CN113355692A - 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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CN113355692A
CN113355692A CN202110524002.0A CN202110524002A CN113355692A CN 113355692 A CN113355692 A CN 113355692A CN 202110524002 A CN202110524002 A CN 202110524002A CN 113355692 A CN113355692 A CN 113355692A
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cobalt
molybdenum disulfide
array electrode
nanosheet
situ
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CN113355692B (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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China Three Gorges University CTGU
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    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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Abstract

The invention provides a preparation method of a molybdenum disulfide nanosheet @ cobalt sulfide nanoparticle composite electrocatalyst. Firstly, a Mo-S or Co-Mo-S nanosheet array grows on the surface of a substrate in a hydrothermal mode; dissolving cobalt salt in a volatile non-aqueous solvent, and coating the cobalt salt on the surface of the Mo-S or Co-Mo-S nanosheet array; finally, the sample was placed in an S atmosphere for in situ deposition of cobalt sulfide nanoparticles. In alkaline, medium and acid electrolyte at room temperature, the concentration of the electrolyte reaches 10 mA cm‑2The overpotential required by overpotential is about 50 mV; for alkaline and acid electrolytes, 600 mA cm is reached‑2The required overpotential is about 200 mV. This performance is very close to, and even surpasses, commercial Pt particles at large current density operation. For OER, 10 mA cm in room temperature alkaline electrolyte‑2And 100 mA cm‑2The required overpotential is 220 mV and 330 mV respectively.

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, belonging to the field of energy storage and conversion materials and devices.
Background
The problem of energy consumption is a bottleneck problem restricting the development of the world. With the gradual depletion of conventional fossil fuels, the problems of energy shortage and global environmental pollution become increasingly severe. To alleviate these problems, the development of efficient, economical and renewable green energy sources is a great pursuit. The hydrogen energy has the advantages of high energy conversion efficiency, cleanness, renewability, zero carbon emission and the like, and is considered to be a novel high-efficiency energy carrier, wherein the electrocatalytic decomposition of water (the decomposition of water into oxygen and hydrogen) is considered to be one of the most potential modes for industrial application. At present, the Hydrogen Evolution Reaction (HER) catalyst with the most efficient performance is still a platinum-based material, and the Oxygen Evolution Reaction (OER) catalyst with good performance and stability is ruthenium oxide or iridium oxide, but the expensive price and rare reserves of noble metals severely limit the large-scale commercial application of the catalyst. Therefore, the search and preparation of non-noble metal-based materials which are free of pollution, low in price and efficient and stable become an important research direction in the field of electrocatalytic water decomposition.
Molybdenum disulfide is a graphite-like two-dimensional layered transition metal sulfide, three atomic layers of S-Mo-S are connected in the layers through covalent bonds, and S-Mo-S layers are combined through Van der Waals bonds. It has been widely paid attention to because of its good stability against acid and alkali and certain electrocatalytic activity against Hydrogen Evolution Reaction (HER). Studies have shown that the active sites of molybdenum disulfide are located at the layer edges. Thus, the preparation of molybdenum disulfide nanoplates grown perpendicular to the substrate or support will be able to substantially expose a substantial majority of the layer edges. However, the HER catalytic performance of the molybdenum disulfide layer edge in alkaline and neutral aqueous solutions is still poor. For this problem, density functional theory calculations and related reports indicate: molybdenum disulfide with strong adsorption property to hydrogen protons or hydrogen atoms in water molecules and other materials with strong adsorption property to hydroxyl groups or oxygen atoms in water molecules form a heterojunction, and a heterojunction interface synergistically improves HER and OER catalytic performances of the molybdenum disulfide-based composite material. For example, Ke Fan et al prepared NiS2And MoS2The formed nano rod and the composite material are purer NiS2And MoS2Both HER and OER performance in alkaline aqueous solution are greatly improvedACS Catal.2017, 7, 6179.); mingliang Du et al prepared Co9S8@MoS2Co less uncomplexed with composite materials of carbon fibres (CNFs)9S8CNFs and MoS2The HER and OER performances of/CNFs in alkaline aqueous solution are also greatly improved (Adv. Mater. 2015, 27, 4752.)。
The types of cobalt sulfide are many, including CoS, CoS2、Co3S4、Co4S3、Co9S8、Co1-xS, etc., because the cobalt sulfide has similar chemical composition, Co atoms in the cobalt sulfide have stronger adsorption property to hydroxide radicals or oxygen atoms in water molecules. Thus, the composite material of molybdenum disulfide and other cobalt sulfide also has excellent capability of synergistically catalyzing hydrogen evolution.
Disclosure of Invention
Accordingly, the present invention is directed to an efficient method for preparing an in-situ electrode of a molybdenum disulfide and cobalt sulfide composite. On one hand, the growth of molybdenum disulfide vertical to the substrate is ensured to accelerate electron transmission and expose more molybdenum disulfide layer edge active sites; on the other hand, the molybdenum disulfide and the cobalt sulfide are ensured to form a rich heterogeneous interface, and the hydrogen evolution and the oxygen evolution are efficiently and synergistically catalyzed. The method is 'hydrothermal-solution coating-vulcanization knot making', and 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.
The method for preparing the molybdenum disulfide nanosheet @ cobalt sulfide nanoparticle in-situ array electrode by hydrothermal-solution coating-vulcanization knot making comprises the following steps:
the first step is hydrothermal: and carrying out hydrothermal growth of 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: the edge of the molybdenum disulfide layer is exposed to the maximum extent; the uniform array structure ensures that uniform gaps are left between the nanosheets so as to facilitate the loading of cobalt sulfide nanoparticles; the introduction of cobalt element in the hydrothermal process is beneficial to improving the content of cobalt sulfide generated in the subsequent sulfurization step, and further improving the OER catalytic activity of the material. It is worth noting that the atomic ratio of Co to Mo in the hydrothermal process does not need to exceed 1:3, otherwise, a precursor material of a nanosheet array structure cannot be obtained.
Second step solution coating: coating cobalt salt such as cobalt chloride, namely dissolving the cobalt salt such as cobalt chloride in a polar volatile non-aqueous solvent such as N, N-dimethylformamide under the condition of stirring at room temperature, wherein the concentration of cobalt element is 300-1500 mM; and coating the solution on a molybdenum disulfide nanosheet array, and drying in dry air, or rapidly drying on a hot bench at 70-100 ℃, or vacuum drying at 70-100 ℃. The significance of this step is: the cobalt element is uniformly dispersed on the surface of the nanosheet, so that uniform loading of subsequent generated cobalt sulfide particles is facilitated.
Thirdly, vulcanization and knot making: and (3) sintering the sample obtained in the step two at 500-600 ℃ for 1-3 h in an S atmosphere, and cooling and taking out the sample along with the furnace to obtain the molybdenum disulfide nanosheet @ cobalt sulfide nanoparticle in-situ array electrode. The significance of this step is: the elemental sulfur gas transported by the carrier gas reacts with the cobalt salt on the molybdenum disulfide nanosheet in situ to generate cobalt sulfide. The original Co-Mo-S nanosheet is recrystallized to partially separate out cobalt sulfide in the annealing process. These cobalt sulfides form rich heterojunctions with molybdenum disulfide synergistically enhancing HER and OER performance.
Drawings
FIG. 1 is a linear voltammogram (LSV) measured on a sample prepared in example 1, wherein (a) is basic HER-LSV, (b) is acidic HER-LSV, and (c) is basic OER-LSV.
FIG. 2 is a linear voltammogram (LSV) measured on 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 voltammogram (LSV) measured for samples prepared in example 3, wherein (a) is basic HER-LSV and (b) is basic OER-LSV.
FIG. 4 is a linear voltammogram (LSV) measured for samples prepared in example 4, wherein (a) basic HER-LSV and (b) acidic HER-LSV.
FIG. 5 is a linear voltammogram (LSV) measured for samples prepared in example 5, wherein (a) basic HER-LSV, (b) acidic HER-LSV, and (c) basic OER-LSV.
FIG. 6 is a linear voltammogram (LSV) measured for samples prepared in example 6, wherein (a) basic HER-LSV, (b) acidic HER-LSV, and (c) basic OER-LSV.
FIG. 7 is a linear voltammogram (LSV) measured for the control of example 6, wherein (a) basic HER-LSV and (b) basic OER-LSV.
FIG. 8 shows the alkaline HER-LSV measured on the sample prepared in example 7.
FIG. 9 shows the measured basic HER-LSV of the sample prepared in example 8.
FIG. 10 shows the measured basic HER-LSV of the sample prepared in example 9.
FIG. 11 shows the measured basic HER-LSV of the sample prepared in example 10.
Fig. 12 is an XRD pattern of the samples prepared in example 2 and example 6. In the figure, "1: 19 "is the atomic ratio of Co to Mo in the first hydrothermal reaction step of 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. "1: 4 hydrothermal reaction "control sample prepared by performing only the first hydrothermal preparation according to example 5," 1:3 CoCl-free soaking of-600oC' direct 600 after first hydrothermal step corresponding to example 6oC vulcanization annealed control for 2 h, "1: 4 CoCl-free soaking of-600oC' direct 600 after first hydrothermal step corresponding to example 5oC vulcanization annealed control for 2 h, "1: 3 CoCl-free soaking-550oC "corresponds to the control of example 6, which was subjected to the first hydrothermal step and then to the direct sulfidation annealing.
FIG. 14 is an SEM photograph of a sample prepared in example 2, wherein A is at a magnification of 1 ten thousand and B is at a magnification of 5.5 ten thousand.
Figure 15 is an SEM image of molybdenum disulfide prepared from example 1 only via step (1), wherein a is at a magnification of 200, B is at a magnification of 1 ten thousand, and C is at a magnification of 5 ten thousand.
Figure 16 is an SEM image of molybdenum disulfide prepared from example 5 only via step (1), wherein a is at a magnification of 1 ten thousand and B is at a magnification of 5 ten thousand.
Detailed Description
Characterizing conditions
The HER test method in the invention embodiment comprises the following steps: in-situ array electrode made of molybdenum disulfide nanosheets @ cobalt sulfide nanoparticlesThe electrode was a working electrode, a carbon rod was used as a counter electrode, and the other electrode was used as a reference electrode, and the scanning speed was 5 mV/s. The alkaline electrolyte is 1M KOH aqueous solution, and the acidic electrolyte is 0.5M H2SO4The aqueous solution, HER and OER tests were conducted with nitrogen and oxygen, respectively, to allow the gas to saturate spontaneously in the aqueous solution and with 200 rpm stirring during the test. The reference electrodes in alkalinity and acidity are respectively saturated Hg/HgO electrode and Hg/HgSO electrode4Electrodes, all of which are potential corrected with a reversible hydrogen electrode, the potentials described hereinafter being relative to the potential of the reversible hydrogen electrode. The electric potential is automatically carried out by using the Shanghai Chen chemical workstation in the LSV testIR) And (6) compensation. An X-ray diffraction (SEM) pattern of the sample was 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
0.1558 g of ammonium molybdate and 0.9591 g of thiourea were added to 42 mL of ultrapure water and dissolved, and the solution was poured into a 70 mL reaction vessel and carbon fiber paper (3X 5 cm)2CFP), carrying out hydrothermal treatment at 180 ℃ for 24 h, cooling, taking out the CFP, washing for 3-4 times by using ultrapure water, and drying on a hot bench. 800 mM CoCl2Adding the solution into 3 mL of DMF for dissolving, then putting the dried CFP with the molybdenum disulfide growing in the solution, standing for 30 min, taking out and drying, putting the solution into a vacuum drying oven for drying overnight, and taking out. 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 voltammogram (LSV) measured on a sample prepared in example 1, wherein (a) is basic HER-LSV, (b) is acidic HER-LSV, and (c) is basic OER-LSV. Tables 1 and 2 list the corresponding performance parameters of the electrocatalyst. As can be seen from FIG. 1 (a) and Table 1, the HER reaction in the alkaline aqueous solution generates hydrogen gas, and the current density when the electrode passes is 10 mA/cm2、100 mA/cm2、600 mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotentials are 48 mV, 108 mV and 224 mV in sequence. As can be seen from FIG. (b) and Table 1, the HER reaction in acidic aqueous solution generates hydrogen,when the current density of the electrode passing through is 10 mA/cm2、100 mA/cm2、400 mA/cm2The corresponding overpotentials were 62 mV, 113 mV, and 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 when the current density passed through the electrode is 100 mA/cm2、600 mA/cm2When the voltage is higher than the predetermined value, the corresponding overpotential is 338 mV and 418 mV in sequence.
Example 2
0.0105 g of cobalt chloride hexahydrate, 0.1479 g of ammonium molybdate and 0.9591 g of thiourea were added to 42 mL of ultrapure water to be dissolved, poured into a reaction kettle with the capacity of 70 mL, and placed into carbon fiber paper (3X 5 cm)2CFP), carrying out hydrothermal treatment at 180 ℃ for 24 h, cooling, taking out the CFP, washing for 3-4 times by using ultrapure water, and drying on a hot bench. 800 mM CoCl2Adding the solution into 3 mL of DMF for dissolving, then putting the dried CFP with the molybdenum disulfide growing in the solution, standing for 30 min, taking out and drying, putting the solution into a vacuum drying oven for drying overnight, and taking out. 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 voltammogram (LSV) measured on a sample prepared in example 2, wherein (a) basic HER-LSV, (b) acidic HER-LSV, and (c) basic OER-LSV. Tables 1 and 2 list the corresponding performance parameters of the electrocatalyst. As can be seen from FIG. 1 (a) and Table 1, the HER reaction in the alkaline aqueous solution generates hydrogen gas, and the current density when the electrode passes is 10 mA/cm2、100 mA/cm2、600 mA/cm2When the voltage is higher than the predetermined value, the corresponding overpotential is 64 mV, 129 mV and 259 mV in sequence. As can be seen from FIG. B and Table 1, hydrogen gas was generated by HER reaction in an acidic aqueous solution, and the current density passed through the electrode was 10 mA/cm2、100 mA/cm2、400 mA/cm2When the voltage is higher than the predetermined value, the corresponding overpotential is 73 mV, 139 mV, and 212 mV in sequence. As can be seen from FIG. C and Table 2, the OER reaction in the alkaline aqueous solution generates oxygen gas when the current density passed through the electrode is 10 mA/cm2、100 mA/cm2、600 mA/cm2When the voltage is higher than the predetermined value, the corresponding overpotentials are 263 mV, 330 mV and 407 mV in sequence.
Example 3
0.021 g of cobalt chloride hexahydrate, 0.1402 g of ammonium molybdate and 0.95914g of thiourea are added into 42 mL of ultrapure water to be dissolved, the solution is poured into a reaction kettle with the capacity of 70 mL, and carbon fiber paper (3 multiplied by 5 cm) is placed into the reaction kettle2CFP), carrying out hydrothermal treatment at 180 ℃ for 24 h, cooling, taking out the CFP, washing for 3-4 times by using ultrapure water, and drying on a hot bench. 800 mM CoCl2Adding the solution into 3 mL of DMF for dissolving, then putting the dried CFP with the molybdenum disulfide growing in the solution, standing for 30 min, taking out and drying, putting the solution into a vacuum drying oven for drying overnight, and taking out. 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 voltammogram (LSV) measured for samples prepared in example 3, wherein (a) is basic HER-LSV and (b) is basic OER-LSV. Tables 1 and 2 list the corresponding performance parameters of the electrocatalyst. As can be seen from FIG. 1 (a) and Table 1, the HER reaction in the alkaline aqueous solution generates hydrogen gas, and the current density when the electrode passes is 10 mA/cm2、100 mA/cm2、600 mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotentials are 54 mV, 120 mV and 252 mV in sequence. As can be seen from FIG. 2 (b) and Table 2, the OER reaction in the alkaline aqueous solution generates oxygen when the current density passed through the electrode is 100 mA/cm2、600 mA/cm2When the voltage is higher than the predetermined value, the corresponding overpotential is 320 mV and 395 mV in sequence.
Example 4
0.0315 g of cobalt chloride hexahydrate, 0.1324 g of ammonium molybdate and 0.95914g of thiourea were added to 42 mL of ultrapure water to be dissolved, poured into a reaction kettle with a capacity of 70 mL, and placed into carbon fiber paper (3X 5 cm)2CFP), carrying out hydrothermal treatment at 180 ℃ for 24 h, cooling, taking out the CFP, washing for 3-4 times by using ultrapure water, and drying on a hot bench. 800 mM CoCl2Adding the solution into 3 mL of DMF for dissolving, then putting the dried CFP with the molybdenum disulfide growing in the solution, standing for 30 min, taking out and drying, putting the solution into a vacuum drying oven for drying overnight, and taking out. 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 is a linear voltammogram (LSV) measured on samples prepared in example 4 (a) basic HER-LSV and (b) acidic HER-LSV. Table 1 lists the corresponding performance parameters of the electrocatalyst. As can be seen from FIG. 1 (a) and Table 1, the HER reaction in the alkaline aqueous solution generates hydrogen gas, and the current density when the electrode passes is 10 mA/cm2、100 mA/cm2、600 mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotentials are 56 mV, 121 mV and 252 mV in sequence. As can be seen from FIG. B and Table 1, hydrogen gas was generated by HER reaction in an acidic aqueous solution, and the current density passed through the electrode was 10 mA/cm2、100 mA/cm2、400 mA/cm2When the voltage is higher than the predetermined value, the corresponding overpotentials are 62 mV, 125 mV and 198 mV in sequence.
Example 5
0.0420 g of cobalt chloride hexahydrate, 0.1246 g of ammonium molybdate and 0.95914g of thiourea were added into 42 mL of ultrapure water to be dissolved, poured into a reaction kettle with the capacity of 70 mL, and placed into carbon fiber paper (3X 5 cm)2CFP), carrying out hydrothermal treatment at 180 ℃ for 24 h, cooling, taking out the CFP, washing for 3-4 times by using ultrapure water, and drying on a hot bench. 800 mM CoCl2Adding the solution into 3 mL of DMF for dissolving, then putting the dried CFP with the molybdenum disulfide growing in the solution, standing for 30 min, taking out and drying, putting the solution into a vacuum drying oven for drying overnight, and taking out. 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 voltammogram (LSV) measured for samples prepared in example 5, wherein (a) basic HER-LSV, (b) acidic HER-LSV, and (c) basic OER-LSV. Tables 1 and 2 list the corresponding performance parameters of the electrocatalyst. As can be seen from FIG. 1 (a) and Table 1, the HER reaction in the alkaline aqueous solution generates hydrogen gas, and the current density when the electrode passes is 10 mA/cm2、100 mA/cm2、600 mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotentials are 62 mV, 132 mV and 279 mV in sequence. As can be seen from FIG. B and Table 1, hydrogen gas was generated by HER reaction in an acidic aqueous solution, and the current density passed through the electrode was 10 mA/cm2、100 mA/cm2、400 mA/cm2When the voltage is higher than the predetermined value, the corresponding overpotential is 67 mV and 132 mV, 214 mV. As can be seen from FIG. C and Table 2, the OER reaction in the alkaline aqueous solution generates oxygen gas when the current density passed through the electrode is 10 mA/cm2、100 mA/cm2、600 mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotentials are 223 mV, 334 mV and 410 mV in sequence.
Example 6
0.0525 g of cobalt chloride hexahydrate, 0.1162 g of ammonium molybdate and 0.95914g of thiourea are added into 42 mL of ultrapure water to be dissolved, the solution is poured into a reaction kettle with the capacity of 70 mL, and carbon fiber paper (3 multiplied by 5 cm) is placed into the reaction kettle2CFP), carrying out hydrothermal treatment at 180 ℃ for 24 h, cooling, taking out the CFP, washing for 3-4 times by using ultrapure water, and drying on a hot bench. 800 mM CoCl2Adding the solution into 3 mL of DMF for dissolving, then putting the dried CFP with the molybdenum disulfide growing in the solution, standing for 30 min, taking out and drying, putting the solution into a vacuum drying oven for drying overnight, and taking out. 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 voltammogram (LSV) measured for samples prepared in example 5, wherein (a) basic HER-LSV, (b) acidic HER-LSV, and (c) basic OER-LSV. Tables 1 and 2 list the corresponding performance parameters of the electrocatalyst. As can be seen from FIG. 1 (a) and Table 1, the HER reaction in the alkaline aqueous solution generates hydrogen gas, and the current density when the electrode passes is 10 mA/cm2、100 mA/cm2、600 mA/cm2When the voltage is higher than the predetermined value, the corresponding overpotential is 65 mV, 130 mV, 264 mV in sequence. As can be seen from FIG. B and Table 1, hydrogen gas was generated by HER reaction in an acidic aqueous solution, and the current density passed through the electrode was 10 mA/cm2、100 mA/cm2、400 mA/cm2When the voltage is higher than the predetermined value, the corresponding overpotential is 68 mV, 131 mV, and 202 mV in sequence. As can be seen from FIG. C and Table 2, the OER reaction in the alkaline aqueous solution generates oxygen gas when the current density passed through the electrode is 10 mA/cm2、100 mA/cm2、600 mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotentials are 236 mV, 327 mV and 383 mV in sequence.
Control of example 6
0.0525 g of cobalt chloride hexahydrate, 0.1162 g of ammonium molybdate and 0.95914g of thiourea were added42 mL of ultrapure water was dissolved, poured into a reaction vessel having a capacity of 70 mL, and carbon fiber paper (3X 5 cm)2CFP), carrying out hydrothermal treatment at 180 ℃ for 24 h, cooling, taking out the CFP, washing for 3-4 times by using ultrapure water, and drying on a hot bench. 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 plot of the linear voltammogram (LSV) measured for the control of example 6 (prepared under the same conditions as example 6 except that no cobalt salt was applied), wherein (a) is basic HER-LSV and (b) is basic OER-LSV. As can be seen from FIG. 1 (a) and Table 1, the HER reaction in the alkaline aqueous solution generates hydrogen gas, and the current density when the electrode passes is 10 mA/cm2、100 mA/cm2、600 mA/cm2The corresponding overpotentials were 87 mV, 151 mV, and 292 mV, respectively. As can be seen from FIG. 2 (b) and Table 2, the OER reaction in the alkaline aqueous solution generates oxygen gas when the current density passed through the electrode is 10 mA/cm2、100 mA/cm2、600 mA/cm2The corresponding overpotentials are 313 mV, 384 mV, 448 mV in this order.
Example 7
0.15575g of ammonium molybdate and 0.95914g of thiourea are added into 42 mL of ultrapure water to be dissolved, the solution is poured into a reaction kettle with the capacity of 70 mL, Carbon Fiber Paper (CFP) is put into the reaction kettle, hydrothermal is carried out for 24 hours at the temperature of 200 ℃, the CFP is taken out after cooling, the solution is washed for 3-4 times by the ultrapure water and is dried on a hot bench. 800 mM CoCl2Adding the solution into 3 mL of DMF for dissolving, then putting the dried CFP with the molybdenum disulfide growing in the solution, standing for 30 min, taking out and drying, putting the solution into a vacuum drying oven for drying overnight, and taking out. 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 alkaline HER-LSV measured on the sample prepared in example 7. Table 1 lists the corresponding performance parameters of the electrocatalyst. As can be seen from the graph and Table 1, hydrogen gas is generated by HER reaction in an alkaline aqueous solution, and when the current density passed through the electrode is 10 mA/cm2、100 mA/cm2、600 mA/cm2When the corresponding overpotential68 mV, 130 mV and 244 mV in sequence.
Example 8
0.15575g of ammonium molybdate and 0.95914g of thiourea are added into 42 mL of ultrapure water to be dissolved, the solution is poured into a reaction kettle with the capacity of 70 mL, Carbon Fiber Paper (CFP) is put into the reaction kettle, hydrothermal is carried out for 24 hours at the temperature of 200 ℃, the CFP is taken out after cooling, the solution is washed for 3-4 times by the ultrapure water and is dried on a hot bench. 800 mM CoCl2Adding the solution into 3 mL of DMF for dissolving, then putting the dried CFP with the molybdenum disulfide growing in the solution, standing for 30 min, taking out and drying, putting the solution into a vacuum drying oven for drying overnight, and taking out. 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 measured basic HER-LSV of the sample prepared in example 8. Table 1 lists the corresponding performance parameters of the electrocatalyst. As can be seen from the graph and Table 1, hydrogen gas is generated by HER reaction in an alkaline aqueous solution, and when the current density passed through the electrode is 10 mA/cm2、100 mA/cm2、600 mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotentials are 78 mV, 150 mV and 286 mV in sequence.
Example 9
0.15575g of ammonium molybdate and 0.95914g of thiourea are added into 42 mL of ultrapure water to be dissolved, the solution is poured into a reaction kettle with the capacity of 70 mL, Carbon Fiber Paper (CFP) is put into the reaction kettle, hydrothermal is carried out for 24 hours at the temperature of 200 ℃, the CFP is taken out after cooling, the solution is washed for 3-4 times by the ultrapure water and is dried on a hot bench. 400 mM CoCl2Adding the solution into 3 mL of DMF for dissolving, then putting the dried CFP with the molybdenum disulfide growing in the solution, standing for 30 min, taking out and drying, putting the solution into a vacuum drying oven for drying overnight, and taking out. 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 measured basic HER-LSV of the sample prepared in example 9. Table 1 lists the corresponding performance parameters of the electrocatalyst. As can be seen from the graph and Table 1, hydrogen gas is generated by HER reaction in an alkaline aqueous solution, and when the current density passed through the electrode is 10 mA/cm2、100 mA/cm2、600 mA/cm2The corresponding overpotentials were 105 mV, 176 mV, and 317 mV in this order.
Example 10
0.15575g of ammonium molybdate and 0.95914g of thiourea are added into 42 mL of ultrapure water to be dissolved, the solution is poured into a reaction kettle with the capacity of 70 mL, Carbon Fiber Paper (CFP) is put into the reaction kettle, hydrothermal is carried out for 24 hours at the temperature of 200 ℃, the CFP is taken out after cooling, the solution is washed for 3-4 times by the ultrapure water and is dried on a hot bench. 1200 mM CoCl2Adding the solution into 3 mL of DMF for dissolving, then putting the dried CFP with the molybdenum disulfide growing in the solution, standing for 30 min, taking out and drying, putting the solution into a vacuum drying oven for drying overnight, and taking out. 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 measured basic HER-LSV of the sample prepared in example 10. Table 1 lists the corresponding performance parameters of the electrocatalyst. As can be seen from the graph and Table 1, hydrogen gas is generated by HER reaction in an alkaline aqueous solution, and when the current density passed through the electrode is 10 mA/cm2、100 mA/cm2、600 mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotentials are 99 mV, 164 mV and 288 mV in sequence.
Figure 12 is an XRD pattern of the samples of example 2 and example 6. By comparing 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 come from the CFP substrate. Fig. 13 is an XRD pattern of the control. For the Co-Mo-S (Co: Mo =1:4) nanosheet prepared through the hydrothermal step only, no diffraction peak of cobalt sulfide is seen, and the phase is molybdenum disulfide. The Co-Mo-S nanosheets prepared by hydrothermal method still have diffraction peaks of molybdenum disulfide basically after high-temperature annealing, and for a control sample of Co-Mo-S (Co: Mo =1:3) nanosheets with high cobalt content and subjected to annealing at 600 ℃, two small peaks of cobalt disulfide appear near 32.2 degrees and 36.2 degrees of 2 theta. Fig. 12 and 13 compare and illustrate that the cobalt disulfide in the composite of molybdenum disulfide and cobalt disulfide in the above example is mainly obtained by reacting the cobalt salt coated in the second step with sulfur vapor, and a small part of the cobalt disulfide precipitated from the Co-Mo-S framework is recrystallized by annealing the hydrothermal product of the first step in a sulfur atmosphere in the third step. The cobalt element introduced hydrothermally in the first step is still more present in doped form in the final product.
FIG. 14 is an SEM image of a 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 highly active molybdenum disulfide layer edges. Cobalt disulfide nano particles are uniformly loaded among gaps of the molybdenum disulfide nano sheets. FIG. 15 is an SEM photograph of Mo-S prepared in example 1 only through step (1). FIG. 16 is an SEM photograph of Co-Mo-S prepared in example 5 only through step (1). It can be seen from the figure that the Mo-S or Co-Mo-S after the first step of hydrothermal treatment is nano-flake and has no particles, and compared with FIG. 14, the nano-particles between the nano-sheets in FIG. 14 should be mainly synthesized in situ through the second cobalt salt coating step and the third annealing step.
Table 1 summary table of HER performance parameters for the example samples and the control.
Figure DEST_PATH_IMAGE001
Table 2 summary of OER performance parameters for the examples and controls.
Figure 255245DEST_PATH_IMAGE002

Claims (7)

1. A preparation method of a molybdenum disulfide nanosheet @ cobalt sulfide nanoparticle in-situ array electrode is characterized in that the in-situ array electrode is a composite electrode of the molybdenum disulfide nanosheet and cobalt sulfide nanoparticles, and the preparation method specifically comprises the following steps:
(1) growing molybdenum disulfide or cobalt molybdenum sulfide on the surface of the substrate in a hydrothermal mode to obtain a Mo-S or Co-Mo-S nanosheet array electrode;
(2) dissolving cobalt salt in a volatile non-aqueous solvent, coating the cobalt salt on the surface of the nanosheet array electrode, and drying for later use;
(3) and (3) putting the sample obtained in the step (2) into an S atmosphere, carrying out in-situ deposition on the cobalt sulfide nanoparticles, and cooling and taking out the sample along with the furnace to obtain the molybdenum disulfide nanosheet @ cobalt sulfide nanoparticle in-situ array electrode.
2. The method for preparing the molybdenum disulfide nanosheet @ cobalt sulfide nanoparticle in-situ array electrode of claim 1, wherein the Co: the Mo atomic ratio is 0.1-0.34: 1.
3. the method for preparing the molybdenum disulfide nanosheet @ cobalt sulfide nanoparticle in-situ array electrode of claim 1, wherein the volatile non-aqueous solvent of step (2) comprises: ethanol, N-dimethylformamide, formamide.
4. The preparation method of the molybdenum disulfide nanosheet @ cobalt sulfide nanoparticle in-situ array electrode as recited in claim 1, wherein the cobalt salt in the step (2) is easily soluble in a polar volatile non-aqueous solvent, and the concentration of cobalt element in the cobalt salt is 200-1200 mM.
5. The method for preparing the molybdenum disulfide nanosheet @ cobalt sulfide nanoparticle in-situ array electrode as defined in claim 1, wherein the cobalt salt in step (2) comprises one or a mixture of cobalt chloride, cobalt acetate, cobalt sulfate and cobalt nitrate.
6. The preparation method of the molybdenum disulfide nanosheet @ cobalt sulfide nanoparticle in-situ array electrode as recited in claim 1, wherein the S atmosphere in the step (3) is generated by evaporation of sulfur powder and is Ar gas or N gas2The gas is carried and transmitted to the surface of the reaction sample by the carrier gas.
7. The preparation method of the molybdenum disulfide nanosheet @ cobalt sulfide nanoparticle in-situ array electrode as claimed in claim 1, wherein the in-situ deposition in the step (3) is carried out at a reaction temperature of 500-600 ℃ for 1-3 h, particularly at a reaction temperature of 550 ℃ for 2 h.
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