CoMoSe4-P-coated NF electrocatalyst and preparation method and application thereof
By preparing CoMoSe4-P@NF electrocatalyst on a foam nickel substrate, the cost of precious metal catalysts is solved, low-cost and efficient full-water electrocatalytic is achieved, and the efficiency of oxygen evolution and hydrogen evolution reactions is improved. It is suitable for large-scale electrolysis of water and hydrogen evolution.
Patent Information
- Application Number
- CN202510565543.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-30
- Publication Date
- 2025-07-29
AI Technical Summary
The existing precious metal-based catalysts are expensive, and the comprehensive performance does not reach an ideal state in the process of fully water-removing hydrogen production, making it difficult to achieve large-scale industrial applications.
The CoMoSe4-P@NF electrocatalyst was prepared by a combination of hydrothermal and high-temperature calcination. By forming a uniform rectangular nanorod structure on the foamed nickel substrate, phosphorus atoms were introduced to improve surface polarity and electron transport capability.
It realizes low-cost and efficient full-water electrocatalysis, reduces the energy consumption of hydrogen production by electrolyzing water, improves the efficiency of oxygen evolution and hydrogen evolution reactions, and has good stability and conductivity.
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Figure CN120384305A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of electrocatalytic materials, and more specifically, to a CoMoSe4-P@NF electrocatalyst and its preparation method and application. Background Art
[0002] With the continuous reduction of the reserves of traditional fossil fuels such as petroleum, coal, and natural gas, as well as the challenges brought about by environmental pollution problems, finding clean and efficient new energy carriers has become an issue that humanity must face in its development.
[0003] Hydrogen, with zero pollution, high energy density, an ultra-high calorific value of 143 MJ / kg (equivalent to three times that of gasoline), and a technical path that can achieve a closed cycle through the electrolysis of renewable energy water, has been defined by the International Hydrogen Energy Council as the "ultimate clean energy carrier in the 21st century" and has become the most ideal energy method. Among common hydrogen production methods, hydrogen production by electrolyzing water is expected to become a hydrogen production method for large-scale industries due to its characteristics of low pollution, independence from fossil fuels, simple equipment, and easy maintenance.
[0004] The core mechanism of the overall water splitting hydrogen production technology stems from the electrochemical action of the electrolytic cell, and its total working voltage is composed of the theoretical decomposition voltage and the system impedance voltage drop. As a key performance parameter, the value of this total voltage directly determines the energy consumption level during the hydrogen production process. When using linear sweep voltammetry for testing, both the anodic oxygen evolution reaction (OER) and the cathodic hydrogen evolution reaction (HER) need to overcome significant activation energy barriers. Through surface functionalization treatment of the electrode material, the reaction barriers of the anode and cathode can be effectively reduced, thereby significantly improving the overall catalytic efficiency.
[0005] Although the platinum-based (Pt / C) and ruthenium-based (RuO2) catalysts commonly used in the current commercial system perform excellently in single oxygen evolution or hydrogen evolution reactions, their industrial applications face two challenges: on the one hand, the high cost of noble metal-based materials restricts large-scale production; on the other hand, the comprehensive efficiency in the overall water splitting co-catalysis has not yet reached an ideal state.
[0006] Therefore, developing new composite electrode materials with simple preparation processes, economic advantages, high catalytic activity, and excellent electrical conductivity has become an important research direction for improving the practical level of the overall water splitting hydrogen production technology. Summary of the Invention
[0007] In view of this, the purpose of the present invention is to provide a CoMoSe4-P@NF electrocatalyst and its preparation method and application to solve the deficiencies in the prior art.
[0008] To achieve the above purpose, the present invention adopts the following technical solutions:
[0009] A preparation method of CoMoSe4-P@NF electrocatalyst specifically includes the following steps:
[0010] (1) Ultrasonically disperse nickel foam in acetone, hydrochloric acid, and anhydrous ethanol solutions in sequence, then dry to obtain pretreated nickel foam for standby.
[0011] (2) Mix cobalt nitrate hexahydrate, ammonium molybdate tetrahydrate, and selenium powder, dissolve them in water, and stir to obtain a mixed salt solution.
[0012] (3) Conduct a hydrothermal reaction on nickel foam and the mixed salt solution, wash, dry, and calcine to obtain a CoMoSe4@NF precursor.
[0013] (4) Calcinate the CoMoSe4@NF precursor and a phosphorus source, cool to room temperature, wash, and dry to obtain the CoMoSe4-P@NF electrocatalyst.
[0014] Further, in the above step (1), the concentration of hydrochloric acid is 1.0 M; the volume ratio of acetone, hydrochloric acid, and anhydrous ethanol is 1:1:(1.0 - 3.0); the ultrasonic dispersion time is 10 - 30 min; the drying equipment is a vacuum drying oven, with a temperature of 30 - 80 °C and a time of 8 - 18 h.
[0015] The beneficial effect of the above is that through ultrasonic dispersion, the surface oxides and other impurities of nickel foam can be removed.
[0016] Further, in the above step (2), the mass ratio of cobalt nitrate hexahydrate to ammonium molybdate tetrahydrate is 1:(1 - 2); the sum of the amounts of substances of cobalt nitrate hexahydrate and ammonium molybdate tetrahydrate is 6; the sum of the concentrations of cobalt ions in cobalt nitrate hexahydrate and molybdenum ions in ammonium molybdate tetrahydrate is 0.08 - 0.13 mol / L; the dosage ratio of selenium powder to water is 5 - 10 mmol:60 mL; the stirring temperature is room temperature, the stirring method is magnetic stirring, and the time is 10 - 30 min.
[0017] The beneficial effect of the above is that selenium (Se) atoms have a strong electron donor effect, which can induce the formation of a new electron cloud distribution on the catalyst surface, helping to enhance the adsorption of key intermediates (such as *OOH).
[0018] Further, in the above step (3), the hydrothermal reaction equipment is a polytetrafluoroethylene hydrothermal autoclave, with a temperature of 120 - 200 °C and a time of 4 - 10 h; wash until the pH is neutral; the drying method is vacuum drying, with a temperature of 60 °C and a time of 12 h; the calcination equipment is a muffle furnace, with a temperature of 200 - 400 °C and a time of 1 - 3 h.
[0019] Further, in the above step (4), the phosphorus source is sodium hypophosphite monohydrate; the mass ratio of the CoMoSe4@NF precursor to the phosphorus source is (0.1 - 0.5):1; the calcination equipment is a tube furnace, the atmosphere is argon, the heating rate is 0.5 - 5 °C / min, the temperature is 200 - 500 °C, the time is 1 - 3 h; the cooling rate when cooling to room temperature is 0.5 - 5 °C / min; the washing reagents are deionized water and absolute ethanol; the drying method is vacuum drying, the temperature is 60 °C, and the time is 12 h.
[0020] The beneficial effect of the above further is that the introduction of phosphorus (P) atoms can significantly improve the surface polarity of the material and promote the adsorption and dissociation of water molecules on the catalyst surface. At the same time, the P treatment also helps to improve the material stability and electron transport ability, thus well compensating for the deficiencies of metal selenides in electrocatalysis.
[0021] The present invention also claims a CoMoSe4-P@NF electrocatalyst prepared by the above preparation method.
[0022] The present invention also claims an application of the CoMoSe4-P@NF electrocatalyst prepared by the above preparation method in overall water splitting electrocatalysis.
[0023] The present invention also claims an application of the CoMoSe4-P@NF electrocatalyst prepared by the above preparation method in the preparation of overall water splitting electrocatalytic equipment.
[0024] An overall water splitting electrocatalytic equipment is composed of an electrochemical workstation, an electrolytic cell, a working electrode, a counter electrode and a reference electrode. Among them, the working electrode uses the CoMoSe4-P@NF electrocatalyst prepared by the above preparation method.
[0025] Further, the electrolyte in the above electrolytic cell is a KOH solution with a concentration of 1.0 mol / L; the working electrode uses nickel foam as the substrate; the counter electrode uses a carbon rod; the reference electrode uses mercury / mercuric oxide.
[0026] At the same time, pure O2 needs to be introduced into the electrolyte to make it reach the oxygen saturation state, and the time for introducing O2 is 20 - 60 min.
[0027] The method of overall water splitting electrocatalysis mainly uses linear sweep voltammetry, and the relevant detection parameters are as follows: the standing time is set to 1 - 10 s, the scanning rate is 0.5 - 100 mV / s, the scanning range is 1.0 - 2.2.2 V, and the overpotential is 200 - 550 mV.
[0028] It can be seen from the above technical solutions that compared with the prior art, the beneficial effects of the present invention are as follows:
[0029] 1. The CoMoSe4-P@NF electrocatalyst was synthesized by a method combining hydrothermal treatment and high-temperature calcination. This material has the characteristics of uniform and regular morphology (cuboid nanorod structure), uniform element distribution, and good electrochemical performance. It can not only achieve efficient electrocatalysis for overall water splitting, including the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER), but also has the advantages of low cost, mild reaction conditions, good stability, and low resistivity.
[0030] 2. The CoMoSe4-P@NF electrocatalyst prepared in this invention was used to replace commercial nanoelectrode materials such as Pt / c and RuO2 for overall water splitting electrocatalysis, achieving a new breakthrough in efficient and low-cost overall water splitting technology, and providing a technical path with high efficiency, economy, and engineering applicability for large-scale electrolytic water hydrogen production.
[0031] 3. The preparation method of this invention has the advantages of easy reaction condition control, simple equipment, and low cost. BRIEF DESCRIPTION OF THE DRAWINGS
[0032] Figure 1 XRD pattern of the CoMoSe4-P@NF electrocatalyst prepared in Example 1;
[0033] Figure 2 TEM image of the CoMoSe4-P@NF electrocatalyst prepared in Example 1;
[0034] Figure 3 Physical picture of the equipment for overall water splitting electrocatalysis using the CoMoSe4-P@NF electrocatalyst prepared in Example 1;
[0035] Figure 4 Current-potential change curve of overall water splitting electrocatalysis of the CoMoSe4-P@NF electrocatalyst prepared in Example 1 at 1 - 2.2 V (V vs. RHE);
[0036] Figure 5 Current-potential change curve of the oxygen evolution reaction (OER) of the CoMoSe4-P@NF electrocatalyst prepared in Example 1 at 0 - 1 V (V vs. RHE);
[0037] Figure 6 Current-potential change curve of the hydrogen evolution reaction (HER) of the CoMoSe4-P@NF electrocatalyst prepared in Example 1 at -1.5 to -1 V (V vs. RHE). DETAILED DESCRIPTION OF THE INVENTION
[0038] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.
[0039] Example 1
[0040] A preparation method of CoMoSe4-P@NF electrocatalyst specifically includes the following steps:
[0041] (1) First, disperse nickel foam in acetone, 1.0 M hydrochloric acid, and anhydrous ethanol solution with a volume ratio of 1:1:(1.0 - 3.0) respectively, and ultrasonically treat for 10 - 30 min. Then place it in a vacuum drying oven and dry at 30 - 80 °C for 8 - 18 h to obtain pretreated nickel foam for standby;
[0042] (2) First, weigh cobalt nitrate hexahydrate and ammonium molybdate tetrahydrate according to the sum of the concentrations of cobalt ions and molybdenum ions being 0.08 - 0.13 mol / L, then mix with 5 - 10 mmol selenium powder, dissolve in 60 mL deionized water, and magnetically stir at room temperature for 10 - 30 min to obtain a mixed salt solution;
[0043] Among them, the mass ratio of cobalt nitrate hexahydrate to ammonium molybdate tetrahydrate is 1:(1 - 2);
[0044] The sum of the amounts of substance of cobalt nitrate hexahydrate and ammonium molybdate tetrahydrate is 6;
[0045] (3) First, place nickel foam and the mixed salt solution in a 100 mL polytetrafluoroethylene hydrothermal autoclave, carry out hydrothermal reaction at 120 - 200 °C for 4 - 10 h, then wash until the pH is neutral, then place it in a vacuum drying oven and dry at 60 °C for 12 h. Finally, place it in a muffle furnace and calcine at 200 - 400 °C for 1 - 3 h to obtain a CoMoSe4@NF precursor;
[0046] (4) First, place 0.1 g of CoMoSe4@NF precursor in a tubular furnace, place 1.0 g of sodium hypophosphite monohydrate as a phosphorus source upstream of the tubular furnace gas, heat it to 200 - 500 °C at a rate of 0.5 - 5 °C / min in an argon atmosphere and calcine for 1 - 3 h, then cool it to room temperature at a rate of 0.5 - 5 °C / min, then wash with deionized water and anhydrous ethanol, and finally place it in a vacuum drying oven and dry at 60 °C for 12 h to obtain the CoMoSe4-P@NF electrocatalyst.
[0047] Comparative Example 1
[0048] The CoMoSe4@NF precursor was prepared in the same way as in Example 1, except that step (4) was not included.
[0049] Comparative Example 2
[0050] The CoMoO4-P@NF electrocatalyst was prepared in the same way as in Example 1, except that selenium powder was not included in step (2).
[0051] Comparative Example 3
[0052] The CoMoO4-PS@NF electrocatalyst was prepared in the same way as in Example 1, except that selenium powder was not included in step (2), and 1.0 g of sodium hypophosphite monohydrate and 0.6 g of selenium powder were placed upstream of the tube furnace gas as the phosphorus source and selenium source respectively in step (4).
[0053] Performance test
[0054] 1. XRD and TEM characterization
[0055] It can be seen from Figure 1 that the CoMoSe4-P@NF electrocatalyst was successfully synthesized in Example 1.
[0056] It can be seen from Figure 2 that the P element was uniformly dispersed on the surface of the CoMoSe4-P@NF electrocatalyst, and the morphology of the CoMoSe4-P@NF electrocatalyst was a cuboid nanorod structure.
[0057] 2. Overall water splitting electrocatalysis test
[0058] The CoMoSe4-P@NF working electrode material prepared in Example 1 was used for overall water splitting electrocatalysis.
[0059] As Figure 3 shown, the overall water splitting electrocatalysis device mainly adopted a three-electrode system, which consisted of an electrochemical workstation, an electrolytic cell, a working electrode, a counter electrode and a reference electrode; a carbon rod was used as the counter electrode, mercury / mercuric oxide was used as the reference electrode, and the working electrode was the CoMoSe4-P@NF electrocatalyst prepared in Example 1 (the area immersed in the electrolyte was 1 cm -2 ), the electrolyte was a KOH solution with a concentration of 1.0 mol / L, and pure O2 was introduced to make it reach oxygen saturation, and the time for introducing O2 was 20 min.
[0060] The method of overall water splitting electrocatalysis mainly adopted linear sweep voltammetry, and the relevant detection parameters were as follows: the standing time was set to 10 s, the scanning rate was 0.5 mV / s, the scanning range was 1.0 - 2.2 V, and its overpotential was 343 mV.
[0061] The results are as Figures 4-6 shown.
[0062] It can be seen from Figure 4 that the current density of the CoMoSe4-P@NF electrocatalyst prepared in Example 1 for the overall water splitting reaction in an alkaline environment is 10 mA cm -2 (common benchmark), and the water splitting voltage is only 1.573 V, which greatly improves the energy conversion efficiency of hydrogen production by electrolyzing water.
[0063] It can be seen from Figure 5 that the CoMoSe4-P@NF electrocatalyst prepared in Example 1 has a low overpotential of 194 mV at a current density of 10 mA cm -2 . The smaller the overpotential, the higher the OER reaction efficiency of the catalyst.
[0064] It can be seen from Figure 6 that the CoMoSe4-P@NF electrocatalyst prepared in Example 1 has an overpotential of 114 mV at a current density of 10 mA cm -2 , which is comparable to that of commercial Pt / C (100 mV). The smaller the overpotential, the higher the HER reaction efficiency of the catalyst.
[0065] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to these embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A preparation method of CoMoSe4-P@NF electrocatalyst, characterized in that, Specifically, it includes the following steps: (1) Ultrasonically disperse nickel foam in acetone, hydrochloric acid, and absolute ethanol solutions in sequence, and dry to obtain pretreated nickel foam for standby; (2) Mix cobalt nitrate hexahydrate, ammonium molybdate tetrahydrate, and selenium powder, dissolve them in water, and stir to obtain a mixed salt solution; (3) Conduct a hydrothermal reaction on nickel foam and the mixed salt solution, wash, dry, and calcine to obtain a CoMoSe4@NF precursor; (4) Calcinate the CoMoSe4@NF precursor and a phosphorus source, cool to room temperature, wash, and dry to obtain the CoMoSe4-P@NF electrocatalyst.
2. The preparation method of a CoMoSe4-P@NF electrocatalyst according to claim 1, characterized in that, In step (1), the concentration of the hydrochloric acid is 1.0 M; the volume ratio of acetone, hydrochloric acid, and absolute ethanol is 1:1:(1.0 - 3.0); the time for ultrasonic dispersion is 10 - 30 min; the drying equipment is a vacuum drying oven, with a temperature of 30 - 80 °C and a time of 8 - 18 h.
3. The preparation method of a CoMoSe4-P@NF electrocatalyst according to claim 1, characterized in that, In step (2), the mass ratio of cobalt nitrate hexahydrate to ammonium molybdate tetrahydrate is 1:(1 - 2); the sum of the amounts of substances of cobalt nitrate hexahydrate and ammonium molybdate tetrahydrate is 6; the sum of the concentrations of cobalt ions in cobalt nitrate hexahydrate and molybdenum ions in ammonium molybdate tetrahydrate is 0.08 - 0.13 mol / L; the dosage ratio of selenium powder to water is 5 - 10 mmol:60 mL; the stirring temperature is room temperature, the stirring method is magnetic stirring, and the time is 10 - 30 min.
4. The preparation method of a CoMoSe4-P@NF electrocatalyst according to claim 1, wherein, In step (3), the hydrothermal reaction equipment is a polytetrafluoroethylene hydrothermal autoclave, with a temperature of 120 - 200 °C and a time of 4 - 10 h; wash until the pH is neutral; the drying method is vacuum drying, with a temperature of 60 °C and a time of 12 h; the calcination equipment is a muffle furnace, with a temperature of 200 - 400 °C and a time of 1 - 3 h.
5. The preparation method of a CoMoSe4-P@NF electrocatalyst according to claim 1, characterized in that, In step (4), the phosphorus source is sodium hypophosphite monohydrate; the mass ratio of the CoMoSe4@NF precursor to the phosphorus source is (0.1 - 0.5):1; the calcination equipment is a tube furnace, the atmosphere is argon, the heating rate is 0.5 - 5 °C / min, the temperature is 200 - 500 °C, and the time is 1 - 3 h; the cooling rate for cooling to room temperature is 0.5 - 5 °C / min; the washing reagents are deionized water and absolute ethanol; the drying method is vacuum drying, with a temperature of 60 °C and a time of 12 h.
6. A CoMoSe4-P@NF electrocatalyst prepared by the preparation method according to any one of claims 1 - 5.
7. Application of a CoMoSe4-P@NF electrocatalyst prepared by the preparation method according to any one of claims 1 - 5 in overall water splitting electrocatalysis.
8. Application of a CoMoSe4-P@NF electrocatalyst prepared by the preparation method according to any one of claims 1 - 5 in the preparation of an overall water splitting electrocatalytic device.
9. A full hydrolysis electrocatalytic device, which is composed of an electrochemical workstation, an electrolytic cell, a working electrode, a counter electrode and a reference electrode, is characterized in that, The working electrode uses a CoMoSe4-P@NF electrocatalyst prepared by the preparation method according to any one of claims 1 - 5.
10. The all-hydrolysis electrocatalytic device according to claim 9, wherein, The electrolyte in the electrolytic cell is a KOH solution with a concentration of 1.0 mol / L; the working electrode uses nickel foam as the substrate; the counter electrode uses a carbon rod; the reference electrode uses mercury / mercuric oxide.