CN113955728B - Preparation of cobalt phosphide/cobalt manganese phosphide with hollow grade structure and application of electrolytic water - Google Patents
Preparation of cobalt phosphide/cobalt manganese phosphide with hollow grade structure and application of electrolytic water Download PDFInfo
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Abstract
The invention discloses a preparation method of cobalt phosphide/cobalt manganese phosphide with a hollow hierarchical structure, which utilizes treated foam nickel and comprises the following steps: mixing cobalt nitrate, ammonium fluoride, urea and deionized water; adding mixed liquid and treated foam nickel into a reaction kettle, and then performing hydrothermal reaction to obtain a cobalt hydroxide precursor material; adding a potassium permanganate solution and a cobalt hydroxide precursor material into a reaction kettle, and then performing a hydrothermal reaction again to obtain a cobalt hydroxide/manganese oxide electrode material; and carrying out a phosphating reaction on the cobalt hydroxide/manganese oxide electrode material and sodium hypophosphite powder to obtain the cobalt phosphide/cobalt manganese phosphide electrode material. The cobalt phosphide/cobalt manganese phosphide electrode material can be used for HER/OER dual-function catalytic electrolysis of water.
Description
Technical Field
The invention belongs to the technical field of preparation of electrolytic water electrode materials, and particularly relates to a preparation method of a cobalt phosphide/cobalt manganese phosphide material with a hollow grade structure and application of the cobalt phosphide/cobalt manganese phosphide material in dual-function catalytic electrolytic water.
Background
With the rapid growth of global energy demand and the growing severity of environmental problems, new generation renewable efficient clean energy is continually being forced to replace traditional fossil fuels. Hydrogen is an ideal clean energy source, has the advantages of high energy density and zero carbon dioxide emission, and the hydrogen production by water electrolysis is certainly efficient, convenient and sustainableHydrogen production technology of (2). The electrolytic water reaction consists of two half reactions, namely a hydrogen evolution reaction of a cathode and an oxygen evolution reaction of an anode. However, in practice, a large overpotential is required to achieve the desired water splitting current density, and therefore, it is necessary to find an efficient electrocatalyst. At present, pt/C and RuO 2 、IrO 2 The noble metal-based catalyst has high activity on HER and OER, and is the best catalyst material in the field of water electrolysis hydrogen production at present. However, these precious metals are low in earth content and expensive, making them impractical for further large-scale commercial use. Therefore, it is important to develop electrocatalysts with lower overpotential to achieve low cost, efficient, stable hydrogen production from electrolyzed water.
Transition metal (e.g., fe, co, ni and Mn) based electrocatalysts have attracted considerable attention and are widely recognized as ideal alternatives to noble metal based materials for HER and OER due to their low cost and excellent electrocatalytic properties. Such as transition metal oxides, transition layered double hydroxides, metal organic framework materials, transition metal phosphides, transition metal sulfides, and the like. Conventional transition metal-based electrocatalysts are typically formed from aggregated particles, whereas bulk metal-based electrocatalysts have no competitive advantage due to their limited active surface area and very few catalytically active sites. Meanwhile, most catalysts have poor electrocatalytic performance to electrolyzed water due to the limitation of microscopic morphology and single material. In order to overcome the above drawbacks, various schemes have been devised in terms of interface engineering, composition design and morphology optimization, achieving enhancement of electrocatalytic performance. The structure of the material has great influence on the electrocatalytic performance, the three-dimensional structure electrocatalyst can be reasonably designed to effectively increase the specific surface area and further improve the catalytic active site, and the electrocatalytic performance can be effectively improved by precisely controlling the shape and the structure of the electrocatalyst.
The publication number CN105107536A discloses a preparation method of a polyhedral cobalt phosphide catalyst for hydrogen production by water electrolysis, wherein a polyhedral metal organic framework ZIF-67 is obtained by cobalt nitrate, 2-methylimidazole and methanol; and calcining ZIF-67 in air atmosphere to obtain cobaltosic oxide, and phosphating the cobaltosic oxide in inert atmosphere to obtain the polyhedral cobalt phosphide catalyst for hydrogen production by electrolyzing water, wherein the prepared cobalt phosphide catalyst material has high crystallinity, the polyhedral shape of the metal organic framework template is maintained, the preparation process flow is simple, but a binder is needed when an electrode is manufactured, and meanwhile, the oxygen evolution performance is not researched.
Publication number CN112246261a discloses a cobalt phosphide hierarchical porous nanowire material, its preparation and application in electrolytic water hydrogen production reaction, firstly synthesizing basic cobalt carbonate nanowire, then performing controllable phosphating under inert atmosphere, phosphating and pore formation simultaneously, although in the synthesized cobalt phosphide hierarchical porous nanowire material, a large number of pores are distributed in the cobalt phosphide nanowire to form a hierarchical porous structure, but in the process of manufacturing an electrode, a binder is needed to influence the stability of the electrode material, and meanwhile, the hydrogen evolution activity is poor.
Disclosure of Invention
The invention aims to provide a preparation method and application of a cobalt phosphide/cobalt manganese phosphide material with a hollow grade structure.
In order to solve the technical problems, the invention provides a preparation method of cobalt phosphide/cobalt manganese phosphide with a hollow grade structure, which utilizes treated foam nickel and comprises the following steps:
s1, adding cobalt nitrate, ammonium fluoride and urea into deionized water, and stirring at room temperature until the cobalt nitrate, the ammonium fluoride and the urea are dissolved to obtain a mixed solution;
cobalt nitrate: ammonium fluoride: urea=1, (2±0.2): molar ratio of (4±0.4);
in the mixed solution, the concentration of cobalt nitrate is 4+/-0.5 mmol/100mL;
s2, adding the mixed solution (about 25 mL) obtained in the step S1 and the treated foam nickel (1 piece) into a reaction kettle (stainless steel reaction kettle with polytetrafluoroethylene as a lining), and performing hydrothermal reaction at 120+/-20 ℃ for 6+/-1 h;
after the reaction is finished and cooled to room temperature, taking out the foam nickel after the reaction, and cleaning and vacuum drying to obtain a cobalt hydroxide precursor material;
s3, adding a potassium permanganate solution (about 30 mL) and the cobalt hydroxide precursor material obtained in the S2 into a reaction kettle (stainless steel reaction kettle with polytetrafluoroethylene as a lining), and carrying out hydrothermal reaction for 1+/-0.1 h at the temperature of 90-150 ℃;
after the reaction is finished and cooled to room temperature, taking out the cobalt hydroxide precursor material after the reaction, and cleaning and vacuum drying to obtain a cobalt hydroxide/manganese oxide electrode material;
and S4, performing a phosphating reaction on the cobalt hydroxide/manganese oxide electrode material obtained in the step S3 and sodium hypophosphite powder to obtain a cobalt phosphide/cobalt manganese phosphide electrode material (namely, cobalt phosphide/cobalt manganese phosphide with a hollow hierarchical structure).
As an improvement of the preparation method of the cobalt phosphide/cobalt manganese phosphide with the hollow grade structure, the invention: the S4 is as follows:
respectively placing cobalt hydroxide/manganese oxide electrode material and sodium hypophosphite powder into two porcelain boats, then placing the two porcelain boats into a tube furnace with an inert gas inlet tube, heating to 350+/-50 ℃ under the protection of inert gas (such as argon), and preserving heat for 2+/-0.5 h, thereby phosphating the cobalt hydroxide/manganese oxide electrode material into cobalt phosphide/cobalt manganese phosphide.
Description: after the reaction is finished, cooling to room temperature under the protection of inert gas (such as argon), and obtaining the cobalt phosphide/cobalt manganese phosphide electrode material.
As a further improvement of the preparation method of the cobalt phosphide/cobalt manganese phosphide with the hollow grade structure, the invention:
in the step S4, the temperature rising rate is 2+/-0.5 ℃/min.
As a further improvement of the preparation method of the cobalt phosphide/cobalt manganese phosphide with the hollow grade structure, the invention:
in the step S4, a porcelain boat filled with sodium hypophosphite is close to an air inlet of inert gas in the tubular furnace, and a porcelain boat filled with cobalt hydroxide/manganese oxide electrode material is close to an air outlet of inert gas;
each piece of the cobalt hydroxide/manganese oxide electrode material prepared from 2cm multiplied by 3cm foam nickel is matched with 300+/-50 mg of sodium hypophosphite.
As a further improvement of the preparation method of the cobalt phosphide/cobalt manganese phosphide with the hollow grade structure, the invention:
the temperature of vacuum drying in the step S2 is 70+/-10 ℃, and the drying time is 12+/-1 h;
and the temperature of vacuum drying in the step S3 is 70+/-10 ℃, and the drying time is 12+/-1 h.
The cleaning in the step S2 is as follows: respectively ultrasonically cleaning with deionized water and absolute ethyl alcohol;
the cleaning in the step S3 is as follows: respectively ultrasonically cleaning with deionized water and absolute ethyl alcohol.
As a further improvement of the preparation method of the cobalt phosphide/cobalt manganese phosphide with the hollow grade structure, the invention:
in the above S3, the concentration of the potassium permanganate solution is 0.02 to 0.04M (preferably 0.03M).
The invention also provides application of the cobalt phosphide/cobalt manganese phosphide with the hollow grade structure prepared by the method: is used for HER/OER double-function catalytic electrolysis of water.
In the present invention: the treatment method of the foam nickel comprises the following steps:
a. adding hydrochloric acid solution with the concentration of 3+/-1 mol/L into a beaker, then adding a plurality of pieces of foam nickel which is cut into 2cm multiplied by 3cm into the beaker containing hydrochloric acid, sealing the mouth of the beaker by using a preservative film, and ultrasonically cleaning for 30+/-10 min;
b. taking out the foam nickel after ultrasonic treatment from the beaker, and washing the foam nickel with deionized water until the pH value of washing water is neutral; respectively ultrasonically cleaning with deionized water and absolute ethyl alcohol to ensure the surface of the foam nickel to be clean;
c. after the foam nickel is washed clean, the foam nickel is placed in a vacuum oven for drying treatment (the time is about 12+/-2 hours) at 70+/-10 ℃ to obtain the treated foam nickel.
The invention has the advantages of simple preparation process, low cost and excellent electrocatalytic performance. Firstly, carrying out acid washing treatment on foam nickel, firstly, growing cobalt hydroxide on the foam nickel through a hydrothermal reaction, then, growing manganese oxide on a cobalt hydroxide precursor through a secondary hydrothermal reaction, namely, growing cobalt hydroxide/manganese oxide on the foam nickel through a two-step hydrothermal method, and then, phosphating the cobalt hydroxide/manganese oxide on the surface of the foam nickel at a low temperature by taking sodium hypophosphite as a phosphorus source to obtain the cobalt phosphide/cobalt manganese phosphide double-function electrode material which is free of adhesives, large in specific surface area, has a hollow grade structure and excellent in electrocatalytic performance.
The invention has the following technical advantages:
1. the invention has simple process, low cost and excellent electrocatalytic performance;
2. the foamed nickel is used as a substrate to prepare the cobalt phosphide/cobalt manganese phosphide electrode material, and any binder is not used, so that good mechanical adhesion is ensured, and good conductivity and stability are ensured;
3. the hollow grade porous structure provides a larger specific surface area, and more catalytic active sites can be exposed, so that the electron transfer efficiency is improved, and a smooth channel is provided for the effective release of gas;
4. the synergistic effect of cobalt and manganese bimetal enriches the catalytic active sites while enhancing the conductivity, and the phosphating treatment can adjust the electronic structure and form defects, so that the catalytic activity is improved.
In conclusion, the foamed nickel is taken as a substrate, the specific surface area is increased through the synergistic effect of cobalt and manganese bimetal, the specific surface area is increased through the hollow grade structure, the electrode conductivity is improved through the phosphating effect, and the cobalt phosphide/cobalt manganese phosphide material with the hollow grade structure and excellent preparation performance has excellent HER and OER electrocatalytic activity and good stability. The electrode material prepared by the invention has excellent conductivity, large specific surface area and rich catalytic active sites; the prepared cobalt phosphide/cobalt manganese phosphide material has excellent catalytic activity as a dual-function electrocatalyst for Hydrogen Evolution (HER) and Oxygen Evolution (OER), and has good application prospect in the field of full water decomposition.
Namely, the hollow grade material obtained by the invention has larger specific surface area, more catalytic active sites and rapid transmission channels, and good catalytic performance; as a bifunctional electrocatalyst, hydrogen evolution and oxygen evolution properties were studied simultaneously.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is an XRD diffraction pattern of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 1.
FIG. 2 is a scanning electron microscope image of a cobalt phosphide/cobalt manganese phosphide electrode material uniformly grown on foamed nickel as prepared in example 1.
FIG. 3 is a transmission electron microscope image of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 1.
FIG. 4 is an OER linear voltammetric scan (LSV) of a cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 1.
Fig. 5 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 1.
FIG. 6 is an OER linear voltammetric scan (LSV) of a cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 2.
Fig. 7 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 2.
FIG. 8 is an OER linear voltammetry (LSV) curve for the cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 3.
Fig. 9 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 3.
FIG. 10 is an OER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 1-1.
Fig. 11 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 1-1.
FIG. 12 is an OER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative examples 1-2.
Fig. 13 is a HER linear voltammetric scan (LSV) of cobalt phosphide/cobalt manganese phosphide electrode materials prepared in comparative examples 1-2.
FIG. 14 is an OER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 2-1.
Fig. 15 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 2-1.
FIG. 16 is an OER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 2-2.
Figure 17 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 2-2.
FIG. 18 is an OER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 3-1.
Fig. 19 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 3-1.
FIG. 20 is an OER linear voltammetric scan (LSV) of a cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 3-2.
Figure 21 is a HER linear voltammetric scan (LSV) of a cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 3-2.
FIG. 22 is an OER linear voltammetric scan (LSV) of a cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 4-1.
FIG. 23 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 4-1.
FIG. 24 is an OER linear voltammetric scan (LSV) of a cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 4-2.
Figure 25 is a HER linear voltammetric scan (LSV) of a cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 4-2.
FIG. 26 is an OER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 5-1.
Figure 27 is a HER linear voltammetric scan (LSV) of a cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 5-1.
FIG. 28 is an OER linear voltammetric scan (LSV) of a cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 5-2.
Fig. 29 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 5-2.
FIG. 30 is an OER linear voltammetric scan (LSV) of a cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 6-1.
FIG. 31 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 6-1.
FIG. 32 is an OER linear voltammetric scan (LSV) of a cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 6-2.
Figure 33 is a HER linear voltammetric scan (LSV) of a cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 6-2.
Detailed Description
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto:
in the present invention, the ultrasonic cleaning is generally carried out at room temperature for 10 minutes.
The preparation method of the treated foam nickel comprises the following steps:
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 containing hydrochloric acid, sealing the mouth of the beaker by using a preservative film, and ultrasonically cleaning for 30min;
b. taking out the foam nickel after ultrasonic treatment from the beaker, and washing the foam nickel with deionized water until the pH value of washing water is neutral; respectively ultrasonically cleaning with deionized water and absolute ethyl alcohol to ensure the surface of the foam nickel to be clean;
c. and (3) after the foam nickel is washed clean, placing the foam nickel in a vacuum oven, drying at 70 ℃ for 12 hours, and obtaining the treated foam nickel.
The reaction kettles used in the following examples are stainless steel reaction kettles with polytetrafluoroethylene as a lining.
Example 1, preparation method of cobalt phosphide/cobalt manganese phosphide electrode material, the following steps were sequentially carried out:
1) Sequentially adding 1mmol of cobalt nitrate, 2mmol of ammonium fluoride and 4mmol of urea into a beaker containing 25mL of deionized water, and stirring at room temperature until the cobalt nitrate, the ammonium fluoride and the urea are dissolved;
2) Transferring all the mixed solution obtained in the step 1) into a reaction kettle, simultaneously placing a piece of treated foam nickel into the reaction kettle, transferring the reaction kettle into a high-temperature oven, and reacting for 6 hours at 120 ℃; after the reaction is finished, taking out foam nickel after the baking oven is cooled to room temperature, and respectively ultrasonically cleaning with deionized water and absolute ethyl alcohol;
placing the washed foam nickel in a vacuum oven to dry for 12 hours at 70 ℃ to obtain a cobalt hydroxide precursor material;
3) Firstly adding 30mL of potassium permanganate solution with the concentration of 0.03M into a reaction kettle, then placing the cobalt hydroxide precursor material obtained in the step 2) into the reaction kettle, and then transferring the reaction kettle into a high-temperature oven for reaction for 1h at 120 ℃; after the reaction is finished, taking out foam nickel after the baking oven is cooled to room temperature, and respectively ultrasonically cleaning with deionized water and absolute ethyl alcohol; then placing the mixture in a vacuum oven to dry for 12 hours at 70 ℃ to obtain a cobalt hydroxide/manganese oxide electrode material;
4) Respectively placing the cobalt hydroxide/manganese oxide electrode material (one piece) obtained in the step 3) and 300mg of sodium hypophosphite powder into two porcelain boats, then placing the two porcelain boats in the center of a tubular furnace, wherein the tubular furnace is provided with an argon gas inlet pipe, placing the porcelain boat filled with sodium hypophosphite on one side close to an argon gas inlet of the tubular furnace, and placing the porcelain boat filled with the cobalt hydroxide/manganese oxide electrode material on one side of an air outlet;
under argon atmosphere, a heating switch of the tubular furnace is turned on, so that the tubular furnace is heated to 350 ℃ from room temperature at a heating rate of 2 ℃/min, and the temperature is kept for 2 hours, so that the cobalt hydroxide/manganese oxide electrode material is phosphated into cobalt phosphide/cobalt manganese phosphide;
and after the phosphating reaction is finished (namely, after the set heat preservation time is reached), continuously cooling the temperature in the tubular furnace to room temperature under the argon atmosphere to obtain the cobalt phosphide/cobalt manganese phosphide electrode material.
And (3) carrying out electrochemical performance test on the prepared cobalt phosphide/cobalt manganese phosphide electrode material.
As shown in fig. 1, the XRD diffraction pattern of the hollow grade cobalt phosphide/cobalt manganese phosphide electrode material prepared in this example 1 shows that the diffraction peaks at 44.3 °, 51.6 ° and 76.1 ° correspond to the (111), (200) and (220) crystal planes of nickel, respectively, and are consistent with the XRD standard card pdf#04-0850 of nickel; diffraction peaks at 31.7 degrees, 36.4 degrees and 48.3 degrees correspond to (011), (111) and (211) crystal faces of cobalt phosphide respectively, and are matched with XRD standard cards PDF#29-0497 of cobalt phosphide; since the crystallinity of the sample is poor and the content of manganese is small, the diffraction peak of cobalt manganese phosphide is not very remarkable. Fig. 2 is a scanning electron microscope morphology diagram of the hollow grade cobalt phosphide/cobalt manganese phosphide electrode material prepared in this example 1, the cobalt phosphide/cobalt manganese phosphide shown in fig. 2 is in a hierarchical structure, and the nano-array uniformly grows on the foam nickel substrate. Fig. 3 is a perspective view of a transmission electron microscope of the hollow grade cobalt phosphide/cobalt manganese phosphide electrode material prepared in this example 1, and it can be seen from fig. 3 that the cobalt phosphide/cobalt manganese phosphide is a hollow structure formed by stacking nano-sheets, and that some porous structures can be seen.
Experiment, OER, HER test:
preparation of test samples: cobalt phosphide/cobalt manganese phosphide electrode material was cut into a "convex" shape comprising a square area of 1cm×1cm (i.e., the lower half of the "convex" shape was 1cm×1cm, and the upper half was 0.5cm×0.5 cm) as a test sample.
The method is characterized in that a 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 testing instrument is an electrochemical workstation of Shanghai Chenhua CHI 760E, an electrolyte is 1M KOH solution, and a linear voltammetric scanning test (the scanning speed is 1 mV/s) is carried out at room temperature to detect the electrocatalytic performance of the cobalt phosphide/cobalt manganese phosphide electrode. The potentials described below are all potentials with respect to the reversible hydrogen electrode.
FIG. 4 is an OER linear voltammetric scan (LSV) of the sample prepared in example 1, as seen when the current density through the electrode was 10mA/cm 2 When the corresponding overpotential is 250mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 326mV. FIG. 5 is a linear voltammetric HER scan (LSV) of the sample prepared in example 1, showing a current density of 10mA/cm when passed through the electrode 2 The corresponding overpotential was 63mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 112mV.
EXAMPLE 2,
With respect to example 1, the following modifications were made: step 3), reacting for 1h at 90 ℃; the remainder was identical to example 1.
FIG. 6 is an OER linear voltammetric scan (LSV) of the sample prepared in example 2, as seen when the current density through the electrode was 10mA/cm 2 In the time-course of which the first and second contact surfaces,the corresponding overpotential was 271mV; when the current density passing through the electrode is 100mA/cm 2 At this time, the corresponding overpotential was 341mV. FIG. 7 is a linear voltammetric HER scan (LSV) of the sample prepared in example 2, showing a current density of 10mA/cm when passed through the electrode 2 When the corresponding overpotential is 100mV; when the current density passing through the electrode is 100mA/cm 2 At this time, the corresponding overpotential was 197mV.
Example 3
With respect to example 1, the following modifications were made: step 3), reacting for 1h at 150 ℃; the remainder was identical to example 1.
FIG. 8 is an OER linear voltammetric scan (LSV) of the sample prepared in example 3, as seen when the current density through the electrode was 10mA/cm 2 At this time, the corresponding overpotential was 294mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 365mV. FIG. 9 is a linear voltammetric HER scan (LSV) of the sample prepared in example 3, showing a current density of 100mA/cm when the electrodes pass 2 The corresponding overpotential was 136mV.
Comparative examples 1-1, cobalt nitrate and urea were used in the same amounts, with no ammonium fluoride added, and the remainder was identical to example 1.
The test results of the obtained material were: FIG. 10 is an OER linear voltammetric scan (LSV) of the sample prepared in comparative example 1-1, showing a current density of 10mA/cm when passed through the electrode 2 At the time, the corresponding overpotential was 292mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 363mV. FIG. 11 is a linear voltammetric HER scan (LSV) of a sample prepared in comparative example 1-1, showing a current density of 10mA/cm when passed through the electrode 2 The corresponding overpotential was 72mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 147mV.
Comparative examples 1-2, cobalt nitrate was used in the same amount, cobalt nitrate: ammonium fluoride: the molar ratio of urea was adjusted up to 1:3:6, the remainder being identical to example 1.
The test results of the obtained material were: FIG. 12 is an OER linear voltammetric scan (LSV) of the samples prepared in comparative examples 1-2, as can be seen when the current density through the electrodes is10mA/cm 2 The corresponding overpotential was 300mV; when the current density passing through the electrode is 100mA/cm 2 At this time, the corresponding overpotential was 379mV. FIG. 13 is a linear voltammetric HER scan (LSV) of the sample prepared in comparative examples 1-2, showing a current density of 10mA/cm when passed through the electrodes 2 The corresponding overpotential was 143mV; when the current density passing through the electrode is 100mA/cm 2 At this point, the corresponding overpotential was 235mV.
Comparative example 2-1, the reaction temperature in step 2) was changed from 120℃to 100℃and the remainder was identical to example 1.
The test results of the obtained material were: FIG. 14 is an OER linear voltammetric scan (LSV) of the sample prepared in comparative example 2-1, showing that the current density through the electrode is 10mA/cm 2 When the corresponding overpotential is 273mV; when the current density passing through the electrode is 100mA/cm 2 At this time, the corresponding overpotential was 342mV. FIG. 15 is a linear voltammetric HER scan (LSV) of a sample prepared in comparative example 2-1, showing a current density of 10mA/cm when passed through the electrode 2 The corresponding overpotential was 71mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 131mV.
Comparative example 2-2, the reaction temperature in step 2) was changed from 120℃to 140℃and the remainder was identical to example 1.
The test results of the obtained material were: FIG. 16 is an OER linear voltammetric scan (LSV) of the sample prepared in comparative example 2-2, showing that the current density through the electrode is 10mA/cm 2 The corresponding overpotential is 256mV; when the current density passing through the electrode is 100mA/cm 2 At this time, the corresponding overpotential was 329mV. FIG. 17 is a HER linear voltammetric scan (LSV) of a sample prepared in comparative example 2-2, showing a current density of 10mA/cm when passed through the electrode 2 The corresponding overpotential was 71mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 128mV.
Comparative example 3-1, the reaction time in step 2) was changed from 6h to 9h, the remainder being identical to example 1.
The test results of the obtained material were: FIG. 18 is an OER linear voltammetric scan (L) of a sample prepared in comparative example 3-1SV) is shown by the graph, the current density passing through the electrode is 10mA/cm 2 At the time, the corresponding overpotential was 274mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 346mV. FIG. 19 is a linear voltammetric HER scan (LSV) of a sample prepared in comparative example 3-1, showing a current density of 10mA/cm when passed through the electrode 2 The corresponding overpotential was 87mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 170mV.
Comparative example 3-2, the reaction time in step 2) was changed from 6h to 12h, the remainder being identical to example 1.
The test results of the obtained material were: FIG. 20 is an OER linear voltammetric scan (LSV) of the sample prepared in comparative example 3-2, showing that the current density through the electrode is 10mA/cm 2 When the corresponding overpotential is 269mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 339mV. FIG. 21 is a linear voltammetric HER scan (LSV) of a sample prepared in comparative example 3-2, showing a current density of 10mA/cm when passed through the electrode 2 When the corresponding overpotential is 77mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 166mV.
Comparative example 4-1, the sodium hypophosphite powder in step 4) was changed from 300mg to 400mg, and the remainder was identical to example 1.
The test results of the obtained material were: FIG. 22 is an OER linear voltammetric scan (LSV) of the sample prepared in comparative example 4-1, showing a current density of 10mA/cm when passed through the electrode 2 When the corresponding overpotential is 262mV; when the current density passing through the electrode is 100mA/cm 2 At this time, the corresponding overpotential was 341mV. FIG. 23 is a linear voltammetric HER scan (LSV) of a sample prepared in comparative example 4-1, showing a current density of 10mA/cm when passed through the electrode 2 The corresponding overpotential was 68mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 132mV.
Comparative example 4-2, the sodium hypophosphite powder in step 4) was changed from 300mg to 500mg, and the remainder was identical to example 1.
The test results of the obtained material were:FIG. 24 is an OER linear voltammetric scan (LSV) of a sample prepared in comparative example 4-2, as can be seen when the current density through the electrode is 10mA/cm 2 At the time, the corresponding overpotential was 254mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 340mV. FIG. 25 is a linear voltammetric HER scan (LSV) of a sample prepared in comparative example 4-2, showing a current density of 100mA/cm when passed through the electrode 2 The corresponding overpotential was 136mV.
Comparative example 5-1, the reaction time of the high temperature oven in step 3) was changed from 1h to 3h, and the remainder was identical to example 1.
The test results of the obtained material were: FIG. 26 is an OER linear voltammetric scan (LSV) of the sample prepared in comparative example 5-1, showing that the current density through the electrode is 10mA/cm 2 When the corresponding overpotential is 266mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 336mV. FIG. 27 is a HER linear voltammetric scan (LSV) of a sample prepared in comparative example 5-1, showing a current density of 10mA/cm when passed through the electrode 2 The corresponding overpotential was 68mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 127mV.
Comparative example 5-2, the reaction time of the high temperature oven in step 3) was changed from 1h to 5h, and the remainder was identical to example 1.
The test results of the obtained material were: FIG. 28 is an OER linear voltammetric scan (LSV) of the sample prepared in comparative example 5-2, as seen when the current density through the electrode is 10mA/cm 2 When the corresponding overpotential is 273mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 339mV. FIG. 29 is a linear voltammetric HER scan (LSV) of a sample prepared in comparative example 5-2, showing a current density of 10mA/cm when passed through the electrode 2 The corresponding overpotential was 74mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 128mV.
Comparative example 6-1 the concentration of the potassium permanganate solution in step 3) was changed from 0.03M to 0.01M, the remainder being identical to example 1.
The test results of the obtained material were: FIG. 30 is a pair ofOER linear voltammetric scanning (LSV) of samples prepared in proportion 6-1, the current density when passed through the electrodes was found to be 10mA/cm 2 At this time, the corresponding overpotential was 278mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 346mV. FIG. 31 is a linear voltammetric HER scan (LSV) of a sample prepared in comparative example 6-1, showing a current density of 10mA/cm when passed through the electrode 2 The corresponding overpotential was 73mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 128mV.
Comparative example 6-2, the concentration of the potassium permanganate solution in step 3) was changed from 0.03M to 0.05M, and the rest was identical to example 1.
The test results of the obtained material were: FIG. 32 is an OER linear voltammetric scan (LSV) of the sample prepared in comparative example 6-2, showing a current density of 10mA/cm when passed through the electrode 2 At this time, the corresponding overpotential was 287mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 365mV. FIG. 33 is a linear voltammetric HER scan (LSV) of a sample prepared in comparative example 6-2, showing a current density of 10mA/cm when passed through the electrode 2 The corresponding overpotential was 69mV; when the current density passing through the electrode is 100mA/cm 2 The corresponding overpotential was 119mV.
Finally, it should also be noted that the above list is merely a few specific embodiments of the present invention. Obviously, the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.
Claims (7)
1. The preparation method of cobalt phosphide/cobalt manganese phosphide with the hollow grade structure utilizes the treated foam nickel and is characterized by comprising the following steps:
s1, adding cobalt nitrate, ammonium fluoride and urea into deionized water, and stirring at room temperature until the cobalt nitrate, the ammonium fluoride and the urea are dissolved to obtain a mixed solution;
cobalt nitrate: ammonium fluoride: urea=1, (2±0.2): molar ratio of (4±0.4);
in the mixed solution, the concentration of the cobalt nitrate is 4+/-0.5 mmol/100mL;
s2, adding the mixed solution obtained in the step S1 and the treated foam nickel into a reaction kettle, and performing hydrothermal reaction at 120+/-20 ℃ for 6+/-1 h;
after the reaction is finished and cooled to room temperature, taking out the foam nickel after the reaction, and cleaning and vacuum drying to obtain a cobalt hydroxide precursor material;
s3, adding a potassium permanganate solution and a cobalt hydroxide precursor material obtained in the step S2 into a reaction kettle, and performing hydrothermal reaction for 1+/-0.1 h at the temperature of 90-120 ℃; the concentration of the potassium permanganate solution is 0.03M;
after the reaction is finished and cooled to room temperature, taking out the cobalt hydroxide precursor material after the reaction, and cleaning and vacuum drying to obtain a cobalt hydroxide/manganese oxide electrode material;
and S4, carrying out a phosphating reaction on the cobalt hydroxide/manganese oxide electrode material obtained in the step S3 and sodium hypophosphite powder to obtain the cobalt phosphide/cobalt manganese phosphide electrode material.
2. The method for preparing cobalt phosphide/cobalt manganese phosphide with hollow hierarchical structure according to claim 1, wherein S4 is:
respectively placing cobalt hydroxide/manganese oxide electrode material and sodium hypophosphite powder into two porcelain boats, then placing the two porcelain boats into a tube furnace with an inert gas inlet tube, heating to 350+/-50 ℃ under the protection of inert gas, and preserving heat for 2+/-0.5 h, thereby phosphating the cobalt hydroxide/manganese oxide electrode material into cobalt phosphide/cobalt manganese phosphide.
3. The method for preparing cobalt phosphide/cobalt manganese phosphide with hollow hierarchical structure according to claim 2, characterized in that said S4: the temperature rising rate is 2+/-0.5 ℃/min.
4. A method for preparing cobalt phosphide/cobalt manganese phosphide according to claim 3, characterized in that said S4: in the tube furnace, a porcelain boat filled with sodium hypophosphite is close to an air inlet of inert gas, and a porcelain boat filled with cobalt hydroxide/manganese oxide electrode material is close to an air outlet of the inert gas;
each piece of the cobalt hydroxide/manganese oxide electrode material prepared from 2cm multiplied by 3cm foam nickel is matched with 300+/-50 mg of sodium hypophosphite.
5. The method for preparing cobalt phosphide/cobalt manganese phosphide with a hollow hierarchical structure according to any one of claims 1 to 4, characterized by comprising the steps of:
the temperature of vacuum drying in the step S2 is 70+/-10 ℃, and the drying time is 12+/-1 h;
and the temperature of vacuum drying in the step S3 is 70+/-10 ℃, and the drying time is 12+/-1 h.
6. The method for preparing the cobalt phosphide/cobalt manganese phosphide with the hollow hierarchical structure according to claim 5, wherein the method comprises the following steps of:
the cleaning in the step S2 is as follows: respectively ultrasonically cleaning with deionized water and absolute ethyl alcohol;
the cleaning in the step S3 is as follows: respectively ultrasonically cleaning with deionized water and absolute ethyl alcohol.
7. Use of cobalt phosphide/cobalt manganese phosphide of hollow grade structure obtained by the process according to any one of claims 1-6, characterized in that: is used for HER/OER double-function catalytic electrolysis of water.
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