CN113755879A - Delta-phase tungsten nitride electrode material and preparation method and application thereof - Google Patents

Delta-phase tungsten nitride electrode material and preparation method and application thereof Download PDF

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CN113755879A
CN113755879A CN202111040477.9A CN202111040477A CN113755879A CN 113755879 A CN113755879 A CN 113755879A CN 202111040477 A CN202111040477 A CN 202111040477A CN 113755879 A CN113755879 A CN 113755879A
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conductive substrate
delta
solution
tungsten nitride
acid
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CN113755879B (en
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孙朱行
徐琛
吴兆
解俊杰
李子峰
刘童
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Xi'an Longji Hydrogen Energy Technology Co ltd
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Longi Green Energy Technology Co Ltd
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Abstract

The invention relates to a delta-phase tungsten nitride electrode material and a preparation method and application thereof, wherein the delta-phase tungsten nitride electrode material comprises a conductive substrate with a pore structure and a delta-phase tungsten nitride layer, and at least part of the delta-phase tungsten nitride layer is covered on the surface of the inner wall of the pore structure; the hole and seam structure comprises a hole extending inwards on the surface of the conductive substrate and/or a slit extending along the surface of the conductive substrate; the surface pore accounts for 5-70%, the opening size of the pore structure is 500nm-500 μm, and the depth of the pore structure is more than 1.5 times of the opening size. The delta-phase tungsten nitride electrode material disclosed by the invention can be used as an acidic or alkaline electrolyte hydrogen production electrode or electrode material, and has excellent hydrogen production performance and stability.

Description

Delta-phase tungsten nitride electrode material and preparation method and application thereof
Technical Field
The disclosure relates to the technical field of hydrogen production by water electrolysis, in particular to a delta-phase tungsten nitride electrode material and a preparation method and application thereof.
Background
Hydrogen is an important clean energy source, and hydrogen energy-based energy production, storage and utilization systems are considered to be ideal alternatives to current fossil fuel-based energy systems. The water electrolysis hydrogen production technology has received extensive attention due to the advantages of simple principle, high hydrogen production purity, clean and pollution-free production process, capability of utilizing renewable energy sources to discard electricity and the like, and research and development of hydrogen production electrode materials and preparation methods thereof have important significance for development of the water electrolysis hydrogen production technology.
The transition metal compound, namely tungsten nitride (WN), is an economic and practical catalytic material, shows surface properties, adsorption characteristics and catalytic activity similar to Pt, and can replace the traditional noble metal catalyst to be used for reactions such as high-efficiency hydrodesulfurization, hydrodenitrogenation and the like. WN has two crystal phases mainly of a cubic phase (i.e., a β phase) and a hexagonal phase (i.e., a δ phase). Wherein, beta-phase WN (beta-WN) is easy to obtain but has limited hydrogen production performance; delta-phase WN (delta-WN) has excellent hydrogen production performance in a wide pH range (acidic and alkaline) electrolysis environment, but the existing tungsten nitride is prepared under the conditions of high temperature and high pressure (as described in patent US9624604B2 and papers Inorg. chem.2017,56,7,3970-3975), and the obtained tungsten nitride is mostly powder particles or thin film materials. The material is difficult to be directly used as a hydrogen production electrode material, and needs to be further combined with a conductive material to be used as the hydrogen production electrode material, but because the binding force of the catalyst and the conductive material is limited, the hydrogen production efficiency of tungsten nitride is damaged, and the overall stability of the electrode material is poor.
Disclosure of Invention
The delta-phase tungsten nitride electrode material can be used as an acidic or alkaline electrolyte hydrogen production electrode or electrode material, a catalyst and a conductive material are tightly combined, and the delta-phase tungsten nitride electrode material has excellent hydrogen production performance and stability.
In order to achieve the above object, a first aspect of the present disclosure provides a δ -phase tungsten nitride electrode material including a conductive substrate having a via structure and a δ -phase tungsten nitride layer, at least a portion of the δ -phase tungsten nitride layer covering an inner wall surface of the via structure;
the aperture structure comprises an aperture extending inwardly of the surface of the conductive substrate and/or a slit extending generally along the surface of the conductive substrate; the surface pore accounts for 5-70%, the opening size of the pore structure is 500nm-500 μm, and the depth of the pore structure is more than 1.5 times of the opening size.
The second aspect of the present disclosure provides a method for preparing a delta-phase tungsten nitride electrode material, which includes: ammoniating a conductive substrate containing tungsten oxide and/or tungstic acid in an ammonia atmosphere;
wherein the conductive substrate containing tungsten oxide and/or tungstic acid has a pore structure, at least part of the tungsten oxide and/or tungstic acid being attached to an inner wall surface of the pore structure; the surface pore accounts for 5-70%, the opening size of the pore structure is 500nm-500 μm, and the depth of the pore structure is more than 1.5 times of the opening size;
the conditions of the amination reaction include: the temperature is 900 plus 1800 ℃ and the time is 30-240 min.
The third aspect of the disclosure provides a delta-phase tungsten nitride electrode material prepared by the method provided by the second aspect of the disclosure.
A fourth aspect of the present disclosure provides a use of the delta-phase tungsten nitride electrode material provided in the first aspect and/or the third aspect of the present disclosure in hydrogen production by water electrolysis.
Through the technical scheme, the delta-phase tungsten nitride electrode material disclosed by the invention can be used as an acidic or alkaline electrolyte hydrogen production electrode or electrode material, and has excellent hydrogen production performance in an electrolysis environment with a wide pH value range (acidic and alkaline); the preparation method of the delta-phase tungsten nitride electrode material disclosed by the invention is mild in process conditions and low in energy consumption.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
fig. 1 is an XRD spectrum of a delta-phase tungsten nitride electrode material prepared in example 1 of the present disclosure;
fig. 2 is a scanning electron micrograph of a δ -phase tungsten nitride electrode material prepared in example 1 of the present disclosure;
FIG. 3 is a plot of hydrogen production polarization in an acid electrolyte for the delta phase tungsten nitride electrode material prepared in example 1 of the present disclosure and the beta phase tungsten nitride electrode material prepared in comparative example 1;
FIG. 4 is a plot of hydrogen production polarization in alkaline electrolyte for the delta phase tungsten nitride electrode material prepared in example 1 of the present disclosure and the beta phase tungsten nitride electrode material prepared in comparative example 1;
fig. 5 is a time-current graph of hydrogen production for the delta-phase tungsten nitride electrode material prepared in example 1 of the present disclosure.
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The first aspect of the present disclosure provides a δ -phase tungsten nitride electrode material, including a conductive substrate having a pore structure and a δ -phase tungsten nitride layer, where at least a portion of the δ -phase tungsten nitride layer covers an inner wall surface of the pore structure; the aperture structure comprises an aperture extending inwardly of the surface of the conductive substrate and/or a slit extending generally along the surface of the conductive substrate; the surface pore accounts for 5-70%, the opening size of the pore structure is 500nm-500 μm, and the depth of the pore structure is more than 1.5 times of the opening size.
According to the present disclosure, a slit extending generally along the surface of the conductive base means that the body of the slit is at the surface of the conductive base. The slot structure is a regular or disordered flat long or tunnel-shaped slot, and when the slot structure is a flat long slot, the opening size of the slot structure is the maximum width of the slot; when the pore structure is a pore-shaped slit, the opening size of the pore structure refers to the maximum diameter of the pore opening. The delta-phase tungsten nitride electrode material disclosed by the invention can be used as an acidic or alkaline electrolyte hydrogen production electrode or electrode material, and has excellent hydrogen production performance and stability in an electrolysis environment with a wide pH value range (acidity and alkalinity).
According to the disclosure, the average thickness of the δ -phase tungsten nitride layer in different areas of the slit structure in the δ -phase tungsten nitride electrode material of the present application may be different, and the deeper the slit structure in which the δ -phase tungsten nitride layer is located, the smaller the average thickness of the δ -phase tungsten nitride layer is. In one embodiment, the delta-phase tungsten nitride layer has an average thickness of 10nm to 20 μm, preferably 1 to 5 μm, and the average thickness of the delta-phase tungsten nitride layer can be measured by scanning electron microscopy. The delta-phase tungsten nitride layer in the range is proper in thickness, conductive contact and mass transfer of the delta-phase tungsten nitride at the outermost layer are facilitated, and the delta-phase tungsten nitride electrode material has better hydrogen production performance.
The second aspect of the present disclosure provides a method for preparing a delta-phase tungsten nitride electrode material, which includes: ammoniating a conductive substrate containing tungsten oxide and/or tungstic acid in an ammonia atmosphere; wherein the conductive substrate containing tungsten oxide and/or tungstic acid has a pore structure, at least part of the tungsten oxide and/or tungstic acid being attached to an inner wall surface of the pore structure; the surface pore accounts for 5-70%, the opening size of the pore structure is 500nm-500 μm, and the depth of the pore structure is more than 1.5 times of the opening size; the conditions of the amination reaction include: the temperature is 900 plus 1800 ℃ and the time is 30-240 min.
The inventors of the present disclosure found that the confinement effect based on the pore structure, i.e., the special atmosphere (higher temperature, pressure or ammonia density) generated in the limited region where the substrate pore is located can promote the formation of delta-phase tungsten nitride (delta-WN) under milder reaction conditions. Compared with the traditional method for synthesizing the delta-WN at high temperature and high pressure, the method disclosed by the invention has the advantages of mild process conditions and low energy consumption.
In one embodiment of the present disclosure, the amination reaction conditions include: the temperature is 950 ℃ and 1150 ℃, and the time is 60-180 min; more preferably, the temperature is 1000-1100 ℃ and the time is 90-120 min. The delta-phase tungsten nitride electrode material prepared under the conditions has better hydrogen production performance when being applied to the hydrogen production process by water electrolysis.
According to the present disclosure, the conductive substrate is made of a conductive material having a slit structure and good high-temperature stability. In one embodiment, the material of the conductive substrate may be selected from one or more of graphite, titanium carbide and titanium diboride, which may be commercially available or synthesized. In another embodiment, the conductive substrate is subjected to a surface treatment, which may be, for example, a potassium hydroxide activation treatment or a surface etching treatment. The shape and size of the conductive substrate are not particularly limited in the present disclosure, and may be any regular shape or irregular shape, for example, may be a sheet, rod, circular column, block or powder, preferably a sheet, rod, circular column or block. When the size of the conductive substrate is large, for example, when one of the length, the width and the height is larger than 50mm, the prepared delta-phase tungsten nitride electrode material can be directly used as a delta-WN three-dimensional independent hydrogen production electrode without subsequent processing and forming, and the contact resistance is relatively small; when the size of the conductive substrate is large, for example, the length, width and height are less than 1mm, the prepared delta-phase tungsten nitride electrode material is a small block or powder material, and can be used as an electrode after subsequent processing and forming, for example, a membrane electrode is prepared on the surface of a glassy carbon electrode by using the small block material and/or the powder material as a working electrode.
According to the disclosure, the opening size of the pore structure is 500nm-500 μm, the depth of the pore structure is more than 1.5 times of the width of the pore, the surface pore proportion is 5-70%, the surface pore proportion represents the ratio of the area occupied by the pore on the surface of the substrate to the surface area of the substrate, and the surface pore proportion can be obtained by taking an electron microscope picture of the material by using a scanning electron microscope and then introducing the electron microscope picture into IMAGE G software for analysis. Preferably, the opening size of the pore structure is 5-200 μm, the depth of the pore structure is 2-10 times of the width of the pore structure, and the surface pore ratio is 30-60%.
According to the present disclosure, the method further comprises: preparing the conductive substrate containing tungsten trioxide and/or tungstic acid in situ by adopting a chemical synthesis method; the chemical synthesis method is selected from one or more of a hydrothermal method, an electrochemical method, a coprecipitation method and a chemical precipitation method.
In one embodiment of the present disclosure, the conductive substrate containing tungsten oxide and/or tungstic acid is prepared in situ by a hydrothermal method comprising the following steps: s1, mixing the first tungsten source, strong acid and solvent, and adjusting the pH value to 1-2 to obtain a first solution; s2, mixing the first solution with weak acid to obtain a tungstic acid precursor; s3, carrying out hydrothermal reaction on the tungstic acid precursor and the first conductive substrate in a heat-resistant closed container to obtain the conductive substrate containing tungsten oxide and/or tungstic acid.
According to the present disclosure, the product obtained from the hydrothermal reaction is washed and dried, the washing solution is a solution that is conventionally used by those skilled in the art, such as ethanol, deionized water, etc., and the drying temperature can be 50-150 ℃ and the drying time can be 8-48 hours.
According to the present disclosure, step S3 may include: and carrying out hydrothermal reaction on the tungstic acid precursor, the end-capping reagent, the surfactant, the template and the first conductive substrate in a heat-resistant closed container. The blocking agent may be well known to those skilled in the art and may be selected from, for example, one or more of ammonium sulfate, sodium lauryl sulfate, and citric acid; the surfactant and the template agent can be respectively and independently selected from one or more of n-butyl alcohol, cyclohexane and hexadecyl trimethyl ammonium bromide.
According to the present disclosure, the molar ratio of the first solution to the weak acid used in step S2 may vary within a wide range, and may be, for example, 1: (2-3), preferably 1: (2-2.5), the first solution being based on the first tungsten source. In step S3, the hydrothermal reaction is well known to those skilled in the art, and may be performed in a heat-resistant closed container, for example, a hydrothermal kettle lined with polytetrafluoroethylene, and the conditions of the hydrothermal reaction may include: the temperature is 120 ℃ and 220 ℃, and the time is 6-48 hours; preferably, the temperature is 160-200 ℃ and the time is 12-24 hours. The first tungsten source can be one or more selected from sodium tungstate, potassium tungstate, zinc tungstate, ammonium metatungstate and tungsten chloride; the strong acid can be selected from one or more of hydrochloric acid, nitric acid and dilute sulfuric acid, the concentration of the strong acid can be changed in a large range, and the strong acid is preferably 1-5 mol/L; the solvent can be one or more selected from deionized water, ethanol, ethylene glycol, isopropanol, N-dimethylformamide and acetonitrile; the weak acid can be selected from one or more of oxalic acid, formic acid, acetic acid and carbonic acid; the first conductive substrate is made of a conductor material which has a pore structure and good high-temperature stability, and is preferably one or more of graphite, titanium carbide and titanium diboride.
In another embodiment of the present disclosure, the conductive substrate containing tungsten oxide and/or tungstic acid is prepared by an electrochemical process comprising the steps of: (1) after the second tungsten source is contacted with the hydrogen peroxide solution for reaction, optionally removing the hydrogen peroxide contained in the solution after the reaction to obtain a second solution; (2) diluting the second solution by using a diluent to obtain an electrolyte; (3) and taking a second conductive substrate as a working electrode, placing the second conductive substrate in the electrolyte, and depositing tungsten oxide and/or tungstic acid on the second conductive substrate by adopting a constant potential method to obtain the conductive substrate containing the tungsten oxide and/or the tungstic acid.
According to the present disclosure, in the step (1), the removing hydrogen peroxide contained in the reacted solution includes: contacting and reacting a catalyst with the reacted solution to obtain a second solution; or heating the reacted solution at 50-90 ℃ to obtain a second solution; wherein the catalyst is one or more of platinum, silver, chromium, manganese dioxide, ferric chloride, copper oxide and catalase, and when the ratio of the volume of the second solution to the volume of the hydrogen peroxide solution initially added in the step (1) is 0.75-0.85, the catalyst is taken out or the heating is stopped. The concentration of the hydrogen peroxide solution can vary within wide limits, preferably in a mass fraction of 25 to 35%.
According to the present disclosure, in step (2), the volume ratio of the second solution to the amount of the diluent may vary within a wide range, preferably 1: (9-29); the diluent contains one or more of water, isopropanol, ethanol, ethylene glycol, acetone, acetonitrile and N, N-dimethylformamide, and preferably contains water and isopropanol, wherein the volume ratio of the water to the isopropanol is 1: (0.4-1).
According to the present disclosure, in step (3), the deposition conditions include: the deposition potential is-0.4V to-5V, and the deposition time is 1-60 min; preferably, the deposition potential is from-1V to-3V and the deposition time is from 5 to 30 min.
In a preferred embodiment, the second conductive substrate is placed in the electrolyte and soaked for 5-15 hours, and then tungsten oxide and/or tungstic acid is deposited on the second conductive substrate by adopting a constant potential method.
According to the present disclosure, the second tungsten source may be selected from one or more of metal tungsten powder, tungsten wire and tungsten sheet, and is more preferably tungsten powder; the second conductive substrate is made of a conductor material which has a pore structure and good high-temperature stability, and preferably can be one or more of graphite, titanium carbide and titanium diboride.
According to the present disclosure, the ammoniation reaction may be performed in a muffle furnace, a tube furnace or a fluidized bed, and when the ammoniation reaction is performed in a sealed reaction furnace such as a muffle furnace, a tube furnace or the like, the volume concentration of ammonia in the ammonia atmosphere may be 10-100%; when the amination reaction is carried out in a fluidized bed, the flow rate of ammonia may be any flow rate, preferably 10 to 100 mL/min. The ammonia atmosphere can be obtained by directly introducing ammonia gas, or by decomposing a compound (such as urea, melamine, ammonium acetate, etc.) which is easily decomposed to generate ammonia gas during the temperature rise.
The third aspect of the disclosure provides a delta-phase tungsten nitride electrode material prepared by the method provided by the second aspect of the disclosure. The delta-phase tungsten nitride electrode material disclosed by the invention is a high-efficiency and economical hydrogen production electrode material which meets the requirements of different electrolytic cell types, is applicable in a wide pH range.
A fourth aspect of the present disclosure provides a use of the delta-phase tungsten nitride electrode material provided in the first aspect and/or the third aspect of the present disclosure in hydrogen production by water electrolysis. In one embodiment, the delta-phase tungsten nitride electrode material is used as a hydrogen-producing electrolytic material for an electrolytic cell.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
The following examples and comparative examples were examined for the phase state of tungsten nitride contained in the electrode material by XRD, and the thickness of the tungsten nitride layer was measured by scanning electron microscopy. The raw materials in the following examples are all commercially available.
Example 1
S1, dissolving 4.1g of sodium tungstate dihydrate in deionized water, vigorously stirring for 30min, and then dropwise and slowly adding 3mol/L hydrochloric acid into the sodium tungstate solution until the pH value is 1.2 to obtain a yellow and transparent first solution;
s2, adding 3.1g of oxalic acid into the first solution to obtain a tungstic acid precursor;
s3, adding 2g of ammonium sulfate into 40mL of tungstic acid precursor as an end-capping reagent, transferring the solution to a hydrothermal kettle which is provided with a graphite rod (the ratio of surface pore gaps is about 30 percent), the surface of which is provided with a pore structure, the pore structure of which is 50-200 mu m in opening size and the depth is 3-10 times of the width of the pore gap, and the graphite rod is placed in advance, and carrying out hydrothermal reaction for 16 hours at 180 ℃. After the hydrothermal kettle is naturally cooled, the dark blue tungsten oxide (WO) grows on the hydrothermal kettle3) Graphite rod (WO)3GR), taking out, respectively rinsing with ethanol and water for 5-7 times, and drying in an oven at 80 ℃ to obtain a conductive substrate containing tungsten oxide, wherein tungsten oxide grows in a pore-gap structure of the conductive substrate;
s4, placing the conductive substrate containing tungsten oxide in a tube furnace, removing air in the tube by using nitrogen, introducing 50mL/min ammonia gas, heating to 1000 ℃ at a speed of 6 ℃/min, keeping the temperature for 120min, and cooling to obtain the delta-phase tungsten nitride electrode material taking the three-dimensional graphite rod as the substrate, wherein the thickness of the delta-phase tungsten nitride layer is 1-5 μm. The XRD spectrum of the delta-phase tungsten nitride electrode material is shown in figure 1, and the scanning electron micrograph is shown in figure 2.
Example 2
S1, dissolving 8.2g of ammonium metatungstate in deionized water and vigorously stirring for 1 hour, and then slowly adding 3mol/L hydrochloric acid dropwise into the solution until the pH value is 1.2 to obtain a yellow and transparent first solution;
s2, adding 6.2g of oxalic acid into the first solution to obtain a tungstic acid precursor;
s3, placing 40mL of tungstic acid precursor in a hydrothermal kettle which is placed in advance with rough graphite sheets (the surface aperture ratio is about 40%, the opening size of the aperture structure is 100-250 μm, and the depth is 3-10 times of the aperture width) with 20mm multiplied by 50mm multiplied by 2mm, and carrying out hydrothermal reaction for 12 hours at 200 ℃. Naturally cooling the hydrothermal kettle, taking out the obtained material, respectively rinsing with ethanol and water for 5-7 times, and drying in an oven at 80 ℃ to obtain a conductive substrate containing tungsten oxide, wherein tungsten oxide grows in a pore seam structure of the conductive substrate;
s4, placing the conductive substrate containing tungsten oxide in a 3L tubular furnace, removing air in the tube by using nitrogen, filling the tube with high-purity ammonia, maintaining a certain positive pressure of 0.1MPa, heating to 950 ℃ at a speed of 2 ℃/min, keeping the temperature for 240min, and cooling to obtain the delta-phase tungsten nitride electrode material taking the three-dimensional graphite sheet as the substrate, wherein the thickness of the delta-phase tungsten nitride layer is 2-7 μm.
Example 3
S1, dissolving 8.2g of ammonium metatungstate in deionized water, vigorously stirring for 30min, and then slowly adding 3mol/L hydrochloric acid into the solution dropwise until the pH value is 1.2 to obtain a yellow and transparent first solution;
s2, adding 6.2g of oxalic acid into the first solution to obtain a tungstic acid precursor;
s3, putting 70mL of tungstic acid precursor into a 100mL hydrothermal kettle with a polytetrafluoroethylene lining, putting a graphite square sheet (the ratio of surface pores to gaps is about 50%, the opening size of a pore structure is 10-50 μm, and the depth is 5-15 times of the width of the pore) which is activated by potassium hydroxide and is 30mm multiplied by 1mm in advance in the kettle, and carrying out hydrothermal treatment at 120 ℃ for 24 hours. Naturally cooling the hydrothermal kettle, taking the obtained material out of the hydrothermal kettle, respectively rinsing with ethanol and water for 5-7 times, and drying in an oven at 80 ℃ to obtain a graphite conductive substrate with tungstic acid growing in the slit;
s4, placing the graphite conductive substrate with tungstic acid growing in the slit in a tube furnace, removing air in the tube by nitrogen, introducing 50mL/min ammonia gas, heating to 1150 ℃ at 4 ℃/min, keeping the temperature for 30min, and cooling to obtain the delta-phase tungsten nitride electrode material taking the three-dimensional graphite square sheet activated by potassium hydroxide as the substrate, wherein the thickness of the delta-phase tungsten nitride layer is 50nm-2 μm.
Example 4
S1, dissolving 8.2g of potassium tungstate in deionized water, vigorously stirring for 45min, and then dropwise and slowly adding 3mol/L of dilute nitric acid into the solution until the pH value is 1.2 to obtain a yellow and transparent first solution;
s2, adding 6.2g of acetic acid into the first solution to obtain a tungstic acid precursor;
s3, putting 70mL of tungstic acid precursor into a 100mL of hydrothermal kettle with polytetrafluoroethylene as a lining, putting graphite powder particles (the surface pore space accounts for about 45%, the opening size of a pore space structure is 80-100 μm, and the depth is 5-10 times of the pore space width) with the size of about 500 μm × 600 μm in advance in the kettle, carrying out hydrothermal treatment at 180 ℃ for 18 hours, naturally cooling, taking the obtained material out of the hydrothermal kettle, respectively rinsing with ethanol and water for 5-7 times, putting the material into an oven at 80 ℃ for drying to obtain a conductive substrate containing tungsten oxide, wherein the tungsten oxide grows in the pore space structure of the conductive substrate;
s4, placing the conductive substrate containing tungsten oxide in a tube furnace, introducing 50mL/min ammonia gas, heating to 1000 ℃ at 4 ℃/min, keeping the temperature for 1 hour, cooling to obtain particles of the delta-phase tungsten nitride electrode material (the thickness of the delta-phase tungsten nitride layer is 1-5 μm) taking graphite powder as the substrate, dispersing the delta-phase tungsten nitride electrode material in isopropanol containing a certain amount of Nafion film solution, and dripping the solution on the surface of a glassy carbon electrode to prepare a film electrode for testing.
Example 5
S1, dissolving 8.2g of potassium tungstate in deionized water, vigorously stirring for 45min, and then dropwise and slowly adding 3M dilute nitric acid into the solution until the pH value is 1.2 to obtain a yellow and transparent first solution;
s2, adding 6.2g of acetic acid into the first solution to obtain a tungstic acid precursor;
s3, putting 70mL of tungstic acid precursor into a 100mL of hydrothermal kettle with polytetrafluoroethylene as a lining, putting titanium carbide porous particles (the surface pore space accounts for about 55%, the opening size of a pore space structure is 50 μm, and the depth is 5-10 times of the pore space width) with the size of about 800 μm × 600 μm in advance in the kettle, carrying out hydrothermal treatment at 180 ℃ for 18 hours, naturally cooling, taking the obtained material out of the hydrothermal kettle, respectively rinsing with ethanol and water for 5-7 times, putting the material into an oven at 80 ℃ for drying to obtain a conductive substrate containing tungsten oxide, wherein the tungsten oxide grows in the pore space structure of the conductive substrate;
s4, placing the conductive substrate containing tungsten oxide in a tube furnace, introducing 50mL/min ammonia gas, heating to 1000 ℃ at 4 ℃/min, keeping the temperature for 1 hour, cooling to obtain particles of the delta-phase tungsten nitride electrode material (the thickness of the delta-phase tungsten nitride layer is 500nm-4 μm) taking porous titanium carbide as the substrate, dispersing the delta-phase tungsten nitride electrode material in isopropanol containing a certain amount of Nafion film solution, and dripping the solution on the surface of a glassy carbon electrode to prepare a film electrode for testing.
Example 6
(1) Then, 1.85g of tungsten powder was dispersed in 15mL of a 30% by mass hydrogen peroxide solution, and the mixture was stirred at room temperature to cause uniform reaction. After the solution after reaction is cooled to room temperature, inserting a platinum sheet to catalyze the decomposition of unreacted hydrogen peroxide, and taking out the platinum sheet when the volume of the solution after reaction V2 (mL)/the volume of the added hydrogen peroxide solution V1(mL) is 0.75-0.85 to obtain a second solution;
(2) water/isopropanol 7: 3, diluting the second solution by 20 times to 300mL, and stirring for 2 hours until the solution is uniform and transparent to obtain an electrolyte;
(3) and a graphite sheet with a pore structure of 25mm multiplied by 50mm multiplied by 1mm is taken as a working electrode, and the graphite sheet (the surface pore ratio is about 40 percent, the opening size of the pore structure is 100-250 mu m, and the depth is 3-10 times of the width of the pore) is soaked in the electrolyte for 10 hours before electrodeposition. Setting the deposition potential to-1.0V, and performing constant potential deposition on the graphite sheet for 30 min. After deposition is finished, taking out the material, washing the material with deionized water for 3-5 times, and drying the material in a drying oven at 60 ℃ to obtain a conductive substrate containing tungsten oxide, wherein tungsten oxide grows in a pore seam structure of the conductive substrate;
(4) placing a conductive substrate of tungsten oxide in a 100mL crucible, covering 10g of urea, placing the crucible in a heating furnace which can be sealed and vacuumized, vacuumizing and sealing, heating to 950 ℃ at the speed of 10 ℃/min, preserving the temperature for 2 hours, and naturally cooling to obtain the delta-phase tungsten nitride electrode material, wherein the thickness of the delta-phase tungsten nitride layer is 10nm-2 mu m.
Example 7
(1) 1.85g of tungsten powder was dispersed in 15mL of a 30% hydrogen peroxide solution by mass fraction, and the mixture was stirred at room temperature to allow uniform reaction. After the reacted solution is cooled to room temperature, inserting silver wires to catalyze unreacted hydrogen peroxide to decompose, and taking out the silver wires when the volume of the reacted solution V2 (mL)/the volume of the added hydrogen peroxide solution V1(mL) is 0.75-0.85 to obtain a second solution;
(2) water/isopropanol 7: 3, diluting the second solution by 20 times to 300mL, and stirring for 2 hours until the solution is uniform and transparent to obtain an electrolyte;
(3) and soaking a titanium carbide sheet with a pore structure and a diameter of 25mm multiplied by 50mm multiplied by 1mm in the electrolyte for 10 hours before electrodeposition, wherein the titanium carbide sheet (the ratio of surface pores to pore space is about 60%, the opening size of the pore structure is 50-200 mu m, and the depth is 3-10 times of the width of the pore space). Setting the deposition potential to-3.0V, and depositing for 5min at constant potential. After deposition is finished, taking out the material, washing the material with deionized water for 3-5 times, and drying the material in a 60 ℃ oven to obtain a conductive substrate containing tungsten oxide, wherein tungsten oxide grows in a pore seam structure of the conductive substrate;
(4) placing a conductive substrate containing tungsten oxide in a 100mL crucible, covering with 10g of urea, placing in a heating furnace which can be sealed and vacuumized, vacuumizing and sealing, heating to 1000 ℃ at a speed of 10 ℃/min, preserving heat for 2 hours, and naturally cooling to obtain the delta-phase tungsten nitride electrode material, wherein the thickness of the delta-phase tungsten nitride layer is 10nm-3 μm.
Example 8
(1) Dispersing 1.85g of tungsten powder in 15mL of hydrogen peroxide solution with the mass fraction of 30%The mixture was stirred at room temperature to allow uniform reaction. After the solution after reaction is cooled to room temperature, the unreacted hydrogen peroxide is catalyzed and decomposed by a platinum sheet, and when the volume of the solution after reaction is V2(mL)/volume of hydrogen peroxide solution added V1(mL) when 0.75 to 0.85, taking out the platinum sheet to obtain a second solution;
(2) water/isopropanol 7: 3, diluting the solution by 20 times to 300mL, and stirring for 1 hour until the solution is uniform and transparent to obtain an electrolyte;
(3) and soaking the titanium diboride sheet (the surface pore ratio is about 50 percent, the opening size of the pore structure is 50-150 mu m, and the depth is 5-10 times of the pore width) in the electrolyte for 10 hours before electrodeposition by taking a 25mm multiplied by 50mm multiplied by 1mm titanium diboride sheet with a pore structure as a working electrode, setting the deposition potential to be-0.8V, and depositing for 25 minutes at constant potential. After deposition is finished, taking out the material, washing the material with deionized water for 3-5 times, and drying the material in a 70 ℃ drying oven to obtain a conductive substrate containing tungsten oxide, wherein tungsten oxide grows in a pore seam structure of the conductive substrate;
(4) placing a conductive substrate containing tungsten oxide in a 100mL crucible, covering with 9.5g of ammonium acetate, placing in a heating furnace which can be sealed and vacuumized, vacuumizing and sealing, heating to 1050 ℃ at a speed of 5 ℃/min, preserving heat for 1 hour, and naturally cooling to obtain the delta-phase tungsten nitride electrode material, wherein the thickness of the delta-phase tungsten nitride layer is 10nm-2 μm.
Example 9
(1) Then, 1.85g of tungsten powder was dispersed in 15mL of a 30% by mass hydrogen peroxide solution, and the mixture was stirred at room temperature to cause uniform reaction. After the solution after reaction is cooled to room temperature, the unreacted hydrogen peroxide is catalyzed and decomposed by a platinum sheet, and when the volume of the solution after reaction is V2(mL)/volume of hydrogen peroxide solution added V1(mL) when 0.75 to 0.85, taking out the platinum sheet to obtain a second solution;
(2) water/isopropanol 7: 3, diluting the solution by 20 times to 300mL, and stirring for 1 hour until the solution is uniform and transparent to obtain an electrolyte;
(3) and soaking the titanium diboride rod with the aperture structure of phi 3mm multiplied by 60mm (the surface aperture ratio is about 70 percent), the opening size of the aperture structure is 50-200 mu m, the depth is 2-8 times of the aperture width) in the electrolyte for 10 hours before electrodeposition, setting the deposition potential to be-0.7V, and depositing at constant potential for 25 min. After deposition is finished, taking out the material, washing the material with deionized water for 3-5 times, and drying the material in a 70 ℃ drying oven to obtain a conductive substrate containing tungsten oxide, wherein tungsten oxide grows in a pore seam structure of the conductive substrate;
(4) placing a conductive substrate containing tungsten oxide in a 100mL crucible, covering 12g of melamine, placing the crucible in a heating furnace which can be sealed and vacuumized, vacuumizing and sealing, heating to 1100 ℃ at the speed of 8 ℃/min, preserving heat for 1.5 hours, and naturally cooling to obtain the delta-phase tungsten nitride electrode material, wherein the thickness of the delta-phase tungsten nitride layer is 10nm-2 mu m.
Example 10
A delta-phase tungsten nitride electrode material was produced in the same manner as in example 1, except that, in step S4, the temperature was raised to 1050 ℃ at 2 ℃/min and maintained at that temperature for 120min, and the thickness of the resulting delta-phase tungsten nitride layer was 100nm to 5 μm.
Example 11
A delta-phase tungsten nitride electrode material was produced in the same manner as in example 1, except that, in step S4, the temperature was raised to 900 ℃ at 2 ℃/min and maintained at that temperature for 120min, and the thickness of the delta-phase tungsten nitride layer was 100nm to 2 μm.
Example 12
The delta-phase tungsten nitride electrode material was prepared by the same method as in example 1, except that, in step S3, 40mL of tungstic acid precursor was taken, 2g of ammonium sulfate was added as a capping agent, and then the solution was transferred to a hydrothermal reactor previously equipped with a graphite rod having a 3mm x 50mm phi surface with a slit structure (the ratio of surface slits to surface slits was about 30%, the size of the opening of the slit structure was 300 to 500 μm, and the depth was 3 to 10 times the width of the slits) and lined with polytetrafluoroethylene, and subjected to hydrothermal reaction at 200 ℃ for 12 hours, with the thickness of the delta-phase tungsten nitride layer being 5 to 10 μm.
Example 13
A delta-phase tungsten nitride electrode material was produced in the same manner as in example 1, except that, in step S2, the hydrothermal reaction was carried out at a temperature of 140 ℃ for 16 hours, and the resulting delta-phase tungsten nitride layer had a thickness of 500nm to 3 μm.
Comparative example 1
A tungsten nitride electrode material was produced in the same manner as in example 1, except that, in step S4, the temperature was raised to 800 ℃ at 6 ℃/min and maintained at that temperature for 120 min. XRD detection shows that the tungsten nitride electrode material prepared in the comparative example is a beta-phase tungsten nitride electrode material.
Comparative example 2
The tungsten nitride electrode material was prepared by the same method as in example 1, except that in step S3, 40mL of tungstic acid precursor was taken, 2g of ammonium sulfate was added as a capping agent, and then the solution was transferred to a hydrothermal reactor lined with polytetrafluoroethylene, in which a solid graphite rod (phi 3mm × 50mm) having a surface pore ratio of 3%, a pore structure having an opening size of 2 to 5 μm, and a depth of the pore structure 3 to 5 times the opening size was placed in advance, and subjected to hydrothermal reaction at 180 ℃ for 16 hours to obtain a tungsten nitride electrode material having a majority of its surface grown as a beta phase.
Comparative example 3
The method described in example 1 of US9624604B2 was used with WCl6And NaN3(ratio 3:2) as precursor, NaCl +10 wt% ZrO2The delta-phase tungsten nitride powder is obtained by reacting at 1400 ℃ and 7.7GPa as a filler, and washing, centrifuging and drying the obtained product. The delta-phase tungsten nitride material is dispersed in isopropanol containing a certain amount of Nafion membrane solution, and is dripped on the surface of a glassy carbon electrode to prepare a membrane electrode for testing.
Test example
(1) In an acid electrolyte (0.5mol/L sulfuric acid), the electrode material or the membrane electrode prepared in the above examples and comparative examples is used as a working electrode, a common graphite rod is used as a counter electrode, silver/silver chloride is used as a reference electrode, and the hydrogen production reaction by water electrolysis is carried out to reach 10mA/cm-2The overpotential required for the current density is shown in table 1, and the hydrogen generation polarization curves of the electrodes prepared in example 1 and comparative example 1 are shown in fig. 3.
(2) In alkaline electrolyte (1.0mol/L potassium hydroxide)The electrolytic material prepared in the above examples and comparative examples is used as a working electrode, a common graphite rod is used as a counter electrode, mercury/mercury oxide is used as a reference electrode, and the hydrogen production reaction by the electric hydrolysis is carried out to reach 10mA/cm-2The overpotential required for the current density is shown in table 1, and the hydrogen generation polarization curves of the electrodes prepared in example 1, example 1 and comparative example 1 are shown in fig. 4.
(3) The electrode materials prepared in examples and comparative examples were subjected to hydrogen production reaction by continuous electrolysis of water for 15 hours in an acid electrolyte (0.5mol/L sulfuric acid), and the change of current density with time was examined, and the time-current density curve of hydrogen production of the electrode prepared in example 1 was shown in FIG. 5.
The above test was performed by Chenghua CHI700E electrochemical workstation, and the current density refers to the current per unit electrode area obtained under a certain voltage.
TABLE 1
Figure BDA0003249087410000171
The method has the advantages that the process conditions are mild, the energy consumption is low, the delta-phase tungsten nitride electrode material can be prepared, and the delta-phase tungsten nitride electrode material prepared by the method is used as an acidic or alkaline electrolyte hydrogen production electrode or electrode material and has excellent hydrogen production activity and stability. Preferably, when the temperature of the ammoniation reaction is 1000-. Preferably, when the opening size of the pore structure of the conductive substrate material is 5-200 μm, the depth of the pore structure is 2-10 times of the width of the pore structure, and the surface pore ratio is 30-60%, the prepared delta-phase tungsten nitride electrode material has better hydrogen production activity and stability. Preferably, when the hydrothermal temperature is 160-.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (13)

1. The delta-phase tungsten nitride electrode material is characterized by comprising a conductive substrate with a pore structure and a delta-phase tungsten nitride layer, wherein at least part of the delta-phase tungsten nitride layer covers the inner wall surface of the pore structure;
the aperture structure comprises an aperture extending inwardly of the surface of the conductive substrate and/or a slit extending generally along the surface of the conductive substrate; the surface pore accounts for 5-70%, the opening size of the pore structure is 500nm-500 μm, and the depth of the pore structure is more than 1.5 times of the opening size.
2. The delta phase tungsten nitride electrode material of claim 1, wherein the mean thickness of the delta phase tungsten nitride layer is 10nm-20 μ ι η.
3. A method of preparing a delta-phase tungsten nitride electrode material, the method comprising: ammoniating a conductive substrate containing tungsten oxide and/or tungstic acid in an ammonia atmosphere;
wherein the conductive substrate containing tungsten oxide and/or tungstic acid has a pore structure, at least part of the tungsten oxide and/or tungstic acid being attached to an inner wall surface of the pore structure; the surface pore accounts for 5-70%, the opening size of the pore structure is 500nm-500 μm, and the depth of the pore structure is more than 1.5 times of the opening size;
the conditions of the amination reaction include: the temperature is 900 plus 1800 ℃ and the time is 30-240 min.
4. The method according to claim 3, wherein the ammoniation reaction conditions comprise: the temperature is 950 ℃ and 1150 ℃, and the time is 60-180 min; preferably, the temperature is 1000-1100 ℃, and the time is 90-120 min.
5. The method according to claim 3, wherein the conductive substrate is made of a conductor material with a pore structure and good high-temperature stability, preferably one or more of graphite, titanium carbide and titanium diboride, and is in a shape of a sheet, a rod, a circular column, a block or powder;
the opening size of the pore structure is 5-200 μm, the depth of the pore structure is 2-10 times of the width of the pore, and the surface pore proportion is 30-60%.
6. The method of claim 3, wherein the method further comprises: preparing the conductive substrate containing tungsten trioxide and/or tungstic acid in situ by adopting a chemical synthesis method; the chemical synthesis method is selected from one or more of a hydrothermal method, an electrochemical method, a coprecipitation method and a chemical precipitation method.
7. The method according to claim 3 or 6, wherein the conductive substrate containing tungsten oxide and/or tungstic acid is prepared in situ using a hydrothermal process comprising the steps of:
s1, mixing the first tungsten source, strong acid and solvent, and adjusting the pH value to 1-2 to obtain a first solution;
s2, mixing the first solution with weak acid to obtain a tungstic acid precursor;
s3, carrying out hydrothermal reaction on the tungstic acid precursor and the first conductive substrate in a heat-resistant closed container to obtain the conductive substrate containing tungsten oxide and/or tungstic acid.
8. The method according to claim 7, wherein in step S2, the molar ratio of the first solution to the amount of weak acid is 1: (2-3), the first solution being based on the first tungsten source;
in step S3, the hydrothermal reaction conditions include: the temperature is 120 ℃ and 220 ℃, and the time is 6-48 hours; preferably, the hydrothermal temperature is 160-200 ℃, and the hydrothermal time is 12-24 hours;
the first tungsten source is selected from one or more of sodium tungstate, potassium tungstate, zinc tungstate, ammonium metatungstate and tungsten chloride; the strong acid is selected from one or more of hydrochloric acid, nitric acid and dilute sulfuric acid, and the concentration of the strong acid is 1-5 mol/L; the solvent is selected from one or more of deionized water, ethanol, ethylene glycol, isopropanol, N-dimethylformamide and acetonitrile; the weak acid is selected from one or more of oxalic acid, formic acid, acetic acid and carbonic acid; the first conductive substrate is made of a conductor material which has a pore structure and good high-temperature stability, and is preferably one or more of graphite, titanium carbide and titanium diboride.
9. The method according to claim 3 or 6, wherein the conductive substrate containing tungsten oxide and/or tungstic acid is prepared by an electrochemical process comprising the steps of:
(1) after the second tungsten source is contacted with the hydrogen peroxide solution for reaction, optionally removing the hydrogen peroxide contained in the solution after the reaction to obtain a second solution;
(2) diluting the second solution by using a diluent to obtain an electrolyte;
(3) and taking a second conductive substrate as a working electrode, placing the second conductive substrate in the electrolyte, and depositing tungsten oxide and/or tungstic acid on the second conductive substrate by adopting a constant potential method to obtain the conductive substrate containing the tungsten oxide and/or the tungstic acid.
10. The method according to claim 9, wherein the removing of the hydrogen peroxide contained in the reacted solution in step (1) comprises: contacting and reacting a catalyst with the reacted solution to obtain a second solution; or heating the reacted solution at 50-90 ℃ to obtain a second solution;
wherein the catalyst is one or more of platinum, silver, chromium, manganese dioxide, ferric chloride, copper oxide and catalase, and when the ratio of the volume of the second solution to the volume of the hydrogen peroxide solution initially added in the step (1) is 0.75-0.85, the catalyst is taken out or the heating is stopped;
in the step (2), the volume ratio of the second solution to the diluent is 1: (9-29); the diluent contains one or more of water, isopropanol, ethanol, ethylene glycol, acetone, acetonitrile and N, N-dimethylformamide, and preferably contains water and isopropanol, wherein the volume ratio of the water to the isopropanol is 1: (0.4-1);
in the step (3), the deposition conditions include: the deposition potential is-0.4V to-5V, and the deposition time is 1-60 min;
the second tungsten source is selected from one or more of metal tungsten powder, tungsten wires and tungsten sheets, and is preferably tungsten powder;
the second conductive substrate is made of a conductor material which has a pore structure and good high-temperature stability, and is preferably one or more of graphite, titanium carbide and titanium diboride.
11. The method according to claim 3, wherein the ammoniation reaction is carried out in a muffle furnace, a tube furnace or a fluidized bed, the ammonia gas atmosphere having a volume concentration of 10-100% or a flow rate of 10-100 mL/min.
12. The delta-phase tungsten nitride electrode material prepared by the method of any one of claims 3 to 11.
13. Use of the delta-phase tungsten nitride electrode material according to any one of claims 1-2 and claim 12 for the production of hydrogen by electrolysis of water.
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Address after: C0101-1F420, No. 48 Keji Road, High tech Zone, Xi'an City, Shaanxi Province, 710075

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Patentee before: Wuxi Longji Hydrogen Energy Technology Co.,Ltd.