CN113355692B - Preparation method of molybdenum disulfide nanosheet@cobalt sulfide nanoparticle composite electrocatalyst - Google Patents

Preparation method of molybdenum disulfide nanosheet@cobalt sulfide nanoparticle composite electrocatalyst Download PDF

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CN113355692B
CN113355692B CN202110524002.0A CN202110524002A CN113355692B CN 113355692 B CN113355692 B CN 113355692B CN 202110524002 A CN202110524002 A CN 202110524002A CN 113355692 B CN113355692 B CN 113355692B
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molybdenum disulfide
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array electrode
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CN113355692A (en
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黄妞
胡颖
邵梅芳
杨柳
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Nanjing Xuanwu High Tech Industry Group Co ltd
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Abstract

The invention provides a preparation method of a molybdenum disulfide nanosheet@cobalt sulfide nanoparticle composite electrocatalyst. Firstly, carrying out hydrothermal growth on a Mo-S or Co-Mo-S nano-sheet array on the surface of a substrate; then cobalt salt is dissolved in a volatile nonaqueous solvent and is coated on the surface of the Mo-S or Co-Mo-S nano-sheet array; finally, the sample is placed in an S atmosphere for in situ deposition of cobalt sulfide nanoparticles. In alkaline, neutral and acidic electrolyte at room temperature, the overpotential required for reaching 10 mA cm ‑2 overpotential is about to 50 mV; for alkali and acid electrolyte, the overpotential required for reaching 600 mA cm ‑2 is about to 200 mV. This performance is very close to that of commercial Pt particles even when operating at large current densities. For OER, the overpotential required to reach 10 mA cm ‑2 and 100 mA cm ‑2 is in 220 mV and 330 mV respectively in room temperature alkaline electrolyte.

Description

Preparation method of molybdenum disulfide nanosheet@cobalt sulfide nanoparticle composite electrocatalyst
Technical Field
The invention relates to an in-situ composite electrode and a preparation method thereof, and belongs to the field of energy storage and conversion materials and devices.
Background
The energy consumption problem is a bottleneck problem restricting the world's development. With the progressive exhaustion of traditional fossil fuels, energy shortage and global environmental pollution problems become increasingly severe. To alleviate such problems, the development of efficient, economical and renewable green energy sources is extremely demanding. Hydrogen energy is regarded as a high-efficiency novel energy carrier because of the advantages of high energy conversion efficiency, cleanliness, regeneration, zero carbon emission and the like, and electrocatalytic decomposition of water (water is separated into oxygen and hydrogen gas) is regarded as one of the modes with the most industrial application potential. At present, the most efficient Hydrogen Evolution Reaction (HER) catalyst is still a platinum-based material, and the Oxygen Evolution Reaction (OER) catalyst with excellent performance and stability is ruthenium oxide or iridium oxide, but the expensive price and rare reserve of noble metal severely limit the large-scale commercial application of the noble metal. Therefore, searching and preparing non-noble metal-based materials which are pollution-free, low in cost and stable and efficient become an important research direction in the field of electrocatalytic decomposition of water.
Molybdenum disulfide is a graphite-like two-dimensional layered transition metal sulfide, the layers are connected by three atomic layers of S-Mo-S through covalent bonds, and the S-Mo-S layers are bonded through Van der Waals bonds. There is a great deal of interest for its good stability against acids and bases and a certain electrocatalytic activity towards hydrogen evolution reactions (hydrogen evolution reaction, HER). Studies have shown that the active sites of molybdenum disulfide are located at the layer edges. Thus, preparing molybdenum disulfide nanoplatelets grown perpendicular to the substrate or support will be able to fully expose a substantial portion of the layer edges. However, the HER catalytic performance of the molybdenum disulfide layer edges in alkaline and neutral aqueous solutions is still poor. For this problem, density functional theory calculations and related reports indicate: the heterojunction is formed by molybdenum disulfide with strong adsorption property to hydrogen atoms in hydrogen protons or water molecules and other materials with strong adsorption property to oxygen atoms in hydroxyl or water molecules, and the HER and OER catalytic performance of the molybdenum disulfide-based composite material can be synergistically improved by the heterojunction interface. For example, ke Fan et al prepared nanorods composed of NiS 2 and MoS 2, and the relatively pure NiS 2 and MoS 2 of this composite material had significantly improved HER and OER performance in alkaline aqueous solutions (ACS catalyst, 2017, 7, 6179); MINGLIANG DU et al prepared that Co 9S8@MoS2/carbon fibers (CNFs) composites also significantly improved HER and OER performance in alkaline aqueous solutions compared to uncomplexed Co 9S8/CNFs and MoS 2/CNFs (adv. Mater. 2015, 27, 4752.).
Cobalt sulfide is of many types, including CoS, coS 2、Co3S4、Co4S3、Co9S8、Co1-x S, etc., and has similar chemical composition, in which the Co atoms have strong adsorption properties for oxygen atoms in hydroxyl groups or water molecules. Thus, the composite material of molybdenum disulfide and other cobalt sulfides will also have excellent ability to synergistically catalyze hydrogen evolution.
Disclosure of Invention
In view of the above, the present invention aims to provide an effective method for preparing an in-situ electrode of a molybdenum disulfide and cobalt sulfide compound. On one hand, the molybdenum disulfide is ensured to grow vertically to accelerate electron transmission and expose more active sites at the edge of the molybdenum disulfide layer; on the other hand, the molybdenum disulfide and the cobalt sulfide form rich heterogeneous interfaces, and hydrogen and oxygen are efficiently and synergistically catalyzed. The method is 'hydro-thermal-solution coating-vulcanization and knot-making', has the advantages of low equipment requirement, low cost of required raw materials, easy control of reaction conditions, simple production process, good consistency of formed products, small environmental pollution and the like, and the prepared electrode is an in-situ electrode without the subsequent processes of slurry coating preparation and the like, thereby having great significance for mass production of high-performance catalysis.
The preparation method of the molybdenum disulfide nanosheet@cobalt sulfide nanoparticle in-situ array electrode by 'hydro-thermal-solution coating-vulcanization junction' comprises the following steps:
the first step of hydrothermal: and carrying out hydrothermal growth on molybdenum disulfide or cobalt molybdenum sulfide on the surfaces of substrates such as carbon paper, carbon cloth and the like to obtain the Mo-S or Co-Mo-S nanosheet array electrode. The significance of this step is: so that the edge of the molybdenum disulfide layer is furthest exposed; the uniform array structure ensures that the nano-sheets leave uniform gaps to facilitate the loading of cobalt sulfide nano-particles; the cobalt element is introduced in the hydrothermal process, so that the content of cobalt sulfide generated in the subsequent vulcanization step is improved, and the OER catalytic activity of the material is improved. It is worth noting that the atomic ratio of Co to Mo in the hydrothermal process does not benefit from exceeding 1:3, otherwise, a precursor material of the nano-sheet array structure cannot be obtained.
And the second step of solution coating: coating cobalt salts such as cobalt chloride, namely dissolving the cobalt salts such as cobalt chloride in polar volatile nonaqueous solvents such as N, N-dimethylformamide under the condition of stirring at room temperature, wherein the concentration of cobalt element is 300-1500 mM; and then the solution is coated on a molybdenum disulfide nanosheet array and dried in dry air, or is quickly dried at 70-100 ℃ on a hot table, or is dried in vacuum at 70-100 ℃. The significance of this step is: the cobalt element is uniformly dispersed on the surface of the nano sheet, which is beneficial to the subsequent generation of uniform loading of cobalt sulfide particles.
And step three, vulcanizing and making a knot: and (3) sintering the sample obtained in the step (II) in the S atmosphere at 500-600 ℃ for 1-3 hours, and cooling along with a furnace and taking out to obtain the molybdenum disulfide nanosheet@cobalt sulfide nanoparticle in-situ array electrode. The significance of this step is: the sulfur simple substance gas transported by the carrier gas reacts with cobalt salt on the molybdenum disulfide nanosheets in situ to generate cobalt sulfide. The original Co-Mo-S nano-sheet is recrystallized to partially separate out cobalt sulfide in the annealing process. These cobalt sulfides form abundant heterojunctions with molybdenum disulfide, synergistically improving HER and OER performance.
Drawings
FIG. 1 is a linear voltammetric scan (LSV) of a sample prepared in example 1, wherein (a) basic HER-LSV, (b) acidic HER-LSV, and (c) basic OER-LSV.
FIG. 2 is a linear voltammetric scan (LSV) of a sample prepared in example 2, wherein (a) basic HER-LSV, (b) acidic HER-LSV, and (c) basic OER-LSV.
FIG. 3 is a linear voltammetric scan (LSV) of a sample prepared in example 3, wherein (a) basic HER-LSV and (b) basic OER-LSV.
FIG. 4 is a linear voltammetric scan (LSV) of a sample prepared in example 4, wherein (a) basic HER-LSV and (b) acidic HER-LSV.
FIG. 5 is a linear voltammetric scan (LSV) of a sample prepared in example 5, wherein (a) basic HER-LSV, (b) acidic HER-LSV, and (c) basic OER-LSV.
FIG. 6 is a linear voltammetric scan (LSV) of a sample prepared in example 6, wherein (a) basic HER-LSV, (b) acidic HER-LSV, and (c) basic OER-LSV.
FIG. 7 is a linear voltammetric scan curve (LSV) of a control sample of example 6, wherein (a) basic HER-LSV, (b) basic OER-LSV.
FIG. 8 shows the basic HER-LSV measured on the samples prepared in example 7.
FIG. 9 shows the basic HER-LSV measured on the samples prepared in example 8.
FIG. 10 shows the basic HER-LSV measured on the samples prepared in example 9.
FIG. 11 shows the basic HER-LSV measured on the samples prepared in example 10.
Fig. 12 is an XRD pattern of the prepared samples of example 2 and example 6. In the figure, "1:19 "is the atomic ratio of Co to Mo in the first hydrothermal reaction in example 2," 1:3 "is the atomic ratio of Co to Mo in the first hydrothermal reaction in example 6.
Fig. 13 is an XRD pattern of the control sample. "1:4 "control sample prepared by hydrothermal reaction in the first step only according to example 5," 1:3 non-CoCl soak-600 o C "corresponding to the control of example 6, direct 600 o C sulfidation anneal 2 h after the first hydrothermal step," 1:4 non-CoCl soak-600 o C "corresponding to the control of example 5, direct 600 o C sulfidation anneal 2 h after the first hydrothermal step," 1:3 CoCl soak-550 o C "corresponds to the control of example 6, which was subjected to a first stage of hydrothermal and then direct vulcanization annealing.
FIG. 14 is an SEM image of a sample prepared according to example 2, wherein A is magnified 1 ten thousand times and B is magnified 5.5 ten thousand times.
Fig. 15 is an SEM image of molybdenum disulfide prepared only through step (1) of example 1, wherein a is magnified 200 times, B is magnified 1 ten thousand times, and C is magnified 5 ten thousand times.
Fig. 16 is an SEM image of molybdenum disulfide prepared only through step (1) of example 5, wherein a is magnified 1 ten thousand times and B is magnified 5 ten thousand times.
Detailed Description
Characterization conditions
The HER test method in the embodiment of the invention comprises the following steps: the molybdenum disulfide nanosheet@cobalt sulfide nanoparticle in-situ array electrode is used as a working electrode, a carbon rod is used as a counter electrode, and other electrodes are used as reference electrodes, and the scanning speed is 5 mV/s. The alkaline electrolyte used was 1M KOH aqueous solution, the acid electrolyte was 0.5 aqueous solution M H 2SO4, and nitrogen and oxygen were respectively introduced during HER and OER testing to allow natural saturation of the gas in the aqueous solution with 200 rpm stirring during the testing. The alkaline and acidic reference electrodes are respectively saturated Hg/HgO electrodes and Hg/HgSO 4 electrodes, which are all potential corrected by a reversible hydrogen electrode, and the potential is the potential relative to the potential of the reversible hydrogen electrode. Potential (IR) compensation was automatically performed with the Shanghai workstation in the LSV test. X-ray diffraction (SEM) images of the samples were obtained using a SMART LAB-9 type X-ray diffractometer. Scanning electron microscope (XRD) images were acquired using an aspect F50 scanning electron microscope (FEI AMERICA).
Example 1
Adding 0.1558 g ammonium molybdate and 0.9591 g thiourea into 42 mL ultrapure water for dissolution, pouring into a reaction kettle with the capacity of 70 mL, putting carbon fiber paper (3×5 cm 2 CFP), hydrothermal 24h at 180 ℃, taking out the CFP after cooling, flushing 3-4 times with ultrapure water, and putting on a hot table for drying. 800mM CoCl 2 is added into DMF of 3mL to be dissolved, then the dried CFP growing with molybdenum disulfide is put into the solution, and is stood for 30 min, then the solution is taken out to be dried, and is taken out after being dried in a vacuum drying oven for one night. Placing 1g S powder at the front end of a tube furnace, placing a sample in the center of the tube furnace, heating to 550 ℃ at 10 ℃ per hour under Ar atmosphere, preserving heat for two hours, naturally cooling, and taking out.
FIG. 1 is a linear voltammetric scan (LSV) of a sample prepared in example 1, wherein (a) basic HER-LSV, (b) acidic HER-LSV, and (c) basic OER-LSV. The corresponding performance parameters of the electrocatalysts are listed in tables 1 and 2. As can be seen from figure (a) and table 1, the HER reaction in alkaline aqueous solution produces hydrogen gas, and the corresponding overpotential is 48 mV, 108 mV, 224 mV in that order when the current density through the electrode is 10 mA/cm 2、100 mA/cm2、600 mA/cm2. As can be seen from figure (b) and table 1, the HER reaction in acidic aqueous solution generates hydrogen gas, and when the current density through the electrode is 10 mA/cm 2、100 mA/cm2、400 mA/cm2, the corresponding overpotential is 62 mV, 113 mV, 169 mV in this order. As can be seen from fig. (c) and table 2, the OER reaction in the alkaline aqueous solution generates oxygen, and when the current density passing through the electrode is 100 mA/cm 2、600 mA/cm2, the corresponding overpotential is 338 mV, 418 mV in turn.
Example 2
Adding 0.0105 g cobalt chloride hexahydrate, 0.1479 g ammonium molybdate and 0.9591 g thiourea into 42 mL ultrapure water for dissolution, pouring into a reaction kettle with the capacity of 70mL, putting carbon fiber paper (3X 5 cm 2 CFP), hydrothermal 24: 24h at 180 ℃, taking out the CFP after cooling, flushing for 3-4 times by using the ultrapure water, and putting on a hot table for drying. 800 mM CoCl 2 is added into DMF of 3mL to be dissolved, then the dried CFP growing with molybdenum disulfide is put into the solution, and is stood for 30min, then the solution is taken out to be dried, and is taken out after being dried in a vacuum drying oven for one night. Placing 1g S powder at the front end of a tube furnace, placing a sample in the center of the tube furnace, heating to 550 ℃ at 10 ℃ per hour under Ar atmosphere, preserving heat for two hours, naturally cooling, and taking out.
FIG. 2 is a linear voltammetric scan (LSV) of a sample prepared in example 2, wherein (a) basic HER-LSV, (b) acidic HER-LSV, and (c) basic OER-LSV. The corresponding performance parameters of the electrocatalysts are listed in tables 1 and 2. As can be seen from figure (a) and table 1, the HER reaction in alkaline aqueous solution produces hydrogen gas, and the corresponding overpotential is 64 mV, 129 mV, 259 mV in that order when the current density through the electrode is 10 mA/cm 2、100 mA/cm2、600 mA/cm2. As can be seen from figure (b) and table 1, the HER reaction in acidic aqueous solution generates hydrogen gas, and when the current density through the electrode is 10 mA/cm 2、100 mA/cm2、400 mA/cm2, the corresponding overpotential is 73 mV, 139 mV, 212 mV in this order. As can be seen from fig. (c) and table 2, the OER reaction in the alkaline aqueous solution generates oxygen, and when the current density passing through the electrode is 10 mA/cm 2、100 mA/cm2、600 mA/cm2, the corresponding overpotential is 263 mV, 330 mV, 407 mV in order.
Example 3
Adding 0.021 g cobalt chloride hexahydrate, 0.1402 g ammonium molybdate and 0.95914 g thiourea into 42 mL ultrapure water for dissolution, pouring into a reaction kettle with the capacity of 70mL, placing carbon fiber paper (3X 5 cm 2 CFP), carrying out hydrothermal treatment at 180 ℃ for 24: 24h, taking out the CFP after cooling, washing with the ultrapure water for 3-4 times, and placing on a hot table for drying. 800 mM CoCl 2 is added into DMF of 3mL to be dissolved, then the dried CFP growing with molybdenum disulfide is put into the solution, and is stood for 30min, then the solution is taken out to be dried, and is taken out after being dried in a vacuum drying oven for one night. Placing 1g S powder at the front end of a tube furnace, placing a sample in the center of the tube furnace, heating to 550 ℃ at 10 ℃ per hour under Ar atmosphere, preserving heat for two hours, naturally cooling, and taking out.
FIG. 3 is a linear voltammetric scan (LSV) of a sample prepared in example 3, wherein (a) basic HER-LSV and (b) basic OER-LSV. The corresponding performance parameters of the electrocatalysts are listed in tables 1 and 2. As can be seen from figure (a) and table 1, the HER reaction in alkaline aqueous solution produces hydrogen gas, and the corresponding overpotential is 54 mV, 120 mV, 252 mV in this order when the current density through the electrode is 10 mA/cm 2、100 mA/cm2、600 mA/cm2. As can be seen from fig. (b) and table 2, the OER reaction in the alkaline aqueous solution generates oxygen, and when the current density passing through the electrode is 100 mA/cm 2、600 mA/cm2, the corresponding overpotential is 320 mV, 395 mV in sequence.
Example 4
Adding 0.0315 g cobalt chloride hexahydrate, 0.1324 g ammonium molybdate and 0.95914 g thiourea into 42 mL ultrapure water for dissolution, pouring into a reaction kettle with the capacity of 70 mL, placing carbon fiber paper (3X 5 cm 2 CFP), hydrothermal 24: 24h at 180 ℃, taking out the CFP after cooling, flushing for 3-4 times by using the ultrapure water, and placing on a hot table for drying. 800 mM CoCl 2 is added into DMF of 3 mL to be dissolved, then the dried CFP growing with molybdenum disulfide is put into the solution, and is stood for 30 min, then the solution is taken out to be dried, and is taken out after being dried in a vacuum drying oven for one night. Placing 1g S powder at the front end of a tube furnace, placing a sample in the center of the tube furnace, heating to 550 ℃ at 10 ℃ per hour under Ar atmosphere, preserving heat for two hours, naturally cooling, and taking out.
FIG. 4 shows linear voltammetric scan curves (LSV) for samples prepared in example 4, (a) basic HER-LSV, (b) acidic HER-LSV. The corresponding performance parameters of the electrocatalysts are listed in table 1. As can be seen from figure (a) and table 1, the HER reaction in alkaline aqueous solution produces hydrogen gas, and the corresponding overpotential is 56 mV, 121 mV, 252 mV in this order when the current density through the electrode is 10 mA/cm 2、100 mA/cm2、600 mA/cm2. As can be seen from figure (b) and table 1, the HER reaction in acidic aqueous solution produces hydrogen gas, and the corresponding overpotential is 62 mV, 125 mV, 198 mV in that order when the current density through the electrode is 10 mA/cm 2、100 mA/cm2、400 mA/cm2.
Example 5
Adding 0.0420 g cobalt chloride hexahydrate, 0.1246 g ammonium molybdate and 0.95914 g thiourea into 42 mL ultrapure water for dissolution, pouring into a reaction kettle with the capacity of 70 mL, placing carbon fiber paper (3X 5 cm 2 CFP), carrying out hydrothermal treatment at 180 ℃ for 24: 24h, taking out the CFP after cooling, washing with the ultrapure water for 3-4 times, and placing on a hot table for drying. 800 mM CoCl 2 is added into DMF of 3 mL to be dissolved, then the dried CFP growing with molybdenum disulfide is put into the solution, and is stood for 30 min, then the solution is taken out to be dried, and is taken out after being dried in a vacuum drying oven for one night. Placing 1g S powder at the front end of a tube furnace, placing a sample in the center of the tube furnace, heating to 550 ℃ at 10 ℃ per hour under Ar atmosphere, preserving heat for two hours, naturally cooling, and taking out.
FIG. 5 is a linear voltammetric scan (LSV) of a sample prepared in example 5, wherein (a) basic HER-LSV, (b) acidic HER-LSV, and (c) basic OER-LSV. The corresponding performance parameters of the electrocatalysts are listed in tables 1 and 2. As can be seen from figure (a) and table 1, the HER reaction in alkaline aqueous solution produces hydrogen gas, and when the current density through the electrode is 10 mA/cm 2、100 mA/cm2、600 mA/cm2, the corresponding overpotential is 62 mV, 132 mV, 279 mV in sequence. As can be seen from figure (b) and table 1, the HER reaction in acidic aqueous solution produces hydrogen gas, and when the current density through the electrode is 10 mA/cm 2、100 mA/cm2、400 mA/cm2, the corresponding overpotential is 67 mV, 132 mV, 214 mV in that order. As can be seen from fig. (c) and table 2, the OER reaction in the alkaline aqueous solution generates oxygen, and when the current density through the electrode is 10 mA/cm 2、100 mA/cm2、600 mA/cm2, the corresponding overpotential is 223 mV, 334 mV, 410 mV in order.
Example 6
Adding 0.0525 g cobalt chloride hexahydrate, 0.1162 g ammonium molybdate and 0.95914 g thiourea into 42 mL ultrapure water for dissolution, pouring into a reaction kettle with the capacity of 70 mL, placing carbon fiber paper (3X 5 cm 2 CFP), carrying out hydrothermal treatment at 180 ℃ for 24: 24h, taking out the CFP after cooling, flushing with the ultrapure water for 3-4 times, and placing on a heat table for drying. 800 mM CoCl 2 is added into DMF of 3 mL to be dissolved, then the dried CFP growing with molybdenum disulfide is put into the solution, and is stood for 30 min, then the solution is taken out to be dried, and is taken out after being dried in a vacuum drying oven for one night. Placing 1g S powder at the front end of a tube furnace, placing a sample in the center of the tube furnace, heating to 550 ℃ at 10 ℃ per hour under Ar atmosphere, preserving heat for two hours, naturally cooling, and taking out.
FIG. 5 is a linear voltammetric scan (LSV) of a sample prepared in example 5, wherein (a) basic HER-LSV, (b) acidic HER-LSV, and (c) basic OER-LSV. The corresponding performance parameters of the electrocatalysts are listed in tables 1 and 2. As can be seen from figure (a) and table 1, the HER reaction in alkaline aqueous solution produces hydrogen gas, and when the current density through the electrode is 10 mA/cm 2、100 mA/cm2、600 mA/cm2, the corresponding overpotential is 65 mV, 130 mV, 264 mV in this order. As can be seen from figure (b) and table 1, the HER reaction in acidic aqueous solution produces hydrogen gas, and the corresponding overpotential is 68 mV, 131 mV, 202 mV in that order when the current density through the electrode is 10 mA/cm 2、100 mA/cm2、400 mA/cm2. As can be seen from fig. (c) and table 2, the OER reaction in the alkaline aqueous solution produces oxygen, and when the current density through the electrode is 10 mA/cm 2、100 mA/cm2、600 mA/cm2, the corresponding overpotential is 236 mV, 327 mV, 383 mV in sequence.
Control of example 6
Adding 0.0525 g cobalt chloride hexahydrate, 0.1162 g ammonium molybdate and 0.95914 g thiourea into 42 mL ultrapure water for dissolution, pouring into a reaction kettle with the capacity of 70 mL, placing carbon fiber paper (3X 5 cm 2 CFP), carrying out hydrothermal treatment at 180 ℃ for 24: 24 h, taking out the CFP after cooling, flushing with the ultrapure water for 3-4 times, and placing on a heat table for drying. Placing 1g S powder at the front end of a tube furnace, placing a sample in the center of the tube furnace, heating to 550 ℃ at 10 ℃ per hour under Ar atmosphere, preserving heat for two hours, naturally cooling, and taking out.
FIG. 7 is a linear voltammetric scan curve (LSV) of a control sample of example 6 (prepared under the same conditions as example 6 except that the cobalt salt was not applied), wherein (a) basic HER-LSV and (b) basic OER-LSV. As can be seen from figure (a) and table 1, the HER reaction in alkaline aqueous solution produces hydrogen gas, and when the current density through the electrode is 10 mA/cm 2、100 mA/cm2、600 mA/cm2, the corresponding overpotential is 87 mV, 151 mV, 292 mV in order. As can be seen from fig. (b) and table 2, the OER reaction in the alkaline aqueous solution generates oxygen, and when the current density through the electrode is 10 mA/cm 2、100 mA/cm2、600 mA/cm2, the corresponding overpotential is 313 mV, 384 mV, 448 mV in sequence.
Example 7
0.15575G of ammonium molybdate and 0.95914g of thiourea are taken and added into 42 mL ultrapure water for dissolution, poured into a reaction kettle with the capacity of 70 mL, carbon Fiber Paper (CFP) is put in, 200 ℃ of hydrothermal treatment is carried out for 24 h, after cooling, the CFP is taken out, washed 3-4 times by the ultrapure water, and then placed on a hot table for drying. 800 mM CoCl 2 is added into DMF of 3 mL to be dissolved, then the dried CFP growing with molybdenum disulfide is put into the solution, and is stood for 30 min, then the solution is taken out to be dried, and is taken out after being dried in a vacuum drying oven for one night. Placing 1g S powder at the front end of a tube furnace, placing a sample in the center of the tube furnace, heating to 500 ℃ at 10 ℃ per hour under Ar atmosphere, preserving heat for two hours, naturally cooling, and taking out.
FIG. 8 shows the basic HER-LSV measured on the samples prepared in example 7. The corresponding performance parameters of the electrocatalysts are listed in table 1. As can be seen from the figure and table 1, the HER reaction in alkaline aqueous solution produces hydrogen gas, and the corresponding overpotential is 68 mV, 130 mV, 244 mV in that order when the current density through the electrode is 10 mA/cm 2、100 mA/cm2、600 mA/cm2.
Example 8
0.15575G of ammonium molybdate and 0.95914g of thiourea are taken and added into 42 mL ultrapure water for dissolution, poured into a reaction kettle with the capacity of 70 mL, carbon Fiber Paper (CFP) is put in, 200 ℃ of hydrothermal treatment is carried out for 24 h, after cooling, the CFP is taken out, washed 3-4 times by the ultrapure water, and then placed on a hot table for drying. 800 mM CoCl 2 is added into DMF of 3 mL to be dissolved, then the dried CFP growing with molybdenum disulfide is put into the solution, and is stood for 30 min, then the solution is taken out to be dried, and is taken out after being dried in a vacuum drying oven for one night. Placing 1g S powder at the front end of a tube furnace, placing a sample in the center of the tube furnace, heating to 600 ℃ at 10 ℃ per hour under Ar atmosphere, preserving heat for two hours, naturally cooling, and taking out.
FIG. 9 shows the basic HER-LSV measured on the samples prepared in example 8. The corresponding performance parameters of the electrocatalysts are listed in table 1. As can be seen from the figure and table 1, the HER reaction in the alkaline aqueous solution produces hydrogen gas, and the corresponding overpotential is 78 mV, 150 mV, 286 mV in this order when the current density through the electrode is 10 mA/cm 2、100 mA/cm2、600 mA/cm2.
Example 9
0.15575G of ammonium molybdate and 0.95914g of thiourea are taken and added into 42 mL ultrapure water for dissolution, poured into a reaction kettle with the capacity of 70 mL, carbon Fiber Paper (CFP) is put in, 200 ℃ of hydrothermal treatment is carried out for 24 h, after cooling, the CFP is taken out, washed 3-4 times by the ultrapure water, and then placed on a hot table for drying. 400 mM CoCl 2 is added into DMF of 3 mL to be dissolved, then the dried CFP growing with molybdenum disulfide is put into the solution, and is stood for 30 min, then the solution is taken out to be dried, and is taken out after being dried in a vacuum drying oven for one night. Placing 1g S powder at the front end of a tube furnace, placing a sample in the center of the tube furnace, heating to 550 ℃ at 10 ℃ per hour under Ar atmosphere, preserving heat for two hours, naturally cooling, and taking out.
FIG. 10 shows the basic HER-LSV measured on the samples prepared in example 9. The corresponding performance parameters of the electrocatalysts are listed in table 1. As can be seen from the figure and table 1, the HER reaction in alkaline aqueous solution produces hydrogen gas, and the corresponding overpotential is 105 mV, 176 mV, 317 mV in this order when the current density through the electrode is 10 mA/cm 2、100 mA/cm2、600 mA/cm2.
Example 10
0.15575G of ammonium molybdate and 0.95914g of thiourea are taken and added into 42 mL ultrapure water for dissolution, poured into a reaction kettle with the capacity of 70 mL, carbon Fiber Paper (CFP) is put in, 200 ℃ of hydrothermal treatment is carried out for 24 h, after cooling, the CFP is taken out, washed 3-4 times by the ultrapure water, and then placed on a hot table for drying. 1200 mM CoCl 2 is added into DMF of 3 mL to be dissolved, then the dried CFP growing with molybdenum disulfide is put into the solution, and is stood for 30 min, then the solution is taken out to be dried, and is taken out after being dried in a vacuum drying oven for one night. Placing 1g S powder at the front end of a tube furnace, placing a sample in the center of the tube furnace, heating to 550 ℃ at 10 ℃ per hour under Ar atmosphere, preserving heat for two hours, naturally cooling, and taking out.
FIG. 11 shows the basic HER-LSV measured on the samples prepared in example 10. The corresponding performance parameters of the electrocatalysts are listed in table 1. As can be seen from the figure and table 1, the HER reaction in alkaline aqueous solution produces hydrogen gas, and the corresponding overpotential is 99 mV, 164 mV, 288 mV in this order when the current density through the electrode is 10 mA/cm 2、100 mA/cm2、600 mA/cm2.
Fig. 12 is an XRD pattern of the samples of example 2 and example 6. By comparison with molybdenum disulfide (PDF 37-1492) and cobalt disulfide (PDF 41-1471), the prepared sample is a composite of molybdenum disulfide and cobalt disulfide, and the rest peaks are from the CFP substrate. Fig. 13 is an XRD pattern of the control sample. For Co-Mo-S (Co: mo=1:4) nanosheets prepared only by hydrothermal step, no diffraction peak of cobalt sulfide is seen, and the phase is molybdenum disulfide. The Co-Mo-S nano-sheet prepared by the hydrothermal method is subjected to high-temperature annealing, basically still is a diffraction peak of molybdenum disulfide, and for a control sample of the Co-Mo-S nano-sheet with high cobalt content (Co: mo=1:3) and subjected to 600 ℃ annealing, two small peaks of cobalt disulfide appear near 32.2 DEG and 36.2 DEG of 2 theta. FIG. 12 is a comparison of FIG. 13 showing that the cobalt disulfide in the molybdenum disulfide and cobalt disulfide composite of the above example is mainly obtained by the reaction of the cobalt salt coated in the second step with sulfur vapor, and the minor part is cobalt disulfide precipitated from the Co-Mo-S skeleton by annealing and recrystallizing the first-step hydrothermal product in the third-step sulfur atmosphere. The cobalt element hydrothermally introduced in the first step is still more present in the final product in doped form.
Fig. 14 is an SEM image of the sample prepared in example 2. The platelets in the figure are molybdenum disulfide nanosheets which grow almost perpendicular to the fiber surface of the CFP, exposing the edges of the highly active molybdenum disulfide layer. Cobalt disulfide nano particles are uniformly loaded between the gaps of the molybdenum disulfide nano sheets. FIG. 15 is an SEM image of Mo-S prepared by the procedure of example 1 only in the step (1). FIG. 16 is an SEM image of Co-Mo-S prepared in example 5 by the process of step (1) alone. As can be seen from the figure, the Mo-S or Co-Mo-S after the first hydrothermal step is nano-flake and has no particles, and as can be seen from comparison of FIG. 14, the nano-particles between the nano-flakes in FIG. 14 are mainly synthesized in situ through the steps of cobalt salt coating and annealing.
Table 1 examples samples and controls are summarized in the table of HER performance parameters.
Table 2 the OER performance parameters of the example samples and the control samples are summarized.

Claims (5)

1. The preparation method of the molybdenum disulfide nanosheet@cobalt sulfide nanoparticle in-situ array electrode is characterized in that the in-situ array electrode is a composite electrode of molybdenum disulfide nanosheets and cobalt sulfide nanoparticles, and the preparation method specifically comprises the following steps:
(1) And carrying out hydrothermal growth of molybdenum disulfide or cobalt molybdenum sulfide on the surface of the carbon fiber paper to obtain a Mo-S or Co-Mo-S nanosheet array electrode, wherein Co in the Co-Mo-S nanosheets: mo atomic ratio is 0.1-0.34: 1, a step of;
(2) Dissolving cobalt salt in a volatile nonaqueous solvent, wherein the concentration of cobalt element in the cobalt salt is 400-1200 mM, coating the cobalt salt on the surface of the nano-sheet array electrode, and drying for later use;
(3) And (2) placing the sample in the step (2) into an S atmosphere, wherein the S atmosphere is generated by evaporating sulfur powder, ar gas or N 2 gas is used as carrier gas to be carried and transmitted to the surface of a reaction sample, in-situ deposition of cobalt sulfide nano particles is carried out, and the in-situ deposition is carried out along with furnace cooling and taking out, so that the molybdenum disulfide nano sheet@cobalt sulfide nano particle in-situ array electrode can be obtained, wherein the in-situ deposition is carried out at the reaction temperature of 500-600 ℃ for 1-3 hours.
2. The method for preparing the molybdenum disulfide nanosheet @ cobalt sulfide nanoparticle in-situ array electrode according to claim 1, wherein the volatilizing nonaqueous solvent in the step (2) comprises: ethanol, N-dimethylformamide, formamide.
3. The method for preparing the molybdenum disulfide nanosheet @ cobalt sulfide nanoparticle in-situ array electrode, as claimed in claim 1, wherein the cobalt salt in the step (2) is easily soluble in a polar volatile non-aqueous solvent.
4. The method for preparing the molybdenum disulfide nanosheet@cobalt sulfide nanoparticle in-situ array electrode, which is characterized in that cobalt salt in the step (2) comprises one or a combination of a plurality of cobalt chloride, cobalt acetate, cobalt sulfate and cobalt nitrate.
5. The method for preparing the molybdenum disulfide nanosheet@cobalt sulfide nanoparticle in-situ array electrode according to claim 1, wherein the in-situ deposition in the step (3) is performed at a reaction temperature of 550 ℃ for a reaction time of 2 h.
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