CN113130216A - Molybdenum disulfide @ ZIF-67@ CoO-NF composite material and synthesis and application thereof - Google Patents
Molybdenum disulfide @ ZIF-67@ CoO-NF composite material and synthesis and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention relates to a molybdenum disulfide @ ZIF-67@ CoO-NF composite material and synthesis and application thereof, wherein the method specifically comprises the following steps: (a) mixing cobalt salt, urea and water to obtain a cobalt salt solution, soaking the treated foamed nickel in the mixed solution, and then sequentially carrying out hydrothermal treatment, drying and calcining to obtain a CoO-NF composite material; (b) mixing 2-methylimidazole with a methanol solution to obtain an imidazole solution, standing the CoO-NF composite material obtained in the step (a) in the imidazole solution for self-loading to obtain a ZIF-67@ CoO-NF composite material; (c) and (b) mixing a molybdenum salt and a sulfide to obtain a mixed solution, and then putting the ZIF-67@ CoO-NF composite material obtained in the step (b) into the mixed solution for electrodeposition to finally obtain the molybdenum disulfide @ ZIF-67@ CoO-NF composite material. Compared with the prior art, the hydrogen evolution material has low Tafel slope and overpotential, low energy barrier for breakthrough in hydrogen evolution, high hydrogen conversion rate and high speed.
Description
Technical Field
The invention belongs to the technical field of hydrogen energy, and particularly relates to a MoS2@ ZIF-67@ CoO-NF composite material and synthesis and application thereof.
Background
The global energy crisis and its associated environmental problems have created an urgent need for clean, economical sustainable energy sources. Hydrogen is known as a clean energy source in the 21 st century and is considered as an ideal energy substitute for fossil fuels due to its high energy density and environmental friendliness. Electrocatalytic water splitting to achieve large-scale hydrogen production from abundant water sources is considered a simple way to achieve this goal. Currently, Pt group metals have proven to be the most effective electrocatalysts for Hydrogen Evolution Reactions (HER). However, the low earth reserves and high cost greatly limit the widespread use of such metals. Therefore, there is a great need to develop alternative catalysts that are low cost, have similar catalytic efficiency, and have good stability towards hydrogen evolution reactions.
In general, high activity HER electrocatalysts require several characteristics (1) inherently high specific surface area; (2) high conductivity and fast electron transfer pathways; (3) a large number of active sites and rapid mass transport pathways (including transport of reaction substrates and diffusion of gaseous products). Therefore, much research effort has been devoted to developing alternatives with high efficiency and stability and with a rich stock. The nickel foam is a commercial metal functional material with three-dimensional open pores and communicated pores with a metal framework, and is widely applied to the fields of nickel-hydrogen battery electrode materials, fuel cells and the like. The material has a large electrochemical reaction interface and has a wide application prospect in the aspect of electrochemical electrode materials.
In order to solve the above problems and further improve the electrochemical activity, several strategies to address the above key problems have been proposed, and some progress has been made to date. For example, Transition Metal Disulfides (TMDs) as catalytic cathode HER, in particular molybdenum disulfide (MoS)2) Has been the focus of extensive research because it has catalytic properties similar to Pt, with near zero free energy hydrogen adsorption
And excellent thermodynamic stability. However, individual MoS2Further significant improvements in the catalytic performance of these TMDs-based catalysts to meet practical applications remain a significant challenge due to less active site exposure and poor electrical conductivity.
Disclosure of Invention
The invention aims to provide a method for in-situ synthesis of a molybdenum disulfide @ ZIF-67@ CoO-NF composite material (hereinafter referred to as MoS)2To represent molybdenum disulfide).
The second purpose of the invention is to provide a MoS2@ ZIF-67@ CoO-NF composite material prepared by the method.
It is a third object of the present invention to provide a MoS as described above2Application of @ ZIF-67@ CoO-NF composite material.
The purpose of the invention is realized by the following technical scheme:
in-situ synthesis MoS2A method of @ ZIF-67@ CoO-NF composite material, the method comprising the steps of:
(a) mixing cobalt salt, urea and water to obtain a cobalt salt solution, soaking the processed foam Nickel (NF) in the cobalt salt solution, and then sequentially carrying out hydrothermal treatment, drying and calcining to obtain a CoO-NF composite material;
(b) mixing 2-methylimidazole and methanol to obtain an imidazole solution, standing the CoO-NF composite material obtained in the step (a) in the imidazole solution for self-loading to obtain a ZIF-67@ CoO-NF composite material;
(c) mixing molybdenum salt, sulfide and water to obtain a mixed solution, adjusting the pH value, placing the ZIF-67@ CoO-NF composite material obtained in the step (b) into the mixed solution for electrodeposition, and finally obtaining MoS2@ ZIF-67@ CoO-NF composite material.
In the step (a), the molar ratio of the cobalt salt to the urea is 1: 2.
In the step (a), the cobalt salt is cobalt nitrate hexahydrate.
In the step (a), the treatment process of the foamed nickel is specifically as follows: cutting the foam nickel substrate into samples with the required size, sequentially carrying out ultrasonic treatment for 25-30 min by using acetone and absolute ethyl alcohol, finally washing by using deionized water, and then drying.
In the step (a), ultrasonic dispersion is adopted during mixing, the ultrasonic power is 500-1000W, and the ultrasonic time is 1-5 minutes.
In the step (a), the hydrothermal temperature is 100-140 ℃, and the sample structure is collapsed or unstable due to overhigh or overlow hydrothermal temperature (the same hydrothermal time), so that the temperature is preferably 120 ℃, and the hydrothermal time is preferably 5-7 h, and preferably 6 h.
In the step (a), drying is carried out in a vacuum drying oven, the drying temperature is 50-70 ℃, preferably 60 ℃, and the drying is carried out overnight.
In the step (a), the calcination is carried out in a resistance furnace, no gas is introduced into the resistance furnace, the calcination temperature is 280-320 ℃, the calcination time is preferably 300 ℃, and the calcination time is 1.5-2.5 h, preferably 2 h.
In the step (b), the molar volume ratio of the 2-methylimidazole to the methanol is 10mmol:20 mL.
In the step (b), the standing temperature is room temperature, the standing time is 3-5 hours, preferably 4 hours, and the washing is carried out for standby after the standing is finished.
In step (c), the molar ratio of molybdenum salt to sulfide is 0.07: 2.
In the step (c), the molybdenum salt is molybdenum nitrate tetrahydrate, and the sulfide is sodium sulfide nonahydrate.
In the step (c), nitric acid is added to adjust the pH, the volume addition amount of the nitric acid is 0.1mL/0.07mmol of molybdenum salt, the pH value of the mixture is about 12, the mixture is acidified to 7 by the nitric acid, and the operation pushes the reaction equilibrium to the product side, so that the formation of molybdenum disulfide is facilitated.
In the step (c), the electrodeposition adopts constant potential electrodeposition or CV electrodeposition;
the voltage of the constant potential electrodeposition is-0.6 to-1.0V, the temperature of the constant potential electrodeposition is 20 to 25 ℃, and the time of the constant potential electrodeposition is 2200 to 2600s, preferably 2400 s;
the voltage of CV electrodeposition is 0.2 to-1.2V, the temperature of CV electrodeposition is 20 to 25 ℃, and the boosting speed is 0.01V/s.
MoS prepared by the method2@ ZIF-67@ CoO-NF composite material, wherein the porosity of the foamed nickel is about 95%, the CoO-NF is taken as an inner core, ZIF-67 and MoS2And sequentially wrapping the outer surface of the CoO-NF.
MoS as described above2The application of the @ ZIF-67@ CoO-NF composite material in the electrocatalytic hydrogen evolution reaction, in particular to the electrocatalytic hydrogen evolution of alkaline solution, and during the application, MoS is used2The @ ZIF-67@ CoO-NF composite material is used as a working electrode in the electrocatalytic hydrogen evolution reaction. The method specifically comprises the following steps:
(1) 1.0M potassium hydroxide solution is prepared and nitrogen is introduced into the potassium hydroxide solution for 30 minutes to drive out the air in the solution, which is used as electrolyte for standby.
(2) The prepared MoS2The @ ZIF-67@ CoO-NF hydrogen evolution material is washed by deionized water and isopropanol once respectively without drying and is directly used as a working electrode in the electrocatalytic hydrogen evolution reaction.
(3) Mixing MoS2The @ ZIF-67@ CoO-NF electrode, the Ag/AgCl electrode and the platinum electrode are respectively connected with the working electrode, the reference electrode and the counter electrode and are mixed with 1.0M hydrogenCleaning MoS with potassium oxide solution2The electrode surface of the @ ZIF-67@ CoO-NF electrode is finally connected with an electrochemical workstation in a potassium hydroxide solution to measure the electrocatalytic hydrogen evolution performance of the hydrogen evolution material.
The invention generates CoO by a hydrothermal and calcination method, then ZIF-67 is self-loaded on NF, and then MoS is generated by molybdenum salt and sulfide2The specific surface area of the material is increased, the contact area of the material and water is increased, hydrogen is easier to prepare, the nano structure of the material is improved, and the hydrogen evolution performance and stability of the material are improved. In the composite material, the 3d orbit of the metal molybdenum is in a half-filled state, has strong adsorption effect on hydrogen atoms, greatly enhances the hydrogen evolution performance of the foamed nickel after being combined with the foamed nickel, further improves the electrochemical performance through the composite effect of two transition metal elements, improves the electrochemical performance and has simple synthesis method; the foam nickel is a sound-absorbing porous metal with a three-dimensional full-through mesh structure and excellent performance, the porosity of the foam nickel is about 95 percent, water or gas can pass through the foam nickel smoothly, the nickel frameworks are hollow and are mutually connected in a metallurgical state, and the foam nickel has the advantages of good stability, high porosity, thermal shock resistance, small bulk density, large specific surface area and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) the Tafel slope and the overpotential of the hydrogen evolution material are low, the energy barrier needed to be broken through by hydrogen evolution is low, the hydrogen conversion rate is high, and the rate is high.
(2)MoS2The @ ZIF-67@ CoO-NF composite material is used as an alloy catalyst, has lower synthesis cost than most catalysts, can be purchased as a hydrogen evolution catalyst raw material, has relatively sufficient earth reserve, and does not contain explosive and toxic-making medicaments.
Drawings
FIG. 1 shows MoS obtained in examples 1, 2, 3 and 4, respectively2A graph comparing electrochemical performances of the @ ZIF-67@ CoO-NF composite material and the ZIF-67@ CoO-NF composite material obtained in comparative example 1;
FIG. 2 shows MoS obtained in examples 1, 2, 3 and 4, respectively2@ ZIF-67@ CoO-NF composite and ZIF-67@ CoO-NF composite obtained in comparative example 1Comparing electrochemical performances of the composite materials;
FIG. 3 shows the MoS obtained in example 22@ ZIF-67@ CoO-NF composite material.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The raw materials used in the examples of the present invention are commercially available unless otherwise specified.
Example 1
Raw materials: cobalt nitrate hexahydrate 1.0mmol
2.0mmol of urea
10mmol of 2-methylimidazole
Methanol 20mL
0.07mmol of molybdenum nitrate tetrahydrate
2.0mmol of sodium sulfide nonahydrate
Nitric acid 0.1mL
MoS2The @ ZIF-67@ CoO-NF composite material is prepared by the following preparation method:
(a) mixing 1.0mmol of cobalt nitrate hexahydrate, 2.0mmol of urea and deionized water to obtain a cobalt salt solution, ultrasonically dispersing for 2 minutes at 1000W during mixing, and soaking the processed foamed nickel (a foamed nickel matrix is cut into a sample of 1cm x 4cm, and then ultrasonically treating the sample with acetone and absolute ethyl alcohol for 25 minutes in sequence, finally washing the sample with deionized water, and then drying the sample, wherein the porosity of the foamed nickel is about 95%) in the cobalt salt solution; then transferring the cobalt salt solution soaked with the foamed nickel into a hydrothermal high-pressure kettle, carrying out hydrothermal treatment for 6h at 120 ℃, and drying the foamed nickel subjected to hydrothermal treatment in a vacuum drying oven overnight at 60 ℃ to obtain a precursor; and putting the precursor into a resistance furnace, calcining for 2h at 300 ℃ under natural conditions, and introducing no gas into the resistance furnace to obtain the CoO-NF composite material.
(b) And then mixing 10mmol of 2-methylimidazole and 20mL of methanol to obtain an imidazole solution, standing the CoO-NF composite material in the imidazole solution for self-loading, wherein the standing temperature is room temperature, and the standing time is 4 hours, so that the ZIF-67@ CoO-NF composite material is finally obtained.
(c) The ZIF-67@ CoO-NF composite material is placed in a container containing 0.07mmol of molybdenum nitrate tetrahydrate,2.0mmol of sodium sulfide nonahydrate and 0.1mL of nitric acid, and performing constant potential electrodeposition, wherein the electrodeposition voltage is as follows: -0.6V; electrodeposition time: 2400s, electrodeposition temperature: at 25 ℃, finally obtaining MoS2@ ZIF-67@ CoO-NF hydrogen evolution material, noted as MoS2@[email protected] 2400。
The MoS of example 1 was used2The @ ZIF-67@ CoO-NF hydrogen evolution material can be directly used as a working electrode in an electrocatalytic hydrogen evolution reaction without drying, and specifically comprises the following steps:
(1)MoS2the @ ZIF-67@ CoO-NF hydrogen evolution material is directly used as a working electrode in the electrocatalytic hydrogen evolution reaction by being washed twice with deionized water and isopropanol respectively without being dried.
(2) Preparing 1.0M potassium hydroxide solution as electrocatalytic electrolyte, introducing nitrogen to drive off air, and then adding MoS2The @ ZIF-67@ CoO-NF, Ag/AgCl and platinum electrodes are respectively used as a working electrode and a reference electrode, a counter electrode is connected with an electrochemical workstation, and the performance of the electrode material in electrocatalytic hydrogen evolution is measured in an electrolyte and is respectively shown in figures 1 and 2 (figure 1 is a relation graph of current density and voltage, figure 2 is a relation graph of overpotential and current density, the same below). As can be seen from FIG. 1, at a current density of 10mA cm-2The overpotential of (2) is 205 mV. As can be seen from FIG. 2, the Tafel slope of this material is 106.61mV dec-1。
Example 2
Raw materials: cobalt nitrate hexahydrate 1.0mmol
2.0mmol of urea
10mmol of 2-methylimidazole
Methanol 20mL
0.07mmol of molybdenum nitrate tetrahydrate
2.0mmol of sodium sulfide nonahydrate
Nitric acid 0.1mL
MoS2The @ ZIF-67@ CoO-NF composite material is prepared by the following preparation method:
(a) mixing 1.0mmol of cobalt nitrate hexahydrate, 2.0mmol of urea and deionized water to obtain a cobalt salt solution, carrying out ultrasonic dispersion for 5 minutes at the power of 1000W during mixing, and soaking the treated foamed nickel in the cobalt salt solution; then transferring the cobalt salt solution soaked with the foamed nickel into a hydrothermal high-pressure kettle, carrying out hydrothermal treatment for 6h at 120 ℃, and drying the foamed nickel subjected to hydrothermal treatment in a vacuum drying oven overnight at 60 ℃ to obtain a precursor; and putting the precursor into a resistance furnace, calcining for 2h at 300 ℃ under natural conditions, and introducing no gas into the resistance furnace to obtain the CoO-NF composite material.
(b) And then mixing 10mmol of 2-methylimidazole and 20mL of methanol to obtain an imidazole solution, standing the CoO-NF composite material in the imidazole solution for self-loading, wherein the standing temperature is room temperature, and the standing time is 4 hours, so that the ZIF-67@ CoO-NF composite material is finally obtained.
(c) Putting the ZIF-67@ CoO-NF composite material into a mixed aqueous solution containing 0.07mmol of molybdenum nitrate tetrahydrate, 2.0mmol of sodium sulfide nonahydrate and 0.1mL of nitric acid for constant potential electrodeposition, wherein the electrodeposition voltage is as follows: -0.8V; electrodeposition time: 2400s, electrodeposition temperature: at 25 ℃, finally obtaining MoS2@ ZIF-67@ CoO-NF hydrogen evolution material, noted as MoS2@[email protected] 2400。
The MoS of example 2 was used2The @ ZIF-67@ CoO-NF hydrogen evolution material can be directly used as a working electrode in an electrocatalytic hydrogen evolution reaction without drying, and specifically comprises the following steps:
(1)MoS2the @ ZIF-67@ CoO-NF hydrogen evolution material is directly used as a working electrode in the electrocatalytic hydrogen evolution reaction by being washed twice with deionized water and isopropanol respectively without being dried.
(2) Preparing 1.0M potassium hydroxide solution as electrocatalytic electrolyte, introducing nitrogen to drive off air, and then adding MoS2The @ ZIF-67@ CoO-NF, Ag/AgCl and platinum electrodes are respectively used as a working electrode and a reference electrode, a counter electrode is connected with an electrochemical workstation, and the electrocatalytic hydrogen evolution performance of the electrode material is measured in electrolyte and is respectively shown in figures 1, 2 and 3. As can be seen from FIG. 1, at a current density of 10mA cm-2Has an overpotential of 226mV, and as can be seen from FIG. 2, the Tafel slope of this material is 64.85mV dec-1As can be seen from fig. 3, the LSV curve after 1000 cycles of CV test and the LSV curve before CV test are not greatly deviated (1 represents before CV test, and 2 represents after 1000 cycles of CV test), indicating that the material has good stability.
Example 3
Raw materials: cobalt nitrate hexahydrate 1.0mmol
2.0mmol of urea
10mmol of 2-methylimidazole
Methanol 20mL
0.07mmol of molybdenum nitrate tetrahydrate
2.0mmol of sodium sulfide nonahydrate
Nitric acid 0.1mL
MoS2The @ ZIF-67@ CoO-NF composite material is prepared by the following preparation method:
(a) mixing 1.0mmol of cobalt nitrate hexahydrate, 2.0mmol of urea and deionized water to obtain a cobalt salt solution, carrying out ultrasonic dispersion for 5 minutes at the power of 1000W during mixing, and soaking the treated foamed nickel in the cobalt salt solution; then transferring the cobalt salt solution soaked with the foamed nickel into a hydrothermal high-pressure kettle, carrying out hydrothermal treatment for 6h at 120 ℃, and drying the foamed nickel subjected to hydrothermal treatment in a vacuum drying oven overnight at 60 ℃ to obtain a precursor; and putting the precursor into a resistance furnace, calcining for 2h at 300 ℃ under natural conditions, and introducing no gas into the resistance furnace to obtain the CoO-NF composite material.
(b) And then mixing 10mmol of 2-methylimidazole and 20mL of methanol to obtain an imidazole solution, standing the CoO-NF composite material in the imidazole solution for self-loading, wherein the standing temperature is room temperature, and the standing time is 4 hours, so that the ZIF-67@ CoO-NF composite material is finally obtained.
(c) Putting the ZIF-67@ CoO-NF composite material into a mixed aqueous solution containing 0.07mmol of molybdenum nitrate tetrahydrate, 2.0mmol of sodium sulfide nonahydrate and 0.1mL of nitric acid for constant potential electrodeposition, wherein the electrodeposition voltage is as follows: -1.0V; electrodeposition time: 2400s, electrodeposition temperature: at 25 ℃, finally obtaining MoS2@ ZIF-67@ CoO-NF hydrogen evolution material, noted as MoS2@[email protected] 2400。
The MoS of example 3 was used2The @ ZIF-67@ CoO-NF hydrogen evolution material can be directly used as a working electrode in an electrocatalytic hydrogen evolution reaction without drying, and specifically comprises the following steps:
(1)MoS2the @ ZIF-67@ CoO-NF hydrogen evolution material is directly used as a working electrode in the electrocatalytic hydrogen evolution reaction by being washed twice with deionized water and isopropanol respectively without being dried.
(2) Preparing 1.0M potassium hydroxide solution as electrocatalytic electrolyte, introducing nitrogen to drive off air, and then adding MoS2The @ ZIF-67@ CoO-NF, Ag/AgCl and platinum electrodes are respectively used as a working electrode and a reference electrode, a counter electrode is connected with an electrochemical workstation, and the electrocatalytic hydrogen evolution performance of the electrode material is measured in electrolyte and is respectively shown in figures 1 and 2. It can be seen from FIG. 1 that at a current density of 10mA cm-2Has an overpotential of 234 mV, and as can be seen in FIG. 2, the Tafel slope of this material is 175.13mV dec-1。
Example 4
Raw materials: cobalt nitrate hexahydrate 1.0mmol
2.0mmol of urea
10mmol of 2-methylimidazole
Methanol 20mL
0.07mmol of molybdenum nitrate tetrahydrate
2.0mmol of sodium sulfide nonahydrate
Nitric acid 0.1mL
MoS2The @ ZIF-67@ CoO-NF composite material is prepared by the following preparation method:
(a) mixing 1.0mmol of cobalt nitrate hexahydrate, 2.0mmol of urea and deionized water to obtain a cobalt salt solution, carrying out ultrasonic dispersion for 5 minutes at the power of 1000W during mixing, and soaking the treated foamed nickel in the cobalt salt solution; then transferring the cobalt salt solution soaked with the foamed nickel into a hydrothermal high-pressure kettle, carrying out hydrothermal treatment for 6h at 120 ℃, and drying the foamed nickel subjected to hydrothermal treatment in a vacuum drying oven overnight at 60 ℃ to obtain a precursor; and putting the precursor into a resistance furnace, calcining for 2h at 300 ℃ under natural conditions, and introducing no gas into the resistance furnace to obtain the CoO-NF composite material.
(b) And then mixing 10mmol of 2-methylimidazole and 20mL of methanol solution to obtain an imidazole solution, standing the CoO-NF composite material in the imidazole solution for self-loading, wherein the standing temperature is room temperature, and the standing time is 4 hours, so that the ZIF-67@ CoO-NF composite material is finally obtained.
(c) Putting the ZIF-67@ CoO-NF composite material into a mixed aqueous solution containing 0.07mmol of molybdenum nitrate tetrahydrate, 2.0mmol of sodium sulfide nonahydrate and 0.1mL of nitric acid for CV electrodeposition (0.2 to-1.2V, 20-25 ℃ and 0.01V)S) to finally obtain MoS2@ ZIF-67@ CoO-NF hydrogen evolution material, noted as MoS2@ZIF-67@CoO-NF CV。
The MoS of example 4 was used2The @ ZIF-67@ CoO-NF hydrogen evolution material can be directly used as a working electrode in an electrocatalytic hydrogen evolution reaction without drying, and specifically comprises the following steps:
(1)MoS2the @ ZIF-67@ CoO-NF hydrogen evolution material is directly used as a working electrode in the electrocatalytic hydrogen evolution reaction by being washed twice with deionized water and isopropanol respectively without being dried.
(2) Preparing 1.0M potassium hydroxide solution as electrocatalytic electrolyte, introducing nitrogen to drive off air, and then adding MoS2The @ ZIF-67@ CoO-NF, Ag/AgCl and platinum electrodes are respectively used as a working electrode and a reference electrode, a counter electrode is connected with an electrochemical workstation, and the electrocatalytic hydrogen evolution performance of the electrode material is measured in electrolyte and is respectively shown in figures 1 and 2. As can be seen from FIG. 1, at a current density of 10mA cm-2The overpotential of (1) is 285 mV, and as can be seen from FIG. 2, the Tafel slope of the material is 72.41mV dec-1。
Comparative example 1
Raw materials: cobalt nitrate hexahydrate 1.0mmol
2.0mmol of urea
10mmol of 2-methylimidazole
Methanol 20mL
A ZIF-67@ CoO-NF composite material is prepared by the following steps:
1.0mmol of cobalt nitrate hexahydrate, 2.0mmol of urea and deionized water are mixed to obtain a cobalt salt solution, ultrasonic dispersion is carried out for 5 minutes at the power of 1000W, and the treated foamed nickel is soaked in the cobalt salt solution; then transferring the cobalt salt solution soaked with the foamed nickel into a hydrothermal high-pressure kettle, carrying out hydrothermal treatment for 6h at 120 ℃, and drying the foamed nickel subjected to hydrothermal treatment in a vacuum drying oven overnight at 60 ℃ to obtain a precursor; putting the precursor into a resistance furnace, calcining for 2h at 300 ℃ under natural conditions, and introducing no gas into the resistance furnace to obtain a CoO-NF composite material; and then mixing 10mmol of 2-methylimidazole and 20mL of methanol to obtain an imidazole solution, standing the CoO-NF composite material in the imidazole solution for self-loading, wherein the standing temperature is room temperature, and the standing time is 4 hours, so that the ZIF-67@ CoO-NF composite material is finally obtained.
Drying the ZIF-67@ CoO-NF hydrogen evolution material of the comparative example 1 to be used as a working electrode in an electrocatalytic hydrogen evolution reaction, specifically comprising the following steps:
(1) the ZIF-67@ CoO-NF hydrogen evolution material is directly used as a working electrode in an electrocatalytic hydrogen evolution reaction after being washed twice by deionized water and isopropanol respectively and dried.
(2) Preparing 1.0M potassium hydroxide solution as an electrocatalytic electrolyte, introducing nitrogen to drive air away, taking ZIF-67@ CoO-NF, Ag/AgCl electrodes and platinum electrodes as a working electrode and a reference electrode respectively, connecting a counter electrode to an electrochemical workstation, and measuring the electrocatalytic hydrogen evolution performance of the electrode material in the electrolyte as shown in figures 1 and 2 respectively. As can be seen from FIG. 2, the Tafel slope of this material is 94.76mV dec-1As can be seen from FIG. 1, at a current density of 10mA cm-2The overpotential of (2) is 402 mV.
Comparing examples 1, 2, 3, 4 and comparative example 1, it can be found that MoS of the present invention2The @ ZIF-67@ CoO-NF composite material has low overpotential and is favorable for hydrogen evolution.
Example 5
MoS2In the preparation method of the @ ZIF-67@ CoO-NF composite material, except for the step (a), the cobalt salt, the urea and the water are dispersed for 1min by adopting the power of 500W when being mixed, the foamed nickel matrix is sequentially subjected to ultrasonic treatment for 30min by using acetone and absolute ethyl alcohol, the hydrothermal temperature is 140 ℃, the hydrothermal time is 5h, the drying temperature is 50 ℃, the calcining temperature is 320 ℃, and the calcining time is 1.5 h; in the step (b), standing for 3 hours; the procedure of example 1 was repeated except that the temperature of the potentiostatic electrodeposition in step (c) was 25 ℃ and the time of the potentiostatic electrodeposition was 2600 seconds. The MoS obtained2The @ ZIF-67@ CoO-NF composite material has good hydrogen evolution capability.
Example 6
MoS2In the preparation method of the @ ZIF-67@ CoO-NF composite material, except for the step (a), the cobalt salt, the urea and the water are dispersed for 2min by adopting 750W power when being mixed, the foam nickel matrix is sequentially subjected to ultrasonic treatment for 27min by using acetone and absolute ethyl alcohol, the hydrothermal temperature is 100 ℃, the hydrothermal time is 7h, and drying is carried outThe temperature is 70 ℃, the calcining temperature is 280 ℃, and the calcining time is 2.5 h; in the step (b), standing for 5 hours; the procedure of example 1 was repeated except that the temperature of the potentiostatic electrodeposition in step (c) was 20 ℃ and the time of the potentiostatic electrodeposition was 2200 seconds. The MoS obtained2The @ ZIF-67@ CoO-NF composite material has good hydrogen evolution capability.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. In-situ synthesis MoS2The @ ZIF-67@ CoO-NF composite material preparation method is characterized by specifically comprising the following steps of:
(a) mixing cobalt salt, urea and water to obtain a cobalt salt solution, soaking the processed foamed nickel in the cobalt salt solution, and sequentially carrying out hydrothermal treatment, drying and calcination to obtain a CoO-NF composite material;
(b) mixing 2-methylimidazole and methanol to obtain an imidazole solution, standing the CoO-NF composite material obtained in the step (a) in the imidazole solution for self-loading to obtain a ZIF-67@ CoO-NF composite material;
(c) mixing molybdenum salt, sulfide and water to obtain a mixed solution, adjusting the pH value, placing the ZIF-67@ CoO-NF composite material obtained in the step (b) into the mixed solution for electrodeposition, and finally obtaining MoS2@ ZIF-67@ CoO-NF composite material.
2. An in situ synthesized MoS according to claim 12The method of @ ZIF-67@ CoO-NF composite material is characterized in that in the step (a), the molar ratio of cobalt salt to urea is 1: 2;
in the step (a), the cobalt salt is cobalt nitrate hexahydrate;
in the step (a), the treatment process of the foamed nickel is specifically as follows: cutting the foam nickel substrate into samples with the required size, sequentially carrying out ultrasonic treatment for 25-30 min by using acetone and absolute ethyl alcohol, finally washing by using deionized water, and then drying.
3. An in situ synthesized MoS according to claim 12The method for preparing the @ ZIF-67@ CoO-NF composite material is characterized in that in the step (a), ultrasonic dispersion is adopted during mixing, the ultrasonic power is 500-1000W, and the ultrasonic time is 1-5 min.
4. An in situ synthesized MoS according to claim 12The method for @ ZIF-67@ CoO-NF composite material is characterized in that in the step (a), the hydrothermal temperature is 100-140 ℃, and the hydrothermal time is 5-7 h;
in the step (a), drying is carried out in a vacuum drying oven at the drying temperature of 50-70 ℃ overnight;
in the step (a), the calcination is carried out in a resistance furnace, no gas is introduced into the resistance furnace, the calcination temperature is 280-320 ℃, and the calcination time is 1.5-2.5 h.
5. An in situ synthesized MoS according to claim 12The method of @ ZIF-67@ CoO-NF composite material is characterized in that in the step (b), the molar volume ratio of 2-methylimidazole to methanol is 10mmol:20 mL.
6. An in situ synthesized MoS according to claim 12The method for preparing the @ ZIF-67@ CoO-NF composite material is characterized in that in the step (b), the standing temperature is room temperature, the standing time is 3-5 hours, and the composite material is washed for later use after the standing is finished.
7. An in situ synthesized MoS according to claim 12A process of @ ZIF-67@ CoO-NF composite material, characterized in that in step (c), the molar ratio of molybdenum salt to sulfide is 0.07: 2;
in the step (c), nitric acid is added to adjust the pH, and the volume addition amount of the nitric acid is 0.1mL/0.07mmol of molybdenum salt;
in the step (c), the molybdenum salt is molybdenum nitrate tetrahydrate, and the sulfide is sodium sulfide nonahydrate.
8. An in situ synthesized MoS according to claim 12The method of @ ZIF-67@ CoO-NF composite material is characterized in that in the step (c), the electrodeposition adopts constant potential electrodeposition or CV electrodeposition;
the voltage of the constant potential electrodeposition is-0.6 to-1.0V, the temperature of the constant potential electrodeposition is 20 to 25 ℃, and the time of the constant potential electrodeposition is 2200 to 2600 s;
the voltage of CV electrodeposition is 0.2 to-1.2V, the temperature of CV electrodeposition is 20 to 25 ℃, and the boosting speed is 0.01V/s.
9. MoS produced by the method of any of claims 1-82@ ZIF-67@ CoO-NF composite material.
10. The MoS of claim 92The application of the @ ZIF-67@ CoO-NF composite material in the electrocatalytic hydrogen evolution reaction is characterized in that MoS2The @ ZIF-67@ CoO-NF composite material is used as a working electrode in the electrocatalytic hydrogen evolution reaction.
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