Laser preparation method of ruthenium-based water electrolysis hydrogen production electrode material and electrode material
Ruthenium-based electrode materials for hydrogen production by water electrolysis were prepared by direct laser scribing technology, which solved the problems of cumbersome preparation and high cost in traditional methods. This resulted in ruthenium-based electrode materials with high activity and stability, suitable for alkaline water electrolysis for hydrogen production.
Patent Information
- Application Number
- CN202511832517.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-08
- Publication Date
- 2026-02-24
AI Technical Summary
Existing methods for preparing ruthenium-based catalysts are cumbersome, time-consuming, and costly, resulting in insufficient exposure of active sites and inadequate stability in alkaline water electrolysis for hydrogen production, which limits their large-scale application.
By employing direct laser scribing technology, a solution of dodecacarbonyltriruthenium was sprayed onto a conductive carrier and then treated with laser to prepare a highly active and stable ruthenium-based water electrolysis electrode material for hydrogen production. The preparation process parameters were optimized to simplify the process and reduce costs.
The method achieves high catalytic activity and stability of ruthenium-based water electrolysis hydrogen production electrode materials, simplifies the preparation process, reduces costs, and is suitable for mass production.
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Figure CN121556074A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of new energy materials technology, and relates to a laser preparation method for a ruthenium-based electrolytic water hydrogen production electrode material and its application in ruthenium-based electrolytic water hydrogen production. Background Technology
[0002] Hydrogen (H2) is considered one of the most promising alternatives to fossil fuels due to its high calorific value, pollution-free products, and wide availability.
[0003] Currently, the main methods for large-scale industrial hydrogen production include coal gasification, steam methane reforming, and water electrolysis. Among these, alkaline water electrolysis technology has become the most widely used hydrogen production technology due to its simple operation, relatively low equipment cost, and long service life. However, the slow kinetics and high overpotential of the hydrogen evolution reaction in alkaline water electrolysis are key bottlenecks restricting its overall energy conversion efficiency and economic viability. Therefore, developing highly active and stable electrocatalysts for the hydrogen evolution reaction in alkaline media is crucial for reducing reaction energy consumption and promoting the industrial application of hydrogen production through water electrolysis.
[0004] Among numerous catalyst materials, platinum (Pt)-based catalysts exhibit excellent performance, but their high cost and scarcity severely limit their large-scale application. Ruthenium (Ru), a platinum group metal with a price only about one-third that of platinum, not only possesses good electrical conductivity but also excellent water dissociation ability and suitable adsorption strength for reaction intermediates. Theoretical calculations and experimental studies have shown that many ruthenium-based catalysts demonstrate hydrogen evolution performance comparable to or even superior to platinum in alkaline media, making Ru-based materials one of the most promising alternatives to Pt for hydrogen evolution catalysts.
[0005] Despite the immense potential of Ru-based catalysts, their research and development still face a series of challenges. Traditional preparation methods, such as high-temperature pyrolysis, hydrothermal synthesis, or impregnation-reduction methods, are typically cumbersome, time-consuming, and energy-intensive. Furthermore, the resulting catalytic materials often suffer from insufficient exposure of active sites, inadequate conductivity and stability, and complex preparation processes. Therefore, there is an urgent need to develop a new method for the simple and rapid preparation of highly active Ru-based hydrogen evolution catalysts.
[0006] Direct laser scribing, as a highly efficient patterning method, bypasses the complex multi-step processes of traditional methods, enabling the direct and in-situ transformation of precursor materials into functional electrodes through a single laser treatment. This technology combines the advantages of high processing speed, low manufacturing cost, and high patterning precision. Here, we propose a method using dodecyltriruthenium carbonyl as a precursor and direct laser scribing to rapidly heat and prepare a highly active and stable electrocatalyst for hydrogen evolution in water electrolysis. Summary of the Invention
[0007] This invention provides a laser preparation method for ruthenium-based water electrolysis hydrogen production electrode materials and their applications. The invention involves placing a dodecyltriruthenium solution on a conductive support and preparing a highly active and stable electrocatalyst for water electrolysis and hydrogen production using a direct laser scribing method. The process parameters are optimized, solving problems such as the high cost of traditional platinum-based catalysts, the complex preparation process of loading powdered catalysts onto the electrode, and the reduction of catalyst-support conductivity by introducing binders.
[0008] The technical solution of the present invention is as follows: A laser preparation method for a ruthenium-based water electrolysis hydrogen production electrode material includes the following steps: (1) Preparation of dodecyltriruthenium carbonyl precursor solution: Dodecyltriruthenium carbonyl was added to an organic solvent and ultrasonically dissolved for 10 min to obtain dodecyltriruthenium carbonyl solution; The aforementioned organic solvents include toluene, xylene, dichloromethane, diethyl ether, etc., with dichloromethane being preferred; Ruthenium dodecylcarbonyl is dissolved in an organic solvent by ultrasonication to obtain a solution with a final concentration of 0.00042-0.002 M, preferably 0.002 M; (2) Preparation of L-Ru: The dodecyltriruthenium carbonyl solution obtained in step (1) is uniformly sprayed onto the surface of a conductive support. After the organic solvent evaporates, the resulting material is denoted as RuCO-CP. The RuCO-CP is treated by direct laser scribing to obtain the catalytic material for the hydrogen evolution reaction, denoted as L-Ru. The parameters for direct laser scribing are set as follows: laser power 3.99-10.38 W (preferably 8.78 W), laser scanning speed 150-450 mm / s (preferably 250 mm / s), and laser frequency 10-40 kHz (preferably 30 kHz).
[0009] Furthermore, the organic solvent is one of toluene, xylene, dichloromethane, and diethyl ether. More preferably, dichloromethane is used as the organic solvent.
[0010] Furthermore, in step (2), the conductive carrier is either carbon paper or nickel felt. More preferably, the conductive carrier is carbon paper.
[0011] Furthermore, in step (2), it is recommended that the amount of dodecyltriruthenium solution added to the conductive support surface be 1.5 mg / cm³. 2 ; Furthermore, in step (1), the ultrasonic dissolution time is 10 min, the ultrasonic frequency is 40KHz, and the ultrasonic power is 500W.
[0012] Furthermore, in step (2), the parameters for direct laser scribing are set as follows: laser power 8.78 W, laser scanning speed 250 mm / s, and laser frequency 30 kHz.
[0013] This case recommends the ruthenium-based electrode material for hydrogen production via water electrolysis, prepared using the method described in this case.
[0014] Another inventive point of this case is the application of the ruthenium-based electrode material for hydrogen production by water electrolysis prepared by the method of this case in the production of hydrogen by water electrolysis.
[0015] Furthermore, the application involves electrolyzing water to produce hydrogen in a 1M KOH solution, with a Hg / HgO electrode as the reference electrode, a C rod as the counter electrode, and the ruthenium-based water electrolysis hydrogen production material as the working electrode.
[0016] This invention quantitatively loads dodecyltriruthenium carbonyl onto a conductive support such as carbon paper and prepares a highly active and stable electrolytic hydrogen production electrode material by direct laser scribing. By controlling the process parameters during the preparation process, this invention solves the problems of complex preparation process of powder catalyst loaded onto the electrode and the introduction of binders that reduce the conductivity between the catalyst and the support.
[0017] Compared with the prior art, the present invention has the following beneficial effects: This invention provides a laser preparation method for ruthenium-based water electrolysis hydrogen production electrode materials. First, a solution of dodecyltriruthenium carbonyl is sprayed onto a conductive support. SEM analysis reveals that the morphology of dodecyltriruthenium carbonyl is an irregular, blocky aggregate. Then, carbonization is performed using direct laser scribing. Characterization by SEM and XRD shows a dramatic change in the morphology of the dodecyltriruthenium carbonyl, transforming from an irregular blocky aggregate into a network structure, forming highly active ruthenium elemental nanoparticles with efficient catalytic activity.
[0018] This invention carbonizes ruthenium-based compound materials into electrode materials using direct laser scribing technology, resulting in materials with good catalytic activity and stability. Furthermore, the method of this invention is simple, easy to implement, and low in cost, and can be mass-produced. Attached Figure Description Figure 1 This is a scanning electron microscope image of sample 1 in Embodiment 1 of the present invention.
[0019] Figure 2 This is a scanning electron microscope image of sample 2 in Embodiment 2 of the present invention.
[0020] Figure 3 This is a scanning electron microscope image of sample 3 in Example 3 of the present invention.
[0021] Figure 4 This is a scanning electron microscope image of sample 4 in Example 4 of the present invention.
[0022] Figure 5 This is a scanning electron microscope image of sample 5 in Example 5 of the present invention.
[0023] Figure 6 These are scanning electron microscope images of dodecacarbonyltriruthenium in Examples 1-11 of this invention.
[0024] Figure 7 This is an electrocatalytic efficiency diagram of samples 1, 2, 3, 4, and 5 in the embodiments of the present invention.
[0025] Figure 8 These are the electrochemical impedance spectroscopy diagrams of samples 1, 2, 3, 4, and 5 in the embodiments of this invention.
[0026] Figure 9 This is an electrocatalytic efficiency diagram of samples 1, 6, 7 and 8 in the embodiments of the present invention.
[0027] Figure 10 This is an electrocatalytic efficiency diagram of samples 1, 9, 10, and 11 in the embodiments of the present invention.
[0028] Figure 11 This is an electrocatalytic efficiency diagram of samples 1, 12, 13, and 14 in the embodiments of the present invention.
[0029] Figure 12 This is an electrocatalytic efficiency diagram of samples 1 and 15 in the embodiments of the present invention.
[0030] Figure 13 This is an electrocatalytic efficiency diagram of samples 1, 16, 17, and 18 in the embodiments of the present invention.
[0031] Figure 14 This is the XRD pattern of RuCO-CP and sample 1 in Embodiment 1 of the present invention. Detailed Implementation
[0032] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. The description is for explanation and not limitation of the present invention.
[0033] In the following examples, the carbon paper used is a relatively hydrophilic carbon paper manufactured by Suzhou Shengernuo Technology Co., Ltd., brand name Toray, model TGP-H-060. The dodecyltriruthenium is manufactured by Bitmain Pharmaceuticals, with a purity of 98%.
[0034] Example 1: 20 mg of dodecacarbonyltriruthenium was dissolved in 15 mL of dichloromethane and sonicated for 10 min at a frequency of 40 kHz and a power of 500 W. The homogenized solution was then loaded with 1.5 mg onto a 1 × 1 cm⁻¹ plate using a spray gun.-2 The sample was labeled RuCO-CP on carbon paper. Sample 1 was obtained by carbonizing RuCO-CP using direct laser scribing with three laser parameters: 8.78 W laser power, 250 mm / s laser scan speed, and 30 kHz laser frequency.
[0035] Example 2: 20 mg of dodecacarbonyltriruthenium was dissolved in 15 mL of dichloromethane and sonicated for 10 min at a frequency of 40 kHz and a power of 500 W. The homogenized solution was then loaded with 1.5 mg onto a 1 × 1 cm⁻¹ plate using a spray gun. -2 The sample was labeled RuCO-CP on carbon paper. Sample 2 was obtained by carbonizing RuCO-CP using direct laser scribing with three laser parameters: 3.99 W laser power, 250 mm / s laser scan speed, and 30 kHz laser frequency.
[0036] Example 3: 20 mg of dodecacarbonyltriruthenium was dissolved in 15 mL of dichloromethane and sonicated for 10 min at a frequency of 40 kHz and a power of 500 W. The homogenized solution was then loaded with 1.5 mg onto a 1 × 1 cm⁻¹ plate using a spray gun. -2 The sample was labeled RuCO-CP on carbon paper. Sample 3 was obtained by carbonizing RuCO-CP using direct laser scribing with three laser parameters: 5.59 W laser power, 250 mm / s laser scan speed, and 30 kHz laser frequency.
[0037] Example 4: 20 mg of dodecacarbonyltriruthenium was dissolved in 15 mL of dichloromethane and sonicated for 10 min at a frequency of 40 kHz and a power of 500 W. The homogenized solution was then loaded with 1.5 mg onto a 1 × 1 cm⁻¹ plate using a spray gun. -2 The sample was labeled RuCO-CP on carbon paper. Sample 4 was obtained by carbonizing RuCO-CP using direct laser scribing with three laser parameters: 7.19 W laser power, 250 mm / s laser scan speed, and 30 kHz laser frequency.
[0038] Example 5: 20 mg of dodecacarbonyltriruthenium was dissolved in 15 mL of dichloromethane and sonicated for 10 min at a frequency of 40 kHz and a power of 500 W. The homogenized solution was then loaded with 1.5 mg onto a 1 × 1 cm⁻¹ plate using a spray gun. -2The sample was labeled RuCO-CP on carbon paper. Sample 5 was obtained by carbonizing RuCO-CP using direct laser scribing with three laser parameters: 10.38 W laser power, 250 mm / s laser scan speed, and 30 kHz laser frequency.
[0039] Example 6: 20 mg of dodecacarbonyltriruthenium was dissolved in 15 mL of dichloromethane and sonicated for 10 min at a frequency of 40 kHz and a power of 500 W. The homogenized solution was then loaded with 1.5 mg onto a 1 × 1 cm⁻¹ plate using a spray gun. -2 The sample was labeled RuCO-CP on carbon paper. Sample 6 was obtained by carbonizing RuCO-CP using direct laser scribing with three laser parameters: 8.78 W laser power, 150 mm / s laser scan speed, and 30 kHz laser frequency.
[0040] Example 7: 20 mg of dodecacarbonyltriruthenium was dissolved in 15 mL of dichloromethane and sonicated for 10 min at a frequency of 40 kHz and a power of 500 W. The homogenized solution was then loaded with 1.5 mg onto a 1 × 1 cm⁻¹ plate using a spray gun. -2 The sample was labeled RuCO-CP on carbon paper. Sample 7 was obtained by carbonizing RuCO-CP using direct laser scribing with three laser parameters: 8.78 W laser power, 350 mm / s laser scan speed, and 30 kHz laser frequency.
[0041] Example 8: 20 mg of dodecacarbonyltriruthenium was dissolved in 15 mL of dichloromethane and sonicated for 10 min at a frequency of 40 kHz and a power of 500 W. The homogenized solution was then loaded with 1.5 mg onto a 1 × 1 cm⁻¹ plate using a spray gun. -2 The sample was labeled RuCO-CP on carbon paper. Sample 8 was obtained by carbonizing RuCO-CP using direct laser scribing with three laser parameters: 8.78 W laser power, 450 mm / s laser scan speed, and 30 kHz laser frequency.
[0042] Example 9: 20 mg of dodecacarbonyltriruthenium was dissolved in 15 mL of dichloromethane and sonicated for 10 min at a frequency of 40 kHz and a power of 500 W. The homogenized solution was then loaded with 1.5 mg onto a 1 × 1 cm⁻¹ plate using a spray gun. -2The sample was labeled RuCO-CP on carbon paper. Sample 9 was obtained by carbonizing RuCO-CP using direct laser scribing with three laser parameters: 8.78 W laser power, 250 mm / s laser scan speed, and 10 kHz laser frequency.
[0043] Example 10: 20 mg of dodecacarbonyltriruthenium was dissolved in 15 mL of dichloromethane and sonicated for 10 min at a frequency of 40 kHz and a power of 500 W. The homogenized solution was then loaded with 1.5 mg onto a 1 × 1 cm⁻¹ plate using a spray gun. -2 The sample was labeled RuCO-CP on carbon paper. Sample 10 was obtained by carbonizing RuCO-CP using direct laser scribing with three laser parameters: 8.78 W laser power, 250 mm / s laser scan speed, and 20 kHz laser frequency.
[0044] Example 11: 20 mg of dodecacarbonyltriruthenium was dissolved in 15 mL of dichloromethane and sonicated for 10 min at a frequency of 40 kHz and a power of 500 W. The homogenized solution was then loaded with 1.5 mg onto a 1 × 1 cm⁻¹ plate using a spray gun. -2 The sample was labeled RuCO-CP on carbon paper. Sample 11 was obtained by carbonizing RuCO-CP using direct laser scribing with three laser parameters: 8.78 W laser power, 250 mm / s laser scan speed, and 40 kHz laser frequency.
[0045] Example 12: 10 mg of dodecacarbonyltriruthenium was dissolved in 15 mL of dichloromethane and sonicated for 10 min at a frequency of 40 kHz and a power of 500 W. The homogenized solution was then loaded with 1.5 mg onto a 1 × 1 cm⁻¹ plate using a spray gun. -2 The sample was labeled RuCO-CP on carbon paper. Sample 12 was obtained by carbonizing RuCO-CP using direct laser scribing with three laser parameters: 8.78 W laser power, 250 mm / s laser scan speed, and 30 kHz laser frequency.
[0046] Example 13: 10 mg of dodecacarbonyltriruthenium was dissolved in 22.5 mL of dichloromethane and sonicated for 10 min at a frequency of 40 kHz and a power of 500 W. The homogenized solution was then loaded with 1.5 mg onto a 1 × 1 cm⁻¹ plate using a spray gun. -2The sample was labeled RuCO-CP on carbon paper. Sample 13 was obtained by carbonizing RuCO-CP using direct laser scribing with three laser parameters: 8.78 W laser power, 250 mm / s laser scan speed, and 30 kHz laser frequency.
[0047] Example 14: 10 mg of dodecacarbonyltriruthenium was dissolved in 37.5 mL of dichloromethane and sonicated for 10 min at a frequency of 40 kHz and a power of 500 W. The homogenized solution was then loaded with 1.5 mg onto a 1 × 1 cm⁻¹ plate using a spray gun. -2 The sample was labeled RuCO-CP on carbon paper. Sample 14 was obtained by carbonizing RuCO-CP using direct laser scribing with three laser parameters: 8.78 W laser power, 250 mm / s laser scan speed, and 30 kHz laser frequency.
[0048] Example 15: 20 mg of dodecacarbonyltriruthenium was dissolved in 15 mL of dichloromethane and sonicated for 10 min at a frequency of 40 kHz and a power of 500 W. The homogenized solution was then loaded with 1.5 mg onto a 1 × 1 cm⁻¹ plate using a spray gun. -2 The nickel felt was labeled RuCO-CP. Sample 15 was obtained by carbonizing RuCO-CP using direct laser scribing with three laser parameters: 8.78 W laser power, 250 mm / s laser scan speed, and 30 kHz laser frequency.
[0049] Example 16: 20 mg of triruthenium dodecylcarbonyl was dissolved in 15 mL of xylene and sonicated for 10 min at a frequency of 40 kHz and a power of 500 W. The homogenized solution was then loaded with 1.5 mg onto a 1 × 1 cm⁻¹ plate using a spray gun. -2 The sample was labeled RuCO-CP on carbon paper. Sample 16 was obtained by carbonizing RuCO-CP using direct laser scribing with three laser parameters: 8.78 W laser power, 250 mm / s laser scan speed, and 30 kHz laser frequency.
[0050] Example 17: 20 mg of dodecyltriruthenium dodecylcarbonyl was dissolved in 15 mL of toluene and sonicated for 10 min at a frequency of 40 kHz and a power of 500 W. The homogenized solution was then loaded with 1.5 mg onto a 1 × 1 cm⁻¹ plate using a spray gun. -2The sample was labeled RuCO-CP on carbon paper. Sample 17 was obtained by carbonizing RuCO-CP using direct laser scribing with three laser parameters: 8.78 W laser power, 250 mm / s laser scan speed, and 30 kHz laser frequency.
[0051] Example 18: 20 mg of dodecacarbonyltriruthenium was dissolved in 15 mL of diethyl ether and sonicated for 10 min at a frequency of 40 kHz and a power of 500 W. The homogenized solution was then loaded with 1.5 mg onto a 1 × 1 cm⁻¹ plate using a spray gun. -2 The sample was labeled RuCO-CP on carbon paper. Sample 18 was obtained by carbonizing RuCO-CP using direct laser scribing with three laser parameters: 8.78 W laser power, 250 mm / s laser scan speed, and 30 kHz laser frequency.
[0052] Example 19
[0053] Untreated dodecyltriruthenium carbonyl powder was fixed on the sample stage, and an FESEM-cold field scanning electron microscope SU8100 was used with an accelerating voltage of 15 kV and a working distance of 15 mm to obtain... Figure 6 The scanning electron microscope image shown indicates that the morphology of the obtained dodecyltriruthenium carbonyl is an irregular blocky aggregate.
[0054] Samples 1, 2, 3, 4, and 5 were fixed on the sample stage. Using a FESEM-cold field scanning electron microscope SU8100, with an accelerating voltage of 15 kV and a working distance of 15 mm, the morphology of the laser-scribed area was observed, and the results are as follows: Figures 1-5 The scanning electron microscope (SEM) image shown is shown below. In the SEM image, the morphology of the sample in the laser-scribed area is a highly uniform dispersion of a large number of spherical nanoparticles on a three-dimensional framework of porous carbon support, exhibiting a network structure.
[0055] Example 20
[0056] Linear scan performance tests were performed on an electrochemical workstation (model: VSP). Samples 1, 2, 3, 4, and 5 were used as working electrodes, a C rod as the counter electrode, an Hg / HgO electrode as the reference electrode, and a 1 M KOH solution as the electrolyte. The scan rate was 20 mV / s. The resulting electrocatalytic efficiency graph is shown below. Figure 7 As shown in the figure, Table 1 displays the performance of samples 1-18 at -10 mA / cm². 2The overpotential at a current density shows that all tested samples exhibit high activity, and the different laser powers have a certain impact on the final sample performance. Among them, sample 1, which was treated with a laser power of 8.78 W, formed more highly active substances, and at -10 mA cm⁻¹ -2 The overpotential at the current density is 33 mV.
[0057] Table 1:
[0058] Electrochemical impedance spectroscopy (EIS) tests were performed on samples 1, 2, 3, 4, and 5 under the same system conditions. The open-circuit potential was -1.1 mV, the AC perturbation amplitude was 10 mV, the frequency range was 100 kHz – 10 mHz, and the data acquisition density was 20. The resulting electrochemical impedance spectroscopy plots are shown below. Figure 8 As shown in the figure, the impedance of all the tested samples meets the requirements of the electrode material (as shown in Table 2). The impedance of the samples after being treated with 8.78 W laser power decreased, and the impedance first decreased and then increased with the increase of laser power. The impedance value of sample 1 was the smallest.
[0059] Table 2:
[0060] Example 21
[0061] To investigate the effect of laser scan rate on sample activity and impedance, electrocatalytic efficiency and electrochemical impedance spectroscopy were performed on samples 1, 6, 7, and 8 under the same conditions as in Example 20. The results are as follows: Figure 9 As shown in the figure, different laser scanning speeds have a certain impact on the performance of the final sample. Sample 1, which is treated with a laser scanning speed of 250 mm / s, forms more highly active substances, and its performance is within -10 mA cm⁻¹. -2 The overpotential at the current density is 33 mV.
[0062] The electrochemical impedance spectroscopy results for samples 1, 6, 7, and 8 are as follows: Figure 10 As shown in the figure, different laser frequencies have a certain impact on the performance of the final sample. Sample 1, which is treated with a laser frequency of 30 kHz, forms more highly active substances at -10 mA cm⁻¹. -2 The overpotential at the current density is 33 mV.
[0063] Example 22
[0064] To investigate the effect of laser scanning speed on the activity and impedance of the samples, electrocatalytic efficiency tests were performed on samples 1, 12, 13 and 14 under the same conditions as in Example 20. Figure 11 The figure shows the electrocatalytic efficiency of samples 1, 12, 13, and 14. It can be seen from the figure that different solution concentrations have a certain impact on the final sample performance. Sample 1, prepared with a 0.002 M solution, exhibits the best performance at -10 mA cm⁻¹. -2 The overpotential at the current density is 33 mV.
[0065] Example 23
[0066] To investigate the effect of carrier type on sample activity and impedance, electrocatalytic efficiency tests were performed on samples 1 and 15 under the same conditions as in Example 20. Figure 12 The graphs show the electrocatalytic efficiency of samples 1 and 15. As can be seen from the graphs, the different conductive substrates have a certain impact on the final sample performance. Sample 1, which uses carbon paper as the conductive substrate, exhibits the best performance at -10 mA cm⁻¹. -2 The overpotential at the current density is 33 mV.
[0067] Example 24
[0068] To investigate the effect of organic solvents on the activity and impedance of samples in step (1), electrocatalytic efficiency tests were performed on samples 1, 16, 17 and 18 under the same conditions as in Example 20. Figure 13 The graphs show the electrocatalytic efficiency of samples 1, 16, 17, and 18. As can be seen from the graphs, the different organic solvents have a certain impact on the final sample performance. Sample 1, using dichloromethane as the organic solvent, exhibits the best performance at -10 mA cm⁻¹. -2 The overpotential at the current density is 33mV.
[0069] Example 25
[0070] The structures of RuCO-CP and sample 1 were analyzed using an X-ray diffractometer (model: DX-27mini, Netherlands). The radiation source was Cu Kα (λ = 0.15406 nm), with an operating voltage and current of 40 kV and 40 mA, respectively. The scanning range (2θ) was 5° to 80°, and the scanning speed was 20° / min. The obtained XRD patterns are shown below. Figure 14 As shown in the figure, the characteristic peaks of dodecacarbonyl-3ruthenium disappear after carbonization treatment using direct laser scribing, and the characteristic peaks of elemental ruthenium appear. This indicates that transforming a low-activity carbonyl-ruthenium compound into a highly active elemental ruthenium nanoparticle exhibits highly efficient catalytic activity.
Claims
1. A laser preparation method for a ruthenium-based water electrolysis hydrogen production electrode material, characterized in that... The preparation of the aforementioned electrocatalytic material for hydrogen evolution includes the following steps: (1) Preparation of dodecyltriruthenium precursor solution: Dodecyltriruthenium was dissolved in an organic solvent and ultrasonically dissolved to obtain a dodecyltriruthenium solution with a final concentration of 0.00042-0.002M; (2) Preparation of L-Ru: The dodecyltriruthenium carbonyl solution obtained in step (1) is uniformly sprayed onto the surface of a conductive support. After the organic solvent evaporates, the resulting material is denoted as RuCO-CP. The RuCO-CP is treated by direct laser scribing to obtain the catalytic material for the hydrogen evolution reaction, denoted as L-Ru. The parameters for direct laser scribing are as follows: laser power 3.99-10.38 W, laser scanning speed 150-450 mm / s, and laser frequency 10-40 kHz.
2. The laser preparation method of the ruthenium-based electrolytic water electrolysis electrode material as described in claim 1, characterized in that, The organic solvent mentioned in step (1) is one of toluene, xylene, dichloromethane, and diethyl ether.
3. The laser preparation method for the ruthenium-based electrolytic water electrolysis electrode material as described in claim 2, characterized in that, The organic solvent is dichloromethane.
4. The laser preparation method of the ruthenium-based electrolytic water electrolysis electrode material as described in claim 1, characterized in that, In step (2), the conductive carrier is either carbon paper or nickel felt.
5. The laser preparation method of the ruthenium-based electrolytic water electrolysis hydrogen production electrode material as described in claim 1, characterized in that, Step (2) recommends adding 1.5 mg / cm³ of the dodecacarbonyltriruthenium solution to the conductive support surface. -2 .
6. The laser preparation method of the ruthenium-based electrolytic water electrolysis hydrogen production electrode material as described in claim 1, characterized in that, In step (1), the ultrasonic dissolution time is 10 min, the ultrasonic frequency is 40KHz, and the ultrasonic power is 500W.
7. The laser preparation method of the ruthenium-based electrolytic water electrolysis electrode material as described in claim 1, characterized in that, In step (2), the parameters for direct laser scribing are set as follows: laser power 8.78 W, laser scanning speed 250 mm / s, and laser frequency 30 kHz.
8. The ruthenium-based electrode material for hydrogen production by water electrolysis prepared by the preparation method according to any one of claims 1 to 7.
9. The application of the ruthenium-based electrode material for hydrogen production by water electrolysis prepared by any one of claims 1 to 7 in hydrogen production by water electrolysis.
10. The application of the ruthenium-based water electrolysis hydrogen production electrode material as described in claim 9 in water electrolysis hydrogen production, wherein the application is to carry out the water electrolysis hydrogen production reaction in 1M KOH solution, the reference electrode is an Hg / HgO electrode, the counter electrode is a C rod, and the ruthenium-based water electrolysis hydrogen production material is the working electrode.