Water splitting electro-catalytic material of bimetallic boride as well as preparation method and application of water splitting electro-catalytic material
By using a magnesothermic reduction-assisted solid-phase synthesis method, the high energy barrier and impurity problems in the synthesis of bimetallic borides were solved, and high-purity crystalline bimetallic borides were successfully prepared, improving electrocatalytic performance, especially the hydrogen production performance of Mo2NiB2 and W2NiB2 through water electrolysis.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-29
- Publication Date
- 2026-04-14
AI Technical Summary
In existing technologies, the synthesis of crystalline bimetallic borides faces challenges such as high energy barriers, long reaction times, and numerous product impurities, hindering their widespread application in electrocatalysis and the study of synergistic effects between metals.
A magnesothermic reduction-assisted solid-state synthesis method was adopted, in which a mixture of metal diborides, metal chlorides and magnesium powder was calcined in a quartz tube. The heat released by the magnesothermic reduction reaction assisted in the synthesis of bimetallic borides. The reaction temperature was low and the steps were simple, resulting in high-purity and crystalline bimetallic boride materials.
Safe and controllable low-temperature synthesis was achieved, and crystalline bimetallic borides, especially Mo2NiB2 and W2NiB2, were successfully synthesized, exhibiting excellent electrocatalytic performance. The structure-activity relationship between electronic structure and catalytic performance was investigated.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of water electrolysis for hydrogen production, specifically to a bimetallic boride water splitting electrocatalytic material, its preparation method, and its application. Background Technology
[0002] Hydrogen is an ideal energy source that is highly efficient and pollution-free. In particular, the production of "green hydrogen" through water electrolysis using renewable energy sources such as wind and solar power is considered a core direction for future new energy, and will further contribute to my country's "dual carbon" goals of peak carbon emissions and carbon neutrality. Noble metal Pt-based materials are the most commonly used catalysts for the hydrogen evolution reaction (HER), but their high cost and scarcity limit their widespread application. Transition metal-based compounds, such as transition metal sulfides, phosphides, carbides, nitrides, and borides, have been extensively studied and used as alternatives to noble metal-based materials due to their low cost, abundant reserves, and good stability.
[0003] Transition metal borides are a class of metalloid boron alloys with unique electronic structures, good electrical conductivity, and corrosion resistance. The boron atoms in these compounds exhibit a zero-charge state, allowing more electrons to be retained at the active metal sites. Various transition metal borides, such as WB2, MoB2, VB2, Ni3B, and RuB2, have shown good electrocatalytic activity in both acidic and alkaline solutions. Doping a second metal into a single-metal boride forms a doped bimetallic boride, such as Cr... 0.4 Mo 0.6 Materials such as B2, 10% Ni-WB2, and NiFe-B can further improve the electrocatalytic performance of single-metal borides. Heterogeneous structures of two metal borides, such as Ni3B / MoB, are also beneficial for enhancing electrocatalytic activity.
[0004] However, research on crystalline bimetallic borides is relatively limited. Due to the high energy barriers and similar formation energies during synthesis, the preparation of most crystalline bimetallic borides faces challenges such as high synthesis temperatures, long reaction times, and numerous product impurities. This hinders further research into the potential catalytic performance of bimetallic borides and the synergistic effects between metals. Summary of the Invention
[0005] This invention aims to provide a bimetallic boride water-splitting electrocatalytic material and its preparation method. The preparation method is a universal magnesothermic reduction-assisted solid-phase synthesis method. Based on a diboride, a metal chloride is added as a second metal source, and magnesium powder is added as an auxiliary. The heat released by the magnesothermic reduction reaction is used to assist the solid-phase synthesis. The reaction temperature is low, and the synthesis steps are simple. Furthermore, the prepared bimetallic boride material exhibits extremely high purity and crystallinity, and demonstrates a Ni>Co>Fe regularity in water electrolysis for hydrogen production, which is beneficial for studying the structure-activity relationship between electronic structure and catalytic performance. This invention solves the problems in the background art.
[0006] To achieve the above objectives, the present invention provides the following technical solution:
[0007] A method for preparing a bimetallic boride water splitting electrocatalytic material includes the following steps:
[0008] S1. Weigh out metal diboride, metal chloride and magnesium powder in a molar ratio of 2:1:1~5, grind and mix them, and then vacuum seal them into a quartz tube.
[0009] S2. Place the quartz tube containing the mixture from step S1 into a muffle furnace for calcination;
[0010] S3. Grind the solid sample obtained after calcination, disperse it in sulfuric acid solution to remove impurities, then wash it by centrifugation with water and ethanol, and dry it to obtain bimetallic boride material.
[0011] Furthermore, in S1, the metal diboride is molybdenum diboride or tungsten diboride.
[0012] Furthermore, in S1, the metal chloride is anhydrous nickel chloride, anhydrous cobalt chloride, or anhydrous ferrous chloride.
[0013] Further, in S2, the step of placing the quartz tube containing the mixture from step S1 into a muffle furnace for calcination includes: calcining the quartz tube containing the mixture from step S1 in a muffle furnace at 2... o C min -1 The heating rate, the temperature rises to 800 o C~1000 o C, calcined for 4-6 hours.
[0014] Furthermore, in S3, the bimetallic boride material obtained is Mo2NiB2, Mo2CoB2, Mo2FeB2, W2NiB2, W2CoB2, or W2FeB2.
[0015] The bimetallic boride material prepared by the above-described method for preparing water splitting electrocatalytic materials is a bimetallic boride material.
[0016] The above-mentioned bimetallic boride materials are used in electrocatalytic water splitting for hydrogen production.
[0017] The beneficial effects of the technical solution are:
[0018] 1. Compared with the traditional high-temperature and high-pressure synthesis method, the preparation method of the present invention adds magnesium powder and uses the heat released by the magnesium thermal reduction reaction to assist solid-phase synthesis. The reaction temperature is lower, the synthesis steps are simpler, and the method is safer and more controllable.
[0019] 2. This invention is a successful and universal preparation method that can synthesize a series of crystalline bimetallic borides, among which Mo2NiB2 and W2NiB2 have extremely high purity and crystallinity.
[0020] 3. The bimetallic boride material prepared by this invention exhibits a regularity of Ni>Co>Fe in its hydrogen production performance through water electrolysis, which is beneficial for studying the structure-activity relationship between electronic structure and catalytic performance. Attached Figure Description
[0021] Figure 1 The X-ray diffraction patterns of the Mo2MB2 type bimetallic borides obtained in Examples 1-3 of this invention are shown below; in the figures, A represents Mo2NiB2; B represents Mo2CoB2; and C represents Mo2FeB2.
[0022] Figure 2 The X-ray diffraction patterns of the W2MB2 type bimetallic borides obtained in Examples 4-6 of this invention are shown below; in the figures, A represents W2NiB2; B represents W2CoB2; and C represents W2FeB2.
[0023] Figure 3 The polarization curves of hydrogen desorption by water cracking of the bimetallic borides obtained in Examples 1-6 of this invention in acidic electrolyte (0.5 M H2SO4); A represents Mo2NiB2, Mo2CoB2, and Mo2FeB2; B represents W2NiB2, W2CoB2, and W2FeB2. Detailed Implementation
[0024] The present invention will now be described in further detail with reference to the accompanying drawings and embodiments:
[0025] Example 1
[0026] Preparation of Mo2NiB2:
[0027] S1. Under infrared lamp irradiation, weigh 1 mmol of molybdenum diboride, 0.5 mmol of anhydrous nickel chloride and 0.5 mmol of magnesium powder in a molar ratio of 2:1:1 and put them into a mortar. Grind them to make them evenly mixed. Transfer the mixed powder into a quartz tube, use a vacuum pump to evacuate for 10 minutes and then seal the tube.
[0028] S2. Place the quartz tube containing the sample from step S1 into a muffle furnace at 2... o C min -1 The heating rate was increased to 1000. o C, calcined for 5 hours.
[0029] S3. After the quartz tube has cooled to room temperature, remove the sample, grind it, and add 0.5 mol L. -1 The impurities were removed by soaking in sulfuric acid solution for 2 hours, followed by washing three times by centrifugation with water and ethanol, and then at 80 °C. o Mo2NiB2 can be obtained by drying in an oven at temperature C.
[0030] Example 2
[0031] Preparation of Mo2CoB2:
[0032] S1. Under infrared lamp irradiation, weigh 1 mmol of molybdenum diboride, 0.5 mmol of anhydrous cobalt chloride and 0.5 mmol of magnesium powder in a molar ratio of 2:1:1 and put them into a mortar. Grind them to make them evenly mixed. Transfer the mixed powder into a quartz tube, use a vacuum pump to evacuate for 10 minutes and then seal the tube.
[0033] S2. Place the quartz tube containing the sample from step S1 into a muffle furnace at 2... o C min -1 The heating rate was increased to 1000. o C, calcined for 5 hours.
[0034] S3. After the quartz tube has cooled to room temperature, remove the sample, grind it, and add 0.5 mol L. -1 The impurities were removed by soaking in sulfuric acid solution for 2 hours, followed by washing three times by centrifugation with water and ethanol, and then at 80 °C. o Mo2CoB2 can be obtained by drying in an oven at temperature C.
[0035] Example 3
[0036] Preparation of Mo2FeB2:
[0037] S1. Under infrared light, weigh 1 mmol of molybdenum diboride, 0.5 mmol of anhydrous ferrous chloride and 0.5 mmol of magnesium powder in a molar ratio of 2:1:1 and put them into a mortar. Grind them to make them evenly mixed. Transfer the mixed powder into a quartz tube, use a vacuum pump to evacuate for 10 minutes and then seal the tube.
[0038] S2. Place the quartz tube containing the sample from step S1 into a muffle furnace at 2... o C min -1 The heating rate was increased to 1000. o C, calcined for 5 hours.
[0039] S3. After the quartz tube has cooled to room temperature, remove the sample, grind it, and add 0.5 mol L. -1 The impurities were removed by soaking in sulfuric acid solution for 2 hours, followed by washing three times by centrifugation with water and ethanol, and then at 80 °C. o Mo2FeB2 can be obtained by drying in an oven at temperature C.
[0040] Example 4
[0041] Preparation of W2NiB2:
[0042] S1. Under infrared light irradiation, weigh 1 mmol of tungsten diboride, 0.5 mmol of anhydrous nickel chloride and 0.5 mmol of magnesium powder in a molar ratio of 2:1:1 and put them into a mortar. Grind them to make them evenly mixed. Transfer the mixed powder into a quartz tube, use a vacuum pump to evacuate for 10 minutes and then seal the tube.
[0043] S2. Place the quartz tube containing the sample from step S1 into a muffle furnace at 2... o C min -1 The heating rate was increased to 1000. o C, calcined for 5 hours.
[0044] S3. After the quartz tube has cooled to room temperature, remove the sample, grind it, and add 0.5 mol L. -1 The impurities were removed by soaking in sulfuric acid solution for 2 hours, followed by washing three times by centrifugation with water and ethanol, and then at 80 °C. o W2NiB2 can be obtained by drying in an oven at C.
[0045] Example 5
[0046] Preparation of W2CoB2:
[0047] S1. Under infrared light, weigh 1 mmol of tungsten diboride, 0.5 mmol of anhydrous cobalt chloride and 0.5 mmol of magnesium powder in a molar ratio of 2:1:1 and put them into a mortar. Grind them to make them evenly mixed. Transfer the mixed powder into a quartz tube, use a vacuum pump to evacuate for 10 minutes and then seal the tube.
[0048] S2. Place the quartz tube containing the sample from step S1 into a muffle furnace at 2... o C min -1 The heating rate was increased to 1000. o C, calcined for 5 hours.
[0049] S3. After the quartz tube has cooled to room temperature, remove the sample, grind it, and add 0.5 mol L. -1 The impurities were removed by soaking in sulfuric acid solution for 2 hours, followed by washing three times by centrifugation with water and ethanol, and then at 80 °C. oW2CoB2 can be obtained by drying in an oven at temperature C.
[0050] Example 6
[0051] Preparation of W2FeB2:
[0052] S1. Under infrared light irradiation, weigh 1 mmol of tungsten diboride, 0.5 mmol of anhydrous ferrous chloride and 0.5 mmol of magnesium powder in a molar ratio of 2:1:1 and put them into a mortar. Grind them to make them evenly mixed. Transfer the mixed powder into a quartz tube, use a vacuum pump to evacuate for 10 minutes and then seal the tube.
[0053] S2. Place the quartz tube containing the sample from step S1 into a muffle furnace at 2... o C min -1 The heating rate was increased to 1000. o C, calcined for 5 hours.
[0054] S3. After the quartz tube has cooled to room temperature, remove the sample, grind it, and add 0.5 mol L. -1 The impurities were removed by soaking in sulfuric acid solution for 2 hours, followed by washing three times by centrifugation with water and ethanol, and then at 80 °C. o W2FeB2 can be obtained by drying in an oven at temperature C.
[0055] The bimetallic boride materials prepared above were characterized and their performance was tested. Figure 1 The X-ray diffraction patterns are those of the Mo2MB2 type (M=Fe, Co, Ni) bimetallic boride materials obtained in Examples 1-3. Figure 2 The X-ray diffraction patterns of the W2MB2 type (M=Fe, Co, Ni) bimetallic boride materials obtained in Examples 4-6 illustrate the successful synthesis of crystalline phases of Mo2NiB2, Mo2CoB2, Mo2FeB2, W2NiB2, W2CoB2, and W2FeB2 bimetallic borides via magnesothermic reduction-assisted solid-state synthesis. Among these, Mo2NiB2 and W2NiB2 exhibit extremely high purity and crystallinity.
[0056] The prepared material was uniformly dispersed in a 10% (v / v) perfluorosulfonic acid resin-isopropanol solution, and then dropped onto a glassy carbon electrode as the working electrode. In a three-electrode system, 0.5 mol L... -1 H2SO4 was used as the electrolyte, a saturated calomel electrode was used as the reference electrode, and a carbon rod was used as the counter electrode for electrochemical testing. Figure 3 A represents the Mo2MB2 type (M=Fe, Co, Ni) bimetallic boride material obtained in Examples 1-3 in an acidic electrolyte (0.5 mol L). -1The polarization curves of hydrogen desorption from water cracking in H2SO4 show that Mo2NiB2, Mo2CoB2, and Mo2FeB2 reach a current density of 10 mA cm⁻¹ at overpotentials of 233 mV, 310 mV, and 364 mV, respectively. -2 . Figure 3 B represents the W2MB2 type (M=Fe, Co, Ni) bimetallic boride material obtained in Examples 4-6 in an acidic electrolyte (0.5 mol L). -1 The polarization curves of hydrogen desorption from water cracking in H2SO4 show that W2NiB2, W2CoB2, and W2FeB2 reach a current density of 10 mA cm⁻¹ at overpotentials of 278 mV, 295 mV, and 504 mV, respectively. -2 Both Mo2MB2 and W2MB2 (M=Fe, Co, Ni) bimetallic boride materials exhibit an electrocatalytic hydrogen evolution activity trend of Ni>Co>Fe, with Mo2NiB2 showing the best properties.
[0057] In summary, compared with traditional high-temperature and high-pressure synthesis methods, the preparation method of this invention adds magnesium powder and utilizes the heat released by the magnesothermic reduction reaction to assist solid-phase synthesis. The reaction temperature is lower, the synthesis steps are simpler, and the process is safer and more controllable. A series of crystalline bimetallic borides can be synthesized, among which Mo2NiB2 and W2NiB2 have extremely high purity and crystallinity. The prepared bimetallic boride materials exhibit a regularity of Ni>Co>Fe in water electrolysis hydrogen production performance, which is beneficial for studying the structure-activity relationship between electronic structure and catalytic performance.
[0058] The above descriptions are merely embodiments of the present invention, and common knowledge regarding specific technical solutions or characteristics is not elaborated upon here. It should be noted that those skilled in the art can make various modifications and improvements without departing from the technical solutions of the present invention, and these should also be considered within the scope of protection of the present invention. These modifications and improvements will not affect the effectiveness of the implementation of the present invention or the practicality of the patent. The scope of protection claimed in this application should be determined by the content of its claims, and the specific embodiments described in the specification can be used to interpret the content of the claims.
Claims
1. A method for preparing a bimetallic boride water splitting electrocatalytic material, characterized in that, Includes the following steps: S1. Weigh out metal diboride, metal chloride and magnesium powder in a molar ratio of 2:1:1~5, grind and mix them, and then vacuum seal them into a quartz tube. S2. Place the quartz tube containing the mixture from step S1 into a muffle furnace for calcination; S3. Grind the solid sample obtained after calcination, disperse it in sulfuric acid solution to remove impurities, then wash it by centrifugation with water and ethanol, and dry it to obtain bimetallic boride material.
2. The method for preparing the bimetallic boride water splitting electrocatalytic material according to claim 1, characterized in that: In S1, the metal diboride is molybdenum diboride or tungsten diboride.
3. The method for preparing the bimetallic boride water splitting electrocatalytic material according to claim 1, characterized in that: In S1, the metal chloride is anhydrous nickel chloride, anhydrous cobalt chloride, or anhydrous ferrous chloride.
4. The method for preparing the bimetallic boride water splitting electrocatalytic material according to claim 1, characterized in that: In S2, the step of placing the quartz tube containing the mixture from step S1 into a muffle furnace for calcination includes: calcining the quartz tube containing the mixture from step S1 in a muffle furnace at a temperature of 2... o C min -1 The heating rate, the temperature rises to 800 o C~1000 o C, calcined for 4-6 hours.
5. The method for preparing the bimetallic boride water splitting electrocatalytic material according to claim 1, characterized in that: In S3, the bimetallic boride materials obtained are Mo2NiB2, Mo2CoB2, Mo2FeB2, W2NiB2, W2CoB2, or W2FeB2.
6. The bimetallic boride material prepared by the method for preparing the bimetallic boride water splitting electrocatalytic material according to any one of claims 1-5.
7. The application of the bimetallic boride material according to claim 6 in electrocatalytic water splitting for hydrogen production.