Preparation method of CoP hydrogen evolution electrocatalyst
By preparing CoP nanoarray electrocatalysts, the problems of high cost and slow reaction rate of existing catalysts have been solved, achieving efficient and stable hydrogen evolution, which is suitable for industrial production.
Patent Information
- Application Number
- CN202511347692.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-19
- Publication Date
- 2025-11-07
AI Technical Summary
Existing HER catalysts, such as platinum-based materials, are scarce and expensive, limiting their application in large-scale industrial production. Furthermore, transition metal-based catalysts are difficult to improve reaction rates in complex electrolyte environments.
CoP nanoarrays were used as electrocatalysts and prepared by thermal phosphating. Their morphology, structure and electronic state were controlled to improve the number of catalytic active sites and electron transport capacity.
It achieves efficient and stable hydrogen evolution, reduces costs, is suitable for both acidic and alkaline electrolytes, and is suitable for large-scale industrial production.
Smart Images
Figure CN120905707A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of new materials, and particularly relates to a CoP electrocatalyst and a preparation method thereof. TECHNICAL BACKGROUND With the rapid development of technological innovation, social productivity has developed rapidly, and technologies such as automated production and artificial intelligence have significantly improved the quality of human life, making people's work and life more convenient and comfortable. However, this has also brought negative effects: non-renewable resources have been rapidly depleted due to overexploitation, forests and mineral resources have been destroyed, and resource depletion has accelerated; industrial and living waste has polluted the environment, air, water and soil quality has declined, and the ecological deterioration is severe. Therefore, people are working hard to explore green and clean energy.
[0002] Green, efficient and sustainable electrocatalytic water splitting technology can convert renewable energy into chemical energy by producing hydrogen and oxygen, which is a key solution to alleviate global environmental problems and energy crisis. Electrolysis of water includes hydrogen evolution reaction (HER) at the cathode and oxygen evolution reaction at the anode. As an important part of renewable energy conversion and storage, HER has also attracted widespread attention. However, the reaction process of HER is limited by the activity and stability of the catalyst, especially in some complex electrolyte environments, the reaction rate is difficult to improve, which to some extent affects the overall efficiency of water electrolysis. Currently, platinum-based materials are considered to be excellent HER electrocatalysts, but such noble metals are scarce in reserves and expensive in price, which seriously restricts their application in large-scale industrial production.
[0003] Therefore, a large number of research work is devoted to designing economical and efficient transition metal-based (Ni, Co, Fe, Cu, Mn, etc.) HER catalysts to replace noble metal-based catalysts, including transition metal oxides / hydroxides, sulfides, selenides, nitrides, phosphides, carbides, etc. Researchers continuously improve the HER catalytic performance of these transition metal-based catalysts by regulating the morphology, structure, electronic state and surface properties of the materials, striving to achieve efficient and stable hydrogen evolution while reducing costs, and promoting the large-scale application of electrocatalytic water splitting technology.
[0004] Transition metal phosphides are an important research direction, and CoP is one of the most concerned. CoP is a compound formed by cobalt and phosphorus, belonging to the transition metal phosphide family. The introduction of phosphorus will cause significant changes in the electronic structure of cobalt. Due to the difference in electronegativity between phosphorus and cobalt, charge transfer will be triggered, causing the d-band center of cobalt to move. This electronic regulation makes the adsorption energy of CoP to the HER reaction intermediate (H*) in the ideal range, with similar catalytic activity to noble metal Pt. At the same time, CoP also has many excellent properties, its cost is much lower than that of platinum-based materials, and it has good electrical conductivity, excellent chemical stability and corrosion resistance, and can maintain good catalytic performance in different electrolytes such as acid and alkali. Compared with single metal phosphides, by regulating the morphology and structure of CoP (such as nanowires, nanosheets, porous structures, etc.) or carrying out doping modification, the number of catalytic active sites and the electronic transmission capacity of CoP can be further optimized, and the HER catalytic performance can be significantly improved. Therefore, CoP as a highly potential HER electrocatalyst has received extensive attention from the scientific community, providing important support for promoting the large-scale application of electrocatalytic water splitting technology. SUMMARY
[0005] In view of the deficiencies of the prior art, the purpose of the present application is to provide a preparation method of CoP hydrogen evolution electrocatalyst.
[0006] To achieve the above purpose, the present application provides the following technical scheme: A preparation method of an electrocatalyst, comprising the following steps: (1) The carbon cloth is sequentially ultrasonically cleaned with acetone, deionized water and ethanol for 15 minutes; 4 mmol of Co(NO3)2·6H2O, 10 mmol of NH4F and 20 mmol of urea are dissolved in 72 ml of deionized water and stirred for 30 min, the solution is poured into a 100 ml polytetrafluoroethylene liner, and then the treated carbon cloth is placed in the solution and then placed in a hydrothermal kettle.
[0007] (2) The hydrothermal kettle is placed in a hydrothermal box at 120±20℃ for 6±1 hours, and then taken out after natural cooling, sequentially cleaned with deionized water and ethanol for 3 times, and then placed in a 60℃ oven for overnight drying to obtain Co(CO3) 0.5 (OH)·0.11H2O / CC.
[0008] (3) Co(CO3) 0.5 (OH)·0.11H2O is converted into CoP by a thermal phosphating method, 150 mg of NaH2PO2·H2O is placed upstream of the quartz tube, and a piece of 2x2 cm 2The precursor is flushed with argon three times after vacuum preservation overnight. The temperature of the tube furnace is raised to 300 DEG C at a rate of 5 DEG C / min, and then the temperature is kept constant for 2 h. After the reaction, the sample is cleaned with deionized water and anhydrous ethanol to remove the impurities on the surface of the sample, and then the sample is placed in an oven at 60 DEG C and dried for 2 h. The obtained sample is CoP / CC.
[0009] Preferably, the molar ratio of the cobalt phosphide is 1:1.
[0010] Preferably, the deionized water is 72 mL.
[0011] Preferably, the precursor is Co(CO3) 0.5 (OH)·0.11H2O, denoted as Co(CO3) 0.5 (OH)·0.11H2O / CC.
[0012] Preferably, the amount of NaH2PO2·H2O is 150 mg.
[0013] Preferably, the vacuum state is -0.1 MPa.
[0014] Preferably, the temperature is 300 DEG C.
[0015] Preferably, the holding time is 120 min.
[0016] Preferably, the room temperature is 15-35 DEG C.
[0017] Advantages of the present application: The method is simple, the synthesized CoP nanometer array is uniformly distributed and has high purity, and as a hydrogen evolution electrocatalyst, has good electrocatalytic decomposition capacity. The temperature rising program provided in the present application can ensure that the reaction proceeds safely and orderly, and will not cause safety problems and nanometer array shedding due to rapid heating. The whole reaction operation is simple, and large-scale industrial production can be realized. BRIEF DESCRIPTION OF DRAWINGS
[0018] To make the features, technical means and achieved purposes and functions of the present application clearer, the present application will be further described in detail below with reference to the drawings and specific examples: Figure 1 The flow chart for implementing the experiment.
[0019] Figure 2 The XRD graph for implementing the influence of the reaction temperature 300 DEG C on the product.
[0020] Figure 3 The LSV graph for implementing the influence of the reaction temperature 300 DEG C on the product. DETAILED DESCRIPTION
[0021] Embodiment (1) Carbon cloth was sequentially cleaned with acetone, deionized water, and ethanol for 15 min. 4 mmol of Co(N03)2·6H20, 10 mmol of NH4F, and 20 mmol of urea were dissolved in 72 ml of deionized water and stirred for 30 min. The solution was poured into a 100 ml polytetrafluoroethylene liner, and then the treated carbon cloth was placed in the solution and then placed in a hydrothermal kettle.
[0022] (2) The hydrothermal kettle was placed in a hydrothermal oven at 120±20 °C for 6±1 h, and then taken out after natural cooling. It was sequentially cleaned with deionized water and ethanol for 3 times, and then placed in a 60 °C oven overnight to dry, to obtain Co(C03) 0.5 (OH)·0.11H20 / CC.
[0023] (3) Co(C03) 0.5 (OH)·0.11H20 was converted to CoP by a thermal phosphating method. 150 mg of NaH2P02·H20 was placed upstream of the quartz tube, and a piece of 2x2 cm 2 precursor was placed downstream of the quartz tube. After vacuum preservation overnight, the sample was flushed with argon three times. During the reaction, the temperature of the tube furnace was increased to 300 °C at a rate of 5 °C / min, and then maintained for 2 h. After the reaction, the sample was cleaned with deionized water and anhydrous ethanol to remove the residual impurities on the surface of the sample, and then placed in a 60 °C oven for 2 h to dry. The obtained sample was CoP / CC.
[0024] Finally, it should be pointed out that the above examples are only for the technical solutions of the present patent, and are not limited thereto. Although the present patent has been described in detail with reference to the foregoing examples, those skilled in the art should understand that they can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacements to the technical features therein, and these modifications or replacements do not make the technical solutions deviate from the spirit and scope of the technical solutions of the present patent embodiment.
Claims
1. A method for preparing a CoP electrocatalyst, characterized in that, Comprising the following steps: (1) The carbon cloth was sequentially cleaned with acetone, deionized water, and ethanol by ultrasonic cleaning for 15 min; 4 mmol of Co(NO3)2·6H2O, 10 mmol of NH4F, and 20 mmol of urea were dissolved in 72 ml of deionized water and stirred for 30 min, the solution was poured into a 100 ml polytetrafluoroethylene liner, and then the treated carbon cloth was placed in the solution and then placed in a hydrothermal kettle; (2) The hydrothermal kettle was placed in the hydrothermal box at 120±20 °C for 6±1 hours, and after natural cooling, it was taken out, washed with deionized water, ethanol for 3 times in turn, and then placed in a 60 °C oven overnight to dry, to obtain Co(C03) 0.5 (OH)·0.11H2O / CC; (3) Co(C03)0.67H20 was converted to CoP by thermal phosphating method, 150 mg of NaH2P02-H20 was placed upstream of the quartz tube, and a piece of 2 x 2 cm 0.5 (OH) 0.11 H20 was converted to CoP, 150 mg of NaH2P02-H20 was placed upstream of the quartz tube, and a piece of 2 x 2 cm 2 The precursor was vacuumed and preserved for one night, and then flushed with argon three times. During the reaction, the temperature of the tube furnace was increased to 300 °C at a rate of 5 °C / min, and then maintained for 2 h. After the reaction, the sample was cleaned with deionized water and anhydrous ethanol to remove the impurities on the surface of the sample, and then placed in an oven at 60 °C for 2 h to dry. The obtained sample was CoP / CC.
2. The method of claim 1, wherein the CoP electrocatalyst is prepared by the steps of: CoP precursor is prepared by a hydrothermal method on the surface of carbon cloth with crystallization water of basic cobalt carbonate nanometer array, and the specific operation steps are as follows: 4 mmol Co (NO3) 2·6H2O, 10 mmol NH4F and 20 mmol urea are dissolved in 72 ml of deionized water and stirred for 30 min, the solution is poured into a 100 ml polytetrafluoroethylene liner, then the treated carbon cloth is placed in the solution, and then placed in a hydrothermal kettle; the hydrothermal kettle is placed in a hydrothermal box at 120 DEG C for 6 hours, naturally cooled, washed with deionized water, ethanol and then placed in a 60 DEG C oven overnight to dry, and Co(CO3) 0.5 (OH)·0.11H2O / CC is obtained.
3. The method of claim 1, wherein the CoP electrocatalyst is prepared by the steps of: The conversion to cobalt phosphide is completed at a lower temperature by a hot phosphating method, and a uniform CoP nanometer array is directly obtained.
4. The method of claim 1, wherein the CoP electrocatalyst is prepared by the steps of: The holding time thereof is 2 h.