Nickel-cobalt-molybdenum disulfide hollow nanocomposite and synthesis method and electrocatalytic hydrogen evolution application thereof
Technical Field
The invention relates to a nickel cobalt-molybdenum disulfide hollow nanocomposite, a synthesis method thereof and an electrocatalytic hydrogen evolution application, belonging to the fields of nanomaterials and electrochemistry.
Background
With the development of society and technology, the increasing industrial demands and the exhaustion of traditional fossil fuels require energy to be innovated. Hydrogen is an emerging energy carrier, which is not as sustainable as wind and solar energy, and is called a most promising fuel to replace fossil fuels due to its high energy and environmental friendliness. There are three main ways to produce hydrogen, and the current society is concerned with producing hydrogen by electrolysis of water. The electrolyzed water comprises two half reactions, namely a hydrogen evolution reaction and an oxygen evolution reaction. However, in alkaline solutions, H is a high kinetic barrier + To H 2 A high overpotential is required for the transfer process. Platinum and its alloys, although the most catalytically active catalysts in alkaline solutions, are severely limited in their wide range of applications by the rarity and expensive cost of platinum and its alloys. Therefore, it is of great importance to find high performance platinum-free hydrogen evolution catalysts.
There has been a great deal of research into alternatives to platinum group noble metals and metal oxides, wherein transition metal chalcogenides are considered as novel electrochemical catalytic materials promising alternatives to noble metal catalysts due to their excellent catalytic activity, low cost and abundant minerals. Among the transition metal sulfides, molybdenum disulfide is the most potential electrochemical hydrogen evolution material due to its gibbs free energy change close to 0. However, researchers found that the active site of disulfide is at the edge instead of the basal plane and the layered structure limits the exposure of the active site, thus reducing the electrochemical hydrogen evolution performance, and for this problem, CN111233041a discloses a method for preparing ionic liquid intercalated nano molybdenum disulfide, which has a layer spacing of 1.0-4.0nm, high dispersibility and a high exposure rate of the active site at the side. On the other hand, there are studies for improving the electrochemical hydrogen evolution performance of molybdenum disulfide by additionally introducing other compounds or metals, such as: CN111389434a discloses a molybdenum disulfide-based composite material, and a preparation method and application thereof, the preparation method comprises: adding the molybdenum disulfide material into the grinding material molybdenum carbide, grinding and mixing, adding into a solvent, introducing inert gas and reaction gas, and performing heat treatment to obtain the molybdenum disulfide-based composite material. The molybdenum disulfide-based composite material prepared by the method has high electrocatalytic activity and has wide application prospects in the fields of water electrolysis hydrogen production, supercapacitors, ion batteries and the like. CN111151272a provides a cobalt-iron doped molybdenum disulfide-based material and a preparation method thereof, the cobalt-iron doped molybdenum disulfide-based material is nano-sheet flower-like structure powder, and two non-noble metal elements are utilized to improve the catalytic activity of sites. However, the flower-like structure of the nano sheet has the problem of poor conductivity, and the electrochemical hydrogen evolution performance is hindered due to the slow electron transport speed of the sheet-like structure.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a nickel cobalt-molybdenum disulfide hollow nanocomposite and a synthesis method thereof.
The invention also provides an electrocatalytic hydrogen evolution application of the nickel cobalt-molybdenum disulfide hollow nanocomposite.
Summary of the invention: the invention utilizes the metal organic framework as a precursor to synthesize the hollow nano material with a special structure, and the hollow nano material is applied to electrocatalytic hydrogen evolution. The method for synthesizing the nickel cobalt-molybdenum disulfide hollow nanocomposite by using the solvothermal method is simple and convenient, the product is convenient and easy to obtain, the environment is not polluted, and the method also has good electrochemical performance on electrochemical hydrogen evolution.
Description of the terminology:
room temperature, having a meaning well known in the art, is generally 23±3 ℃.
ZIF-67 precursor refers to an organometallic framework precursor formed by the reaction of a cobalt source and an organic ligand.
The technical scheme of the invention is as follows:
the hollow nickel-cobalt-molybdenum disulfide nano composite material has the shape of polyhedral nano particles with the particle size of 250-500nm;
the nickel cobalt-molybdenum disulfide hollow nanocomposite is prepared by taking an organic metal skeleton precursor formed by a cobalt source and an organic ligand as a self-sacrifice template, reacting with a nickel source in a solvent, and then adding a sulfur source and a molybdenum source for hydrothermal reaction.
According to the invention, the nickel cobalt-molybdenum disulfide hollow nano composite material has a dodecahedron hollow structure, and the particle size is 300-400nm; preferably, the thickness of the molybdenum disulfide at the edge is 60-65nm. Further preferably, the dodecahedron is a rhombic dodecahedron.
According to the invention, a method for synthesizing a nickel cobalt-molybdenum disulfide hollow nanocomposite comprises the following steps:
dissolving a cobalt source and an organic ligand in a solvent, and reacting at room temperature to form an organometallic framework precursor (ZIF-67 precursor);
dispersing the obtained precursor into a solvent, adding a nickel source, and stirring at room temperature;
and then adding a sulfur source and a molybdenum source to perform a one-step hydrothermal reaction step.
Preferably according to the invention, the molar ratio of cobalt source to organic ligand is from 1:6 to 9, preferably from 1:7 to 8; the cobalt source is cobalt nitrate hexahydrate, and the organic ligand is 2-methylimidazole.
Preferably, according to the present invention, the nickel source is nickel nitrate hexahydrate. The molar ratio of the cobalt source to the nickel source is 1-5:1, namely, the molar ratio of the cobalt nitrate hexahydrate to the nickel nitrate hexahydrate is 1-5:1. It is further preferred that the molar ratio of cobalt source to nickel source is 3.5-4:1, particularly 3.9:1.
According to the invention, the molar ratio of molybdenum source to sulfur source is preferably 1:3-5, most preferably the molar ratio of molybdenum source to sulfur source is 1:4. The sulfur source is thioacetamide, and the molybdenum source is sodium molybdate dihydrate.
According to the invention, the molar ratio of molybdenum source to cobalt source is preferably between 0.1 and 4:1. further preferably, the molar ratio of molybdenum source to cobalt source is 1-3:1, a step of; most preferably the molar ratio of molybdenum source to cobalt source is in the range of 2.0 to 2.5:1. Too low or too high molybdenum-cobalt molar ratio is detrimental to product electrocatalytic hydrogen evolution. In the preferred embodiment of the invention, the molar ratio of the molybdenum source to the cobalt source is 2.2:1.
preferably, according to the present invention, the solvent is methanol or ethanol. Further preferably, the solvent in which the cobalt source reacts with the organic ligand is methanol; the solvent in which the ZIF-67 precursor is dissolved is ethanol.
According to the invention, the cobalt source is reacted with the organic ligand for a period of time ranging from 20 to 28 hours at room temperature, more preferably 24 hours.
According to the invention, preferably, the precursor is dispersed into a solvent and stirred with a nickel source at room temperature for reaction time of 30-60min; it is further preferable that the reaction time is 45 minutes.
According to the present invention, the hydrothermal reaction temperature is preferably 180 to 210 ℃, and more preferably, the hydrothermal reaction temperature is 200 ℃. The hydrothermal reaction time is 6-18h, and more preferably, the hydrothermal reaction time is 12h.
In more detail, the synthesis method of the nickel cobalt-molybdenum disulfide hollow nanocomposite material comprises the following steps:
(1) Respectively dissolving cobalt nitrate hexahydrate of a cobalt source and 2-methylimidazole of an organic ligand in methanol, mixing, standing at room temperature for reaction for 20-28h, centrifuging after the reaction is finished, and drying to obtain a ZIF-67 precursor;
(2) Dissolving the ZIF-67 precursor obtained in the step (1) in an ethanol solvent, adding nickel source nickel nitrate hexahydrate, stirring at room temperature for reaction for 30-60min, and obtaining a product for centrifugal washing;
(3) Redispersing the product obtained in the step (2) in an ethanol solvent, and adding molybdenum source sodium molybdate dihydrate and sulfur source thioacetamide;
(4) Pouring the mixed solution obtained in the step (3) into a hydrothermal kettle, and reacting for 6-18h at 180-210 ℃;
(5) And after the reaction is finished, cooling to room temperature, and centrifugally washing and drying the product to obtain the nickel-cobalt-molybdenum disulfide hollow nanocomposite.
In the step (2), the ZIF-67 precursor is sacrificed, and a hollow structure of the double metal hydroxide, namely nickel cobalt hydroxide, is synthesized by utilizing the reaction of the ZIF-67 precursor and nickel ion exchange, so that a framework of the nickel cobalt-molybdenum disulfide hollow nanocomposite is formed subsequently.
According to the invention, preferred reactions include one or more of the following conditions:
in the step (1), the concentration of the cobalt nitrate hexahydrate methanol solution is 0.04 to 0.055mol L -1 Preferably 0.05mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The concentration of the 2-methylimidazole methanol solution is 0.3-0.5mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably 0.4mol L -1 . The ZIF-67 precursor of the product obtained in the step (1) is purple powder.
In the step (3), the concentration of the sodium molybdate dihydrate in the ethanol solvent is controlled to be 0.01 to 0.19mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably 0.12 to 0.13mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the Most preferably 0.124mol L -1 . The concentration of thioacetamide in the ethanol solvent is controlled to be 0.06-0.7mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably 0.4 to 0.5mol L -1 . Most preferably 0.496mol L -1 。
In the step (4), the reaction temperature is 200 ℃ and the reaction time is 12 hours.
According to the invention, the nickel cobalt-molybdenum disulfide hollow nanocomposite is applied to hydrogen evolution of an electrocatalyst.
The invention is characterized in that ZIF-67 is used as a self-sacrifice template, a hollow framework of double hydroxide is synthesized by utilizing a reaction with nickel ions, then a nickel cobalt-molybdenum disulfide hollow structure with rhombic dodecahedron (a framework which keeps ZIF-67) and a large number of active sites is exposed is prepared by a one-step hydrothermal method, the hollow composite nano material has the advantages of providing a larger specific surface area, accelerating electron transmission and the like, and the synergistic effect between nickel cobalt double metal hydroxide and molybdenum disulfide promotes the electrocatalytic hydrogen evolution performance, so that the prepared catalyst has high electrocatalytic activity and stability.
The invention has the beneficial effects that:
1. the invention firstly prepares an organic metal frame as a precursor, namely a ZIF-67 precursor, and prepares a hollow nickel cobalt-molybdenum disulfide nanocomposite by taking the metal organic frame as a self-sacrifice template. The hollow structure can provide a larger specific surface area, and accelerate the electron transfer process, so that the electrocatalytic hydrogen evolution performance is improved.
2. The synthesized nickel cobalt-molybdenum disulfide (NiCo-MoS) 2 ) The hollow nano composite material has good electrochemical hydrogen evolution performance, and is 10mA cm -2 The overpotential reaches 156mV at current density with Tafel slope of 87.6mV Dec -1 . Can be applied to the field of electrocatalytic hydrogen evolution.
3. The inventor finds that the electrocatalytic hydrogen evolution performance of the hollow nano composite material of the synthesized nickel cobalt-molybdenum disulfide can be regulated and controlled through the molybdenum-cobalt ratio, and when the molybdenum-cobalt molar ratio is too low (such as lower than 0.1:1), the raw materials participating in the reaction are too few, which is unfavorable for electrocatalytic hydrogen evolution of the product. With the increase of the mole ratio of the molybdenum source and the cobalt source, the electrocatalytic hydrogen evolution performance is increased, and when the mole ratio of the molybdenum to the cobalt is 2.0-2.5:1, the catalytic performance is close to the optimal state. The mole ratio of molybdenum to cobalt exceeds 4: in the case of 1, too much molybdenum material rather hinders the catalytic activity.
4. The size of the synthesized nickel cobalt-molybdenum disulfide hollow nano composite material is controllable, experimental data show that different molybdenum cobalt ratios have obvious influence on the appearance of the catalyst, when the mole ratio of molybdenum cobalt is smaller, the obtained nickel cobalt-molybdenum disulfide composite material has smaller size, the size increases along with the increase of the proportion, but after the highest value is reached, the size of the molybdenum cobalt ratio increases again, but the size is reduced. The molybdenum-cobalt ratio can be mastered according to actual demands, and the nickel-cobalt-molybdenum disulfide hollow nanocomposite with proper size is obtained.
5. The method for synthesizing the nickel cobalt-molybdenum disulfide hollow nanocomposite is simple and easy to operate, and the product is simple and easy to obtain and does not pollute the environment.
Drawings
FIG. 1 is a transmission electron microscope picture of ZIF-67 prepared in example 1;
FIG. 2 is a transmission electron microscope photograph of nickel cobalt hydroxide nanoparticles prepared in example 1;
FIG. 3 is a transmission electron microscope photograph of the hollow nickel cobalt-molybdenum disulfide nanoparticle prepared in example 1;
FIG. 4 is a high resolution transmission electron microscope photograph of the hollow nickel cobalt-molybdenum disulfide nanoparticle prepared in example 1;
FIG. 5 is an X-ray diffraction pattern of the hollow nickel cobalt-molybdenum disulfide nanoparticles prepared in example 1;
FIG. 6 is a graph showing polarization curves of the hollow nickel cobalt-molybdenum disulfide nanoparticles prepared in example 1 and the samples of comparative examples 1-3; the abscissa is the standard hydrogen electrode potential for an Ag/AgCl reference electrode;
FIG. 7 is a graph of cyclic voltammograms of hollow nickel cobalt-molybdenum disulfide nanoparticles prepared in example 1 at different sweep rates;
FIG. 8 is an alternating current impedance picture of the hollow nickel cobalt-molybdenum disulfide nanoparticle prepared in example 1;
FIG. 9 is a Tafil plot of the nickel cobalt-molybdenum disulfide hollow nanoparticles prepared in example 1;
FIG. 10 is a graph of nickel cobalt-molybdenum disulfide hollow nanoparticles prepared in example 1, tested at-0.156V (vs. Ag/AgCl electrode) for 24h constant voltage;
fig. 11 is a graph showing polarization curves of the nickel cobalt-molybdenum disulfide hollow nanoparticles prepared in example 1 and examples 2 to 5.
FIG. 12 is a transmission electron microscope image of the hollow nanomaterial of nickel cobalt-molybdenum disulfide obtained in example 2;
FIG. 13 is a transmission electron microscope image of the hollow nanomaterial of nickel cobalt-molybdenum disulfide obtained in example 3;
FIG. 14 is a transmission electron microscope image of the hollow nanomaterial of nickel cobalt-molybdenum disulfide obtained in example 4;
FIG. 15 is a transmission electron microscope image of the hollow nanomaterial of nickel cobalt-molybdenum disulfide obtained in example 5;
fig. 16 is a process flow diagram of the hollow nanomaterial of nickel cobalt-molybdenum disulfide prepared in example 1.
Detailed Description
The method for preparing the nickel cobalt-molybdenum disulfide hollow nanocomposite according to the present invention is described in detail below with reference to specific examples and accompanying drawings. The starting materials and reagents in the examples are all commercially available products.
The main experimental reagents and instruments used in the examples are listed below:
cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·2H 2 O), 2-methylimidazole (C) 4 H 6 N 2 ) Methanol, sodium molybdate dihydrate (Na 2 MoO 4 .2H 2 O), thioacetamide (CH) 3 CSNH 2 ) Absolute ethanol, nafion (5 wt%), 20% Pt/C, magnetic stirrer (Color quick [ white)]) Bench-top high-speed centrifuges (TG 16-WS), analytical electronic balances (BS 210S), electrothermal blowing dry boxes (DHG-9015A), ultrasonic cleaners (KQ 2200B type), X-ray diffractometers (X' Pert PROMPD), transmission electron microscopes (JEM-2100 (UHR), electrochemical workstations (CHI 660E).
The method of the electrochemical experiments in the examples is as follows:
working electrode preparation: 5mg of the powder catalyst sample was dispersed into 15. Mu.L of a mixed solution of 5wt% Nafion and 500. Mu.L of absolute ethanol, sonicated for 30min to form a uniform solution, and 100. Mu.L of the mixed solution was then extracted and dropped onto pretreated carbon paper (area 1cm 2 The loading concentration was 1mg cm -2 ) As a working electrode.
The polarization curve (LSV) and Cyclic Voltammogram (CV) were tested in 1M KOH solution using CHI660E electrochemical workstation, ag/AgCl (in 3M KCl) was used as reference electrode, carbon rod electrode was used as counter electrode, and the electrolyte was pre-purged with nitrogen for 30min before each experiment to remove oxygen, and the sweep rate was set at 5 mV.s -1 And a stable polarization curve was obtained after 20 scans.
In the alternating current impedance (EIS) test, the open circuit potential parameter was set at-0.18V (vs. Ag/AgCl electrode) and the frequency was set from 100000Hz to 0.1Hz.
The overpotential (η) versus log (j) yields a tafel curve, and then the tafel slope is calculated to evaluate the catalyst's electrocatalytic hydrogen production kinetics.
All potential values in the experiment are corrected through a standard hydrogen electrode, and the polar potential calibration equation is as follows:
E RHE =E Ag/AgCl +0.059pH+E 0 Ag/AgCl (E 0 Ag/AgCl =0.209V)。
example 1 preparation of Nickel cobalt molybdenum disulfide hollow nanocomposite
1.455g (5 mmol) of cobalt nitrate hexahydrate and 3.28g (40 mmol) of 2-methylimidazole were weighed into beakers each containing 100mL of methanol, and the cobalt nitrate hexahydrate solution was poured into the 2-methylimidazole solution by magnetic stirring. After stirring for 10min, the mixture was allowed to stand at room temperature for 24h to give a purple product, which was dried by centrifugation to give ZIF-67 precursor (about 0.37 g).
Dispersing 0.04g ZIF-67 into 25mL of ethanol, performing ultrasonic dispersion to form a uniform solution, adding 0.08g (0.275 mmol) of nickel nitrate hexahydrate, stirring at room temperature for 45min, centrifuging (nickel cobalt-hydroxide) the obtained deep purple precipitate, then redispersing in 10mL of ethanol, adding 300mg (1.24 mmol) of sodium molybdate dihydrate (the molar ratio of a molybdenum source to a cobalt source is 2.2:1), 372mg (4.96 mmol) of thioacetamide into the solution, heating at 200 ℃ for 12h, naturally cooling to room temperature, and performing centrifugal drying to obtain the nickel cobalt-molybdenum disulfide hollow nanocomposite product.
Test example 1, electrochemical Hydrogen production Performance test
Linear sweep voltammetry was carried out by dispersing 5mg of a powder catalyst sample into 15. Mu.L of a mixed solution of 5wt% Nafion and 500. Mu.L of absolute ethanol, sonicating for 30min to form a uniform solution, and then dropping 100. Mu.L of the mixed solution onto pretreated carbon paper (area 1cm 2 The loading concentration was 1mg cm -2 ) As a working electrode.
The polarization curve (LSV) and Cyclic Voltammogram (CV) were tested in a 1.0M KOH solution using a CHI660E electrochemical workstation, ag/AgCl (in 3M KCl) was used as a reference electrode, a graphite electrode was used as a counter electrode, and the electrolyte was pre-purged with nitrogen for 30min before each experiment to remove oxygen, and the sweep rate was set at 5 mV.s -1 And a stable polarization curve was obtained after 20 scans. The polarization curve (LSV) of the hollow nickel cobalt-molybdenum disulfide nanocomposite of example 1 is shown in FIG. 6, the cyclic voltammogram at different sweep rates is shown in FIG. 7, the sweep rate is 5-40mV/s, the method comprisesFig. 6 shows that the hydrogen evolution performance of the nickel cobalt-molybdenum disulfide hollow nanocomposite is superior to that of the pure-phase molybdenum disulfide and the two molybdenum disulfide-based nanocomposites.
The nickel cobalt-molybdenum disulfide hollow nanocomposite of example 1 was subjected to a 24h constant voltage test at-0.156V (vs. Ag/AgCl electrode) as shown in fig. 10. From fig. 10, it can be seen that the nickel cobalt-molybdenum disulfide hollow nanocomposite has good stability in hydrogen evolution reaction.
An alternating current impedance (EIS) test, the open circuit potential parameter was set at-0.18V (vs. Ag/AgCl electrode) and the frequency was set from 100000Hz to 0.1Hz. The ac impedance image of the hollow nickel cobalt-molybdenum disulfide nanocomposite of example 1 is shown in fig. 8, and it is clear from fig. 8 that the hollow nickel cobalt-molybdenum disulfide nanocomposite has a small electron transfer resistance.
The overpotential (η) versus log (j) yields a tafel curve, and then the tafel slope is calculated to evaluate the catalyst's electrocatalytic hydrogen production kinetics. From FIG. 9, it can be seen that the nickel cobalt-molybdenum sulfide hollow nanocomposite has a small Tafil slope of 87.6mV Dec -1 。
Test example 2, characterization test
A transmission electron microscope picture of the ZIF-67 precursor prepared according to the method of example 1 is shown in FIG. 1, and as can be seen from FIG. 1, the ZIF-67 precursor is rhombic dodecahedron.
The transmission electron microscope picture of the nickel cobalt metal hydroxide prepared according to the method of example 1 is shown in fig. 2, and it is clear from fig. 2 that the prepared nickel cobalt metal hydroxide has a hollow cubic structure and a hydroxide with a lamellar structure around.
The transmission electron microscope picture of the nickel cobalt-molybdenum disulfide hollow nanomaterial prepared in example 1 is shown in fig. 3, and the high resolution transmission electron microscope picture is shown in fig. 4. As can be seen from fig. 3, the prepared powder nickel cobalt-molybdenum disulfide hollow nanomaterial has a hollow structure, and the particle size of the product is about 370nm; as can be seen from fig. 4, the (002) interplanar spacing of the synthesized nickel cobalt-molybdenum disulfide hollow nanomaterial was 0.62nm, which can be determined as molybdenum disulfide, and the XRD result was consistent.
The X-ray diffraction pattern of the hollow nano material of nickel cobalt-molybdenum disulfide prepared according to the method of example 1 is shown in fig. 5, and molybdenum disulfide with 2H phase is obtained from fig. 5.
Example 2 preparation of Nickel cobalt molybdenum disulfide hollow nanocomposite
ZIF-67 precursors were prepared as described in example 1. The difference is that:
dispersing 0.04g of ZIF-67 purple powder into 25mL of ethanol, performing ultrasonic dispersion to form a uniform solution, adding 0.08g (0.275 mmol) of nickel nitrate hexahydrate, stirring at room temperature for 45min, centrifuging the obtained purple precipitate, re-dispersing in 10mL of ethanol, adding 37.5mg (0.155 mmol) of sodium molybdate dihydrate (the molar ratio of a molybdenum source to a cobalt source is 0.287:1) and 46.5mg (0.62 mmol) of thioacetamide into the solution, heating for 12h at 200 ℃, naturally cooling to room temperature, and performing centrifugal drying to obtain a nickel cobalt-molybdenum disulfide hollow nanomaterial product, wherein a transmission electron microscope picture of the product is shown in FIG. 12, and the particle size of the product is about 220nm. The polarization curve (LSV) of the resulting nickel cobalt-molybdenum disulfide hollow nanocomposite is shown in fig. 11.
Example 3 preparation of Nickel cobalt molybdenum disulfide hollow nanocomposite
ZIF-67 precursors were prepared as described in example 1. The difference is that:
dispersing 0.04g of ZIF-67 purple powder into 25mL of ethanol, performing ultrasonic dispersion to form a uniform solution, adding 0.08g (0.275 mmol) of nickel nitrate hexahydrate, stirring at room temperature for 45min, centrifuging the obtained purple precipitate, re-dispersing in 10mL of ethanol, adding 75mg (0.31 mmol) of sodium molybdate dihydrate (the molar ratio of a molybdenum source to a cobalt source is 0.57:1) and 78mg (1.04 mmol) of thioacetamide into the solution, heating at 200 ℃ for 12h, naturally cooling to room temperature, and performing centrifugal drying to obtain a nickel cobalt-molybdenum disulfide hollow nanomaterial product, wherein the particle size of the product is about 270nm as shown in a transmission electron microscope picture of the product. The polarization curve (LSV) of the resulting nickel cobalt-molybdenum disulfide hollow nanocomposite is shown in fig. 11.
Example 4 preparation of Nickel cobalt molybdenum disulfide hollow nanocomposite
1.6g (5.5 mmol) of cobalt nitrate hexahydrate and 4.1g (50 mmol) of 2-methylimidazole were weighed into beakers each containing 100mL of methanol, and the cobalt nitrate hexahydrate solution was poured into the 2-methylimidazole solution by magnetic stirring. After stirring for 10min, the mixture was allowed to stand at room temperature for 24h to give a purple product, which was dried by centrifugation to give ZIF-67 (0.407 g).
Dispersing 0.04g of ZIF-67 purple powder into 25mL of ethanol, performing ultrasonic dispersion to form a uniform solution, adding 0.08g (0.275 mmol) of nickel nitrate hexahydrate, stirring at room temperature for 45min, centrifuging the obtained purple precipitate, re-dispersing in 10mL of ethanol, adding 150mg (0.62 mmol) of sodium molybdate dihydrate (the molar ratio of a molybdenum source to a cobalt source is 1.15:1), 186mg (2.48 mmol) of thioacetamide into the solution, heating for 12h at 200 ℃, naturally cooling to room temperature, and performing centrifugal drying to obtain a nickel cobalt-molybdenum disulfide hollow nanomaterial product, wherein the particle size of the product is about 340nm as shown in a transmission electron microscope picture of the product. The polarization curve (LSV) of the resulting nickel cobalt-molybdenum disulfide hollow nanocomposite is shown in fig. 11.
Example 5 preparation of Nickel cobalt molybdenum disulfide hollow nanocomposite
ZIF-67 precursors were prepared as described in example 1. The difference is that:
dispersing 0.04g of ZIF-67 purple powder into 25mL of ethanol, performing ultrasonic dispersion to form a uniform solution, adding 0.04g (0.1375 mmol) of nickel nitrate hexahydrate, stirring at room temperature for 45min, centrifuging the obtained purple precipitate, re-dispersing in 10mL of ethanol, adding 450mg (1.86 mmol) of sodium molybdate dihydrate (the molar ratio of a molybdenum source to a cobalt source is 3.44:1)), 628mg (8.37 mmol) of thioacetamide into the solution, heating for 12h at 200 ℃, naturally cooling to room temperature, and performing centrifugal drying to obtain a nickel cobalt-molybdenum disulfide hollow nanomaterial product, wherein the particle size of the product is about 270nm as shown in a transmission electron microscope picture of the product. The polarization curve (LSV) of the resulting nickel cobalt-molybdenum disulfide hollow nanocomposite is shown in fig. 11.
To evaluate the hydrogen evolution performance of the nickel cobalt-molybdenum disulfide hollow nanocomposite of the present invention, comparison was made with the products of comparative examples 1 to 3 below.
Comparative example 1 preparation of molybdenum disulfide-based Material (Ni-MoS 2 )
Dispersing 0.08g of nickel nitrate hexahydrate into 10mL of ethanol, performing ultrasonic dispersion to form a uniform solution, adding 300mg (1.24 mmol) of sodium molybdate dihydrate and 312mg (4.16 mmol) of thioacetamide into the solution, heating at 200 ℃ for 12h, naturally cooling to room temperature, and performing centrifugal drying to obtain Ni-MoS 2 And (5) a product.
Comparative example 2 preparation of molybdenum disulfide-based Material (Co-MoS 2 )
Dispersing 0.04g ZIF-67 purple powder into 10mL ethanol, performing ultrasonic dispersion to obtain a uniform solution, adding 300mg (1.24 mmol) sodium molybdate dihydrate and 312mg (4.16 mmol) thioacetamide into the solution, heating at 200deg.C for 12h, naturally cooling to room temperature, and centrifuging and drying to obtain Co-MoS 2 And (5) a product.
Comparative example 3 preparation of molybdenum disulfide Material
300mg (1.24 mmol) of sodium molybdate dihydrate and 312mg (4.16 mmol) of thioacetamide are dispersed into 10mL of ethanol solvent, heated for 12h at 200 ℃, naturally cooled to room temperature, and centrifugally dried to obtain the molybdenum disulfide.
The polarization curves (LSVs) of the nickel cobalt-molybdenum disulfide hollow nanoparticles prepared in example 1 and the samples of comparative examples 1-3 are shown in FIG. 6, cyclic voltammograms at different sweep rates are shown in FIG. 7, the sweep rate is 5-40mV/s, and FIG. 6 shows that the hydrogen evolution performance of the nickel cobalt-molybdenum disulfide hollow nanocomposite is superior to that of the pure-phase molybdenum disulfide (comparative example 3) and the two molybdenum disulfide-based nanomaterials (comparative examples 1-2).
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.