CN113130216B - 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
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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 and 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) Mixing molybdenum salt and 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 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.
Description
Technical Field
The present invention belongs to the field of hydrogen energy technologyThe technical field, in particular to a MoS 2 @ 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 to 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 rich storage. 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 MoS 2 Further 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) 2 To represent molybdenum disulfide).
The second purpose of the invention is to provide the 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 above 2 Application of @ ZIF-67@ CoO-NF composite material.
The purpose of the invention is realized by the following technical scheme:
in-situ synthesis MoS 2 A 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, placing the ZIF-67@ CoO-NF composite material obtained in the step (b) in the mixed solution for electrodeposition, and finally obtaining MoS 2 @ ZIF-67@ CoO-NF composite materials.
In step (a), the molar ratio of cobalt salt to urea is 1.
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 6h.
In the step (a), drying is carried out in a vacuum drying oven at the drying temperature of 50-70 ℃, preferably 60 ℃ 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 is preferably 300 ℃, and the calcination time is 1.5-2.5 h, preferably 2h.
In the step (b), the molar volume ratio of 2-methylimidazole to methanol was 10mmol.
In the step (b), the standing temperature is room temperature, the standing time is 3-5 h, preferably 4h, 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.
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 2400s;
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.
Prepared by the methodMoS of (1) 2 @ ZIF-67@ CoO-NF composite material, wherein the porosity of foamed nickel is about 95%, coO-NF is core, ZIF-67 and MoS 2 Sequentially wrapping the outer surface of the CoO-NF.
MoS as described above 2 The application of the @ ZIF-67@ CoO-NF composite material in the electrocatalytic hydrogen evolution reaction, in particular to the application in the aspect of electrocatalytic hydrogen evolution of alkaline solution, and during the application, moS is added 2 The @ 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 MoS 2 The @ 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 MoS 2 The @ 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 the MoS is cleaned by 1.0M potassium hydroxide solution 2 And the electrode surface of the @ ZIF-67@ CoO-NF electrode is connected with an electrochemical workstation finally 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 sulfide 2 The 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 sound-absorbing porous metal with 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, and the nickel framework is hollow and hollowAre mutually connected in a metallurgical state, and have 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)MoS 2 The @ 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, respectively 2 A comparative electrochemical performance diagram of the @ ZIF-67@ CoO-NF composite material and the ZIF-67@ CoO-NF composite material obtained in the comparative example 1;
FIG. 2 shows MoS obtained in examples 1, 2, 3 and 4, respectively 2 The electrochemical performance comparison graph of the @ ZIF-67@ CoO-NF composite material and the ZIF-67@ CoO-NF composite material obtained in the comparative example 1;
FIG. 3 shows the MoS obtained in example 2 2 The material stability graph of the @ 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
MoS 2 The @ 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 substrate is cut into a sample of 1cm x 4cm, and then ultrasonically treated with acetone and absolute ethyl alcohol for 25 minutes, finally washed with deionized water and then dried, 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) 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: -0.6V; electrodeposition time: 2400s, electrodeposition temperature: at 25 ℃, finally obtaining MoS 2 @ ZIF-67@ CoO-NF hydrogen evolution material, noted as MoS 2 @ZIF-67@CoO-NF-0.6 2400。
The MoS of example 1 was used 2 The @ ZIF-67@ CoO-NF hydrogen evolution material is directly used as a working electrode in the electrocatalytic hydrogen evolution reaction without drying, and specifically comprises the following steps:
(1)MoS 2 the @ ZIF-67@ CoO-NF hydrogen evolution material is washed twice by deionized water and isopropanol respectively and directly used as a working electrode in electrocatalytic hydrogen evolution reaction without drying.
(2) Preparing 1.0M potassium hydroxide solution as electrocatalytic electrolyte, introducing nitrogen to drive off air, and then adding MoS 2 The @ ZIF-67@ CoO-NF, ag/AgCl and platinum electrodes are respectively used as a working electrode and a reference electrode, the counter electrode is connected with an electrochemical workstation, and the electrocatalytic hydrogen evolution performance of the electrode material is measured in an electrolyte and is respectively shown in figures 1 and 2 (figure 1 is currentDensity versus voltage, fig. 2 versus overpotential versus current density, the same below). As can be seen from FIG. 1, at a current density of 10mA cm -2 The 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
2-Methylimidazole 10mmol
Methanol 20mL
0.07mmol of molybdenum nitrate tetrahydrate
2.0mmol of sodium sulfide nonahydrate
Nitric acid 0.1mL
MoS 2 The @ 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) 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 MoS 2 @ ZIF-67@ CoO-NF hydrogen evolution material, noted as MoS 2 @ZIF-67@CoO-NF-0.8 2400。
MoS of example 2 2 @ ZIF-67@ CoO-NF hydrogen evolution materialThe method can be directly used as a working electrode in the electrocatalytic hydrogen evolution reaction without drying, and specifically comprises the following steps:
(1)MoS 2 the @ ZIF-67@ CoO-NF hydrogen evolution material is washed twice by deionized water and isopropanol respectively and directly used as a working electrode in electrocatalytic hydrogen evolution reaction without drying.
(2) Preparing 1.0M potassium hydroxide solution as electrocatalytic electrolyte, introducing nitrogen to drive off air, and then adding MoS 2 The @ ZIF-67@ CoO-NF, ag/AgCl electrode and platinum electrode 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 -2 Has an overpotential of 226mV, and as can be seen from FIG. 2, the Tafel slope of this material is 64.85mV dec -1 As 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), which indicates 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
MoS 2 The @ 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) 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 MoS 2 @ ZIF-67@ CoO-NF hydrogen evolution material, noted as MoS 2 @ZIF-67@CoO-NF-1.0 2400。
MoS of example 3 2 The @ ZIF-67@ CoO-NF hydrogen evolution material can be directly used as a working electrode in electrocatalytic hydrogen evolution reaction without drying, and specifically comprises the following steps:
(1)MoS 2 the @ ZIF-67@ CoO-NF hydrogen evolution material is washed twice by deionized water and isopropanol respectively and directly used as a working electrode in electrocatalytic hydrogen evolution reaction without drying.
(2) Preparing 1.0M potassium hydroxide solution as electrocatalytic electrolyte, introducing nitrogen to drive off air, and then adding MoS 2 The @ ZIF-67@ CoO-NF, ag/AgCl electrode and platinum electrode are respectively used as a working electrode, a reference electrode and a counter electrode to be 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 -2 Has 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
MoS 2 @ZIF-67@CoO-NFThe composite material is prepared by the preparation method comprising the following steps:
(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) Then mixing 10mmol of 2-methylimidazole and 20mL of methanol solution to obtain 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, and finally obtaining the ZIF-67@ CoO-NF composite material.
(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 ℃, 0.01V/s) to finally obtain MoS 2 @ ZIF-67@ CoO-NF hydrogen evolution material, noted as MoS 2 @ZIF-67@CoO-NF CV。
The MoS of example 4 was used 2 The @ ZIF-67@ CoO-NF hydrogen evolution material can be directly used as a working electrode in electrocatalytic hydrogen evolution reaction without drying, and specifically comprises the following steps:
(1)MoS 2 the @ 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 MoS 2 The @ ZIF-67@ CoO-NF, ag/AgCl electrode and platinum electrode are respectively used as a working electrode, a reference electrode and a counter electrode to be 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 -2 Is 285 mV, and as can be seen in FIG. 2, the Tafel slope of this material is 72.41mV dec -1 。
Comparative example 1
Raw materials: cobalt nitrate hexahydrate 1.0mmol
2.0mmol of urea
2-Methylimidazole 10mmol
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; 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 the electrocatalytic hydrogen evolution reaction, and specifically comprising the following steps:
(1) The ZIF-67@ CoO-NF hydrogen evolution material is directly used as a working electrode in the electrocatalytic hydrogen evolution reaction after being washed twice by deionized water and isopropanol and dried.
(2) 1.0M potassium hydroxide solution is prepared to be used as electrocatalysis electrolyte, nitrogen is introduced to drive off air, ZIF-67@ CoO-NF, ag/AgCl electrodes and platinum electrodes are respectively used as a working electrode, a reference electrode and a counter electrode to be connected with an electrochemical workstation, and the electrocatalysis hydrogen evolution performance of the electrode material is measured in the electrolyte and is respectively shown in figures 1 and 2. As can be seen from FIG. 2, the Tafel slope of this material is 94.76mV dec -1 As can be seen from FIG. 1, at a current density of 10mA cm -2 Is 402mV.
Comparing examples 1, 2, 3, 4 and comparative example 1, it can be found that MoS of the present invention 2 @ZIF-67@CoOThe overpotential of the-NF composite material is low, which is beneficial to hydrogen evolution.
Example 5
MoS 2 In 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 foam 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 1.5h; 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. Obtained MoS 2 The @ ZIF-67@ CoO-NF composite material has good hydrogen evolution capability.
Example 6
MoS 2 In 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, the drying temperature is 70 ℃, the calcining temperature is 280 ℃, and the calcining time is 2.5h; 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 obtained 2 The @ 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 modifications and alterations without departing from the scope of the present invention.
Claims (8)
1. In-situ synthesis MoS 2 Method for @ ZIF-67@ CoO-NF composite material, characterized in thatThe method specifically comprises the following steps:
(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, putting the ZIF-67@ CoO-NF composite material obtained in the step (b) into the mixed solution for electrodeposition, and finally obtaining MoS 2 @ ZIF-67@ CoO-NF composite;
the MoS 2 @ ZIF-67@ CoO-NF composite material takes CoO-NF as inner core, ZIF-67 and MoS 2 The nickel foam is sequentially wrapped on the outer surface of CoO-NF, and the porosity of the nickel foam is 95%;
in the step (b), the molar volume ratio of the 2-methylimidazole to the methanol is 10mmol; and standing for 3 to 5 hours at room temperature, and washing for later use after standing is finished.
2. An in situ synthesized MoS according to claim 1 2 The 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;
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 25-30min by using acetone and absolute ethyl alcohol, finally washing by using deionized water, and then drying.
3. The in situ synthesized MoS of claim 1 2 The method of 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 1-5min.
4. The in situ synthesized MoS of claim 1 2 A method of @ ZIF-67@ CoO-NF composite material, characterized in that in the step (a), the hydrothermal temperature is 100 to 140 ℃ and the hydrothermal time is 5 to 7h;
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 1 2 A process of @ ZIF-67@ coo-NF composite, characterized in that in step (c) the molar ratio of molybdenum salt to sulfide is 0.07;
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.
6. The in situ synthesized MoS of claim 1 2 The 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 2600s;
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.
7. MoS produced by the method of any one of claims 1 to 6 2 @ ZIF-67@ CoO-NF composite material.
8. MoS according to claim 7 2 The application of the @ ZIF-67@ CoO-NF composite material in the electrocatalytic hydrogen evolution reaction is characterized in that MoS 2 The @ ZIF-67@ CoO-NF composite material is used as a working electrode in the electrocatalytic hydrogen evolution reaction.
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