CN114045500A - Preparation method of self-supporting multi-level structure electrode - Google Patents
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Abstract
The invention provides a preparation method of a self-supporting multi-level structure electrode. The nitrogen-doped cobalt phosphide multistage array structure electrode with the nano-wire growing on the surface of the nanosheet is prepared by combining a gradient constant-temperature hydrothermal method and a synchronous nitriding and phosphating method, and the multistage micro-nano structure is beneficial to full exposure of the active surface area of the catalytic material and full contact with electrolyte and has a remarkable effect of further improving the catalytic performance of the material. The double-function catalyst is used for the oxidation conversion of glycerol in the environment and the energy-saving hydrogen production, under the anode voltage, the glycerol is oxidized into dihydroxyacetone, glyceraldehyde, glyceric acid, tartaric acid and the like, and simultaneously, the existence of the glycerol in the electrolyte greatly reduces the potential required by the cathode hydrogen production under the same current, thereby having far-reaching significance for simultaneously realizing the oxidation conversion of the glycerol at the anode and the energy-saving hydrogen production at the cathode. 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
Technical Field
The invention relates to the field of catalysis, in particular to preparation of a multifunctional nitrogen-doped cobalt phosphide multi-level structure electrode and application thereof in aspects of electrochemical glycerol oxidation and hydrogen energy preparation.
Background
Glycerol is a by-product of biodiesel production, and in recent years, the rapid development of the biodiesel industry has led to a significant supply and demand of glycerol in the world market. Furthermore, glycerol is a polar molecule with three hydroxyl groups, which makes it a promising candidate for conversion into more valuable fine chemicals and products. The oxidation products, such as Dihydroxyacetone (DHA), hydroxyacetone, Glyceraldehyde (GD), glyceric acid (GLA), tartaric acid, etc., are chemical raw materials having a greater application value than glycerol. In addition, the electrolysis of water to produce hydrogen is one of the environmentally friendly and effective methods for producing hydrogen energy, however, the oxygen evolution reaction of the anode is severely restricted to be further implemented in a large area due to higher overpotential. Therefore, the glycerol can be oxidized to replace the complex oxygen evolution reaction of the anode, and the reaction of synchronously preparing hydrogen energy at low potential and electrolyzing the glycerol can be realized. Therefore, the electrocatalytic oxidation method not only can realize the rapid oxidation conversion of the glycerol, but also can realize the low-potential hydrogen production, and corresponds to the energy conservation and emission reduction advocated by the state.
The electrochemical oxidation method relates to a catalytic reaction process, so that the development of an efficient electrocatalyst is the key for realizing the oxidation of the glycerol and saving energy and producing hydrogen. At present, noble metal catalysts are the best performing catalysts, but their low reserves and poor stability severely hamper their further use. Transition metal materials are currently the most promising materials to replace noble metal catalysts. Especially, transition metal phosphide has received much attention from domestic and foreign scholars due to its excellent bifunctional characteristics. The regulation and control of the micro-nano structure of the catalyst is an effective strategy for improving the catalytic performance of the catalyst, not only can the exposed area of the catalyst be increased, but also the contact area with electrolyte can be increased, and the catalyst has a remarkable effect on improving the catalytic stability. The catalyst is combined with an in-situ technology, so that the catalytic activity and the stability of the catalyst can be further improved, and the catalyst has profound significance for further realizing the glycerol oxidation and the industrialization of energy-saving hydrogen production.
Disclosure of Invention
Aiming at the problems of environmental pollution, energy shortage and the like at present, the invention provides a preparation method of a self-supporting multi-stage structure electrode based on an electrochemical oxidation method, and the preparation method is applied to the oxidation of glycerol and the energy-saving hydrogen production.
In order to achieve the purpose, the invention provides the following technical scheme:
(1) preparing a self-supporting precursor multi-stage structure: weighing a certain amount of cobalt nitrate hexahydrate, urea and ammonium fluoride, dispersing the weighed cobalt nitrate hexahydrate, urea and ammonium fluoride in a certain volume of deionized water by adopting a gradient constant-temperature hydrothermal method, transferring the obtained product into a reaction kettle with a certain volume, ultrasonically dissolving the obtained product, packaging a shell, transferring the obtained product into a vacuum oven, keeping a certain temperature for a certain time, heating the obtained product to another temperature for a certain time, growing a multi-stage micro-nano structure on the surface of the foamed nickel, cooling the obtained product to room temperature, repeatedly washing an electrode with deionized water and ethanol, and transferring the obtained product into the vacuum oven for drying;
(2) preparing a self-supporting nitrogen-doped cobalt phosphide hierarchical structure: and (2) adopting a synchronous nitriding and phosphorizing method, placing the foamed nickel with the surface growth precursor multilevel structure obtained in the step (1) into a porcelain boat, placing the porcelain boat at the downstream of a tubular furnace, placing a certain amount of sodium hypophosphite and a certain amount of ammonium bicarbonate at the upstream and the midstream respectively, introducing inert gas, raising the temperature of the tubular furnace to a certain temperature at a specific temperature raising rate, maintaining for a certain time, and naturally cooling to obtain the self-supporting nitrogen-doped cobalt phosphide multilevel structure electrode.
Preferably, in the step (1), the thickness of the nickel foam is 1.0-1.7 mm, and the size of the nickel foam is 3cm × 6 cm.
Preferably, in the step (1), the dosage of the cobalt nitrate hexahydrate is 1.5-2.5 g, the dosage of the urea is 1.0-2.0 g, the dosage of the ammonium fluoride is 0.3-0.6 g, the volume of the deionized water is 50-70 mL, and the volume of the reaction kettle is 100 mL.
Preferably, in the step (1), the heating rate of the vacuum oven is 10 ℃/min, the initial heating temperature of the vacuum oven is 80-100 ℃, the heat preservation time is 2-3 h, the subsequent heating temperature is 110-130 ℃, and the heat preservation time is 3-4 h.
Preferably, in the step (2), the inert gas may be one of argon and nitrogen, and the gas flow rate is 20-50 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 300-400 ℃, and the heat preservation time is set to be 100-200 min.
Preferably, in the step (2), the amount of the sodium hypophosphite is 200-300 mg, and the amount of the ammonium bicarbonate is 20-50 mg.
The invention has the advantages and beneficial effects that:
1. the invention provides a preparation method of a self-supporting multi-stage structure electrode, which combines a gradient constant-temperature hydrothermal method and a synchronous nitriding and phosphorizing method to prepare the self-supporting nitrogen-doped cobalt phosphide multi-stage structure electrode, wherein the multi-stage structure consists of a nano sheet and nano wires growing around the nano sheet, and has larger electrocatalytic activity specific surface area. Compared with ex-situ synthesis and multi-step synthesis methods, the method has the advantages of simple equipment, easiness in control, good process repeatability, stable product quality and the like, and compared with nanosheets or nanowires with single structures, the nanoscale multilevel structure is beneficial to full exposure of the active surface area of the catalytic material and full contact with electrolyte.
2. The invention provides a preparation method of a self-supporting multi-stage structure electrode, which is used as a bifunctional electrocatalyst for electrocatalytic oxidation of glycerol in the environment, and in addition, the existence of the glycerol in the electrolyte can obviously reduce the potential required by cathode hydrogen production, and the invention has wide application prospects in rapid and effective realization of glycerol oxidation conversion, energy saving and hydrogen production and the like.
Drawings
FIG. 1: the invention provides a flow chart of a preparation method of a self-supporting multi-level structure electrode;
FIG. 2: in the scanning electron microscope picture of the self-supporting nitrogen-doped cobalt phosphide multi-level structure electrode obtained in the embodiment 1 of the invention, the surface of the substrate is of a micro-nano composite structure constructed by nanowires and nanosheets;
FIG. 3: according to the X-ray diffraction pattern of the nitrogen-doped cobalt phosphide multistage structure obtained in the embodiment 3, the peak shape of the prepared nitrogen-doped cobalt phosphide is consistent with that of orthorhombic cobalt phosphide;
FIG. 4: according to the X-ray photoelectron spectrum of the nitrogen-doped cobalt phosphide multilevel structure obtained in the embodiment 3, cobalt elements, phosphorus elements and nitrogen elements exist at the same time, and the nitrogen element proportion is minimum;
FIG. 5: the polarization curve of the self-supporting nitrogen-doped cobalt phosphide multi-level structure electrode obtained in the embodiment 2 of the invention as a bifunctional catalytic material in alkaline electrolyte containing and not containing glycerol shows that the relative current density is higher in the electrolyte containing glycerol, namely, the energy is saved.
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 self-supporting precursor multi-stage structure: adopting a gradient constant-temperature hydrothermal method, taking clean foamed nickel (3cm multiplied by 6cm multiplied by 1.0mm) as a substrate, weighing 1.5g of cobalt nitrate hexahydrate, 1.0g of urea and 0.3g of ammonium fluoride, dispersing the weighed materials in 70mL of deionized water, transferring the obtained product to a 100mL reaction kettle, carrying out ultrasonic dissolution, packaging a shell, transferring the obtained product to a vacuum oven, keeping the obtained product at 80 ℃ for 2h, then heating to 130 ℃ for 4h, growing a multi-stage micro-nano structure on the surface of the foamed nickel, cooling to room temperature, repeatedly washing an electrode with the deionized water and ethanol, and transferring the obtained product to a vacuum oven for drying;
(2) preparing a self-supporting nitrogen-doped cobalt phosphide hierarchical structure: and (2) putting the foamed nickel with the surface growth precursor multilevel structure obtained in the step (1) into a porcelain boat by adopting a synchronous nitriding and phosphorizing method, putting the foamed nickel into the downstream of a tube furnace, respectively putting 200mg of sodium hypophosphite and 50mg of ammonium bicarbonate into the upstream and the midstream, introducing nitrogen, heating the tube furnace to 300 ℃ at the heating rate of 1 ℃/min, maintaining for 100min, and naturally cooling to obtain the self-supporting nitrogen-doped cobalt phosphide multilevel structure electrode.
Example 2:
(1) preparing a self-supporting precursor multi-stage structure: adopting a gradient constant-temperature hydrothermal method, taking clean foamed nickel (3cm multiplied by 6cm multiplied by 1.5mm) as a substrate, weighing 2.0g of cobalt nitrate hexahydrate, 1.5g of urea and 0.5g of ammonium fluoride, dispersing the weighed materials in 60mL of deionized water, transferring the materials into a 100mL reaction kettle, ultrasonically dissolving, packaging a shell, transferring the shell into a vacuum oven, keeping the temperature at 90 ℃ for 3h, then heating to 120 ℃ for 3h, growing a multi-stage micro-nano structure on the surface of the foamed nickel, cooling to room temperature, repeatedly washing an electrode with the deionized water and ethanol, and transferring the electrode into the vacuum oven to be dried;
(2) preparing a self-supporting nitrogen-doped cobalt phosphide hierarchical structure: and (2) putting the foamed nickel with the surface growth precursor multilevel structure obtained in the step (1) into a porcelain boat by adopting a synchronous nitriding and phosphorizing method, putting the foamed nickel into the downstream of a tube furnace, respectively putting 250mg of sodium hypophosphite and 40mg of ammonium bicarbonate into the upstream and the midstream, introducing nitrogen, heating the tube furnace to 350 ℃ at the heating rate of 2 ℃/min, maintaining for 150min, and naturally cooling to obtain the self-supporting nitrogen-doped cobalt phosphide multilevel structure electrode.
Example 3:
(1) preparing a self-supporting precursor multi-stage structure: adopting a gradient constant-temperature hydrothermal method, taking clean foamed nickel (3cm multiplied by 6cm multiplied by 1.7mm) as a substrate, weighing 2.5g of cobalt nitrate hexahydrate, 2.0g of urea and 0.6g of ammonium fluoride, dispersing the weighed materials in 70mL of deionized water, transferring the obtained product to a 100mL reaction kettle, carrying out ultrasonic dissolution, packaging a shell, transferring the obtained product to a vacuum oven, keeping the obtained product at 100 ℃ for 4h, then heating to 130 ℃ for 2h, growing a multi-stage micro-nano structure on the surface of the foamed nickel, cooling to room temperature, repeatedly washing an electrode with the deionized water and ethanol, and transferring the obtained product to a vacuum oven for drying;
(2) preparing a self-supporting nitrogen-doped cobalt phosphide hierarchical structure: and (2) putting the foamed nickel with the surface growth precursor multilevel structure obtained in the step (1) into a porcelain boat by adopting a synchronous nitriding and phosphorizing method, putting the foamed nickel into the downstream of a tube furnace, respectively putting 300mg of sodium hypophosphite and 30mg of ammonium bicarbonate into the upstream and the midstream, introducing nitrogen, heating the tube furnace to 400 ℃ at the heating rate of 3 ℃/min, maintaining for 200min, and naturally cooling to obtain the self-supporting nitrogen-doped cobalt phosphide multilevel structure electrode.
Claims (8)
1. A preparation method of a self-supporting multi-stage structure electrode comprises the following steps:
(1) preparing a self-supporting precursor multi-stage structure: weighing a certain amount of cobalt nitrate hexahydrate, urea and ammonium fluoride, dispersing the weighed cobalt nitrate hexahydrate, urea and ammonium fluoride into a certain volume of deionized water by adopting a gradient constant-temperature hydrothermal method, transferring the obtained product into a certain volume of reaction kettle, ultrasonically dissolving, packaging a shell, transferring the obtained product into a vacuum oven, keeping a certain temperature for a certain time, heating the obtained product to another temperature for a certain time, growing a multi-stage micro-nano structure on the surface of the foamed nickel, cooling the obtained product to room temperature, repeatedly washing an electrode with deionized water and ethanol, and transferring the obtained product into the vacuum oven for drying;
(2) preparing a self-supporting nitrogen-doped cobalt phosphide hierarchical structure: and (2) adopting a synchronous nitriding and phosphorizing method, placing the foamed nickel with the surface growth precursor multilevel structure obtained in the step (1) into a porcelain boat, placing the porcelain boat at the downstream of a tubular furnace, placing a certain amount of sodium hypophosphite and a certain amount of ammonium bicarbonate at the upstream and the midstream respectively, introducing inert gas, raising the temperature of the tubular furnace to a certain temperature at a specific temperature raising rate, maintaining for a certain time, and naturally cooling to obtain the self-supporting nitrogen-doped cobalt phosphide multilevel structure electrode.
2. The method for preparing a self-supporting multi-stage structured electrode according to claim 1, wherein: in the step (1), the size of the foamed nickel is about 3 multiplied by 6cm, and the thickness of the foamed nickel is 1.0-1.7 mm.
3. The method for preparing a self-supporting multi-stage structured electrode according to claim 1, wherein: in the step (1), the dosage of the cobalt nitrate hexahydrate is 1.5-2.5 g, the dosage of the urea is 1.0-2.0 g, the dosage of the ammonium fluoride is 0.3-0.6 g, the volume of the used deionized water is 50-70 mL, and the volume of the used reaction kettle is 100 mL.
4. The method for preparing a self-supporting multi-stage structured electrode according to claim 1, wherein: in the step (1), the heating rate of the vacuum oven is 5 ℃/min, the initial heating temperature of the vacuum oven is 80-100 ℃, and the subsequent heating temperature is 110-130 ℃.
5. The method for preparing a self-supporting multi-stage structured electrode according to claim 1, wherein: in the step (1), the initial heat preservation time of the vacuum oven is 2-3 hours, and the subsequent heat preservation time is 3-4 hours.
6. The method for preparing a self-supporting multi-stage structured electrode according to claim 1, wherein: in the step (2), the amount of sodium hypophosphite is 200-300 mg, and the amount of ammonium bicarbonate is 20-50 mg.
7. The method for preparing a self-supporting multi-stage structured electrode according to claim 1, wherein: in the step (2), the temperature rise rate of the tubular furnace is 1-3 ℃/min, the constant temperature is 300-400 ℃, and the heat preservation time is 100-200 min.
8. The method for preparing a self-supporting multi-stage structured electrode according to claim 1, wherein: in the step (2), the inert gas can be one of argon and nitrogen, and the gas flow rate is 20-50 sccm.
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