CN113445071B - Preparation method of self-supporting coral-like array structure electrode - Google Patents

Preparation method of self-supporting coral-like array structure electrode Download PDF

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CN113445071B
CN113445071B CN202110634262.3A CN202110634262A CN113445071B CN 113445071 B CN113445071 B CN 113445071B CN 202110634262 A CN202110634262 A CN 202110634262A CN 113445071 B CN113445071 B CN 113445071B
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nickel
urea
cerium dioxide
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deionized water
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CN113445071A (en
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郑金龙
吕超杰
成伽润
吴凯利
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University of Science and Technology Beijing USTB
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Abstract

The invention provides a preparation method of a self-supporting coralline array structure electrode, which is used for preparing and degrading pollutant urea by electrocatalysis hydrogen energy. The construction of the nickel phosphide/cerium dioxide heterojunction can adjust the charge structure of the intrinsic catalyst, accelerate charge transmission in the reaction process, and form more active sites on the interface, thereby obviously improving the catalytic performance of the material. As a bifunctional catalyst, the urea in the sewage is degraded and energy-saving hydrogen production is realized at the same time. Under the anode voltage, urea is oxidized and decomposed into carbon dioxide, nitrogen, water and other pollution-free substances, and hydrogen is separated out from the cathode. In the alkaline electrolyte, the addition of urea greatly reduces the potential required by cathode hydrogen production under the same current. And secondly, the catalytic activity and stability of the catalyst are improved by an in-situ growth technology, and the method has profound significance for further realizing urea degradation and energy-saving hydrogen production industrialization. The preparation method has the advantages of simple equipment, easy control, good process repeatability, stable product quality and the like, and has wide application prospect.

Description

Preparation method of self-supporting coral-like array structure electrode
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to preparation of a self-supporting coralline array structure electrode and application of the self-supporting coralline array structure electrode as a dual-function electrode in preparation of electro-catalytic hydrogen energy and oxidation degradation of pollutant urea.
Background
At present, hydrogen energy is considered to be an ideal alternative energy carrier for traditional fossil fuels due to its environmental efficiency and high energy density. Compared with the traditional hydrogen production method with serious environmental pollution, the method for producing hydrogen by electrolyzing water is a promising high-purity hydrogen production method. Generally, water electrolysis involves a cathodic Hydrogen Evolution Reaction (HER) and an anodic Oxygen Evolution Reaction (OER), both of which require additional energy to overcome the reaction barrier, particularly the OER process. Therefore, a highly active electrocatalyst is essential to increase the reaction rate and to reduce the overpotential during the process. In contrast to HER, the OER process involves multiple complex proton-coupled electron transfer steps, resulting in slow kinetics, significantly reducing the energy conversion efficiency of water electrolysis. In order to avoid the over-potential of the anode generated by OER, the OER is replaced by easily oxidized substances such as hydrazine, urea, glycerol and the like, so that the method is an efficient and energy-saving hydrogen production method.
Among them, urea is one of the most commonly used chemical fertilizers for increasing crop yield at present, but there are many unreasonable phenomena in the application process, which not only causes much waste, but also seriously pollutes agricultural environment and groundwater resources. The electrochemical degradation of urea is one of the most effective and most effective methods for treating urea pollution at present, and under the condition of anode voltage, urea molecules are oxidized into non-toxic and harmless substances (CO (NH), such as nitrogen, carbon dioxide and the like2)2+6OH-→N2+5H2O+CO2+6e-Or, UOR). Therefore, the electrocatalysis degradation method not only can realize the rapid treatment of urea, but also can realize the low-potential hydrogen energy preparation, and corresponds to the energy conservation and emission reduction advocated by the state.
However, the urea oxidation reaction is a typical six-electron process, so that the search for a bifunctional catalyst with rich reserves and excellent performance is urgently needed, urea electrolysis is realized in the same electrolyte, incompatibility can be avoided, and the synthesis cost can be reduced. Transition metal phosphide has received wide attention from domestic and foreign scholars due to its excellent bifunctional characteristics. However, the phosphide alone has low activity and cannot meet the current human needs. The construction of the heterojunction composite material is one of effective strategies for improving the catalytic activity of the catalyst at present. The construction of the heterogeneous interface can adjust the charge structure of the intrinsic catalyst, accelerate the charge transmission in the reaction process, and form more active sites in the interface, thereby obviously improving the catalytic performance of the material. Secondly, the array structure is prepared by the in-situ growth technology, so that the full contact between the catalyst and the electrolyte can be improved, the catalytic activity and the stability of the catalyst are further improved, and the method has profound significance for further realizing urea degradation and energy-saving hydrogen production industrialization.
Disclosure of Invention
Aiming at the problems of urea abuse, serious pollution, energy shortage and the like in the environment, the invention provides a preparation method of a self-supporting coral-shaped array structure dual-function electrode based on an electrochemical degradation method, and simultaneously realizes cathode hydrogen evolution and anode urea degradation.
In order to achieve the purpose, the invention provides the following technical scheme:
(1) preparing a precursor array structure: using foamed nickel as a substrate, washing the foamed nickel by using dilute nitric acid, ethanol and deionized water for multiple times to remove organic impurities and an oxide layer on the surface, and naturally drying the foamed nickel. Weighing a certain amount of nickel nitrate hexahydrate, cerium nitrate hexahydrate, urea and ammonium fluoride, dispersing in a certain volume of deionized water, transferring to a certain volume of a reaction kettle, stirring uniformly for dissolving, transferring foamed nickel into the reaction kettle, packaging, transferring to an oven, keeping the temperature for a certain time, and naturally cooling. And taking the product out of the reaction kettle, repeatedly washing the product with deionized water and ethanol, and drying the product in a vacuum oven to obtain the nickel hydroxide/cerium dioxide nanosheet array.
(2) Preparation of nickel phosphide/cerium dioxide coral-like nanoarrays: putting the nickel hydroxide/cerium dioxide nanosheet array obtained in the step (1) into a porcelain boat, putting a certain amount of sodium hypophosphite into another porcelain boat, putting the porcelain boat into an upward wind direction, then introducing inert gas, heating the tube furnace to a certain temperature at a specific heating rate, maintaining the temperature for a certain period of time, and carrying out selective phosphating treatment on the nickel hydroxide/cerium dioxide nanosheet array to obtain the nickel phosphide/cerium dioxide coralliform nano array.
Preferably, in the step (1), the thickness of the foamed nickel is 0.5-1.7 mm, the concentration of nitric acid used in the cleaning process is 5% -30%, and the washing times are 3-5 times.
Preferably, in the step (1), the amount of nickel nitrate hexahydrate is 0.9-1.8 g, the amount of cerium nitrate hexahydrate is 0.4-0.9 g, the amount of urea is 1.2-2.4 g, the amount of ammonium fluoride is 0.4-0.9 g, and the volume of deionized water is 30-90 mL.
Preferably, in the step (1), the volume of the reaction kettle used is 50 or 100 ml.
Preferably, in the step (1), the temperature of the vacuum oven is selected to be 100-120 ℃, and the heat preservation time is 6-10 hours.
Preferably, in the step (2), the inert gas may be one of argon and nitrogen, and the gas flow rate is 30 to 100 sccm.
Preferably, in the step (2), the temperature rise rate of the tube furnace is set to be 1-3 ℃/min, the temperature is set to be 250-400 ℃, and the heat preservation time is set to be 100-300 min.
Preferably, in the step (2), the amount of sodium hypophosphite is 50-100 mg.
The invention has the advantages and beneficial effects that:
1. the invention provides a preparation method of a self-supporting coral-like array structure electrode, which is characterized in that a heterojunction nickel phosphide/cerium dioxide coral-like nano array is prepared through selective phosphating treatment, the construction of a nickel phosphide/cerium dioxide heterogeneous interface can improve active sites on the surface of a material, and in addition, the charge structure of nickel phosphide can be adjusted, so that the charge transmission capability at the interface is accelerated. Compared with ex-situ synthesis, the method has the advantages of simple equipment, easiness in control, good process repeatability, stable product quality and the like, and compared with a catalyst with a single structure, the composite heterojunction nano-array structure has higher catalytic activity and conductivity.
2. The invention provides a preparation method of a self-supporting coralline array structure electrode, namely a nickel phosphide/cerium dioxide coralline nano array, which is used as a bifunctional electrocatalyst for the electrocatalytic degradation of urea and the preparation of hydrogen energy, the addition of urea can obviously reduce the potential required by cathode hydrogen production, and the invention has wide application prospects in rapidly and effectively improving the urea pollution problem, saving energy, producing hydrogen and the like.
Drawings
FIG. 1: the invention provides a flow chart of a preparation method of a self-supporting coral-like array structure electrode;
FIG. 2: scanning electron microscope photos of the nickel phosphide/cerium dioxide coralliform nano-arrays obtained in the embodiment 1 of the invention;
FIG. 3: x-ray diffraction pattern of nickel phosphide/ceria-based coral-like nanoarrays obtained in example 3 of the present invention;
FIG. 4: the nickel phosphide/cerium dioxide coral-like nano-array electrode obtained in the embodiment of the invention is used as a polarization curve of a bifunctional catalyst in an alkaline electrolyte (1M KOH) containing urea and not containing urea.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples, but the scope of the present invention is not limited to the following examples.
Example 1:
(1) preparing a precursor array structure: taking foamed nickel as a substrate, washing with 5% dilute nitric acid, ethanol and deionized water for three times to remove organic impurities and an oxide layer on the surface, naturally drying, weighing 0.9g of nickel nitrate hexahydrate, 0.4g of cerium nitrate hexahydrate, 1.2g of urea and 0.4g of ammonium fluoride, dispersing in 30mL of deionized water, transferring to a 50mL reaction kettle, uniformly stirring for dissolving, transferring the foamed nickel into the reaction kettle, packaging, transferring to an oven, keeping the temperature at 100 ℃ for 8 hours, and naturally cooling. And taking the product out of the reaction kettle, repeatedly washing the product with deionized water and ethanol, and drying the product in a vacuum oven to obtain the nickel hydroxide/cerium dioxide nanosheet array.
(2) Preparation of nickel phosphide/cerium dioxide coral-like nanoarrays: putting the nickel hydroxide/cerium dioxide nanosheet array obtained in the step (1) into a porcelain boat, putting 50mg of sodium hypophosphite into another porcelain boat, placing the porcelain boat in an upwind direction, then introducing inert gas Ar with the gas flow rate of 30sccm, heating a tube furnace to 300 ℃ at the heating rate of 1 ℃/min, maintaining for 100min, and carrying out selective phosphating treatment on the nickel hydroxide/cerium dioxide nanosheet array to obtain the nickel phosphide/cerium dioxide coral-like nanoarray.
Example 2:
(1) preparing a precursor array structure: taking foamed nickel as a substrate, washing the substrate with 15% dilute nitric acid, ethanol and deionized water for five times to remove organic impurities and an oxide layer on the surface, naturally drying the substrate, weighing 1.4g of nickel nitrate hexahydrate, 0.65g of cerium nitrate hexahydrate, 1.8g of urea and 0.7g of ammonium fluoride, dispersing the weighed substances in 30mL of deionized water, transferring the obtained product to a 50mL reaction kettle, uniformly stirring the obtained product to dissolve the obtained product, transferring the foamed nickel into the reaction kettle, packaging the obtained product, transferring the obtained product to an oven, keeping the temperature at 120 ℃ for 10 hours, and naturally cooling the obtained product. And taking the product out of the reaction kettle, repeatedly washing the product with deionized water and ethanol, and drying the product in a vacuum oven to obtain the nickel hydroxide/cerium dioxide nanosheet array.
(2) Preparation of nickel phosphide/cerium dioxide coral-like nanoarrays: putting the nickel hydroxide/cerium dioxide nanosheet array obtained in the step (1) into a porcelain boat, putting 80mg of sodium hypophosphite into another porcelain boat, putting the porcelain boat in an upwind direction, and then introducing inert gas N2And (3) heating the tubular furnace to 250 ℃ at the heating rate of 2 ℃/min at the gas flow rate of 50sccm, maintaining for 200min, and performing selective phosphating treatment on the nickel hydroxide/cerium dioxide nanosheet array to obtain the nickel phosphide/cerium dioxide coral-shaped nano array.
Example 3:
(1) preparing a precursor array structure: taking foamed nickel as a substrate, washing the substrate with 30% dilute nitric acid, ethanol and deionized water for five times to remove organic impurities and an oxide layer on the surface, naturally drying the substrate, weighing 1.8g of nickel nitrate hexahydrate, 0.9g of cerium nitrate hexahydrate, 2.4g of urea and 0.9g of ammonium fluoride, dispersing the weighed substances in 80mL of deionized water, transferring the obtained product to a 100mL reaction kettle, uniformly stirring the obtained product to dissolve the obtained product, transferring the foamed nickel into the reaction kettle, packaging the obtained product, transferring the obtained product to an oven, keeping the temperature at 100 ℃ for 6 hours, and naturally cooling the obtained product. And taking the product out of the reaction kettle, repeatedly washing the product with deionized water and ethanol, and drying the product in a vacuum oven to obtain the nickel hydroxide/cerium dioxide nanosheet array.
(2) Preparation of nickel phosphide/cerium dioxide coral-like nanoarrays: putting the nickel hydroxide/cerium dioxide nanosheet array obtained in the step (1) into a porcelain boat, putting 100mg of sodium hypophosphite into another porcelain boat, putting the porcelain boat in an upwind direction, and then introducing inert gas N2And (3) heating the tubular furnace to 400 ℃ at the heating rate of 3 ℃/min at the gas flow rate of 100sccm, maintaining for 300min, and performing selective phosphating treatment on the nickel hydroxide/cerium dioxide nanosheet array to obtain the nickel phosphide/cerium dioxide coral-shaped nano array.

Claims (1)

1. A preparation method of a self-supporting coral-like array structure electrode comprises the following steps:
(1) preparing a precursor array structure: taking foamed nickel as a substrate, washing the substrate with dilute nitric acid, ethanol and deionized water for multiple times to remove organic impurities and oxide layers on the surface, naturally drying the substrate, weighing a certain amount of nickel nitrate hexahydrate, cerium nitrate hexahydrate, urea and ammonium fluoride, dispersing the weighed materials in deionized water with a certain volume, transferring the deionized water into a reaction kettle, uniformly stirring the materials to dissolve the materials, transferring the foamed nickel into the reaction kettle, packaging the foamed nickel, transferring the foamed nickel into a drying oven, keeping the temperature for a certain time, naturally cooling the foamed nickel, taking out a product from the reaction kettle, repeatedly washing the foamed nickel with deionized water and ethanol, and drying the product in a vacuum drying oven to obtain a nickel hydroxide/cerium dioxide nanosheet array;
in the step (1), the thickness of the foamed nickel is 0.5-1.7 mm, the concentration of the used nitric acid is 5% -30%, the washing times are 3-5 times, the dosage of nickel nitrate hexahydrate is 0.9-1.8 g, the dosage of cerium nitrate hexahydrate is 0.4-0.9 g, the dosage of urea is 1.2-2.4 g, the dosage of ammonium fluoride is 0.4-0.9 g, the volume of the used deionized water is 30-90 mL, the volume of the used reaction kettle is 50 or 100mL, the temperature of a vacuum oven is 100-120 ℃, and the heat preservation time is 6-10 hours;
(2) preparation of nickel phosphide/cerium dioxide coral-like nanoarrays: putting the nickel hydroxide/cerium dioxide nanosheet array obtained in the step (1) into a porcelain boat, putting a certain amount of sodium hypophosphite into another porcelain boat, putting the porcelain boat into an upwind direction, then introducing inert gas, heating the tube furnace to a certain temperature at a specific heating rate, maintaining the temperature for a certain period of time, and carrying out selective phosphating treatment on the nickel hydroxide/cerium dioxide nanosheet array to obtain a nickel phosphide/cerium dioxide coralliform nano array;
in the step (2), the amount of sodium hypophosphite is 50-100 mg, the inert gas can be one of argon or nitrogen, the gas flow rate is 30-100 sccm, the temperature rise rate of the tube furnace is 1-3 ℃/min, the constant temperature is 250-400 ℃, and the heat preservation time is 100-300 min.
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