CN111359636A - Mo-S/NF hydrogen evolution material and preparation method and application thereof - Google Patents
Mo-S/NF hydrogen evolution material and preparation method and application thereof Download PDFInfo
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- CN111359636A CN111359636A CN202010151960.3A CN202010151960A CN111359636A CN 111359636 A CN111359636 A CN 111359636A CN 202010151960 A CN202010151960 A CN 202010151960A CN 111359636 A CN111359636 A CN 111359636A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 121
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 121
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000000463 material Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 63
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 31
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001354 calcination Methods 0.000 claims abstract description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 42
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 229920000557 Nafion® Polymers 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000012670 alkaline solution Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000007772 electrode material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000006260 foam Substances 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B01J35/33—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a Mo-S/NF hydrogen evolution material and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) mixing ammonium tetrathiomolybdate and thiourea with water, and performing ultrasonic dispersion to obtain a mixed solution; 2) adding the mixed solution into a reaction kettle, adding foamed nickel serving as a carrier into the reaction kettle, and performing hydrothermal reaction to obtain Mo-S/NF; 3) and calcining the Mo-S/NF under an anaerobic condition to obtain the Mo-S/NF hydrogen evolution material, wherein the hydrogen evolution material is applied to an electro-catalytic hydrogen evolution reaction. Compared with the prior art, the Mo-S/NF hydrogen evolution material prepared by the invention has the advantages of low raw material cost, simple preparation method and good hydrogen evolution effect in alkaline solution, and is expected to be oriented to industrial development.
Description
Technical Field
The invention belongs to the technical field of hydrogen energy, and relates to a Mo-S/NF hydrogen evolution material, and a preparation method and application thereof.
Background
With the increasing exhaustion of fossil fuels, various new energy sources are continuously developed and utilized. The hydrogen energy is used as a renewable secondary energy source, has wide source, high heat value, cleanness and good combustion stability, and is a new generation of energy carrier widely adopted after non-renewable energy sources such as fossil fuel and the like. The alkaline electrolysis of water for hydrogen production is the most potential technical means leading to hydrogen economy, but the reaction energy consumption is larger due to the existence of hydrogen evolution and oxygen evolution overpotential in the electrolysis process. In order to reduce energy consumption, it is of great significance to develop a cathode electrode material with low cost and high catalytic activity. 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. Obviously, the material has a large electrochemical reaction interface and has a wide application prospect in the aspect of electrochemical electrode materials. However, the foamed nickel material has insufficient performance in an acid solution because it is easily reacted in an acid solution.
Disclosure of Invention
The invention aims to overcome the problems of catalytic hydrogen evolution in the prior art, and provides a Mo-S/NF hydrogen evolution material, a preparation method thereof and application thereof in the aspect of electrocatalytic hydrogen evolution. The Mo-S/NF hydrogen evolution material is used as an alloy catalyst, has lower synthesis cost than most catalysts, and has sufficient earth reserve of main elements. In the metal molybdenum, the 3d orbit is in a half-filled state, has strong adsorption effect on hydrogen atoms, and greatly enhances the hydrogen evolution performance of the foamed nickel after being combined with the foamed nickel, improves the electrochemical performance and has simple synthesis method.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a Mo-S/NF hydrogen evolution material comprises the following steps:
1) mixing ammonium tetrathiomolybdate and thiourea with water, and performing ultrasonic dispersion to obtain a mixed solution;
2) adding the mixed solution into a reaction kettle, adding foamed Nickel (NF) serving as a carrier into the reaction kettle, and performing hydrothermal reaction to obtain Mo-S/NF;
3) and calcining the Mo-S/NF under an anaerobic condition to obtain the Mo-S/NF hydrogen evolution material.
Further, in the step 1), the molar ratio of the ammonium tetrathiomolybdate to the thiourea is 1 (1-5), and the ratio of the molar amount of the ammonium tetrathiomolybdate to the volume of the water is 1mmol (15-25) mL.
Further, in the step 1), the ultrasonic dispersion time is 5-10min, and a clear mixed solution is obtained after the ultrasonic dispersion.
Further, in the step 2), the temperature in the hydrothermal reaction is 150-200 ℃ and the time is 10-15 h.
Further, in the step 3), the calcination is performed in a resistance furnace, and nitrogen is introduced during the calcination.
Further, in the step 3), the temperature is 300-500 ℃ and the time is 2-4h in the calcination.
The Mo-S/NF hydrogen evolution material is prepared by the method.
Furthermore, in the hydrogen evolution material, the loading amount of Mo in the nickel foam is 15-20%.
An application of Mo-S/NF hydrogen evolution material in electrocatalytic hydrogen evolution reaction.
Further, when in application, the Mo-S/NF hydrogen evolution material and the Nafion solution are uniformly mixed, and then are dripped on a glassy carbon electrode, and the glassy carbon electrode for hydrogen evolution is obtained after drying and is used as a working electrode in the electrocatalytic hydrogen evolution reaction.
The application method specifically comprises the following steps:
(1) weighing 1mg of Mo-S/NF hydrogen evolution material, dissolving the Mo-S/NF hydrogen evolution material in 100 mu L of prepared 0.5 wt% of a Nation solution, uniformly dispersing for half an hour under ultrasonic, absorbing 12-18 mu L of the solution on a glassy carbon electrode, and naturally airing to obtain the hydrogen evolution glassy carbon electrode;
(2) preparing 1.0M potassium hydroxide solution as electrocatalytic electrolyte, introducing nitrogen to drive out air, cleaning with 1.0M potassium hydroxide solution to obtain the surface of the hydrogen evolution glassy carbon electrode, connecting the obtained hydrogen evolution glassy carbon electrode, Ag/AgCl electrode and platinum electrode to an electrochemical workstation, and carrying out electrocatalytic hydrogen evolution reaction in the electrolyte.
In the present invention, the hydrothermal reaction is aimed at: the high-temperature and high-pressure environment promotes the reaction, and the obtained product is uniform, free of agglomeration, good in crystal form and capable of being better loaded on the foamed nickel. The purpose of the calcination is: under the protection of nitrogen at high temperature, other elements on the foamed nickel can be effectively removed by calcination, and the Mo-S/NF hydrogen evolution material is obtained.
Compared with the prior art, the invention has the following characteristics:
1) in the invention, 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 without resistance, 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; the 3d orbit of the molybdenum is in a half-filled state, has strong adsorption effect on hydrogen atoms, and greatly improves the hydrogen evolution performance of the foamed nickel after being combined with the foamed nickel. Therefore, the metal which is not filled with the orbit is introduced to be combined with the foamed nickel, so that the desorption of hydrogen atoms adsorbed on the surface of the electrode is facilitated, and the hydrogen evolution performance of the metal nickel electrode is improved;
2) the Mo-S/NF hydrogen evolution material prepared by the method has the advantages of low raw material cost, simple preparation method and low Tafel slope and overpotential of the hydrogen evolution material, so the hydrogen evolution effect is good, and the material has good stability due to the introduction of non-noble metal elements.
3) The Mo-S/NF hydrogen evolution material prepared by the method disclosed by the invention can be used for electrolyzing water in an alkaline medium, and has a good hydrogen evolution effect and lower cost.
Drawings
FIG. 1 is a Tafel slope diagram of the Mo-S/NF hydrogen evolution material obtained in example 1;
FIG. 2 is a polarization curve of the Mo-S/NF hydrogen evolution material obtained in example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
The raw materials used in the examples of the present invention are commercially available unless otherwise specified.
Example 1:
ammonium tetrathiomolybdate 0.5mmol
Thiourea 0.5mmol
10mL of deionized water
The hydrogen evolution material is prepared by the preparation method comprising the following steps:
dissolving 0.5mmol of ammonium tetrathiomolybdate and 0.5mmol of thiourea in 10mL of deionized water, carrying out ultrasonic treatment in an ultrasonic oscillator for 5min until the solution is stirred and dissolved, transferring the solution to a high-pressure reaction kettle after no solid particles exist in the solution, adding 8mm × 8mm × 1mm foamed nickel, carrying out hydrothermal treatment at 180 ℃ for 12h, taking out Mo-S/NF, placing the treated Mo-S/NF into a resistance furnace, introducing nitrogen, and calcining at 300 ℃ for 2h to finally obtain the Mo-S/NF hydrogen evolution material.
Application example 1:
the Mo-S/NF hydrogen evolution material of example 1 is grinded, the surface of the glassy carbon electrode is grinded by 0.05 μm alumina, the residual sample is removed, and the material is washed by ethanol and deionized water and dried.
(1) 0.5 wt% of Nation solution was prepared with anhydrous methanol. Weighing 1mg of Mo-S/NF hydrogen evolution material, dissolving in 100 mu L of prepared Nation solution, and uniformly dispersing for 2h under ultrasound. Then, 12. mu.L of the solution was pipetted onto a glassy carbon electrode and air-dried naturally.
(2) Preparing 1.0M potassium hydroxide solutionThe liquid is used as an electrocatalytic electrolyte, nitrogen is introduced to drive away air, the electrode surface of the hydrogen evolution glassy carbon electrode is cleaned by using 1.0M potassium hydroxide solution, then the hydrogen evolution glassy carbon electrode, the Ag/AgCl electrode and the platinum electrode are connected with an electrochemical workstation, and the electrocatalytic hydrogen evolution performance of the electrode material is measured in the electrolyte. As shown in FIG. 1 and FIG. 2, the Tafel slope of the material is 137mV dec-1At a current density of 10mA cm-2The overpotential of (3) is 343 mV. And the deviation between the LSV curve after 1000 cycles of CV test and the LSV curve before CV test is not large, which shows that the material has good stability.
Example 2:
ammonium tetrathiomolybdate 0.5mmol
1.0mmol of Thiourea
10mL of deionized water
The hydrogen evolution material is prepared by the preparation method comprising the following steps:
dissolving 0.5mmol of ammonium tetrathiomolybdate and 1.0mmol of thiourea in 10mL of deionized water, carrying out ultrasonic treatment in an ultrasonic oscillator for 5min until the solution is stirred and dissolved, transferring the solution to a high-pressure reaction kettle after no solid particles exist in the solution, adding 8mm × 8mm × 1mm foamed nickel, carrying out hydrothermal treatment at 180 ℃ for 12h, taking out Mo-S/NF, placing the treated Mo-S/NF into a resistance furnace, introducing nitrogen, and calcining at 400 ℃ for 2h to finally obtain the Mo-S/NF hydrogen evolution material.
Application example 2:
the Mo-S/NF hydrogen evolution material of the embodiment 2 is grinded, the surface of the glassy carbon electrode is grinded by 0.05 μm alumina, the residual sample is removed, and the material is washed by ethanol and deionized water and dried.
(1) 0.5 wt% of Nation solution was prepared with anhydrous methanol. Weighing 1mg of Mo-S/NF hydrogen evolution material, dissolving in 100 mu L of prepared Nation solution, and uniformly dispersing for 2h under ultrasound. Then, the solution was pipetted by 18. mu.L onto a glassy carbon electrode and air-dried naturally.
(2) Preparing 1.0M potassium hydroxide solution as electrocatalytic electrolyte, introducing nitrogen to drive out air, cleaning the electrode surface of the hydrogen evolution glassy carbon electrode by using 1.0M potassium hydroxide solution, connecting the hydrogen evolution glassy carbon electrode, the Ag/AgCl electrode and the platinum electrode to an electrochemical workstation, and electrolyzingThe electrocatalytic hydrogen evolution performance of the electrode material is measured in liquid, and the Tafel slope of the material is 98mV dec-1At a current density of 10mA cm-2The overpotential of (2) is 225 mV. And the deviation between the LSV curve after 1000 cycles of CV test and the LSV curve before CV test is not large, which shows that the material has good stability.
Example 3:
ammonium tetrathiomolybdate 0.5mmol
Thiourea 2.5mmol
10mL of deionized water
The hydrogen evolution material is prepared by the preparation method comprising the following steps:
0.5mmol of ammonium tetrathiomolybdate and 2.5mmol of thiourea are dissolved in 10mL of deionized water, and are subjected to ultrasonic treatment in an ultrasonic oscillator for 5min until the solution is stirred and dissolved, after no solid particles exist in the solution, the solution is transferred to a high-pressure reaction kettle, 8mm × 8mm × 1mm nickel foam is added, the solution is subjected to hydrothermal treatment at 180 ℃ for 12h, Mo-S/NF is taken out, treated and then is put into a resistance furnace, nitrogen is introduced, and the solution is calcined at 400 ℃ for 2h, so that the Mo-S/NF hydrogen evolution material is finally obtained.
Application example 3:
the Mo-S/NF hydrogen evolution material of example 3 is grinded, the surface of the glassy carbon electrode is grinded by 0.05 μm alumina, the residual sample is removed, and the material is washed by ethanol and deionized water and dried.
(1) 0.5 wt% of Nation solution was prepared with anhydrous methanol. Weighing 1mg of Mo-S/NF hydrogen evolution material, dissolving in 100 mu L of prepared Nation solution, and uniformly dispersing for 2h under ultrasound. Then, the solution was pipetted by 18. mu.L onto a glassy carbon electrode and air-dried naturally.
(2) Preparing 1.0M potassium hydroxide solution as electrocatalytic electrolyte, introducing nitrogen to drive away air, cleaning the electrode surface of the hydrogen evolution glassy carbon electrode by using 1.0M potassium hydroxide solution, connecting the hydrogen evolution glassy carbon electrode, the Ag/AgCl electrode and the platinum electrode to an electrochemical workstation, and measuring the electrocatalytic hydrogen evolution performance of the electrode material in the electrolyte, wherein the Tafel slope of the material is 113mV dec-1At a current density of 10mA cm-2The overpotential of (2) is 256 mV. And the deviation of the LSV curve after 1000 cycles of CV test and the LSV curve before CV test is not generatedLarge, indicating that the material possesses good stability.
Comparative example 1:
changing the molar ratio of ammonium tetrathiomolybdate to thiourea to be 1: 10:
ammonium tetrathiomolybdate 0.5mmol
Thiourea 5mmol
10mL of deionized water
The hydrogen evolution material is prepared by the preparation method comprising the following steps:
dissolving 0.5mmol of ammonium tetrathiomolybdate and 5mmol of thiourea in 10mL of deionized water, performing ultrasonic treatment in an ultrasonic oscillator for 5min until the solution is stirred and dissolved, transferring the solution to a high-pressure reaction kettle after no solid particles exist in the solution, putting 8mm × 8mm × 1mm foamed nickel into the high-pressure reaction kettle, performing hydrothermal treatment at 180 ℃ for 12h, taking out Mo-S/NF, putting the treated Mo-S/NF into a resistance furnace, introducing nitrogen, and calcining at 400 ℃ for 2h to finally obtain the Mo-S/NF hydrogen evolution material.
Application comparative example 1:
and (3) grinding the Mo-S/NF hydrogen evolution material of the comparative example 1, grinding the surface of the glassy carbon electrode by using 0.05 mu m of alumina, removing a residual sample, washing by using ethanol and deionized water, and airing.
(1) 0.5 wt% of Nation solution was prepared with anhydrous methanol. Weighing 1mg of Mo-S/NF hydrogen evolution material, dissolving in 100 mu L of prepared Nation solution, and uniformly dispersing for two hours under ultrasound. Then, the solution was pipetted by 18. mu.L onto a glassy carbon electrode and air-dried naturally.
(2) Preparing 1.0M potassium hydroxide solution as electrocatalytic electrolyte, introducing nitrogen to drive away air, cleaning the electrode surface of the hydrogen evolution glassy carbon electrode by using 1.0M potassium hydroxide solution, connecting the hydrogen evolution glassy carbon electrode, the Ag/AgCl electrode and the platinum electrode to an electrochemical workstation, and measuring the electrocatalytic hydrogen evolution performance of the electrode material in the electrolyte, wherein the Tafel slope of the material is 171mV dec-1At a current density of 10mA cm-2The overpotential of (2) is 419 mV. The LSV curve after 1000 cycles of CV test and the LSV curve before CV test have certain deviation, which indicates that the material has poor stability.
Comparative example 2:
the molar ratio of ammonium tetrathiomolybdate to thiourea was varied to 2: 1.
Ammonium tetrathiomolybdate 1mmol
Thiourea 0.5mmol
10mL of deionized water
The hydrogen evolution material is prepared by the preparation method comprising the following steps:
dissolving 1mmol of ammonium tetrathiomolybdate and 0.5mmol of thiourea in 10mL of deionized water, carrying out ultrasonic treatment in an ultrasonic oscillator for 5min until the solution is stirred and dissolved, transferring the solution to a high-pressure reaction kettle after no solid particles exist in the solution, putting 8mm × 8mm × 1mm foamed nickel into the high-pressure reaction kettle, carrying out hydrothermal treatment at 180 ℃ for 12h, taking out Mo-S/NF, putting the treated Mo-S/NF into a resistance furnace, introducing nitrogen, and calcining at 400 ℃ for 2h to finally obtain the Mo-S/NF hydrogen evolution material.
Application comparative example 2:
and (3) grinding the Mo-S/NF hydrogen evolution material of the comparative example 2, grinding the surface of the glassy carbon electrode by using 0.05 mu m of alumina, removing a residual sample, washing by using ethanol and deionized water, and airing.
(1) 0.5 wt% of Nation solution was prepared with anhydrous methanol. Weighing 1mg of Mo-S/NF hydrogen evolution material, dissolving in 100 mu L of prepared Nation solution, and uniformly dispersing under ultrasound for 2. Then, the solution was pipetted by 18. mu.L onto a glassy carbon electrode and air-dried naturally.
(2) Preparing 1.0M potassium hydroxide solution as electrocatalytic electrolyte, introducing nitrogen to drive away air, cleaning the electrode surface of the hydrogen evolution glassy carbon electrode by using 1.0M potassium hydroxide solution, connecting the hydrogen evolution glassy carbon electrode, the Ag/AgCl electrode and the platinum electrode to an electrochemical workstation, and measuring the electrocatalytic hydrogen evolution performance of the electrode material in the electrolyte, wherein the Tafel slope of the material is 162mV dec-1At a current density of 10mA cm-2The overpotential of (2) is 303 mV. And certain deviation is generated between the LSV curve after 1000 cycles of CV test and the LSV curve before the CV test, which indicates that the material has poor stability.
As can be seen from examples 1-3 and comparative examples 1-2, when the molar ratio of ammonium tetrathiomolybdate to thiourea is 1 (1-5), the electrochemical performance of the Mo-S/NF hydrogen evolution material is the best, and increasing the amount of either raw material leads to deterioration of the material performance. Therefore, when other variables except the raw materials are changed, the molar ratio of the ammonium tetrathiomolybdate to the thiourea is controlled to be 1 (1-5).
Example 4:
a preparation method of a Mo-S/NF hydrogen evolution material comprises the following steps:
1) mixing ammonium tetrathiomolybdate and thiourea with water, and performing ultrasonic dispersion to obtain a mixed solution;
2) adding the mixed solution into a reaction kettle, adding foamed nickel serving as a carrier into the reaction kettle, and performing hydrothermal reaction to obtain Mo-S/NF;
3) and calcining the Mo-S/NF under an anaerobic condition to obtain the Mo-S/NF hydrogen evolution material. In the hydrogen evolution material, the loading of Mo in the foamed nickel is 17%.
In the step 1), the molar ratio of ammonium tetrathiomolybdate to thiourea is 1:1, and the ratio of the molar amount of ammonium tetrathiomolybdate to the volume of water is 1mmol:25 mL. The ultrasonic dispersion time is 5min, and a clear mixed solution is obtained after the ultrasonic dispersion.
In the step 2), the temperature is 200 ℃ and the time is 10 hours in the hydrothermal reaction.
In the step 3), the calcination is carried out in a resistance furnace, and nitrogen is introduced in the calcination process. In the calcination, the temperature is 500 ℃ and the time is 2 h.
When the Mo-S/NF hydrogen evolution material is applied to the electrocatalytic hydrogen evolution reaction, the Mo-S/NF hydrogen evolution material and Nafion solution are uniformly mixed, and then the mixture is dripped on a glassy carbon electrode and dried to obtain the hydrogen evolution glassy carbon electrode which is used as a working electrode in the electrocatalytic hydrogen evolution reaction.
Example 5:
a preparation method of a Mo-S/NF hydrogen evolution material comprises the following steps:
1) mixing ammonium tetrathiomolybdate and thiourea with water, and performing ultrasonic dispersion to obtain a mixed solution;
2) adding the mixed solution into a reaction kettle, adding foamed nickel serving as a carrier into the reaction kettle, and performing hydrothermal reaction to obtain Mo-S/NF;
3) and calcining the Mo-S/NF under an anaerobic condition to obtain the Mo-S/NF hydrogen evolution material. In the hydrogen evolution material, the loading of Mo in the foamed nickel is 20%.
In the step 1), the molar ratio of ammonium tetrathiomolybdate to thiourea is 1:5, and the ratio of the molar amount of ammonium tetrathiomolybdate to the volume of water is 1mmol:15 mL. The ultrasonic dispersion time is 10min, and a clear mixed solution is obtained after the ultrasonic dispersion.
In the step 2), the temperature is 150 ℃ and the time is 15h in the hydrothermal reaction.
In the step 3), the calcination is carried out in a resistance furnace, and nitrogen is introduced in the calcination process. In the calcination, the temperature is 300 ℃ and the time is 4 h.
When the Mo-S/NF hydrogen evolution material is applied to the electrocatalytic hydrogen evolution reaction, the Mo-S/NF hydrogen evolution material and Nafion solution are uniformly mixed, and then the mixture is dripped on a glassy carbon electrode and dried to obtain the hydrogen evolution glassy carbon electrode which is used as a working electrode in the electrocatalytic hydrogen evolution reaction.
Example 6:
a preparation method of a Mo-S/NF hydrogen evolution material comprises the following steps:
1) mixing ammonium tetrathiomolybdate and thiourea with water, and performing ultrasonic dispersion to obtain a mixed solution;
2) adding the mixed solution into a reaction kettle, adding foamed nickel serving as a carrier into the reaction kettle, and performing hydrothermal reaction to obtain Mo-S/NF;
3) and calcining the Mo-S/NF under an anaerobic condition to obtain the Mo-S/NF hydrogen evolution material. In the hydrogen evolution material, the loading of Mo in the foamed nickel is 15%.
In the step 1), the molar ratio of ammonium tetrathiomolybdate to thiourea is 1:3, and the ratio of the molar amount of ammonium tetrathiomolybdate to the volume of water is 1mmol:20 mL. The ultrasonic dispersion time is 7min, and a clear mixed solution is obtained after the ultrasonic dispersion.
In the step 2), the temperature is 170 ℃ and the time is 12 hours in the hydrothermal reaction.
In the step 3), the calcination is carried out in a resistance furnace, and nitrogen is introduced in the calcination process. In the calcination, the temperature is 400 ℃ and the time is 3 h.
When the Mo-S/NF hydrogen evolution material is applied to the electrocatalytic hydrogen evolution reaction, the Mo-S/NF hydrogen evolution material and Nafion solution are uniformly mixed, and then the mixture is dripped on a glassy carbon electrode and dried to obtain the hydrogen evolution glassy carbon electrode which is used as a working electrode in the electrocatalytic hydrogen evolution reaction.
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. A preparation method of a Mo-S/NF hydrogen evolution material is characterized by comprising the following steps:
1) mixing ammonium tetrathiomolybdate and thiourea with water, and performing ultrasonic dispersion to obtain a mixed solution;
2) adding the mixed solution into a reaction kettle, adding foamed nickel serving as a carrier into the reaction kettle, and performing hydrothermal reaction to obtain Mo-S/NF;
3) and calcining the Mo-S/NF under an anaerobic condition to obtain the Mo-S/NF hydrogen evolution material.
2. The method for preparing a Mo-S/NF hydrogen evolution material according to claim 1, wherein in the step 1), the molar ratio of ammonium tetrathiomolybdate to thiourea is 1 (1-5), and the ratio of the molar amount of ammonium tetrathiomolybdate to the volume of water is 1mmol (15-25) mL.
3. The preparation method of the Mo-S/NF hydrogen evolution material as claimed in claim 1, wherein in the step 1), the ultrasonic dispersion time is 5-10min, and a clear mixed solution is obtained after the ultrasonic dispersion.
4. The method for preparing a Mo-S/NF hydrogen evolution material as claimed in claim 1, wherein in the step 2), the temperature is 150-200 ℃ and the time is 10-15h in the hydrothermal reaction.
5. The method for preparing the Mo-S/NF hydrogen evolution material as claimed in claim 1, wherein in the step 3), the calcination is performed in a resistance furnace, and nitrogen is introduced during the calcination.
6. The method as claimed in claim 1, wherein the temperature of the calcination step 3) is 300-500 ℃ and the time is 2-4 h.
7. A Mo-S/NF hydrogen evolution material, characterized in that it is prepared by a method according to any of claims 1 to 6.
8. The Mo-S/NF hydrogen evolution material as claimed in claim 7, wherein the loading of Mo in the hydrogen evolution material is 15-20% of that in foamed nickel.
9. Use of the Mo-S/NF hydrogen evolution material of claim 7 in electrocatalytic hydrogen evolution reactions.
10. The application of the Mo-S/NF hydrogen evolution material in the electrocatalytic hydrogen evolution reaction as claimed in claim 9, wherein in the application, the Mo-S/NF hydrogen evolution material is uniformly mixed with Nafion solution, and then is dripped on a glassy carbon electrode, and the glassy carbon electrode is dried to obtain the hydrogen evolution glassy carbon electrode which is used as a working electrode in the electrocatalytic hydrogen evolution reaction.
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