CN113955728A - Preparation of hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide and its application in water electrolysis - Google Patents

Preparation of hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide and its application in water electrolysis Download PDF

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CN113955728A
CN113955728A CN202111080749.8A CN202111080749A CN113955728A CN 113955728 A CN113955728 A CN 113955728A CN 202111080749 A CN202111080749 A CN 202111080749A CN 113955728 A CN113955728 A CN 113955728A
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cobalt
phosphide
manganese
electrode material
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郭兴忠
王凡
刘富
邹畅
杨辉
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Zhejiang University ZJU
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Abstract

The invention discloses a preparation method of hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide, which utilizes processed foam nickel and comprises the following steps: mixing cobalt nitrate, ammonium fluoride, urea and deionized water; adding the mixed solution and the treated nickel foam into a reaction kettle, and then carrying out hydrothermal reaction to obtain a cobalt hydroxide precursor material; adding a potassium permanganate solution and a cobalt hydroxide precursor material into the reaction kettle, and then carrying out 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 water electrolysis.

Description

Preparation of hollow-grade-structure cobalt phosphide/cobalt manganese phosphide and application of hollow-grade-structure cobalt phosphide/cobalt manganese phosphide in electrolytic water
Technical Field
The invention belongs to the technical field of electrolytic water electrode material preparation, and particularly relates to a preparation method of a hollow-grade-structure cobalt phosphide/cobalt manganese phosphide material and application of the material in bifunctional catalytic electrolytic water.
Background
With the rapid increase in global energy demand and the growing environmental problems, people are continuously forced to seek new generation of renewable, high-efficiency and clean energy to replace the 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 undoubtedly an efficient, convenient and sustainable hydrogen production technology. The electrolytic water reaction consists of two half reactions, namely a cathodic hydrogen evolution reaction and an anodic oxygen evolution reaction. However, in practical applications, 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 RuO2、IrO2The noble metal-based catalyst has high activity on HER and OER, and is the best catalyst material in the field of hydrogen production by water electrolysis at present. However, these precious metals are present in small amounts in the earth and are expensive, making their large-scale commercial use impractical. Therefore, it is very important to develop an electrocatalyst with a lower overpotential to realize low-cost, efficient and stable hydrogen production by water electrolysis.
Transition metal (e.g., Fe, Co, Ni, and Mn) based electrocatalysts have attracted considerable attention and are widely recognized as ideal substitutes for HER and OER noble metal based materials 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, etc. Conventional transition metal-based electrocatalysts are generally formed from aggregated particles, whereas bulk metal-based electrocatalysts do not have a competitive advantage due to their limited active surface area and few catalytically active sites. Meanwhile, most of the catalysts have poor electrocatalytic performance on electrolyzed water due to the limitation of microscopic morphology and single material. In order to overcome the above disadvantages, various schemes have been devised in the aspects of interface engineering, composition design and morphology optimization to achieve enhancement of electrocatalytic performance. The structure of the material has great influence on the electrocatalysis performance, the three-dimensional structure electrocatalyst is reasonably designed, the specific surface area can be effectively increased, the catalytic activity sites can be further improved, and the electrocatalysis performance can be effectively improved by accurately controlling the form and the structure of the electrocatalyst.
Publication No. CN105107536A discloses a preparation method of a polyhedral cobalt phosphide catalyst for water electrolysis hydrogen production, which comprises the steps of firstly obtaining a polyhedral metal organic framework ZIF-67 through cobalt nitrate, 2-methylimidazole and methanol; and then calcining the ZIF-67 in the air atmosphere to obtain cobaltosic oxide, and phosphorizing the cobaltosic oxide in the inert atmosphere to obtain the polyhedral cobaltous phosphide catalyst for hydrogen production by electrolyzing water, wherein although the prepared cobaltous phosphide catalyst material has high crystallinity, the polyhedral morphology of a metal organic framework template is maintained, the preparation process flow is simple, a binder is required during electrode manufacturing, and meanwhile, the oxygen evolution performance is not researched.
The publication No. CN112246261A discloses a cobalt phosphide hierarchical porous nanowire material, its preparation and application in the hydrogen production reaction by electrolyzing water, firstly synthesizing basic cobalt carbonate nanowire, then carrying out controllable phosphorization under inert atmosphere, phosphorization and air hole formation are carried out simultaneously, although in the synthesized cobalt phosphide hierarchical porous nanowire material, a large number of air holes are distributed in the cobalt phosphide nanowire to form a hierarchical porous structure, a binder is needed when manufacturing an electrode, the stability of the electrode material is affected, and simultaneously the hydrogen evolution activity is not good.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method and application of a cobalt phosphide/cobalt manganese phosphide material with a hollow hierarchical structure.
In order to solve the technical problem, the invention provides a preparation method of hollow-grade-structure cobalt phosphide/cobalt manganese phosphide, which utilizes the processed 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: the molar ratio of urea to urea is 1 (2 plus or minus 0.2) to (4 plus or minus 0.4);
in the mixed solution, the concentration of the cobalt nitrate is 4 +/-0.5 mmol/100 mL;
s2, adding the mixed solution (about 25mL) obtained in the step S1 and the treated nickel foam (1 piece) into a reaction kettle (a stainless steel reaction kettle with a polytetrafluoroethylene lining), and carrying out hydrothermal reaction at 120 +/-20 ℃ for 6 +/-1 h;
after the reaction is finished and the temperature is cooled to room temperature, taking out the reacted foam nickel, cleaning and drying in vacuum to obtain a cobalt hydroxide precursor material;
s3, adding a potassium permanganate solution (about 30mL) and the cobalt hydroxide precursor material obtained in the step S2 into a reaction kettle (a stainless steel reaction kettle with a polytetrafluoroethylene lining), and carrying out hydrothermal reaction at 90-150 ℃ for 1 +/-0.1 h;
after the reaction is finished and the temperature is cooled to room temperature, taking out the cobalt hydroxide precursor material after the reaction, 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 a cobalt phosphide/cobalt manganese phosphide electrode material (namely, cobalt phosphide/cobalt manganese phosphide with a hollow hierarchical structure).
The improvement of the preparation method of the hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide is as follows: the S4 is as follows:
respectively putting the cobalt hydroxide/manganese oxide electrode material and sodium hypophosphite powder into two porcelain boats, then putting the two porcelain boats into a tubular furnace with an inert gas inlet pipe, heating to 350 +/-50 ℃ under the protection of inert gas (such as argon), and preserving heat for 2 +/-0.5 h, thereby phosphorizing the cobalt hydroxide/manganese oxide electrode material into cobalt phosphide/cobalt manganese phosphide.
Description of the drawings: after the reaction is finished, cooling to room temperature under the protection of inert gas (such as argon) to obtain the cobalt phosphide/cobalt manganese phosphide electrode material.
The preparation method of the hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide is further improved as follows:
in the step S4, the heating rate is 2 +/-0.5 ℃/min.
The preparation method of the hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide is further improved as follows:
in the S4, in the tube furnace, the porcelain boat filled with sodium hypophosphite is close to the gas inlet of the inert gas, and the porcelain boat filled with the cobalt hydroxide/manganese oxide electrode material is close to the gas outlet of the inert gas;
the cobalt hydroxide/manganese oxide electrode material prepared by each piece of 2cm multiplied by 3cm of foamed nickel is matched with 300 plus or minus 50mg of sodium hypophosphite.
The preparation method of the hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide is further improved as follows:
the vacuum drying temperature in the S2 is 70 +/-10 ℃, and the drying time is 12 +/-1 h;
the temperature of vacuum drying in the S3 is 70 +/-10 ℃, and the drying time is 12 +/-1 h.
The cleaning in the step S2 is as follows: ultrasonic cleaning with deionized water and absolute ethyl alcohol respectively;
the cleaning in the step S3 is as follows: and respectively ultrasonically cleaning by using deionized water and absolute ethyl alcohol.
The preparation method of the hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide is further improved as follows:
in the S3, the concentration of the potassium permanganate solution is 0.02-0.04M (preferably 0.03M).
The invention also provides the application of the hollow-grade-structure cobalt phosphide/cobalt manganese phosphide prepared by the method: used for HER/OER dual-function catalytic water electrolysis.
In the present invention: the treatment method of the foamed 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 the hydrochloric acid, sealing the opening of the beaker by using a preservative film, and ultrasonically cleaning for 30 +/-10 min;
b. taking the foamed nickel subjected to ultrasonic treatment out of the beaker, and washing the foamed nickel by using 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 clean, placing the foamed nickel in a vacuum oven to be dried at 70 +/-10 ℃ (the time is about 12 +/-2 h) to obtain the treated foamed nickel.
The invention has the advantages of simple preparation process, low cost and excellent electrocatalytic performance. Firstly, carrying out acid pickling treatment on foamed nickel, firstly, carrying out hydrothermal reaction on the foamed nickel to grow cobalt hydroxide, and then, growing manganese oxide on a cobalt hydroxide precursor through secondary hydrothermal, namely, growing cobalt hydroxide/manganese oxide on the foamed nickel through a two-step hydrothermal method, then, using sodium hypophosphite as a phosphorus source, and phosphorizing the cobalt hydroxide/manganese oxide on the surface of the foamed nickel at low temperature to obtain cobalt phosphide/cobalt manganese phosphide, thereby preparing the cobalt phosphide/cobalt manganese phosphide dual-function electrode material which has no binder, large specific surface area, hollow hierarchical structure and excellent electro-catalytic performance.
The invention has the following technical advantages:
1. the invention has simple process, low cost and excellent electrocatalysis performance;
2. the cobalt phosphide/cobalt manganese phosphide electrode material is prepared by taking foamed nickel as a substrate, and no binder is used, so that good mechanical adhesion and good conductivity and stability are ensured;
3. the hollow-grade porous structure provides a larger specific surface area, and can expose more catalytic active sites, thereby improving the electron transfer efficiency and providing a smooth channel for the effective release of gas;
4. the synergistic effect of the cobalt-manganese double metals enriches catalytic active sites while enhancing the conductivity, and the phosphating treatment can adjust an electronic structure and form defects, thereby improving the catalytic activity.
In conclusion, the invention takes the foamed nickel as the substrate, improves the conductivity of the electrode by the synergy of cobalt and manganese double metals, the specific surface area of the hollow hierarchical structure is increased, and the phosphorization effect, and the prepared hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide material with excellent 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 abundant catalytic active sites; the prepared cobalt phosphide/cobalt manganese phosphide material has excellent catalytic activity as a bifunctional electrocatalyst for Hydrogen Evolution (HER) and Oxygen Evolution (OER), and has good application prospect in the field of full water splitting.
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 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 micrograph of a cobalt phosphide/cobalt manganese phosphide electrode material uniformly grown on foamed nickel produced in example 1.
FIG. 3 is a transmission electron micrograph of a cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 1.
FIG. 4 is an OER linear voltammetric sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 1.
Figure 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 sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 2.
Figure 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 voltammetric sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 3.
Figure 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 sweep (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 sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 1-2.
FIG. 13 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 1-2.
FIG. 14 is an OER linear voltammetric sweep (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 sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 2-2.
FIG. 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 sweep (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 voltammogram (LSV) scan of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 3-2.
FIG. 21 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 3-2.
FIG. 22 is an OER linear voltammetric sweep (LSV) of the 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 sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 4-2.
FIG. 25 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 4-2.
FIG. 26 is an OER linear voltammetric sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 5-1.
FIG. 27 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 5-1.
FIG. 28 is an OER linear voltammetric sweep (LSV) of the 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 voltammogram (LSV) scan of the 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 sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 6-2.
FIG. 33 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 6-2.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
in the present invention, ultrasonic cleaning is generally performed at room temperature for 10 min.
The preparation method of the processed 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 the hydrochloric acid, sealing the opening of the beaker by using a preservative film, and ultrasonically cleaning for 30 min;
b. taking the foamed nickel subjected to ultrasonic treatment out of the beaker, and washing the foamed nickel by using 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 clean, placing the foamed nickel in a vacuum oven for drying treatment at 70 ℃, and drying for 12h to obtain the treated foamed nickel.
The following examples all used stainless steel reactors lined with polytetrafluoroethylene.
Example 1, a method for preparing a cobalt phosphide/cobalt manganese phosphide electrode material, sequentially comprising the following steps:
1) sequentially adding 1mmol of cobalt nitrate, 2mmol of ammonium fluoride and 4mmol of urea into a beaker filled with 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 putting the treated piece of foamed 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, after the oven is cooled to room temperature, taking out the foamed nickel, and respectively carrying out ultrasonic cleaning by using deionized water and absolute ethyl alcohol;
putting the washed foam nickel into a vacuum oven to be dried for 12 hours at 70 ℃ to obtain a cobalt hydroxide precursor material;
3) firstly, adding 30mL of 0.03M potassium permanganate solution into a reaction kettle, then putting the cobalt hydroxide precursor material obtained in the step 2) into the reaction kettle, transferring the reaction kettle into a high-temperature oven, and reacting for 1h at 120 ℃; after the reaction is finished, after the oven is cooled to room temperature, taking out the foamed nickel, and respectively carrying out ultrasonic cleaning by using 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 tube furnace, wherein the tube furnace is provided with an argon gas inlet pipe, placing the porcelain boat filled with the sodium hypophosphite at one side close to the argon gas inlet of the tube furnace, and placing the porcelain boat filled with the cobalt hydroxide/manganese oxide electrode material at one side of a gas outlet;
opening a heating switch of the tubular furnace under the argon atmosphere, heating the tubular furnace from room temperature to 350 ℃ at the heating rate of 2 ℃/min, and preserving heat for 2 hours at the temperature, so as to phosphorize the cobalt hydroxide/manganese oxide electrode material into cobalt phosphide/cobalt manganese phosphide;
and after the phosphating reaction is finished (namely the set heat preservation time is up), 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 carrying out electrochemical performance test on the prepared cobalt phosphide/cobalt manganese phosphide electrode material.
FIG. 1 is an XRD diffraction pattern of the hollow grade cobalt phosphide/cobalt manganese phosphide electrode material prepared in the embodiment 1, and from XRD test curves, it can be seen that diffraction peaks at 44.3 °, 51.6 ° and 76.1 ° respectively correspond to (111), (200) and (220) crystal planes of nickel, 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 respectively correspond to (011), (111) and (211) crystal faces of cobalt phosphide and are matched with an XRD standard card PDF #29-0497 of the cobalt phosphide; the diffraction peak of cobalt manganese phosphide is not very significant because the crystallinity of the sample is poor and the content of manganese is low. Fig. 2 is a scanning electron microscope topography of the hollow grade cobalt phosphide/cobalt manganese phosphide electrode material prepared in the present example 1, wherein the cobalt phosphide/cobalt manganese phosphide shown in fig. 2 is in a grade structure, and the nano-arrays are uniformly grown on the foamed nickel substrate. Fig. 3 is a transmission electron microscope topography of the hollow grade cobalt phosphide/cobalt manganese phosphide electrode material prepared in the embodiment 1, and it can be seen from fig. 3 that the cobalt phosphide/cobalt manganese phosphide is of a hollow structure, the hollow structure is formed by stacking nanosheets, and some porous structures can be seen at the same time.
Experiment, OER, HER test:
preparation of test samples: the 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 × 0.5cm) as a test sample.
A test sample is taken as a working electrode, a platinum sheet is taken as a counter electrode, an Ag/AgCl electrode is taken as a reference electrode, a test instrument is a CHI 760E type electrochemical workstation in Shanghai Chen Hua, a 1M KOH solution is used as an electrolyte, and a linear volt-ampere scanning test (the scanning speed is 1mV/s) is carried out at room temperature to detect the electrocatalysis performance of the cobalt phosphide/cobalt manganese phosphide electrode. The potentials described hereinafter are relative to the reversible hydrogen electrode.
FIG. 4 is the OER linear voltammetric scan (LSV) of the sample prepared in example 1, from which it can be seen that the current density when passing through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 250 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 326 mV. FIG. 5 is a HER Linear voltammetric scan (LSV) of the sample prepared in example 1, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 63 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 112 mV.
Examples 2,
With respect to example 1, the following modifications were made: step 3), reacting for 1h at 90 ℃; the rest is equivalent to embodiment 1.
FIG. 6 is the OER linear voltammetric scan (LSV) of the sample prepared in example 2, from which it can be seen that the current density when passing through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 271 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 341 mV. FIG. 7 is a HER Linear voltammetric scan (LSV) of the sample prepared in example 2, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 100 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 197 mV.
Example 3
With respect to example 1, the following modifications were made: step 3), reacting for 1h at 150 ℃; the rest is equivalent to embodiment 1.
FIG. 8 is the OER linear voltammetric scan (LSV) of the sample prepared in example 3, from which it can be seen that the current density when passing through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 294 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 365 mV. FIG. 9 is a HER Linear voltammetric scan (LSV) of the sample prepared in example 3, from which it can be seen that the current density passed by the electrode is 100mA/cm2The corresponding overpotential is 136 mV.
Comparative example 1-1, cobalt nitrate and urea were used in the same amounts, without addition of ammonium fluoride, 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, from which it can be seen that when the electrode passes a current density of 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 292 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 363 mV. FIG. 11 is a HER Linear voltammetric scan (LSV) of the sample prepared in comparative example 1-1, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 72 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 147 mV.
Comparative examples 1-2, the amount of cobalt nitrate was unchanged, and the ratio of cobalt nitrate: ammonium fluoride: the molar ratio of urea is adjusted up to 1: 3: 6, the rest was 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, from which it can be seen that when the electrode passes a current density of 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 300 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 379 mV. FIG. 13 is a HER Linear voltammetric scan (LSV) of the samples prepared in comparative examples 1-2, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 143 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 235 mV.
Comparative example 2-1, the reaction temperature in step 2) was changed from 120 ℃ to 100 ℃, and the rest was the same as 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, from which it can be seen that when the electrode passes a current density of 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 273 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 342 mV. FIG. 15 is a HER Linear voltammetric scan (LSV) of the sample prepared in comparative example 2-1, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 71 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 131 mV.
Comparative example 2-2, the reaction temperature in step 2) was changed from 120 ℃ to 140 ℃, and the rest was the same as in 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, from which the current density when the electrode passesIs 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 256 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 329 mV. FIG. 17 is a HER Linear voltammetric scan (LSV) of the samples prepared in comparative examples 2-2, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 71 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 128 mV.
Comparative example 3-1, the reaction time in step 2) was changed from 6h to 9h, and the rest was identical to example 1.
The test results of the obtained material were: FIG. 18 is an 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/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 274 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 346 mV. FIG. 19 is a HER Linear voltammetric scan (LSV) of the sample prepared in comparative example 3-1, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 87 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 170 mV.
Comparative example 3-2, the reaction time in step 2) was changed from 6h to 12h, and the rest was 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, from which it can be seen that when the electrode passes a current density of 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 269 mV; when the current density of the electrode passing through is 100mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 339 mV. FIG. 21 is a HER Linear voltammetric scan (LSV) of the samples prepared in comparative examples 3-2, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 77 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 166 mV.
Comparative example 4-1, the sodium hypophosphite powder in step 4) was changed from 300mg to 400mg, and the rest was identical to example 1.
The test results of the obtained material were: FIG. 22 is an OER linear voltammetric scan (LS) of the sample prepared in comparative example 4-1V), it can be seen from the graph that the current density when the electrode passes through is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 262 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 341 mV. FIG. 23 is a HER Linear voltammetric scan (LSV) of the sample prepared in comparative example 4-1, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 68 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 132 mV.
Comparative example 4-2, the sodium hypophosphite powder in step 4) was changed from 300mg to 500mg, and the rest was identical to example 1.
The test results of the obtained material were: FIG. 24 is an 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/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 254 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 340 mV. FIG. 25 is a HER 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 100mA/cm2The corresponding overpotential is 136 mV.
In comparative example 5-1, the reaction time of the high-temperature oven in step 3) was changed from 1h to 3h, and the rest was the same as in 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, from which it can be seen that when the electrode passes a current density of 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 266 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 336 mV. FIG. 27 is a HER Linear voltammetric scan (LSV) of the sample prepared in comparative example 5-1, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 68 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 127 mV.
Comparative example 5-2, the reaction time of the high temperature oven in step 3) was changed from 1h to 5h, and the rest was the same as 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, from which it can be seen thatWhen the current density of the electrode passing through is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 273 mV; when the current density of the electrode passing through is 100mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 339 mV. FIG. 29 is a HER Linear voltammetric scan (LSV) of the sample prepared in comparative example 5-2, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 74 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 128 mV.
Comparative example 6-1, the concentration of the potassium permanganate solution in step 3) was changed from 0.03M to 0.01M, and the remainder was the same as in example 1.
The test results of the obtained material were: FIG. 30 is an OER linear voltammetric scan (LSV) of the sample prepared in comparative example 6-1, from which it can be seen that when the electrode passes a current density of 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 278 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 346 mV. FIG. 31 is a HER Linear voltammetric scan (LSV) of the sample prepared in comparative example 6-1, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 73 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 128 mV.
Comparative example 6-2, the concentration of the potassium permanganate solution in step 3) was changed from 0.03M to 0.05M, and the remainder was the same as in 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, from which it can be seen that when the electrode passes a current density of 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 287 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 365 mV. FIG. 33 is a HER Linear voltammetric scan (LSV) of the sample prepared in comparative example 6-2, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 69 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 119 mV.
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 (9)

1.中空等级结构磷化钴/磷化钴锰的制备方法,利用处理后的泡沫镍,其特征在于包括以下步骤:1. the preparation method of hollow grade structure cobalt phosphide/cobalt manganese phosphide, utilizing the foamed nickel after treatment, is characterized in that comprising the following steps: S1、将硝酸钴、氟化铵、尿素加入去离子水中,室温搅拌至溶解,得混合液;S1, adding cobalt nitrate, ammonium fluoride, and urea into deionized water, and stirring at room temperature until dissolved to obtain a mixed solution; 硝酸钴:氟化铵:尿素=1:(2±0.2):(4±0.4)的摩尔比;Cobalt nitrate: ammonium fluoride: urea = 1: (2 ± 0.2): (4 ± 0.4) molar ratio; S2、反应釜中加入S1所得的混合液以及加入处理后的泡沫镍,然后于120±20℃水热反应6±1h;S2. Add the mixture obtained from S1 and the treated nickel foam into the reaction kettle, and then hydrothermally react at 120±20°C for 6±1h; 反应结束冷却至室温后,取出反应后泡沫镍,清洗、真空干燥,得到氢氧化钴前驱体材料;After the reaction is completed and cooled to room temperature, the nickel foam after the reaction is taken out, cleaned and dried in vacuum to obtain a cobalt hydroxide precursor material; S3、反应釜中加入高锰酸钾溶液以及加入S2所得的氢氧化钴前驱体材料,于90~150℃水热反应1±0.1h;S3, adding potassium permanganate solution and the cobalt hydroxide precursor material obtained by adding S2 into the reaction kettle, and hydrothermally reacting at 90~150℃ for 1±0.1h; 反应结束冷却至室温后,取出反应后的氢氧化钴前驱体材料,清洗、真空干燥,得到氢氧化钴/锰氧化物电极材料;After the reaction is completed and cooled to room temperature, the reacted cobalt hydroxide precursor material is taken out, washed, and dried in vacuum to obtain a cobalt hydroxide/manganese oxide electrode material; S4、将S3所得的氢氧化钴/锰氧化物电极材料和次磷酸钠粉末进行磷化反应,得磷化钴/磷化钴锰电极材料。S4. The cobalt hydroxide/manganese oxide electrode material obtained in S3 is subjected to a phosphating reaction with sodium hypophosphite powder to obtain a cobalt phosphide/cobalt manganese phosphide electrode material. 2.根据权利要求1所述的中空等级结构磷化钴/磷化钴锰的制备方法,其特征在于所述S4为:2. the preparation method of hollow grade structure cobalt phosphide/cobalt manganese phosphide according to claim 1, is characterized in that described S4 is: 将氢氧化钴/锰氧化物电极材料和次磷酸钠粉末分别放入两个瓷舟中,然后将两个瓷舟放入带有惰性气体通入管的管式炉内,于惰性气体保护下,升温至350±50℃,保温2±0.5h,从而将氢氧化钴/锰氧化物电极材料磷化成磷化钴/磷化钴锰。Put the cobalt hydroxide/manganese oxide electrode material and sodium hypophosphite powder into two porcelain boats respectively, and then put the two porcelain boats into a tube furnace with an inert gas inlet tube, under the protection of inert gas, The temperature is raised to 350±50° C., and the temperature is kept for 2±0.5 h, so that the cobalt hydroxide/manganese oxide electrode material is phosphated into cobalt phosphide/cobalt manganese phosphide. 3.根据权利要求2所述的中空等级结构磷化钴/磷化钴锰的制备方法,其特征在于所述S4:升温速率为2±0.5℃/min。3 . The preparation method of hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide according to claim 2 , wherein the S4 : the heating rate is 2±0.5° C./min. 4 . 4.根据权利要求3所述的中空等级结构磷化钴/磷化钴锰的制备方法,其特征在于所述S4:管式炉内,装有次磷酸钠的瓷舟靠近惰性气体的进气口,装有氢氧化钴/锰氧化物电极材料的瓷舟靠近惰性气体的出气口;4. the preparation method of hollow grade structure cobalt phosphide/cobalt manganese phosphide according to claim 3, it is characterized in that described S4: in the tubular furnace, the porcelain boat that is housed with sodium hypophosphite is close to the intake of inert gas port, the porcelain boat with cobalt hydroxide/manganese oxide electrode material is close to the gas outlet of the inert gas; 每一片2cm×3cm的泡沫镍制备而得的氢氧化钴/锰氧化物电极材料,配用300±50mg的次磷酸钠。Each piece of cobalt hydroxide/manganese oxide electrode material prepared from nickel foam of 2cm×3cm is equipped with 300±50mg of sodium hypophosphite. 5.根据权利要求1~4任一所述的中空等级结构磷化钴/磷化钴锰的制备方法,其特征在于:5. The preparation method of the hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide according to any one of claims 1 to 4, characterized in that: 所述S2中真空干燥的温度为70±10℃,干燥时间为12±1h;The temperature of vacuum drying in the S2 is 70±10°C, and the drying time is 12±1h; 所述S3中真空干燥的温度为70±10℃,干燥时间为12±1h。The temperature of vacuum drying in the S3 is 70±10° C., and the drying time is 12±1 h. 6.根据权利要求5所述的中空等级结构磷化钴/磷化钴锰的制备方法,其特征在于:6. the preparation method of hollow grade structure cobalt phosphide/cobalt manganese phosphide according to claim 5, is characterized in that: 所述S2中的清洗为:分别用去离子水和无水乙醇超声清洗;The cleaning in the described S2 is: ultrasonic cleaning with deionized water and absolute ethanol respectively; 所述S3中的清洗为:分别用去离子水和无水乙醇超声清洗。The cleaning in S3 is as follows: ultrasonic cleaning with deionized water and absolute ethanol respectively. 7.根据权利要求1~6任一所述的中空等级结构磷化钴/磷化钴锰的制备方法,其特征在于:7. The preparation method of the hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide according to any one of claims 1 to 6, characterized in that: 所述S1的混合液中,硝酸钴的浓度为4±0.5mmol/100mL。In the mixed solution of S1, the concentration of cobalt nitrate is 4±0.5mmol/100mL. 8.根据权利要求7所述的中空等级结构磷化钴/磷化钴锰的制备方法,其特征在于:8. the preparation method of hollow grade structure cobalt phosphide/cobalt manganese phosphide according to claim 7, is characterized in that: 所述S3中,高锰酸钾溶液的浓度为0.02~0.04M。In the S3, the concentration of the potassium permanganate solution is 0.02-0.04M. 9.如权利要求1~8任一方法制备所得的中空等级结构磷化钴/磷化钴锰的用途,其特征在于:用于HER/OER双功能催化电解水。9. The use of the hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide prepared by any method of claims 1 to 8, characterized in that: it is used for HER/OER bifunctional catalytic electrolysis of water.
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CN115386910A (en) * 2022-07-27 2022-11-25 浙江大学 Preparation method and application of heterostructure manganese-cobalt-iron-phosphorus difunctional electrolytic water electrode material
CN115852423A (en) * 2022-11-07 2023-03-28 广西民族大学 Preparation method of a stable Ni2P/MnP4/CF bifunctional electrode under high current
CN117509575A (en) * 2023-11-01 2024-02-06 扬州大学 Multi-metal phosphide hollow material and preparation method and application thereof
CN117772244A (en) * 2023-12-18 2024-03-29 洛阳理工学院 Core-shell nanowire FeOOH@CoMnP composite material and preparation method and application thereof
CN118441310A (en) * 2024-05-06 2024-08-06 四川农业大学 A Mn-doped CoP/CoO@NF material and its preparation method and application
CN118441310B (en) * 2024-05-06 2025-01-17 四川农业大学 Mn doped CoP/CoO@NF material and preparation method and application thereof

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