CN110227480B - Preparation method of NiMo hydrogen evolution electrocatalyst - Google Patents
Preparation method of NiMo hydrogen evolution electrocatalyst Download PDFInfo
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- CN110227480B CN110227480B CN201910544886.9A CN201910544886A CN110227480B CN 110227480 B CN110227480 B CN 110227480B CN 201910544886 A CN201910544886 A CN 201910544886A CN 110227480 B CN110227480 B CN 110227480B
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- 229910003294 NiMo Inorganic materials 0.000 title claims abstract description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000001257 hydrogen Substances 0.000 title claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 43
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 29
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims abstract description 27
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 19
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 238000007599 discharging Methods 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 21
- 229910000510 noble metal Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 3
- 229910001947 lithium oxide Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B01J35/33—
-
- 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
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- 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 discloses a preparation method of a NiMo hydrogen evolution electrocatalyst, belonging to the field of electrocatalysis hydrogen evolution. Firstly, respectively preparing nickel nitrate hexahydrate and sodium molybdate dihydrate into solutions; then, transferring the two solutions into a reaction kettle, adding foamed nickel into the solutions, and carrying out hydrothermal reaction to obtain a nickel molybdate precursor material; then, placing the prepared nickel molybdate precursor in a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere to obtain nickel molybdate; and finally, assembling the nickel molybdate serving as a working electrode, the lithium sheet or the sodium sheet serving as a counter electrode and the lithium hexafluorophosphate or the sodium hexafluorophosphate serving as an electrolyte to obtain a lithium battery or a sodium battery, and discharging the battery after the battery is kept stand for a set time to obtain the NiMo hydrogen evolution electrocatalyst. The method of the invention does not need high temperature and strong reducing agent, has relatively mild process and can accurately control the composition of the material.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis hydrogen evolution, and particularly relates to a preparation method of a NiMo hydrogen evolution electrocatalyst.
Background
The hydrogen evolution reaction is a half reaction of water electrolysis by electricity, and is one of important ways for converting renewable energy sources such as solar energy, wind energy, tidal energy and the like into chemical energy. Although the platinum-based catalyst has the most excellent hydrogen evolution performance, its commercialization progress is limited by the scarce reserves of platinum element and the high price. Therefore, the development and design of a non-noble metal hydrogen evolution electrocatalyst with platinum-like activity and low price have important significance for promoting the large-scale application of the electrolyzed water (see the literatures Guoqiang ZHao, Kun Rui, Shi Xue Dou, Wenping Sun, heterogeneous for electrochemical hydrogen evolution reaction: a review, Advanced Functional Materials,2018,28, 1803291).
In recent years, despite the continuous emergence of various hydrogen evolution electrocatalysts (such as transition metal phosphides, sulfides, selenides, carbides, and the like), NiMo materials still receive the most eager attention from the scientific research community. This is because NiMo materials have an electronic structure similar to platinum, and this intrinsic property makes it a more promising alternative to the noble metal platinum. Theoretical calculations prove that nickel atoms are active sites for water decomposition, molybdenum atoms are beneficial to adsorption of hydrogen intermediates, and the synergistic effect of the nickel atoms and the molybdenum atoms can promote rapid progress of water decomposition elementary reactions (such as a Volmer step, a Tafel step and a Heyrovsky step). Under the continuous efforts of researchers, some NiMo materials with good effects are prepared, such as NiMo nano powder, NiMo nano wires, NiMo hollow nano rods and the like. However, the preparation of the NiMo material often requires the use of a strong reducing agent or at high temperature, which has a large environmental impact and high requirements for equipment.
Therefore, the development of a mild method for preparing the NiMo electrocatalyst is urgent and has great significance.
Disclosure of Invention
In view of the above-identified deficiencies in the art or needs for improvement, the present invention provides a method for preparing a NiMo hydrogen evolution electrocatalyst, which aims to successfully reduce nickel molybdate into a NiMo material by discharging a lithium or sodium battery. The NiMo material prepared by the method has good catalytic hydrogen evolution activity in alkaline solution, and the hydrogen evolution overpotential of the NiMo material is 10mA cm in current density-2When the method is used, the value of the platinum alloy is only 50mV less than that of the noble metal Pt/C, and the platinum alloy is very hopeful to replace the noble metal platinum to be applied to industrial production.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a NiMo hydrogen evolution electrocatalyst, comprising the steps of:
(1) respectively adding nickel nitrate hexahydrate and sodium molybdate dihydrate into deionized water, and stirring to completely dissolve the nickel nitrate hexahydrate and the sodium molybdate dihydrate; (2) transferring the two solutions prepared in the step (1) into a reaction kettle, adding foamed nickel, and carrying out hydrothermal reaction to obtain a nickel molybdate precursor material; (3) placing the nickel molybdate precursor material prepared in the step (2) in a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere to obtain nickel molybdate; (4) and (3) taking the nickel molybdate prepared in the step (3) as a working electrode, a lithium sheet or a sodium sheet as a counter electrode and lithium hexafluorophosphate or sodium hexafluorophosphate as an electrolyte, assembling the lithium battery or the sodium battery in a glove box to obtain a lithium battery or a sodium battery, standing the lithium battery or the sodium battery for a set time (for example, four hours), discharging the lithium battery or the sodium battery, and cleaning a discharge product by 95% ethanol and water to obtain the NiMo hydrogen evolution electrocatalyst.
Preferably, the mass concentrations of the nickel nitrate hexahydrate and the sodium molybdate dihydrate in the deionized water are 7-8 mg/ml and 5.83-6.66 mg/ml respectively, and the molar ratio of nickel and molybdenum elements of the nickel nitrate hexahydrate and the sodium molybdate dihydrate is 1: 1.
Preferably, the hydrothermal reaction temperature is 160 ℃, and the hydrothermal reaction time is 5-6 hours.
Preferably, the heat treatment temperature is room temperature-350 ℃, and the heat treatment time is 1-3 hours.
Preferably, the discharge cut-off voltage is 0.3-0.1V, and the discharge current is 0.05-0.5 mA.
The reaction mechanism of the invention is as follows: in lithium-ion or sodium-ion batteries, transition metal oxides belong to the conversion electrode materials. Unlike intercalation materials, when discharge occurs, lithium or sodium ions enter the crystal lattice of the transition metal oxide and are reduced to form elemental metal and lithium oxide. In particular, according to the invention, the following reaction, NiMoO, takes place4+8Li+(8Na+)+8e-→Ni+Mo+4Li2O(Na2O). Lithium oxide and sodium oxide may be dissolved in water to obtain a NiMo material.
According to another aspect of the present invention, there is provided a NiMo hydrogen evolution electrocatalyst prepared as above, which exhibits good catalytic hydrogen evolution activity in alkaline solutions.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
1. the intercalation of lithium or sodium ions may directly reduce nickel molybdate to form a NiMo material using a discharge reaction of a lithium or sodium battery. Compared with other methods, the method does not need high-temperature and strong reducing agents, so that the whole process is relatively mild. In addition, the composition of the material can be precisely controlled by controlling the discharge current and the cut-off voltage of the battery, which also means that the properties of the target material can be continuously changed.
2. The NiMo material shows good catalytic hydrogen evolution activity in alkaline solution, and the hydrogen evolution overpotential of the NiMo material is 10mA cm at current density-2And the catalyst is 50mV less than that of noble metal Pt/C, and is very hopeful to replace noble metal platinum to be applied to practical production, so that the hydrogen production cost by electrically decomposing water is effectively reduced.
Drawings
FIG. 1(a) is a scanning electron microscope photograph of nickel molybdate prepared in example 1 of the present invention, and FIG. 1(b) is a scanning electron microscope photograph of NiMo prepared in example of the present invention;
FIG. 2 is a line scan plot of nickel molybdate, NiMo and noble metal Pt/C prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In the invention, the NiMo hydrogen evolution electrocatalyst is prepared by utilizing the electrochemical reaction of a lithium battery or a sodium battery, and the principle of the NiMo hydrogen evolution electrocatalyst is as follows: when the battery is discharged, lithium ions or sodium ions enter crystal lattices of the transition metal oxide, so that the transition metal oxide is reduced to generate a metal simple substance and lithium oxide or sodium oxide. Actually, lithium (sodium) electrochemical regulation refers to that a target material is made into an electrode of a lithium (sodium) battery, and the electrocatalytic performance of the material is changed by utilizing charging and discharging of the battery. By changing the cut-off voltage, the cycle number and the current density of charging and discharging, the structure, the composition and the morphology of the material can be accurately controlled, so that the catalytic performance of the material is influenced. The whole process can be carried out at room temperature without adding a reducing agent.
The invention discloses a preparation method of a NiMo hydrogen evolution electrocatalyst, which comprises the following steps: (1) respectively adding nickel nitrate hexahydrate and sodium molybdate dihydrate into deionized water, and stirring to completely dissolve the nickel nitrate hexahydrate and the sodium molybdate dihydrate, wherein the mass concentrations of the nickel nitrate hexahydrate and the sodium molybdate dihydrate in the deionized water are 7-8 mg/ml and 5.83-6.66 mg/ml respectively, and the molar ratio of nickel and molybdenum elements of the nickel nitrate hexahydrate and the sodium molybdate dihydrate is 1: 1; (2) transferring the two solutions prepared in the step (1) into a reaction kettle, adding foamed nickel, and carrying out hydrothermal reaction to obtain a nickel molybdate precursor material, wherein the hydrothermal reaction temperature is 160 ℃, and the hydrothermal reaction time is 5-6 hours; (3) placing the nickel molybdate precursor material prepared in the step (2) in a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere to obtain nickel molybdate, wherein the heat treatment temperature is room temperature-350 ℃, and the heat treatment time is 1-3 hours; (4) and (3) taking the nickel molybdate prepared in the step (3) as a working electrode, a lithium sheet or a sodium sheet as a counter electrode, and lithium hexafluorophosphate or sodium hexafluorophosphate as an electrolyte, assembling the lithium battery or the sodium battery in a glove box to obtain a lithium battery or a sodium battery, standing the lithium battery or the sodium battery for a set time (for example, four hours), and discharging the lithium battery or the sodium battery, wherein the discharge cut-off voltage is 0.3-0.1V, the discharge current is 0.05-0.5 mA, and the discharge product is cleaned by 95% ethanol and water to obtain the NiMo hydrogen evolution electrocatalyst.
In order to make the present invention more understandable to those skilled in the art, the following will describe in detail the preparation method of the NiMo hydrogen evolution electrocatalyst according to the present invention with reference to specific examples.
Example 1
The preparation method of the NiMo hydrogen evolution electrocatalyst in the embodiment comprises the following steps:
(1) 290.8mg of nickel nitrate hexahydrate and 241.9mg of sodium molybdate dihydrate are respectively added into 40ml of deionized water, the two are stirred to be completely dissolved, the molar concentrations of the nickel nitrate hexahydrate and the sodium molybdate dihydrate in the deionized water are both 25mmol/L, and the mass concentrations of the nickel nitrate hexahydrate and the sodium molybdate dihydrate in the deionized water are respectively 7.27mg/ml and 6.05 mg/ml;
(2) transferring the solution prepared in the step (1) into a reaction kettle, adding foamed nickel, and carrying out hydrothermal reaction for 5 hours at 160 ℃ to obtain a nickel molybdate precursor material;
(3) placing the sample prepared in the step (2) in a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere, wherein the heat treatment temperature is 350 ℃, and the heat treatment time is 1 hour, so as to obtain nickel molybdate;
(4) and (4) assembling the sodium battery in a glove box by taking the sample prepared in the step (3) as a working electrode, a sodium sheet as a counter electrode and sodium hexafluorophosphate as an electrolyte. After the cell was left to stand for four hours, it was discharged at a discharge cut-off voltage of 0.01V and a discharge current of 0.1 mA. And cleaning the discharge product by 95% ethanol and water to obtain the NiMo hydrogen evolution electrocatalyst.
The prepared catalyst is subjected to performance test according to the following method:
electrochemical tests were carried out on a CHI 660D electrochemical workstation, using NiMo prepared as described above as the working electrode, a platinum sheet as the counter electrode, Hg/HgO as the reference electrode, in a 1mol/L KOH solution at 2mV s-1The linear sweep curve of the catalyst was measured.
The noble metal Pt/C and nickel molybdate were also tested for performance as described above and will not be described further herein.
FIG. 1 is a scanning electron microscope photograph of nickel molybdate (a) and NiMo (b) prepared in example 1 of the present invention. As shown in fig. 1, nickel molybdate initially exhibits a rod-like structure with a smooth surface; after sodium ion intercalation, the obtained material is obviously bent, and the surface is slightly rough, which indicates that the structure is obviously changed.
FIG. 2 is a graph of linear scans of nickel molybdate, NiMo and noble metal Pt/C prepared in example 1 of the present invention, as shown in FIG. 2, when the current density is 10mA cm-2The overpotentials of the nickel molybdate, NiMo and the noble metal Pt/C are 198mV, 62mV and 12mV respectively, which shows that the catalytic hydrogen evolution activity is greatly enhanced after sodium ions are embedded into the nickel molybdate and is close to the noble metal Pt/C.
Example 2
The preparation method of the NiMo hydrogen evolution electrocatalyst in the embodiment comprises the following steps:
(1) respectively adding 320mg of nickel nitrate hexahydrate and 266.4mg of sodium molybdate dihydrate into 40ml of deionized water, and stirring to completely dissolve the nickel nitrate hexahydrate and the sodium molybdate dihydrate, wherein the molar concentrations of the nickel nitrate hexahydrate and the sodium molybdate dihydrate in the deionized water are both 27.5mmol/L, and the mass concentrations of the nickel nitrate hexahydrate and the sodium molybdate dihydrate in the deionized water are respectively 8.0mg/ml and 6.66 mg/ml;
(2) transferring the solution prepared in the step (1) into a reaction kettle, adding foamed nickel, and carrying out hydrothermal reaction for 6 hours at 160 ℃ to obtain a nickel molybdate precursor material;
(3) placing the sample prepared in the step (2) in a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere, wherein the heat treatment temperature is room temperature, and the heat treatment time is 2 hours, so as to obtain nickel molybdate;
(4) and (4) assembling the lithium battery in a glove box by taking the sample prepared in the step (3) as a working electrode, a lithium sheet as a counter electrode and lithium hexafluorophosphate as an electrolyte. After the cell was left to stand for four hours, it was discharged at a discharge cut-off voltage of 0.1V and a discharge current of 0.05 mA. And cleaning the discharge product by 95% ethanol and water to obtain the NiMo hydrogen evolution electrocatalyst.
The catalyst was subjected to a performance test in the same manner as in example 1.
Example 3
The preparation method of the NiMo hydrogen evolution electrocatalyst in the embodiment comprises the following steps:
(1) respectively adding 280mg of nickel nitrate hexahydrate and 233.2mg of sodium molybdate dihydrate into 40ml of deionized water, and stirring to completely dissolve the nickel nitrate hexahydrate and the sodium molybdate dihydrate, wherein the molar concentrations of the nickel nitrate hexahydrate and the sodium molybdate dihydrate in the deionized water are both 24.1mmol/L, and the mass concentrations of the nickel nitrate hexahydrate and the sodium molybdate dihydrate in the deionized water are respectively 7.0mg/ml and 5.83 mg/ml;
(2) transferring the solution prepared in the step (1) into a reaction kettle, adding foamed nickel, and carrying out hydrothermal reaction at 160 ℃ for 5.5 hours to obtain a nickel molybdate precursor material;
(3) placing the sample prepared in the step (2) in a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere, wherein the heat treatment temperature is 200 ℃, and the heat treatment time is 2 hours, so as to obtain nickel molybdate;
(4) and (4) assembling the lithium battery in a glove box by taking the sample prepared in the step (3) as a working electrode, a lithium sheet as a counter electrode and lithium hexafluorophosphate as an electrolyte. After the cell was left to stand for four hours, it was discharged at a discharge cut-off voltage of 0.3V and a discharge current of 0.5 mA. And cleaning the discharge product by 95% ethanol and water to obtain the NiMo hydrogen evolution electrocatalyst.
The catalyst was subjected to a performance test in the same manner as in example 1.
Example 4
The preparation method of the NiMo hydrogen evolution electrocatalyst in the embodiment comprises the following steps:
(1) adding 310mg of nickel nitrate hexahydrate and 258.3mg of sodium molybdate dihydrate into 40ml of deionized water respectively, and stirring to completely dissolve the nickel nitrate hexahydrate and the sodium molybdate dihydrate, wherein the mass concentrations of the nickel nitrate hexahydrate and the sodium molybdate dihydrate in the deionized water are 7.75mg/ml and 6.46mg/ml respectively;
(2) transferring the solution prepared in the step (1) into a reaction kettle, adding foamed nickel, and carrying out hydrothermal reaction at 160 ℃ for 5.7 hours to obtain a nickel molybdate precursor material;
(3) placing the sample prepared in the step (2) in a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere, wherein the heat treatment temperature is 280 ℃, and the heat treatment time is 2.5 hours, so as to obtain nickel molybdate;
(4) and (4) assembling the lithium battery in a glove box by taking the sample prepared in the step (3) as a working electrode, a lithium sheet as a counter electrode and lithium hexafluorophosphate as an electrolyte. After the cell was left to stand for four hours, it was discharged at a discharge cut-off voltage of 0.2V and a discharge current of 0.3 mA. And cleaning the discharge product by 95% ethanol and water to obtain the NiMo hydrogen evolution electrocatalyst.
The catalyst was subjected to a performance test in the same manner as in example 1.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (5)
1. A preparation method of a NiMo hydrogen evolution electrocatalyst is characterized by comprising the following steps:
(1) respectively adding nickel nitrate hexahydrate and sodium molybdate dihydrate into deionized water to respectively prepare uniform solutions;
(2) transferring the two solutions prepared in the step (1) into a reaction kettle, adding foamed nickel into the solutions, and carrying out hydrothermal reaction to obtain a nickel molybdate precursor material;
(3) placing the nickel molybdate precursor material prepared in the step (2) in a tubular furnace, and carrying out heat treatment in a nitrogen atmosphere to obtain nickel molybdate; the heat treatment temperature is room temperature-350 ℃, and the heat treatment time is 1-3 hours;
(4) assembling the nickel molybdate prepared in the step (3) as a working electrode, a lithium sheet or a sodium sheet as a counter electrode and lithium hexafluorophosphate or sodium hexafluorophosphate as an electrolyte to obtain a lithium battery or a sodium battery, and discharging the battery after the battery is kept stand for a set time period, thereby obtaining the NiMo hydrogen evolution electrocatalyst;
the cut-off voltage of the discharge is 0.3V-0.1V, and the current of the discharge is 0.05-0.5 mA.
2. The method for preparing a NiMo hydrogen evolution electrocatalyst according to claim 1, wherein the mass concentrations of the nickel nitrate hexahydrate and the sodium molybdate dihydrate in the deionized water are 7-8 mg/mL and 5.83-6.66 mg/mL respectively, and the molar ratio of nickel and molybdenum elements in the nickel nitrate hexahydrate and the sodium molybdate dihydrate is 1: 1.
3. The method for preparing a NiMo hydrogen evolution electrocatalyst according to claim 2, wherein the hydrothermal reaction temperature is 160 ℃, and the hydrothermal reaction time is 5-6 hours.
4. The method of claim 3, wherein in the step (4), the cell is left to stand for 4 hours before discharging.
5. The method for preparing a NiMo hydrogen evolution electrocatalyst according to claim 4, wherein in the step (4), the NiMo hydrogen evolution electrocatalyst is obtained by washing the obtained product with 95% ethanol and water after the nickel molybdate used as the working electrode is discharged by a battery.
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| CN111468160A (en) * | 2020-04-15 | 2020-07-31 | 电子科技大学 | Preparation of nickel-molybdenum-nitrogen co-doped carbon-based catalyst based on sodium chloride template |
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| CN112725826B (en) * | 2020-12-18 | 2022-04-12 | 安徽师范大学 | One-dimensional Ni-doped copper selenium/molybdenum selenium compound nano array @ foam copper material, and preparation method and application thereof |
| CN113637999A (en) * | 2021-08-19 | 2021-11-12 | 武汉工程大学 | Cu-based nano array composite nickel-molybdenum oxide electrode material and preparation method and application thereof |
| CN113684497A (en) * | 2021-08-19 | 2021-11-23 | 武汉工程大学 | Foam copper loaded nickel-molybdenum-phosphorus-based composite material and preparation method and application thereof |
| CN114293215B (en) * | 2021-11-23 | 2023-02-28 | 中国华能集团清洁能源技术研究院有限公司 | Preparation method of cathode for hydrogen production by water electrolysis |
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