Three-dimensional through-porous Ni4Mo / C alloy electrode material and preparation method thereof
By synthesizing three-dimensional interconnected porous Ni4Mo/C alloy electrode materials on a nickel foam framework in one step, the problems of cumbersome preparation process and poor catalytic activity were solved, and efficient water electrolysis for hydrogen production under a wide range of pH conditions and improved stability of the electrode materials were achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- QINGDAO UNIV OF SCI & TECH
- Filing Date
- 2026-04-03
- Publication Date
- 2026-06-09
AI Technical Summary
Existing methods for preparing Ni4Mo/C catalysts are cumbersome and complex, with poor catalytic activity and stability, making it difficult to efficiently produce hydrogen through water electrolysis under a wide range of pH conditions.
A three-dimensional interconnected porous Ni4Mo/C alloy electrode material was synthesized in one step on a foamed nickel metal framework by in-situ pyrolysis reaction of liquid precursor. The three-dimensional interconnected structure was constructed by compositing Ni4Mo/C alloy nanoparticles with graphite-structured carbon materials to form porous nanosheets.
This method enables efficient hydrogen production through water electrolysis under a wide range of pH conditions, improves electrocatalytic activity and cycle stability, reduces the complexity of the preparation steps, and enhances the electronic structure control capability of the electrode materials.
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Figure CN122169123A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of clean energy hydrogen production technology in green technology, and relates to a method for preparing a three-dimensional porous Ni4Mo / C alloy electrode material. Specifically, it relates to a three-dimensional porous Ni4Mo / C alloy electrode material for hydrogen production by water electrolysis under a wide range of pH conditions. Background Technology
[0002] Hydrogen is an ideal green and clean energy source due to its high energy density and zero emissions during combustion, which can help solve environmental pollution and the energy crisis. Electrocatalytic water splitting for hydrogen production has attracted much attention due to its low operating cost. Currently, precious metals are gaining attention for their excellent performance in electrocatalytic water splitting for hydrogen production. However, the scarcity and high cost of precious metals limit their large-scale application. Therefore, developing non-precious metal electrocatalysts that are abundant in Earth's resources, possess high catalytic activity under a wide range of pH conditions, and are low-cost is crucial for hydrogen production.
[0003] Among numerous catalysts, nickel-molybdenum (NiMo) alloys have attracted considerable attention due to their superior HER catalytic performance. However, because of their thermodynamic instability in alkaline media, NiMo alloys undergo molybdenum leaching during the catalytic process, resulting in poor durability. Constructing Ni4Mo / C heterostructures is an effective method for developing efficient and stable HER electrocatalysts. However, current methods for preparing Ni4Mo / C heterostructures are cumbersome and require multiple steps.
[0004] For the reasons mentioned above, the main problem to be solved by this invention is how to find a Ni4Mo / C electrode material that has a relatively simple process, can be prepared in one step to form a tightly coupled Ni4Mo with C, and has good HER performance and cycle stability. Summary of the Invention
[0005] This invention addresses the shortcomings of existing Ni4Mo / C catalyst preparation methods, such as cumbersome and complex processes, multiple synthesis steps, poor catalytic activity, and poor stability. It proposes a three-dimensional interconnected porous Ni4Mo / C alloy electrode material and its preparation method. The electrode material is characterized by being a three-dimensional interconnected porous Ni4Mo / C alloy electrode material grown in situ on a nickel foam framework. This material is formed by compositing Ni4Mo / C alloy nanoparticles with graphite-structured carbon materials to create porous nanosheets, which are then assembled in situ to form a three-dimensional interconnected porous structure. The electrode material is used for hydrogen production via water electrolysis under a wide range of pH conditions. It is obtained through in-situ reaction of a liquid precursor and one-step alloying, specifically including the following steps: (1) The effect of 0.1-0.2 M HCl solution on nickel foam (1-10)×(1-10) cm 2Perform ultrasonic treatment for 5-20 minutes, then ultrasonically wash with deionized water and anhydrous ethanol in sequence, and dry in a vacuum drying oven; (2) 0.1-10 mmol NiCl2·6H2O, 0.1-10 mmol MoCl2, 0.5-70 mmol urea, and 0.1-10 mmol hexamethylenetetramine are continuously stirred and heated in an oil bath at 50-90 ℃ for 15 min-2 h to form a homogeneous liquid; (3) Apply 10-2000 μL of the liquid obtained in step (2) evenly to the surface of the nickel foam obtained in step (1), place it in a tube furnace, heat it to 500-850 ℃ at a heating rate of 1-10 ℃ / min under a nitrogen atmosphere, keep it at the temperature for 1-5 h, and cool it to room temperature to obtain a three-dimensional through porous Ni4Mo / C alloy electrode material.
[0006] The advantages of this invention are as follows: The method is simple, synthesizing a three-dimensional porous Ni4Mo / C electrode material composed of graphite-structured carbon materials in situ grown on a nickel foam framework through an in-situ pyrolysis reaction of a liquid precursor. The electrode material is formed by in-situ one-step alloying with a liquid precursor, resulting in a three-dimensional interconnected structure with abundant active sites, which is beneficial for improving electrocatalytic efficiency and cycle stability. Simultaneously, the Ni4Mo / C alloy electrode material allows for efficient modulation of its electronic structure, further enhancing electrocatalytic activity and cycle stability. The composite of graphite-structured carbon materials improves the cycle stability of the Ni4Mo / C alloy electrode material, exhibiting excellent hydrogen production performance under alkaline conditions, making it suitable for use in green technologies for producing clean energy hydrogen. Attached Figure Description
[0007] Figure 1 The XRD pattern is shown in the figure. The three-dimensional through-porous Ni4Mo / C alloy electrode material prepared by the method described in Example 1 and Comparative Example 1 of the present invention.
[0008] Figure 2 The Raman spectra of the three-dimensional through-porous Ni4Mo / C alloy electrode material prepared by the method described in Example 1 of this invention and the electrode material of Comparative Example 1 are shown.
[0009] Figure 3 This is a SEM image of a three-dimensional through-porous Ni4Mo / C alloy electrode material prepared using the method described in Example 1 of this invention.
[0010] Figure 4 This is a TEM image of a three-dimensional through-porous Ni4Mo / C alloy electrode material prepared using the method described in Embodiment 1 of the present invention.
[0011] Figure 5 ADF images and corresponding elemental distribution diagrams of the three-dimensional through-porous Ni4Mo / C alloy electrode material prepared using the method described in Embodiment 1 of this invention.
[0012] Figure 6 The LSV curve (a) and cycle stability curve (b) of the three-dimensional through-porous Ni4Mo / C alloy electrode material and the comparative electrode material prepared by the method described in Example 1 of this invention are shown. Detailed Implementation
[0013] The present invention will be further described in detail below through examples and comparative examples: Example
[0014] (1) 0.1M HCl solution on nickel foam 1×1 cm 2 Perform ultrasonic treatment for 15 minutes, then ultrasonically wash with deionized water and anhydrous ethanol in sequence, and dry in a vacuum drying oven. (2) 1 mmol NiCl2·6H2O, 1 mmol MoCl2, 7 mmol urea and 1 mmol hexamethylenetetramine were continuously stirred and heated in an oil bath at 60 °C for 30 min to form a homogeneous liquid; (3) Apply 200 μL of the liquid obtained in step (2) evenly to the surface of the nickel foam obtained in step (1), place it in a tube furnace, heat it to 650 °C at a heating rate of 5 °C / min under a nitrogen atmosphere, keep it at that temperature for 3 h, and cool it to room temperature to obtain a three-dimensional through porous Ni4Mo / C alloy electrode material. Example
[0015] (1) 0.1M HCl solution on nickel foam 1×1 cm 2 Perform ultrasonic treatment for 15 minutes, then ultrasonically wash with deionized water and anhydrous ethanol in sequence, and dry in a vacuum drying oven. (2) 1 mmol NiCl2·6H2O, 1 mmol MoCl2, 7 mmol urea and 2 mmol hexamethylenetetramine were continuously stirred and heated in an oil bath at 60 °C for 30 min to form a homogeneous liquid; (3) Apply 200 μL of the liquid obtained in step (2) evenly to the surface of the nickel foam obtained in step (1), place it in a tube furnace, heat it to 650 °C at a heating rate of 5 °C / min under a nitrogen atmosphere, keep it at that temperature for 3 h, and cool it to room temperature to obtain a three-dimensional through porous Ni4Mo / C alloy electrode material. Example
[0016] (1) 0.1M HCl solution on nickel foam 1×1 cm2 Perform ultrasonic treatment for 5 minutes, then ultrasonically wash with deionized water and anhydrous ethanol in sequence, and dry in a vacuum drying oven; (2) 0.1 mmol NiCl2·6H2O, 0.1 mmol MoCl2, 0.5 mmol urea and 0.1 mmol hexamethylenetetramine were continuously stirred and heated in an oil bath at 50 °C for 15 min to form a homogeneous liquid; (3) Apply 10 μL of the liquid obtained in step (2) evenly to the surface of the nickel foam obtained in step (1), place it in a tube furnace, heat it to 500 °C at a heating rate of 1 °C / min under a nitrogen atmosphere, keep it at that temperature for 5 h, and cool it to room temperature to obtain a three-dimensional through porous Ni4Mo / C alloy electrode material. Example
[0017] (1) 0.2 M HCl solution on nickel foam 10 × 10 cm 2 Perform ultrasonic treatment for 20 minutes, then ultrasonically wash with deionized water and anhydrous ethanol in sequence, and dry in a vacuum drying oven; (2) 10 mmol NiCl2·6H2O, 10 mmol MoCl2, 70 mmol urea and 10 mmol hexamethylenetetramine were continuously stirred and heated in an oil bath at 90 °C for 2 h to form a homogeneous liquid; (3) Apply 2000 μL of the liquid obtained in step (2) evenly to the surface of the nickel foam obtained in step (1), place it in a tube furnace, heat it to 850 °C at a heating rate of 10 °C / min under a nitrogen atmosphere, keep it at that temperature for 1 h, and cool it to room temperature to obtain a three-dimensional through porous Ni4Mo / C alloy electrode material.
[0018] Example 5: (1) 0.2 M HCl solution on 5×5 cm nickel foam 2 Perform ultrasonic treatment for 10 minutes, then ultrasonically wash with deionized water and anhydrous ethanol in sequence, and dry in a vacuum drying oven; (2) 5 mmol NiCl2·6H2O, 5 mmol MoCl2, 60 mmol urea and 5 mmol hexamethylenetetramine were continuously stirred and heated in an oil bath at 80 °C for 1 h to form a homogeneous liquid; (3) 1000 μL of the liquid obtained in step (2) is uniformly coated on the surface of the nickel foam obtained in step (1), and placed in a tube furnace. The temperature is raised to 700 °C at a heating rate of 5 °C / min under a nitrogen atmosphere and held for 2 h. The material is then cooled to room temperature to obtain a three-dimensional through-porous Ni4Mo / C alloy electrode material. Example
[0019] (1) 0.15 M HCl solution on 2×2 cm nickel foam 2 Perform ultrasonic treatment for 10 minutes, then ultrasonically wash with deionized water and anhydrous ethanol in sequence, and dry in a vacuum drying oven; (2) 1 mmol NiCl2·6H2O, 2 mmol MoCl2, 10 mmol urea and 2 mmol hexamethylenetetramine were continuously stirred and heated in an oil bath at 70 °C for 30 min to form a homogeneous liquid; (3) Apply 500 μL of the liquid obtained in step (2) evenly to the surface of the nickel foam obtained in step (1), place it in a tube furnace, heat it to 650 °C at a heating rate of 2 °C / min under a nitrogen atmosphere, keep it at the temperature for 4 h, and cool it to room temperature to obtain a three-dimensional through porous Ni4Mo / C alloy electrode material. Example
[0020] 1) 0.1 M HCl solution on 1×1 cm nickel foam 2 Perform ultrasonic treatment for 10 minutes, then ultrasonically wash with deionized water and anhydrous ethanol in sequence, and dry in a vacuum drying oven; (2) 2 mmol NiCl2·6H2O, 3 mmol MoCl2, 10 mmol urea and 1 mmol hexamethylenetetramine were continuously stirred and heated in an oil bath at 60 °C for 30 min to form a homogeneous liquid; (3) 400 μL of the liquid obtained in step (2) is uniformly coated on the surface of the nickel foam obtained in step (1), and placed in a tube furnace. The temperature is raised to 750 °C at a heating rate of 5 °C / min under a nitrogen atmosphere and held for 3 h. The material is then cooled to room temperature to obtain a three-dimensional through-porous Ni4Mo / C alloy electrode material.
[0021] (1) 0.1M HCl solution on nickel foam 1×1 cm 2 Perform ultrasonic treatment for 15 minutes, then ultrasonically wash with deionized water and anhydrous ethanol in sequence, and dry in a vacuum drying oven. (2) 2 mmol NiCl2·6H2O, 7 mmol urea and 1 mmol hexamethylenetetramine were continuously stirred and heated in an oil bath at 60 °C for 30 min to form a homogeneous liquid; (3) Apply 200 μL of the liquid obtained in step (2) evenly to the surface of the nickel foam obtained in step (1), place it in a tube furnace, heat it to 650 °C at a heating rate of 5 °C / min under a nitrogen atmosphere, keep it at that temperature for 3 h, and cool it to room temperature to obtain the Ni / C electrode material.
[0022] Comparative Example 2: (1) 0.1M HCl solution on nickel foam 1×1 cm 2 The electrode was subjected to ultrasonic treatment for 15 minutes, followed by ultrasonic washing with deionized water and anhydrous ethanol in sequence, and then dried in a vacuum drying oven to obtain a nickel foam electrode.
[0023] Comparative Example 3: (1) 0.1M HCl solution on nickel foam 1×1 cm 2 Perform ultrasonic treatment for 15 minutes, then ultrasonically wash with deionized water and anhydrous ethanol in sequence, and dry in a vacuum drying oven. (2) Add 5 mg of Pt / C to 490 μL of dispersion solution (anhydrous ethanol:deionized water = 1:1) and 10 μL of Nafion, and sonicate for 1 h to obtain uniformly dispersed Pt / C ink. Coat 20 μL of Pt / C ink uniformly onto the surface of the nickel foam obtained in step (1), and let it dry naturally to obtain a Pt / C / NF electrode.
[0024] Figure 1 The XRD patterns of the three-dimensional through-porous Ni4Mo / C alloy electrode materials prepared using the methods described in Example 1 and Comparative Example 1 of this invention are shown in the figures. As can be seen from the figures, the diffraction peaks at 44.5°, 51.8°, and 76.3° are attributed to the (111), (200), and (220) crystal planes of cubic nickel (JCPDS No. 04-0850), respectively. The diffraction peaks marked with "*" at 43.7°, 50.6°, and 74.5° correspond to the (121), (310), and (312) crystal planes of tetragonal Ni4Mo alloy (JCPDS No. 65-5480), respectively.
[0025] Figure 2 The Raman spectra of the three-dimensional porous Ni4Mo / C alloy electrode material (a) and the comparative example electrode material (b) prepared using the method described in Example 1 of this invention are shown. Figure a shows two distinct Raman peaks: the G peak at approximately 1580 cm⁻¹ and the D peak at approximately 1350 cm⁻¹. The intensity of the G peak is greater than that of the D peak, indicating that the obtained electrode material contains carbon materials with a graphite structure. Figure b shows that the comparative example electrode material has a similar Raman spectrum to the electrode material in Example 1, indicating that the comparative example electrode material also contains carbon materials with a graphite structure.
[0026] Figure 3This image shows a SEM image of the three-dimensional interconnected porous Ni4Mo / C alloy electrode material prepared using the method described in Example 1 of this invention. As can be seen from the image, the electrode material is formed by the interlocking assembly of sheet-like materials to create a three-dimensional interconnected structure. This structure facilitates electrolyte diffusion and the rapid release of generated gases.
[0027] Figure 4 TEM images of the three-dimensional interconnected porous Ni4Mo / C alloy electrode material prepared using the method described in Example 1 of this invention further demonstrate that the prepared composite electrocatalyst exhibits a porous structure. The porous structure facilitates the full exposure of active sites on the surface of the electrochemical catalyst, thus contributing to improved catalytic activity.
[0028] Figure 5 STEM ADF images and corresponding elemental distribution maps of the three-dimensional through-porous Ni4Mo / C alloy electrode material prepared using the method described in Example 1 of this invention are shown. The STEM ADF images more clearly show the porous structure of the electrode material, and the corresponding elemental distribution maps confirm the uniform distribution of Ni, Mo, and C elements.
[0029] Figure 6 The LSV curves (a) and cycle stability curves (b) of the three-dimensional through-porous Ni4Mo / C alloy electrode material and the comparative electrode material prepared by the method described in Example 1 of this invention are shown. Figure 6 As can be seen, in a 1.0 M KOH medium, the electrode material of Example 1 can achieve 10 mA cm⁻¹ at low overpotentials of 38 mV, 183 mV, and 241 mV. -2 100 mA cm -2 and 200 mA cm -2 The current density and overpotential of this electrode are significantly lower than those of Comparative Example 1 and Comparative Example 2, indicating that its electrocatalytic hydrogen production performance is far superior to that of Comparative Example 1 and Comparative Example 2. At 10 mAcm⁻¹ -2 and 100 mA cm -2 The overpotential at the current density is comparable to that of the comparative example three commercial Pt / C electrodes, at 23 mV and 184 mV. At 200 mA cm⁻¹... -2 At a current density of 241 mV, its overpotential is lower than that of the 257 mV of the commercial Pt / C electrode in Comparative Example 3, indicating that under high current conditions, the electrode material of Embodiment 1 of this invention has superior HER performance compared to the Pt / C electrode material in Comparative Example 3. Figure 6 The cycle stability curve in Figure b shows that, under a bias voltage of 38 mV, the electrode material of Embodiment 1 of this invention maintains a cycle stability of 10 mA cm⁻¹. -2The current intensity did not change significantly within 48 hours, indicating that the electrode material of Example 1 of the present invention has long-lasting catalytic stability.
[0030] The figure shows the three-dimensional porous Ni4Mo / C alloy electrode material prepared by the method described in Example 1 of this invention being used for water splitting to produce hydrogen under acidic and neutral conditions. The overpotential of the electrode material in Example 1 is also much lower than that of the electrode materials in Comparative Example 1 and Comparative Example 2, indicating that its electrocatalytic hydrogen production performance is also superior to that of the electrode materials in Comparative Example 1 and Comparative Example 2 under both acidic and neutral conditions.
[0031] As can be seen from the examples, the three-dimensional through-porous Ni4Mo / C alloy electrode material prepared by the method described in Example 1 of the present invention has excellent performance in hydrogen production by water electrolysis over a wide pH range.
[0032] The electrode material prepared by the method described in the embodiments of the present invention is used for the electrocatalytic redox conversion of biomass organic small molecules. It has good electrocatalytic reduction selectivity for fine organic chemicals and can be used for the electrocatalytic redox conversion preparation of fine organic chemicals.
[0033] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, substitutions, simplifications, etc. made without departing from the principle and process of the present invention are equivalent substitutions and should be included within the protection scope of the present invention.
Claims
1. A three-dimensional through-porous Ni4Mo / C alloy electrode material and its preparation method, characterized in that, The electrode material is a three-dimensional interconnected porous Ni4Mo / C alloy electrode material grown in situ on a nickel foam metal framework. This three-dimensional interconnected porous Ni4Mo / C alloy electrode material is formed by compositing Ni4Mo alloy nanoparticles with graphite-structured carbon materials to create porous nanosheets, which are then assembled in situ to form a three-dimensional interconnected porous structure. This electrode material is used for hydrogen production through water electrolysis under a wide range of pH conditions. It is obtained through in-situ reaction of a liquid precursor and one-step alloying, specifically including the following steps: (1) The effect of 0.1-0.2 M HCl solution on nickel foam (1-10)×(1-10) cm 2 Perform ultrasonic treatment for 5-20 minutes, then ultrasonically wash with deionized water and anhydrous ethanol in sequence, and dry in a vacuum drying oven; (2) 0.1-10 mmol NiCl2·6H2O, 0.1-10 mmol MoCl2, 0.5-70 mmol urea, and 0.1-10 mmol hexamethylenetetramine are continuously stirred and heated in an oil bath at 50-90 ℃ for 15 min-2 h to form a homogeneous liquid; (3) Apply 10-2000 μL of the liquid obtained in step (2) evenly to the surface of the nickel foam obtained in step (1), place it in a tube furnace, heat it to 500-850 ℃ at a heating rate of 1-10 ℃ / min under a nitrogen atmosphere, keep it at the temperature for 1-5 h, and cool it to room temperature to obtain a three-dimensional through porous Ni4Mo / C alloy electrode material.