CN112342563A - Preparation method and application of nickel self-supporting electrode loaded with ferric hydroxide and manganese carbonate - Google Patents
Preparation method and application of nickel self-supporting electrode loaded with ferric hydroxide and manganese carbonate Download PDFInfo
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- CN112342563A CN112342563A CN202011201891.9A CN202011201891A CN112342563A CN 112342563 A CN112342563 A CN 112342563A CN 202011201891 A CN202011201891 A CN 202011201891A CN 112342563 A CN112342563 A CN 112342563A
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Abstract
A preparation method and application of nickel self-supporting electrode loaded with ferric hydroxide and manganese carbonate belong to electrocatalytic nanometer heterojunction materials. Ultrasonically washing foamed nickel, adding the washed foamed nickel into a stainless steel hydrothermal reaction kettle filled with a mixed solution of manganese chloride and urea, and immersing the foamed nickel into the solution to perform hydrothermal reaction; and then in a ferric nitrate solution, performing electrodeposition by adopting a three-electrode system to finally obtain the self-supporting electrode of ferric hydroxide/manganese carbonate-foamed nickel. The electrode has a three-dimensional cubic structure coated by the nano-sheets, so that the specific surface area of the material is increased, and more active sites can be exposed. Meanwhile, the electrode contains a manganese carbonate material, and the manganese element has a rich valence structure, so that the transfer rate of charges can be improved. The electrode has high-efficiency performance for electrocatalytic water oxidation and has good commercial value.
Description
Technical Field
The invention belongs to an electro-catalytic nano heterojunction material, and particularly relates to a preparation method of a self-supporting foam nickel electrode loaded with ferric hydroxide and manganese carbonate for efficient electro-catalytic water oxidation.
Background
Due to the excessive use of traditional fossil energy (coal, oil and natural gas), serious problems of environmental pollution, greenhouse effect, energy crisis and the like are caused. This makes people to explore clean energy sources that can replace traditional fossil energy sources, and the clean energy sources that have been put into use at present are: solar energy, wind energy, geothermal energy, tidal energy, hydrogen energy, and the like. The hydrogen energy as a clean energy has the following advantages: (1) the source of hydrogen is wide; (2) hydrogen has a large energy density (120 mg/kJ); (3) the combustion product of the hydrogen is water, and has no pollution to the environment. Through years of research, people find that the electrocatalytic water decomposition hydrogen production is a high-efficiency and feasible technology. The water splitting reaction is divided into an anodic water oxidation reaction and a cathodic proton reduction reaction, wherein the water oxidation reaction requires high free energy through the transfer of multiple electrons and protons, and therefore the water oxidation reaction is a key reaction for restricting the water splitting. This requires a highly efficient water oxidation catalyst to catalyze the reaction. The catalysts which are put into practical use at present are often noble metal catalysts (ruthenium, iridium and platinum), but the noble metals are expensive and low in reserves, so that the noble metals cannot be put into large-scale application. Therefore, research into non-noble metal catalysts is currently being conducted. Secondly, the selection of the substrate is also important, the foamed nickel has a three-dimensional porous structure which is beneficial to the permeation of electrolyte and the exposure of active sites, and the iron hydroxide/manganese carbonate self-supporting electrode is prepared on the foamed nickel by a hydrothermal method and an electrodeposition method and has the shape of a three-dimensional cubic structure coated by nano-sheets, so that the specific surface area of the material is increased, and more active sites can be exposed. Meanwhile, the manganese element in the manganese carbonate has a rich valence structure, so that the transfer rate of charges can be improved.
Disclosure of Invention
The invention aims to provide a preparation method of a self-supporting foam nickel electrode loaded with ferric hydroxide and manganese carbonate for high-efficiency electrocatalytic water oxidation, which mainly solves the problems of low catalytic activity, high overpotential, poor stability and the like in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a nickel self-supporting electrode loaded with ferric hydroxide and manganese carbonate comprises the following steps:
(S1) cutting the required substrate nickel foam into small pieces of 2 × 3cm, and ultrasonically washing the small pieces with dilute hydrochloric acid, absolute ethyl alcohol and ultrapure water for 20 minutes respectively;
(S2) adding a mixed solution of manganese chloride and urea into a 50ml of polytetrafluoroethylene-lined hydrothermal reaction kettle, immersing the foamed nickel subjected to ultrasonic washing in the mixed solution (S1), and carrying out hydrothermal reaction at 120 ℃ for 8-15h to obtain a manganese carbonate-loaded foamed nickel electrode; the concentration of the urea is 0.1-0.2 mol/L; the concentration of the manganese chloride solution is 0.01-0.05 mol/L;
(S3) cutting the manganese carbonate-loaded foamed nickel electrode obtained in the step (S2) into a size of 1 x 1cm, and then carrying out electrodeposition in a ferric nitrate solution by adopting a three-electrode system to obtain an iron hydroxide/manganese carbonate-foamed nickel self-supporting electrode, wherein the deposition potential is-0.8V-1.5V (vsAg/AgCl electrode), and the deposition time is 100-600S; the concentration of the ferric nitrate is 0.005-0.02 mol/L;
(S4) the obtained self-supporting electrode is washed with ultrapure water to remove surface residual ions, and then naturally dried.
The iron hydroxide/manganese carbonate-foamed nickel self-supporting electrode is applied to electrocatalysis water oxidation reaction.
Compared with the prior art, the invention has the following beneficial effects:
(1) the substrate foamed nickel adopted by the invention has a three-dimensional porous structure which is beneficial to the permeation of electrolyte and the exposure of active sites
(2) The iron hydroxide/manganese carbonate-foamed nickel self-supporting electrode prepared by the invention is a nanosheet-coated three-dimensional cubic structure, and the structure is favorable for increasing the specific surface area of the material and can expose more active sites.
(3) The manganese carbonate material in the electrode material prepared by the invention has a rich valence structure, and can improve the charge transfer rate.
Drawings
FIG. 1 is a schematic view of the flow structure of the present invention.
FIG. 2 is a scanning electron microscope photograph of the surface of the iron hydroxide/manganese carbonate-nickel foam self-supporting electrode at different hydrothermal temperatures.
FIG. 3 is a graph showing the catalytic performance and stability of the water oxidation reaction of the iron hydroxide/manganese carbonate-nickel foam self-supporting electrode of the present invention.
Detailed Description
The present invention is further illustrated by the following figures and examples, which include, but are not limited to, the following examples.
A preparation method of a self-supporting foam nickel electrode loaded with ferric hydroxide and manganese carbonate for high-efficiency electrocatalysis water oxidation comprises the following steps:
(S1) cutting the required substrate nickel foam into small pieces of 2 × 3cm, and ultrasonically washing the small pieces with dilute hydrochloric acid, absolute ethyl alcohol and ultrapure water for 20 minutes respectively;
(S2) adding a mixed solution of manganese chloride and urea into a 50ml of polytetrafluoroethylene-lined hydrothermal reaction kettle, immersing the foamed nickel subjected to ultrasonic washing in the mixed solution (S1), and carrying out hydrothermal reaction at 120 ℃ for 8-15h to obtain a manganese carbonate-loaded foamed nickel electrode; the concentration of the urea is 0.1-0.2 mol/L; the concentration of the manganese chloride solution is 0.01-0.05 mol/L;
(S3) cutting the manganese carbonate-loaded foamed nickel electrode obtained in the step (S2) into a size of 1 x 1cm, and then carrying out electrodeposition in a ferric nitrate solution by adopting a three-electrode system to obtain an iron hydroxide/manganese carbonate-foamed nickel self-supporting electrode, wherein the deposition potential is-0.8V-1.5V (vsAg/AgCl electrode), and the deposition time is 100-600S; the concentration of the ferric nitrate is 0.005-0.02 mol/L;
(S4) the obtained self-supporting electrode is washed with ultrapure water to remove surface residual ions, and then naturally dried.
The specific embodiments are as follows:
example 1
Fig. 1 is a flow chart of electrode preparation, which comprises the following specific steps: cutting the purchased foam nickel substrate into 3 x 2cm, and respectively carrying out ultrasonic washing for 20 minutes by using dilute hydrochloric acid, absolute ethyl alcohol and ultrapure water to remove oxides and organic impurities remained on the foam nickel. Then 40ml of mixed aqueous solution of manganese chloride and urea is added into a stainless steel hydrothermal reaction kettle, wherein the concentration of the manganese chloride solution is 0.025 mol/L, and the concentration of the urea solution is 0.125 mol/L. Immersing the foamed nickel in the solution to carry out hydrothermal reaction at 120 ℃ for 11 hours; then, electrodeposition was carried out in a 0.01 mol/L ferric nitrate solution using a three-electrode system at a deposition potential of-1V (vsAg/AgCl electrode) for a deposition time of 300 s. Finally obtaining the self-supporting electrode of ferric hydroxide/manganese carbonate-foamed nickel. A self-supporting electrode of iron hydroxide/manganese carbonate-nickel foam was applied to electrocatalytic water oxidation reactions.
As can be seen from fig. 2, at a hydrothermal temperature of 100 ℃, a cubic structure has not yet been formed; when the hydrothermal temperature is 120 ℃, the shape is a three-dimensional cubic structure coated by the nano-sheets; at a hydrothermal temperature of 150 ℃, the surfaces of the cubes become very smooth; at a hydrothermal temperature of 180 ℃, the cubic structure starts to crack.
As can be seen from FIG. 3, the electrodes were tested for their catalytic performance by linear voltammetry (LSV) at electrochemical workstation CHI660e, which showed the best electrocatalytic effect at a hydrothermal temperature of 120 ℃ and a current density of 10 mA/cm2When the voltage is high, the overpotential is only 213mV, and the Tafel slope is 31.8 mV/dec. Can be stabilized for more than 23h in the stability test of constant current long-time electrolysis, and the effect is basically kept unchanged.
The above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, but all changes that can be made by applying the principles of the present invention and performing non-inventive work on the basis of the principles shall fall within the scope of the present invention.
Claims (2)
1. A preparation method of a nickel self-supporting electrode loaded with ferric hydroxide and manganese carbonate is characterized by comprising the following steps:
(S1) cutting the foamed nickel substrate into small pieces, and respectively carrying out ultrasonic washing by using dilute hydrochloric acid, absolute ethyl alcohol and ultrapure water to obtain an ultrasonically-washed foamed nickel substrate;
(S2) adding a mixed solution of manganese chloride and urea into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, immersing the foamed nickel substrate subjected to ultrasonic washing into the mixed solution, and carrying out hydrothermal reaction at 120 ℃ for 8-15h to obtain a manganese carbonate-loaded foamed nickel electrode; the concentration of the urea in the mixed solution is 0.1-0.2mol/L, and the concentration of the manganese chloride solution is 0.01-0.05 mol/L;
(S3) carrying out electrodeposition on the manganese carbonate-loaded foam nickel electrode in ferric nitrate solution by adopting a three-electrode system to obtain an iron hydroxide/manganese carbonate-foam nickel self-supporting electrode, wherein the deposition potential is-0.8V-1.5V, and the deposition time is 100-600S; the concentration of the ferric nitrate solution is 0.005-0.02 mol/L;
(S4) washing the iron hydroxide/manganese carbonate-foam nickel self-supporting electrode with ultrapure water, removing residual ions on the surface, and naturally airing.
2. The application of the electrode prepared by the preparation method of the nickel self-supporting electrode loaded with iron hydroxide and manganese carbonate according to claim 1 is characterized in that: the ferric hydroxide/manganese carbonate-foam nickel self-supporting electrode is applied to electrocatalytic water oxidation reaction.
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Citations (6)
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| CN102655231A (en) * | 2012-05-08 | 2012-09-05 | 广州市香港科大霍英东研究院 | Novel preparation method of anode material LiMn2O4 of high-power-performance lithium ion battery |
| CN105000598A (en) * | 2015-05-08 | 2015-10-28 | 青岛科技大学 | Method for preparing manganese carbonate hollow spheres |
| CN107195878A (en) * | 2017-05-08 | 2017-09-22 | 陕西科技大学 | A kind of preparation method of manganese monoxide/N doping redox graphene combination electrode material |
| CN107973333A (en) * | 2016-10-25 | 2018-05-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | Metal composite oxide, its preparation method and application with hollow sea urchin shape structure |
| CN108557892A (en) * | 2018-06-07 | 2018-09-21 | 江苏大学 | A kind of oxide preparation method and application for the manganese that object is mutually controllable |
| CN110975907A (en) * | 2019-12-02 | 2020-04-10 | 大连理工大学 | Preparation method of foam nickel electrode loaded with iron and basic cobalt carbonate for catalyzing oxidation of water or organic matters |
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- 2020-11-02 CN CN202011201891.9A patent/CN112342563A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102655231A (en) * | 2012-05-08 | 2012-09-05 | 广州市香港科大霍英东研究院 | Novel preparation method of anode material LiMn2O4 of high-power-performance lithium ion battery |
| CN105000598A (en) * | 2015-05-08 | 2015-10-28 | 青岛科技大学 | Method for preparing manganese carbonate hollow spheres |
| CN107973333A (en) * | 2016-10-25 | 2018-05-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | Metal composite oxide, its preparation method and application with hollow sea urchin shape structure |
| CN107195878A (en) * | 2017-05-08 | 2017-09-22 | 陕西科技大学 | A kind of preparation method of manganese monoxide/N doping redox graphene combination electrode material |
| CN108557892A (en) * | 2018-06-07 | 2018-09-21 | 江苏大学 | A kind of oxide preparation method and application for the manganese that object is mutually controllable |
| CN110975907A (en) * | 2019-12-02 | 2020-04-10 | 大连理工大学 | Preparation method of foam nickel electrode loaded with iron and basic cobalt carbonate for catalyzing oxidation of water or organic matters |
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