
description of the drawings: the amount of deionized water is at least required to ensure that 4 of the above-mentioned urea is dissolved, generally, 25 +/-5 mL of deionized water is used for every 4mmol of urea;
s2, placing the treated foamed nickel into a polytetrafluoroethylene lining of a reaction kettle, pouring the solution obtained in the step S1 into the lining, immersing the treated foamed nickel, transferring the reaction kettle into a high-temperature oven, and carrying out hydrothermal reaction at 120 +/-10 ℃ for 1-6 h (preferably 3 h); after the reaction is finished and the temperature is cooled to the room temperature, taking out the foamed nickel, and respectively carrying out ultrasonic cleaning by using deionized water and absolute ethyl alcohol;
then placing the nickel foam in a vacuum oven for vacuum drying to obtain foam nickel with a cobalt iron hydroxide precursor;
s3, putting the foamed nickel with the cobalt iron hydroxide precursor obtained in the step S2 into a polytetrafluoroethylene lining of a reaction kettle, pouring a potassium permanganate solution with the concentration of 0.01-0.1M into the lining and immersing the foamed nickel, then transferring the reaction kettle into a high-temperature oven, and carrying out hydrothermal reaction at 120 +/-10 ℃ for 1 +/-0.1 h; after the reaction is finished and the temperature is cooled to room temperature, taking out the reaction product, and respectively carrying out ultrasonic cleaning by using deionized water and absolute ethyl alcohol;
then placing the nickel foam in a vacuum oven for vacuum drying to obtain the nickel foam with the manganese-cobalt-iron precursor;
s4, respectively putting the nickel foam with the manganese-cobalt-iron precursor and the sodium hypophosphite powder obtained in the step S3 into two porcelain boats, placing the porcelain boats filled with the sodium hypophosphite at one side close to an argon inlet of the tube furnace, and placing the porcelain boats filled with the nickel foam at one side of an air outlet;
under inert gas (such as argon atmosphere), heating from room temperature to reaction temperature at a constant heating rate, and then carrying out heat preservation reaction (phosphating reaction) at the reaction temperature for 2 +/-0.2 h; the reaction temperature is 350 +/-30 ℃;
and after the reaction time is up, continuing to cool the temperature in the tubular furnace to room temperature under the protection of inert gas (under the atmosphere of argon) to obtain the manganese cobalt iron phosphorus electrode material.
Description of the drawings: the step is to phosphorize the manganese-cobalt-iron precursor into the manganese-cobalt-iron-phosphorus electrode material.
Generally, the amount of sodium hypophosphite used is 100 to 600mg (preferably 300 mg) for 2cm by 3cm nickel foam.
The preparation method of the heterostructure manganese-cobalt-iron-phosphorus difunctional electrolytic water electrode material is improved by the following steps:
in the step S2, the drying temperature of the vacuum oven is 70 +/-10 ℃, and the drying time is 12 +/-1 h;
in the step S3, the drying temperature of the vacuum oven is 70 +/-10 ℃, and the drying time is 12 +/-1 h.
The preparation method of the heterostructure manganese-cobalt-iron-phosphorus difunctional electrolytic water electrode material is further improved as follows:
in step S4, the temperature rise rate is 2 ℃/min.
As a further improvement of the preparation method of the heterostructure manganese-cobalt-iron-phosphorus difunctional electrolytic water electrode material, the preparation method of the processed foam nickel in the step S2 comprises the following steps:
a. putting foamed nickel (cut into 2cm multiplied by 3cm foamed nickel) into 3mol/L hydrochloric acid solution, and ultrasonically cleaning for 30min;
b. washing the acid-washed foam nickel with deionized water until the pH value of the washing water is neutral; then ultrasonic cleaning is respectively carried out by deionized water and absolute ethyl alcohol, thereby ensuring that the surface of the foamed nickel is clean;
c. and (3) putting the cleaned foam nickel into a vacuum oven to perform vacuum drying treatment at 70 +/-10 ℃ for 12 +/-1 h to obtain the treated foam nickel.
The invention also provides the application of the electrode material obtained by any one of the methods in OER/HER bifunctional catalytic electrolysis water.
The preparation method of the heterostructure manganese-cobalt-iron-phosphorus difunctional electrolytic water electrode material (the three-dimensional self-supporting heterostructure manganese-cobalt-iron-phosphorus difunctional electrolytic water electrode material) provided by the invention has the advantages of simple preparation method, good stability, excellent catalytic performance and the like. Selecting foamed nickel as a supporting substrate, synthesizing a manganese-cobalt-iron-phosphorus composite material on the self-supporting foamed nickel through a hydrothermal method and a phosphorization effect, and preparing the manganese-cobalt-iron-phosphorus electrode material with a 'sheet-sheet' heterostructure through regulating and controlling the cobalt-iron precursor ratio, wherein the obtained manganese-cobalt-iron-phosphorus electrode material has excellent difunctional electrocatalysis performance.
The invention has the following beneficial effects:
1. the manganese-cobalt-iron-phosphorus electrode material with the sheet-sheet heterostructure is prepared by a simple hydrothermal method and a phosphating method, has the advantages of simple preparation process, low cost and the like, and is suitable for large-scale production;
2. the foam nickel is selected as a self-supporting substrate, and the manganese-cobalt-iron-phosphorus electrode material is synthesized on the foam nickel through in-situ growth, so that the stability and the conductivity of the electrode material are improved;
3. the three-dimensional sheet-sheet heterostructure enlarges the specific surface area of the electrode material, thereby exposing more active sites and improving the electrocatalytic performance;
4. the synergistic effect of multiple metals and the heterostructure optimizes the internal structure of the electrode material, improves the conductivity, provides rich sites, promotes charge transfer and substance transfer, and effectively enhances the catalytic activity.
In summary, the invention relates to a heterostructure manganese-cobalt-iron-phosphorus difunctional electrolytic water electrode material, which is prepared by growing a cobalt-iron precursor nanosheet on treated nickel foam by a hydrothermal method, growing a manganese nanosheet on the cobalt-iron precursor by secondary hydrothermal, obtaining a shape-controllable sheet-sheet precursor material by regulating and controlling the proportion of the cobalt-iron precursor, and finally obtaining the sheet-sheet heterostructure manganese-cobalt-iron-phosphorus electrode material by phosphating, thereby preparing the three-dimensional self-supporting manganese-cobalt-iron-phosphorus electrode material with no binder, a heterostructure and excellent performance. The manganese-doped cobalt phosphide/iron phosphide heterostructure electrode material is prepared, the specific surface area is increased and more catalytic active sites are provided due to the three-dimensional structure, the catalyst is directly grown on the foamed nickel, the stability and the conductivity are improved, the catalytic performance is effectively improved due to the synergistic effect of the manganese, the cobalt and the iron and the synergistic effect of the heterostructure, so that the manganese-cobalt-iron phosphide electrode material has excellent bifunctional electrolytic water performance, and is a potential electrocatalytic full-hydrolytic catalyst.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 is an XRD diffraction pattern of the manganese cobalt iron phosphorus electrode material prepared in example 1.
FIG. 2 is a scanning electron micrograph of the MnCoFeP electrode material prepared in example 1.
FIG. 3 is a TEM image of the MnCoFeP electrode material prepared in example 1.
FIG. 4 is an OER linear voltammogram (LSV) scan of the Mn-Co-Fe-P electrode material prepared in example 1.
Figure 5 is a HER linear voltammetric scan (LSV) of the manganese cobalt iron phosphorus electrode material prepared in example 1.
FIG. 6 is an OER linear voltammogram (LSV) scan of the Mn-Co-Fe-P electrode material prepared in comparative example 1-1.
Fig. 7 is a HER linear voltammetric sweep (LSV) curve of the manganese cobalt iron phosphorus electrode material prepared in comparative example 1-1.
FIG. 8 is an OER linear voltammogram (LSV) scan of the Mn-Co-Fe-P electrode materials prepared in comparative examples 1-2.
Fig. 9 is a HER linear voltammetric sweep (LSV) curve of the manganese cobalt iron phosphorus electrode materials prepared in comparative examples 1-2.
FIG. 10 is an OER linear voltammogram (LSV) scan curve of the Mn-Co-Fe-P electrode material prepared in comparative example 2-1.
Fig. 11 is a HER linear voltammetric scan (LSV) of the manganese cobalt iron phosphorus electrode material prepared in comparative example 2-1.
FIG. 12 is an OER linear voltammogram (LSV) scan of the Mn-Co-Fe-P electrode material prepared in comparative examples 2-2.
Figure 13 is a HER linear voltammetric scan (LSV) of the manganese cobalt iron phosphorus electrode material prepared in comparative examples 2-2.
FIG. 14 is an OER linear voltammogram (LSV) scan of the Mn-Co-Fe-P electrode material prepared in comparative example 3-1.
Fig. 15 is a HER linear voltammetric sweep (LSV) curve of the manganese cobalt iron phosphorus electrode material prepared in comparative example 3-1.
FIG. 16 is an OER linear voltammogram (LSV) scan of the Mn-Co-Fe-P electrode material prepared in comparative example 3-2.
Fig. 17 is a HER linear voltammetric sweep (LSV) curve of the manganese cobalt iron phosphorus electrode material prepared in comparative example 3-2.
FIG. 18 is an OER linear voltammogram (LSV) scan curve of the Mn-Co-Fe-P electrode material prepared in comparative example 4-1.
Fig. 19 is a HER linear voltammetric scan (LSV) of the manganese cobalt iron phosphorus electrode material prepared in comparative example 4-1.
FIG. 20 is an OER linear voltammogram (LSV) scan of the Mn-Co-Fe-P electrode material prepared in comparative example 4-2.
Fig. 21 is a HER linear voltammetric scan (LSV) of the manganese cobalt iron phosphorus electrode material prepared in comparative example 4-2.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of protection of the invention is not limited thereto:
1. the preparation method of the processed foam nickel comprises the following steps in sequence:
a. adding hydrochloric acid solution with the concentration of 3mol/L into a beaker, then adding a plurality of pieces of foam nickel which is cut into 2cm multiplied by 3cm into the beaker filled with hydrochloric acid, and carrying out ultrasonic cleaning for 30min;
b. washing the acid-washed foam nickel with deionized water until the pH value of the washing water is neutral; then ultrasonic cleaning is carried out by using deionized water and absolute ethyl alcohol respectively to ensure that the surface of the foamed nickel is clean;
c. and after the foamed nickel is washed cleanly, placing the foamed nickel in a vacuum oven to carry out vacuum drying treatment at 70 ℃, and drying for 12 hours to obtain the treated foamed nickel.
The treated nickel foam used in the examples below was obtained by the treatment described above.
2. When the prepared heterostructure manganese-cobalt-iron-phosphorus difunctional electrolytic water electrode material is used for performance detection:
preparation of test samples: the sample was cut into a "raised" shape containing a 1cm x 1cm square area, i.e., the lower half of the "raised" shape was a 1cm x 1cm square area.
The OER and HER testing method is a conventional technology, and specifically comprises the following steps: the test sample is used as a working electrode, a platinum sheet is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, a test instrument is a Shanghai Hua CHI 760E type electrochemical workstation, and the electrolyte is 1M KOH solution. Before linear scanning, CV (cyclic voltammetry) scanning activation is carried out on the electrode, the scanning interval is 0-0.8V vs.Ag/AgCl (OER) and-0.8-1.6V vs.Ag/AgCl (HER), the scanning speed is 50mV/s, and 20 scanning circles are carried out to achieve the purpose of full activation. For LSV (Linear volt-ampere scanning test), the scanning interval is set to be 0-1.4V vs. Ag/AgCl (OER) and-0.7-2V vs. Ag/AgCl (HER), and the scanning speed is 2mV/s. The frequency range of the alternating current impedance test (EIS) is 10 5 -0.01 Hz, amplitude value of 10mV, applied polarization voltage values of 0.56v vs. ag/AgCl (OER) and-1.1 v vs. ag/AgCl (HER), respectively. The electrocatalytic performance of the manganese-cobalt-iron-phosphorus electrode was tested by the above test method. The potentials described hereinafter are relative to the reversible hydrogen electrode.
Embodiment 1, a method for preparing a three-dimensional self-supporting heterostructure mn-co-fe-p bifunctional electrolytic water electrode material, sequentially comprising the following steps:
s1, dissolving 0.5mmol of cobalt nitrate, 0.5mmol of ferric nitrate, 2mmol of ammonium fluoride and 4mmol of urea in 25mL of deionized water in sequence, and stirring for 30min until the cobalt nitrate, the ferric nitrate, the ammonium fluoride and the urea are dissolved;
s2, placing the processed nickel foam into a polytetrafluoroethylene lining of a reaction kettle, pouring the solution obtained in the step S1 into the lining, immersing the nickel foam, transferring the reaction kettle into a high-temperature oven, and carrying out hydrothermal reaction at 120 ℃ for 3 hours; after the reaction is finished, cooling the oven to room temperature, taking out the foamed nickel, and respectively carrying out ultrasonic cleaning by using deionized water and absolute ethyl alcohol (carrying out ultrasonic cleaning until the solution is not turbid);
putting the washed foam nickel into a vacuum oven, and carrying out vacuum drying for 12 hours at 70 ℃ to obtain foam nickel with a cobalt iron hydroxide precursor;
s3, putting the foamed nickel with the cobalt-iron hydroxide precursor obtained in the step S2 into a polytetrafluoroethylene lining of a reaction kettle, pouring 0.05M potassium permanganate solution (about 30 ml) into the lining and immersing the foamed nickel, then transferring the reaction kettle into a high-temperature oven, and carrying out hydrothermal reaction at 120 ℃ for 1h; after the reaction is finished, cooling the oven to room temperature, taking out the foamed nickel, and respectively ultrasonically cleaning the foamed nickel by using deionized water and absolute ethyl alcohol;
then placing the nickel foam in a vacuum oven for vacuum drying for 12 hours at 70 ℃ to obtain foam nickel with a manganese-cobalt-iron precursor;
s4, respectively putting the foamed nickel with the manganese-cobalt-iron precursor obtained in the step S3 and 300mg of sodium hypophosphite powder into two porcelain boats, putting the porcelain boats filled with the sodium hypophosphite on one side close to an argon gas inlet of the tube furnace, and putting the porcelain boats filled with the foamed nickel on one side of a gas outlet;
under the argon atmosphere, heating from room temperature to 350 ℃ at the heating rate of 2 ℃/min, and preserving heat for 2 hours at 350 ℃, so as to phosphorize the manganese-cobalt-iron precursor into a manganese-cobalt-iron-phosphorus electrode;
and after the phosphorization reaction is finished, continuously cooling the temperature in the tubular furnace to room temperature in the argon atmosphere to obtain the manganese-cobalt-iron-phosphorus electrode material.
The manganese-cobalt-iron-phosphorus electrode material prepared in the above way is firstly cut into a convex shape containing a square area of 1cm multiplied by 1cm, and then an electrochemical performance test is carried out.
As shown in FIG. 1, the XRD diffraction pattern of the Mn-Co-Fe-P electrode material prepared in this example 1 shows that the diffraction peaks at 31.6 °,36.3 °,48.2 ° and 56.8 ° correspond to the (011), (111), (211) and (301) crystal planes of CoP (PDF # 29-0497), and the diffraction peaks at 41.1 ° and 45.8 ° correspond to Fe 3 The (321) and (141) crystal planes of P (PDF # 89-2712). No characteristic peak of Mn was observed in the Mn-co-fe-p electrode material, indicating that Mn should be present in doped form. Fig. 2a-c are scanning electron microscope topography images of the cofe precursor (i.e., the cofe hydroxide precursor material obtained in step S2), the mn-cofe precursor (obtained in step S3) and the mn-cofe-p electrode material prepared in this example 1, from which it can be seen that a cofe precursor nanosheet vertically grows on the surface of the nickel foam, and after the secondary hydrothermal treatment, a "sheet-sheet" shaped manganese-cofe precursor is formed,after phosphorization, the appearance of the electrode material is basically kept unchanged, and the manganese-cobalt-iron-phosphorus electrode material with the sheet-sheet heterostructure is obtained. Fig. 3 is a transmission electron microscope topography of the manganese cobalt iron phosphorus electrode material prepared in this example 1, and it can be seen from the figure that the manganese cobalt iron phosphorus electrode material is composed of fine nano-sheets.
FIG. 4 is a graph of OER Linear voltammetric sweep (LSV) of the sample prepared in example 1, and it can be seen from FIG. 4 that when the electrode passes a current density of 10mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 192mV; when the current density of the electrode passing through is 100mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 279mV. FIG. 5 is a graph of HER Linear voltammetric scanning (LSV) of the samples prepared in example 1, and it can be seen from FIG. 5 that when the electrode passes a current density of 10mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 98mV; when the current density of the electrode passing through is 100mA/cm 2 The corresponding overpotential is 152mV.
As can be seen from FIG. 4, the current density when the electrode passes through the electrode is 10mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 192mV; when the current density of the electrode passing through is 100mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 279mV. FIG. 5 is a graph of HER Linear voltammetric scanning (LSV) of the samples prepared in example 1, and it can be seen from FIG. 5 that when the electrode passes a current density of 10mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 98mV; when the current density of the electrode passing through is 100mA/cm 2 The corresponding overpotential is 152mV.
Comparative example 1-1, urea and ammonium fluoride were used in the same amounts, and the amounts of cobalt nitrate and iron nitrate were changed to 0.25 and 0.75mmol, and the remainder was the same as in example 1.
The test results of the obtained material were: FIG. 6 is a graph of OER linear voltammetric scan (LSV) of the sample prepared in comparative example 1-1, from which it can be seen that when the electrode passes a current density of 10mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 155mV; when the current density of the electrode passing through is 100mA/cm 2 The corresponding overpotential is 284mV. FIG. 7 is a graph of HER Linear voltammetric scanning (LSV) for the samples prepared in comparative examples 1-1, from which it can be seen that the current density passed through the electrode was 10mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 104mV; when the current density of the electrode passing through is 100mA/cm 2 The corresponding overpotential is 187mV.
Comparative examples 1-2, urea and ammonium fluoride were used in the same amounts, and the amounts of cobalt nitrate and iron nitrate were changed to 0.75 and 0.25mmol, and the rest was identical to example 1.
The test results of the obtained material were: FIG. 8 is a graph of OER linear voltammetric scans (LSV) of the samples prepared in comparative examples 1-2, from which it can be seen that when the electrode passes a current density of 10mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 148mV; when the current density of the electrode passing through is 100mA/cm 2 The corresponding overpotential is 295mV. FIG. 9 is a graph of HER Linear voltammetric scans (LSV) for the samples prepared in comparative examples 1-2, from which it can be seen that the current density passed by the electrodes is 10mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 87mV; when the current density of the electrode passing through is 100mA/cm 2 The corresponding overpotential is 164mV.
In comparative example 2-1, the reaction time in the high-temperature oven in step S2 was changed from 3 hours to 1 hour, and the rest was the same as in example 1.
The test results of the obtained material are: FIG. 10 is a graph of OER linear voltammetric scan (LSV) of the sample produced in comparative example 2-1, from which it can be seen that when the electrode passes a current density of 10mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 161mV; when the current density of the electrode passing through is 100mA/cm 2 The corresponding overpotential is 291mV. FIG. 11 is a graph of HER Linear voltammetric scanning (LSV) of the sample prepared in comparative example 2-1, from which it can be seen that the current density when the electrode passes is 10mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 118mV; when the current density of the electrode passing through is 100mA/cm 2 The corresponding overpotential is 191mV.
Comparative example 2-2, the reaction time in the high temperature oven in step S2 was changed from 3h to 6h, and the rest was the same as in example 1.
The test results of the obtained material were: FIG. 12 is a graph of OER linear voltammetric scans (LSV) of the samples prepared in comparative examples 2-2, from which it can be seen that when the electrode passes a current density of 10mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 132mV; when the current density of the electrode passing through is 100mA/cm 2 The corresponding overpotential is 294mV. FIG. 13 is a graph of HER Linear voltammetric scanning (LSV) of the samples prepared in comparative examples 2-2, from which it can be seen that the current density when the electrode passes is 10mA/cm 2 Then the corresponding overpotential is 105mV; when the current density of the electrode passing through is 100mA/cm 2 The corresponding overpotential is 180mV.
Comparative example 3-1 the concentration of the potassium permanganate solution in step S3 was changed from 0.05M to 0.01M, the remainder being identical to example 1.
The test results of the obtained material are: FIG. 14 is a graph of OER linear voltammetric scan (LSV) of the sample prepared in comparative example 3-1, from which it can be seen that when the electrode passes a current density of 10mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 140mV; when the current density of the electrode passing through is 100mA/cm 2 The corresponding overpotential is 284mV. FIG. 15 is a graph of HER Linear voltammetric scanning (LSV) for the samples prepared in comparative example 3-1, from which it can be seen that the current density when passed through the electrode is 10mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 82mV; when the current density of the electrode passing through is 100mA/cm 2 The corresponding overpotential is 161mV.
Comparative example 3-2 the concentration of the potassium permanganate solution in step S3 was changed from 0.05M to 0.1M, and the remainder was identical to example 1.
The test results of the obtained material are: FIG. 16 is a graph of OER linear voltammetric scan (LSV) of the sample produced in comparative example 3-2, from which it can be seen that when the electrode passes a current density of 10mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 238mV; when the current density of the electrode passing through is 100mA/cm 2 The corresponding overpotential is 294mV. FIG. 17 is a graph of HER Linear voltammetric scanning (LSV) of the samples prepared in comparative examples 3-2, from which it can be seen that the current density when the electrode passes is 10mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 87mV; when the current density of the electrode passing through is 100mA/cm 2 The corresponding overpotential is 158mV.
Comparative example 4-1, the sodium hypophosphite powder in step S4 was changed from 300mg to 100mg, and the rest was the same as in example 1.
The test results of the obtained material were: FIG. 18 is a graph of OER linear voltammetric scan (LSV) of the sample produced in comparative example 4-1, from which it can be seen that the current density when the electrode passes is 10mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 156mV; when the current density of the electrode passing through is 100mA/cm 2 The corresponding overpotential is 298mV. FIG. 19 is a sample produced in comparative example 4-1The HER linear voltammetry scan (LSV) graph shows that when the current density passing through the electrode is 10mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 90mV; when the current density of the electrode passing through is 100mA/cm 2 The corresponding overpotential is 167mV.
Comparative example 4-2, the sodium hypophosphite powder in step S4 was changed from 300mg to 600mg, and the rest was the same as in example 1.
The test results of the obtained material were: FIG. 20 is a graph of OER linear voltammetric scan (LSV) of the sample prepared in comparative example 4-2, from which it can be seen that when the electrode passes a current density of 10mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 166mV; when the current density of the electrode passing through is 100mA/cm 2 The corresponding overpotential is 290mV. FIG. 21 is a graph of HER Linear voltammetric scanning (LSV) for the samples prepared in comparative examples 4-2, from which it can be seen that the current density when passed through the electrode is 10mA/cm 2 When the voltage is higher than the threshold voltage, the corresponding overpotential is 93mV; when the current density of the electrode passing through is 100mA/cm 2 The corresponding overpotential is 183mV.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.

Claims (5)

1. The preparation method of the heterostructure manganese-cobalt-iron-phosphorus difunctional electrolytic water electrode material is characterized by comprising the following steps of:
s1, placing cobalt nitrate, ferric nitrate, ammonium fluoride and urea in deionized water, and stirring until the cobalt nitrate, the ferric nitrate, the ammonium fluoride and the urea are dissolved;
cobalt nitrate: iron nitrate: ammonium fluoride: urea = 0.5-1.5;
s2, placing the treated foamed nickel into a polytetrafluoroethylene lining of a reaction kettle, pouring the solution obtained in the step S1 into the lining, immersing the treated foamed nickel, transferring the reaction kettle into a high-temperature oven, and carrying out hydrothermal reaction at 120 +/-10 ℃ for 1-6 hours; after the reaction is finished and the temperature is cooled to the room temperature, taking out the foamed nickel, and respectively carrying out ultrasonic cleaning by using deionized water and absolute ethyl alcohol;
then placing the nickel foam in a vacuum oven for drying to obtain foamed nickel with a cobalt iron hydroxide precursor;
s3, putting the foamed nickel with the cobalt-iron hydroxide precursor obtained in the step S2 into a polytetrafluoroethylene lining of a reaction kettle, pouring a potassium permanganate solution with the concentration of 0.01-0.1M into the lining and immersing the foamed nickel, then transferring the reaction kettle into a high-temperature oven, and carrying out hydrothermal reaction at 120 +/-10 ℃ for 1 +/-0.1 h; after the reaction is finished and the temperature is cooled to room temperature, taking out the reaction product, and respectively carrying out ultrasonic cleaning by using deionized water and absolute ethyl alcohol;
then placing the nickel foam into a vacuum oven for drying to obtain foam nickel with a manganese-cobalt-iron precursor;
s4, respectively putting the foamed nickel powder with the manganese-cobalt-iron precursor and the sodium hypophosphite powder obtained in the step S3 into two porcelain boats, putting the porcelain boats filled with the sodium hypophosphite at one side close to an argon gas inlet of the tube furnace, and putting the porcelain boats filled with the foamed nickel at one side of a gas outlet;
under the inert gas, heating from room temperature to reaction temperature at a constant heating rate, and then carrying out heat preservation reaction at the reaction temperature for 2 +/-0.2 h; the reaction temperature is 350 +/-30 ℃;
and after the reaction time is up, under the protection of inert gas, cooling the temperature in the tubular furnace to room temperature to obtain the manganese-cobalt-iron-phosphorus electrode material.
2. The preparation method of the heterostructure Mn-Co-Fe-P bi-functional electrolytic water electrode material as claimed in claim 1, wherein the preparation method comprises the following steps:
in the step S2, the drying temperature of the vacuum oven is 70 +/-10 ℃, and the drying time is 12 +/-1 h;
in the step S3, the drying temperature of the vacuum oven is 70 +/-10 ℃, and the drying time is 12 +/-1 h.
3. The preparation method of the heterostructure manganese-cobalt-iron-phosphorus difunctional electrolytic water electrode material as claimed in claim 2, is characterized in that:
in step S4, the temperature rise rate is 2 ℃/min.
4. The preparation method of the heterostructure Mn-Co-Fe-P bifunctional electrolytic water electrode material according to any one of claims 1 to 3, characterized by comprising the following steps: the preparation method of the processed foam nickel in the step S2 comprises the following steps:
a. putting the foamed nickel into a 3mol/L hydrochloric acid solution, and ultrasonically cleaning for 30min;
b. washing the acid-washed foam nickel with deionized water until the pH value of the washing water is neutral; then ultrasonic cleaning is carried out respectively by deionized water and absolute ethyl alcohol;
c. and (3) putting the washed foam nickel into a vacuum oven to perform vacuum drying treatment at 70 +/-10 ℃ for 12 +/-1 h to obtain the treated foam nickel.
5. Use of the electrode material obtained by the method of any one of claims 1 to 4 in OER/HER bifunctional catalyzed electrolysis of water.
CN202210892529.3A 2022-07-27 2022-07-27 Preparation method and application of heterostructure manganese-cobalt-iron-phosphorus difunctional electrolytic water electrode material Pending CN115386910A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117463382A (en) * 2023-12-27 2024-01-30 山东海化集团有限公司 Ultra-fast preparation of porous Fe with strain effect 2 P/Co 2 Method for preparing P heterojunction catalyst and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117463382A (en) * 2023-12-27 2024-01-30 山东海化集团有限公司 Ultra-fast preparation of porous Fe with strain effect 2 P/Co 2 Method for preparing P heterojunction catalyst and application thereof
CN117463382B (en) * 2023-12-27 2024-04-05 山东海化集团有限公司 Ultra-fast preparation of porous Fe with strain effect 2 P/Co 2 Method for preparing P heterojunction catalyst and application thereof

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