Preparation and application of Mo-doped CuCo nanosheet material
By preparing MoS2/CuCo2S4/CC-2 nanosheets, the problems of few active sites and low carrier transport rate of MoS2 nanosheets in the catalytic hydrogen evolution process were solved, achieving high efficiency in hydrogen evolution performance, reducing costs, and making it suitable as a substitute for the noble metal Pt.
Patent Information
- Application Number
- CN202410607744.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-05-16
- Publication Date
- 2025-11-18
AI Technical Summary
Existing MoS2 nanosheet materials suffer from problems such as complicated nanoscale control, few active sites, low carrier transport rate and high contact impedance in the catalytic hydrogen evolution process. Furthermore, the immobilization method is limited and it is difficult to replace the noble metal Pt.
MoS2/CuCo2S4/CC-2 nanosheets were used to immobilize MoS2 on conductive carbon cloth through a simple and green synthesis method, forming a MoS2/CuCo2S4/CC-2 electrocatalyst. This improved the exposure of active sites and the carrier transport rate, and reduced the contact impedance.
The MoS2-based catalyst achieved highly efficient hydrogen evolution performance, approaching the catalytic activity of the noble metal Pt, and was inexpensive, making it suitable for large-scale industrial applications.
Smart Images
Figure CN120967407A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the field of research on catalysts for hydrogen production by electrolysis of water, and mainly relates to a preparation method of a MoS2 / CuCo2S4 / CC-2 nanosheet material hydrogen evolution electrocatalyst. BACKGROUND
[0003] The noble metal Pt is considered to be the most efficient hydrogen evolution catalyst, and its initial overpotential is close to zero, however, the scarce content in the earth and high cost seriously limit its large-scale use in industrial production, and more and more scientific researchers pay attention to transition metal sulfides (TMDs), which are metal materials, and are generally considered to be the materials with relatively superior electrocatalytic performance at present, and have many advantages suitable for development in actual application, such as rich storage on the earth, relatively low price, relatively convenient development and use, and relatively simple production and preparation process.
[0004] Among them, the molybdenum disulfide (MoS2) material is a nanosheet array with relatively excellent hydrogen evolution free energy and a special structure, and the rich active sites are exposed on the edge, and the hydrogen adsorption free energy almost does not exist in the alkaline medium, the structure of MoS2 is similar to that of graphene, and it is considered to be a catalyst that can replace noble metal materials, but the controllability of the thin layerization and nanocrystallization regulation strategy of MoS2 is poor, the steps are complicated, the sheet structure leads to the accumulation of MoS2 itself, thereby reducing the number of exposed hydrogen evolution active sites, and the spatial structure design means for exposing more active sites is lacking, in order to promote the efficient migration of electrons between the catalyst and the electrode, MoS2 is usually fixed on the surface of conductive carbon material, gold or nickel by chemical growth, the fixed method is single, and the contact properties between the catalyst and the conductive electrode material are rarely studied, therefore, developing a simple and efficient MoS2 nanocrystallization method can effectively improve the carrier transport rate between MoS2 nanosheet layers, and can effectively reduce the contact impedance between the fixed electrode and the MoS2 nanosheet layer, thereby obtaining a super-high catalytic hydrogen evolution electrode construction technology, and further obtaining a super-high catalytic hydrogen evolution electrode construction technology, and further obtaining a super-high catalytic hydrogen evolution electrode construction technology. SUMMARY
[0005] According to the problems existing in the above-mentioned method, the application provides a synthesis method of a MoS2 / CuCo2S4 / CC-2 electrocatalyst, which has the advantages of simple synthesis, green environmental protection, no pollution and high electrocatalytic activity.
[0006] To realize the technical scheme provided by the application, the following steps are included:
[0007] 1. Preparation of hydrogen evolution electrocatalyst made of MoS2 / CuCo2S4 / CC-2 nanosheet material.
[0008] Carbon cloth pretreatment:
[0009] First, the dry carbon cloth is processed to become hydrophilic carbon cloth before it can be loaded with materials.
[0010] Synthesis of MoS2 / CuCo2S4 / CC-2 nanosheets:
[0011] H in deionized water 24 Mo7N6O 24 ·4H2O, CuSO4·5H2O, Co(NO3)2·6H2O, NH4F and CH4N2S were added and stirred. The mixture was transferred to a polytetrafluoroethylene autoclave and a piece of treated carbon cloth was placed on it. The polytetrafluoroethylene autoclave was then placed in an oven and the temperature and time were set. After the reaction was completed, the sample was taken out and washed with distilled water and ethanol. The washed sample was then placed in a vacuum drying oven. The product was named MoS2 / CuCo2S4 / CC-2.
[0012] 2. Electrochemical Measurement of Hydrogen Evolution Performance
[0013] The electrocatalytic performance of the catalyst material for hydrogen evolution was tested on a Princeton electrochemical workstation using nanosheet composite materials. The results were obtained using a traditional three-electrode system established on the workstation. A typical sample synthesized in this paper, MoS2 / CuCo2S4 / CC-2 (2×3 cm), was used. 2 The working electrode was a platinum sheet, the reference electrode was a Hg / HgO electrode, and the counter electrode was a platinum sheet. All experimental electrocatalytic hydrogen evolution tests were performed in 1M KOH electrolyte. Unless otherwise specified, the potentials in the electrochemical measurements were converted to the potentials of the relative reversible hydrogen electrode (RHE), as shown in the following formula: E(RHE)=E(Hg / HgO)+0.0592*PH+0.098
[0014] 3. Material structure and characterization
[0015] The morphology, phase composition, and elemental composition of typical samples are shown by scanning electron microscopy (SEM) images. The phase composition of typical samples is analyzed by X-ray diffraction (XRD) patterns. Then, the microstructure and atomic arrangement of typical samples are further studied by transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The chemical composition of the samples can be detected and analyzed by X-ray photoelectron spectroscopy (XPS). Attached Figure Description
[0016] Figure 1SEM image of MoS2 / CuCo2S4 / CC-2
[0017] Figure 2 HRTEM image of MoS2 / CuCo2S4 / CC-2
[0018] Figure 3 XRD image of MoS2 / CuCo2S4 / CC-2
[0019] Figure 4 Images showing the electrochemical performance of MoS2 / CuCo2S4 / CC-2 and a comparative sample. Detailed Implementation
[0020] The following embodiments are provided to better illustrate the technical solutions of the present invention, and are not intended to limit the scope of protection of the present invention.
[0021] Example 1
[0022] First, the dry carbon cloth needs to be treated to become hydrophilic before it can be loaded with materials. Cut the dry carbon cloth into 2*3cm pieces. 2 Next, the carbon cloth was placed in a beaker and treated with concentrated HNO3 at 100°C for 1 hour. Then, it was washed repeatedly in small amounts with deionized water and anhydrous ethanol in the beaker. After drying at 60°C for 12 hours, the desired hydrophilic carbon cloth was obtained.
[0023] 0.05 mmol H 24 Mo7N6O 24 ·4H2O, 0.05mmol CuSO4·5H2O, 0.1mmol Co(NO3)2·6H2O, 2mmol NH4F and 4.5mmol thiourea were added to 35mL of deionized (DI) water and stirred for 30min. The mixture was then transferred to a polytetrafluoroethylene autoclave and a piece of treated carbon cloth was placed on it. The oven was set to run at 200℃ for 30h. After the reaction was completed, the sample was taken out and washed three times with distilled water and three times with ethanol. The sample was then placed in a vacuum drying oven and dried at 60℃ for 12h. The product was named MoS2 / CuCo2S4 / CC-2.
[0024] Comparative Example 1
[0025] 0.03 mmol H 24 Mo7N6O 24·4H2O, 0.05mmol CuSO4·5H2O, 0.1mmol Co(NO3)2·6H2O, 2mmol NH4F and 4.5mmol thiourea were added to 35mL of deionized (DI) water and stirred for 30min. The mixture was then transferred to a polytetrafluoroethylene autoclave and a piece of treated carbon cloth was placed on it. The oven was set to run at 200℃ for 30h. After the reaction was completed, the sample was taken out and washed three times with distilled water and three times with ethanol. The sample was then placed in a vacuum drying oven and dried at 60℃ for 12h. The product was named MoS2 / CuCo2S4 / CC-1.
[0026] Comparative Example 2
[0027] 0.07 mmol H 24 Mo7N6O 24 ·4H2O, 0.05mmol CuSO4·5H2O, 0.1mmol Co(NO3)2·6H2O, 2mmol NH4F and 4.5mmol thiourea were added to 35mL of deionized (DI) water and stirred for 30min. The mixture was then transferred to a polytetrafluoroethylene autoclave and a piece of treated carbon cloth was placed on it. The oven was set to run at 200℃ for 30h. After the reaction was completed, the sample was taken out and washed three times with distilled water and three times with ethanol. The sample was then placed in a vacuum drying oven and dried at 60℃ for 12h. The product was named MoS2 / CuCo2S4 / CC-3.
[0028] from Figure 4 The linear sweep voltammetry curves of Example 1 and Comparative Examples 1 and 2 are shown above. Only with a suitable Mo doping amount can the MoS2 / CuCo2S4 / CC nanosheet electrocatalyst exhibit excellent hydrogen evolution activity. The results obtained by the electrochemical workstation show that the best effect can be achieved when the doping amount is 0.05 mmol.
[0029] The above embodiments are not intended to limit the scope of this invention.
Claims
1. A preparation method for studying the hydrogen evolution performance of Mo-doped CuCo nanosheets, characterized in that, Includes the following steps: H in deionized water 24 Mo7N6O 24 ·4H2O, CuSO4·5H2O, Co(NO3)2·6H2O, NH4F and CH4N2S were added and stirred. The mixture was transferred to a polytetrafluoroethylene autoclave and a piece of treated carbon cloth was placed on it. The polytetrafluoroethylene autoclave was then placed in an oven and the temperature and time were set. After the reaction was completed, the sample was taken out and washed with distilled water and ethanol. The washed sample was then placed in a vacuum drying oven. The product was named MoS2 / CuCo2S4 / CC-2.
2. The preparation method for studying the hydrogen evolution performance of Mo-doped CuCo nanosheets according to claim 1, characterized in that: The 0.03 mmol H 24 Mo7N6O 24 ·4H2O, 0.05mmol CuSO4·5H2O, 0.1mmol Co(NO3)2·6H2O, 2mmol NH4F and 4.5mmol CH4N2S.
3. The preparation method for studying the hydrogen evolution performance of Mo-doped CuCo nanosheets according to claim 1, characterized in that the amount of deionized (DI) water is 35 mL.
4. The preparation method for studying the hydrogen evolution performance of Mo-doped CuCo nanosheets according to claim 1, characterized in that... Compared to using a simple one-step hydrothermal method.
5. The preparation method for studying the hydrogen evolution performance of Mo-doped CuCo nanosheets according to claim 1, characterized in that: The required reaction temperature is 200℃ and the reaction time is 24h.
6. The preparation method for studying the hydrogen evolution performance of Mo-doped CuCo nanosheets according to claim 1, characterized in that: The drying temperature is 60℃ and the time is 12 hours.
7. The preparation method for studying the hydrogen evolution performance of Mo-doped CuCo nanosheets according to claim 1, characterized in that: Hydrogen evolution performance testing needs to be performed on an electrochemical workstation.
8. The preparation method for studying the hydrogen evolution performance of Mo-doped CuCo nanosheets according to claim 1, characterized in that: In a three-electrode system, in a 1M KOH alkaline electrolyte, the MoS2 / CuCo2S4 / CC-2 nanosheet composite material is used as the working electrode, the counter electrode is a platinum sheet electrode, and the reference electrode is a Hg / HgO electrode.
9. The preparation method for studying the hydrogen evolution performance of Mo-doped CuCo nanosheets according to claim 1, characterized in that: MoS2 / CuCo2S4 / CC-2 nanosheet catalysts promote hydrogen evolution performance.