CN111992227A - Nickel cobalt-molybdenum disulfide hollow nano composite material, synthetic method thereof and application of nickel cobalt-molybdenum disulfide hollow nano composite material in electrocatalytic hydrogen evolution - Google Patents
Nickel cobalt-molybdenum disulfide hollow nano composite material, synthetic method thereof and application of nickel cobalt-molybdenum disulfide hollow nano composite material in electrocatalytic hydrogen evolution Download PDFInfo
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- CN111992227A CN111992227A CN202010884947.9A CN202010884947A CN111992227A CN 111992227 A CN111992227 A CN 111992227A CN 202010884947 A CN202010884947 A CN 202010884947A CN 111992227 A CN111992227 A CN 111992227A
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- MULUSVHZQWQJJX-UHFFFAOYSA-N [Mo].[Ni]=S.[Co]=S Chemical compound [Mo].[Ni]=S.[Co]=S MULUSVHZQWQJJX-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000001257 hydrogen Substances 0.000 title claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000010189 synthetic method Methods 0.000 title abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 34
- 239000010941 cobalt Substances 0.000 claims abstract description 34
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 29
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 28
- 239000011733 molybdenum Substances 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000013110 organic ligand Substances 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical group CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 16
- 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 group [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 description 15
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 15
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical compound [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010411 electrocatalyst Substances 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 19
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
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- 229910021607 Silver chloride Inorganic materials 0.000 description 10
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 10
- 238000004502 linear sweep voltammetry Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000001132 ultrasonic dispersion Methods 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- -1 transition metal chalcogenides Chemical class 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
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- 230000008859 change Effects 0.000 description 2
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- 239000002803 fossil fuel Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 229910052961 molybdenite Inorganic materials 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 1
- 229910039444 MoC Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 239000000446 fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 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
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
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Abstract
The invention relates to a nickel cobalt-molybdenum disulfide hollow nano composite material, a synthetic method thereof and application of electrocatalytic hydrogen evolution. The nickel cobalt-molybdenum disulfide hollow nano composite material is in the shape of polyhedral nano particles, the particle size of the particles is 250-500nm, and the nickel cobalt-molybdenum disulfide hollow nano composite material is prepared by taking an organic metal framework precursor formed by a cobalt source and an organic ligand as a self-sacrifice template, firstly reacting with a nickel source in a solvent, and then adding a sulfur source and a molybdenum source to carry out hydrothermal reaction. The synthesis size of the nickel cobalt-molybdenum disulfide nano material is controllable. The synthesis method is simple, no environmental pollution is caused, and the synthesized nano composite material has good electrochemical performance and can be applied to electrocatalytic hydrogen evolution.
Description
Technical Field
The invention relates to a nickel cobalt-molybdenum disulfide hollow nano composite material, a synthetic method thereof and application of electrocatalytic hydrogen evolution, belonging to the fields of nano materials and electrochemistry.
Background
With the development of society and science, the increasing industrial demand and the exhaustion of traditional fossil fuels require energy to be innovated. Hydrogen is an emerging energy carrier, not as sustainable as wind and solar energy, and is called one of the most promising fuels to replace fossil fuels due to its high energy and environmental friendliness. There are three main ways to produce hydrogen, and what is more concerned in the current society is the production of hydrogen by electrolysis of water. The electrolysis water comprises two half-reactions, namely a hydrogen evolution reaction and an oxygen evolution reaction. However, in alkaline solutions, due to high kinetic barriers, H+To H2The transfer process of (a) requires a high overpotential. Although platinum and its alloys are the best catalysts for catalytic activity in alkaline solutions, their wide application is severely limited by the rarity and expensive cost of platinum and its alloys. Therefore, the search for a high-performance platinum-free hydrogen evolution catalyst is of great significance.
There have been a great deal of research on alternatives to noble metals and metal oxides of the platinum group, and among them, transition metal chalcogenides are considered as novel electrochemical catalytic materials promising for the substitution of noble metal catalysts due to their excellent catalytic activity, low price and abundant deposits. Among transition metal sulfides, molybdenum disulfide is the most potential electrochemical hydrogen evolution material due to its gibbs free energy change close to 0. However, in order to solve the problem that the active sites of disulfide are located at the edge rather than the basal plane and the layered structure limits the exposure of the active sites, thereby reducing the electrochemical hydrogen evolution performance, CN111233041A discloses a method for preparing ionic liquid intercalated nano molybdenum disulfide, wherein the prepared ionic liquid intercalated nano molybdenum disulfide has the interlayer spacing of 1.0-4.0nm, high dispersibility and high exposure rate of the active sites at the edge. On the other hand, there are studies to improve the electrochemical hydrogen evolution performance of molybdenum disulfide by additionally introducing other compounds or metals, such as: CN111389434A discloses a molybdenum disulfide-based composite material, a preparation method and an application thereof, wherein the preparation method comprises the following steps: adding a grinding material molybdenum carbide into the molybdenum disulfide material, grinding and mixing, adding into a solvent, introducing inert gas and reaction gas, and carrying out heat treatment to obtain the molybdenum disulfide-based composite material. The molybdenum disulfide-based composite material prepared by the method has high electrocatalytic activity and has wide application prospects in the fields of hydrogen production by water electrolysis, supercapacitors, ion batteries and the like. CN111151272A provides a cobalt and iron doped molybdenum disulfide base material and a preparation method thereof, wherein the cobalt and iron doped molybdenum disulfide base material is powder with a nanosheet flower-like structure, and two non-noble metal elements are utilized to improve the catalytic activity of sites. However, the nano-sheet flower-like structure has a problem of poor conductivity, and the electron transport speed is slow due to the sheet-like structure, thereby hindering the electrochemical hydrogen evolution performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a nickel cobalt-molybdenum disulfide hollow nano composite material and a synthetic method thereof.
The invention also provides the application of the nickel cobalt-molybdenum disulfide hollow nano composite material in electrocatalytic hydrogen evolution.
Summary of the invention: the invention utilizes a metal organic framework as a precursor to synthesize a hollow nano material with a special structure, and the hollow nano material is applied to electrocatalytic hydrogen evolution. The nickel cobalt-molybdenum disulfide hollow nano composite material is synthesized by a solvothermal method, the synthesis method is simple and convenient, the product is convenient and easy to obtain, no pollution is caused to the environment, and good electrochemical performance is shown for electrochemical hydrogen evolution.
Description of terms:
room temperature, having a meaning well known in the art, typically 23 ± 3 ℃.
The ZIF-67 precursor refers to an organic metal framework precursor formed by the reaction of a cobalt source and an organic ligand.
The technical scheme of the invention is as follows:
a nickel cobalt-molybdenum disulfide hollow nano composite material is provided, the shape of which is polyhedral nano particles, the particle diameter of which is 250-500 nm;
the nickel cobalt-molybdenum disulfide hollow nano composite material is prepared by taking an organic metal framework precursor formed by a cobalt source and an organic ligand as a self-sacrifice template, firstly reacting with a nickel source in a solvent, and then adding a sulfur source and a molybdenum source to carry out hydrothermal reaction.
According to the optimization of the invention, the nickel cobalt-molybdenum disulfide hollow nano composite material has a dodecahedron hollow structure, and the particle size is 300-400 nm; preferably, the thickness of the molybdenum disulfide at the edge is 60-65 nm. Further preferably, the dodecahedron is a rhombic dodecahedron.
According to the invention, the synthesis method of the nickel cobalt-molybdenum disulfide hollow nano composite material comprises the following steps:
dissolving a cobalt source and an organic ligand in a solvent, and reacting at room temperature to form an organic metal framework precursor (ZIF-67 precursor);
dispersing the obtained precursor into a solvent, adding a nickel source, and stirring at room temperature;
and then adding a sulfur source and a molybdenum source to perform a hydrothermal reaction step.
According to a preferred embodiment of the invention, the molar ratio of cobalt source to organic ligand is from 1:6 to 9, preferably from 1:7 to 8; the cobalt source is cobalt nitrate hexahydrate, and the organic ligand is 2-methylimidazole.
Preferably, according to the invention, the nickel source is nickel nitrate hexahydrate. The molar ratio of the cobalt source to the nickel source is 1-5:1, namely the molar ratio of the cobalt nitrate hexahydrate to the nickel nitrate hexahydrate is 1-5: 1. It is further preferred that the molar ratio of cobalt source to nickel source is from 3.5 to 4:1, particularly preferably 3.9: 1.
Preferably, according to the invention, the molar ratio of molybdenum source to sulfur source is 1: 3-5, and the molar ratio of the molybdenum source to the sulfur source is 1:4 is optimally preferred. The sulfur source is thioacetamide, and the molybdenum source is sodium molybdate dihydrate.
Preferably, according to the invention, the molar ratio of molybdenum source to cobalt source is between 0.1 and 4: 1. further preferably, the molar ratio of the molybdenum source to the cobalt source is 1 to 3: 1; most preferably, the molar ratio of molybdenum source to cobalt source is 2.0-2.5: 1. The molar ratio of molybdenum to cobalt is too low or too high, which is unfavorable for electrocatalytic hydrogen evolution of the product. The embodiment 1 of the invention is the best embodiment, the mol ratio of the molybdenum source to the cobalt source is 2.2: 1.
preferably, according to the invention, the solvent is methanol or ethanol. Further preferably, the solvent for the reaction of the cobalt source and the organic ligand is methanol; the solvent for dissolving the ZIF-67 precursor is ethanol.
According to the invention, the reaction time of the cobalt source and the organic ligand at room temperature is preferably 20 to 28h, more preferably 24 h.
According to the invention, preferably, the precursor is dispersed into the solvent and stirred with the nickel source at room temperature for reaction for 30-60 min; further preferably, the reaction time is 45 min.
According to the invention, the hydrothermal reaction temperature is preferably 180-210 ℃, and more preferably 200 ℃. The hydrothermal reaction time is 6-18h, and more preferably 12 h.
In more detail, the method for synthesizing the nickel cobalt-molybdenum disulfide hollow nano composite material comprises the following steps:
(1) respectively dissolving cobalt nitrate hexahydrate serving as a cobalt source and 2-methylimidazole serving as an organic ligand in methanol, mixing, standing at room temperature for reacting for 20-28 hours, and centrifuging and drying after the reaction is finished to obtain a ZIF-67 precursor;
(2) dissolving the ZIF-67 precursor obtained in the step (1) in an ethanol solvent, adding nickel nitrate hexahydrate serving as a nickel source, stirring and reacting at room temperature for 30-60min to obtain a product, and centrifuging and washing;
(3) re-dispersing the product obtained in the step (2) into an ethanol solvent, and adding molybdenum source sodium molybdate dihydrate and sulfur source thioacetamide;
(4) pouring the mixed solution obtained in the step (3) into a hydrothermal kettle, and reacting for 6-18h at the temperature of 180-;
(5) after the reaction is finished, cooling to room temperature, and centrifugally washing and drying the product to obtain the nickel-cobalt-molybdenum disulfide hollow nano composite material.
In the step (2), the ZIF-67 precursor is sacrificed, and a hollow structure of the double metal hydroxide, namely the nickel-cobalt hydroxide, is synthesized by utilizing the exchange reaction with nickel ions and is used for forming a framework of the nickel-cobalt-molybdenum disulfide hollow nano composite material subsequently.
According to the present invention, preferred reactions include one or more of the following conditions:
in the step (1), the concentration of the methanol solution of cobalt nitrate hexahydrate is 0.04-0.055mol L-1Preferably 0.05mol L-1(ii) a The concentration of the 2-methylimidazole methanol solution is 0.3-0.5mol L-1(ii) a Preferably 0.4mol L-1. And (2) the precursor ZIF-67 of the product obtained in the step (1) is purple powder.
In the step (3), the concentration of the sodium molybdate dihydrate in the ethanol solvent is controlled to be 0.01-0.19mol L-1(ii) a Preferably 0.12 to 0.13mol L-1(ii) a Most preferably 0.124mol L-1. The concentration of thioacetamide in ethanol solvent is controlled to be 0.06-0.7mol L-1(ii) a Preferably 0.4 to 0.5mol L-1. Most preferably 0.496mol L-1。
In the step (4), the reaction temperature is 200 ℃, and the reaction time is 12 h.
According to the invention, the nickel cobalt-molybdenum disulfide hollow nano composite material is applied to hydrogen evolution of an electrocatalyst.
The invention is characterized in that ZIF-67 is used as a self-sacrificial template, a hollow framework of double hydroxide is synthesized by an exchange reaction with nickel ions, and then a nickel-cobalt-molybdenum disulfide hollow structure with a rhombic dodecahedron (keeping the framework of the ZIF-67) and exposed with a large number of active sites is prepared by a one-step hydrothermal method.
The invention has the beneficial effects that:
1. the invention firstly prepares an organic metal frame as a precursor, namely a ZIF-67 precursor, and prepares the hollow nickel-cobalt-molybdenum disulfide nano composite material by taking the metal organic frame as a self-sacrifice template. The hollow structure can provide a larger specific surface area and accelerate the electron transfer process, thereby improving the electrocatalytic hydrogen evolution performance.
2. The nickel cobalt-molybdenum disulfide (NiCo-MoS) synthesized by the invention2) The hollow nano composite material has good performance of electrochemical hydrogen evolution, 10mA cm-2The overpotential can reach 156mV under the current density, and the Tafel slope is 87.6mV Dec-1. Can be applied to the field of electrocatalysis hydrogen evolution.
3. The inventor finds that the electrocatalytic hydrogen evolution performance of the synthetic nickel-cobalt-molybdenum disulfide hollow nano composite material can be regulated and controlled through the molybdenum-cobalt ratio, and when the molar ratio of the molybdenum to the cobalt is too low (such as lower than 0.1: 1), the raw materials participating in the reaction are too few, which is unfavorable for electrocatalytic hydrogen evolution of the product. Along with the increase of the molar ratio of the molybdenum source to the cobalt source, the electrocatalytic hydrogen evolution performance is increased, and when the molar ratio of the molybdenum to the cobalt reaches 2.0-2.5:1, the catalytic performance approaches the optimal state. The molybdenum-cobalt molar ratio is more than 4:1, too much molybdenum raw material rather hinders the catalytic activity.
4. The size of the nickel cobalt-molybdenum disulfide hollow nano composite material synthesized by the method is controllable, experimental data show that different molybdenum cobalt ratios have obvious influence on the appearance of the catalyst, when the molar ratio of molybdenum cobalt is smaller, the obtained nickel cobalt-molybdenum disulfide composite material has smaller size, the size is increased along with the increase of the ratio, but after the maximum value is reached, the size is decreased along with the increase of the ratio of molybdenum cobalt. The molybdenum-cobalt ratio can be mastered according to actual requirements, and the nickel-cobalt-molybdenum disulfide hollow nano composite material with a proper size can be obtained.
5. The synthetic process method for synthesizing the nickel cobalt-molybdenum disulfide hollow nano composite material is simple and easy to operate, the product is simple and easy to obtain, and no pollution is caused to the environment.
Drawings
FIG. 1 is a transmission electron microscope photograph of ZIF-67 prepared in example 1;
fig. 2 is a transmission electron microscope picture of the nickel cobalt hydroxide nanoparticles prepared in example 1;
fig. 3 is a transmission electron microscope photograph of the nickel cobalt-molybdenum disulfide hollow nanoparticles prepared in example 1;
fig. 4 is a high resolution transmission electron microscope picture of the nickel cobalt-molybdenum disulfide hollow nanoparticles prepared in example 1;
figure 5 is an X-ray diffraction pattern of nickel cobalt-molybdenum disulfide hollow nanoparticles prepared in example 1;
FIG. 6 is a photograph of polarization curves for the nickel cobalt-molybdenum disulfide hollow nanoparticles prepared in example 1 and the samples of comparative examples 1-3; the abscissa is the standard hydrogen electrode potential for an Ag/AgCl reference electrode;
fig. 7 is a picture of cyclic voltammograms at different scan rates of the nickel cobalt-molybdenum disulfide hollow nanoparticles prepared in example 1;
fig. 8 is an ac impedance picture of the nickel cobalt-molybdenum disulfide hollow nanoparticles prepared in example 1;
fig. 9 is a tafel plot picture of nickel cobalt-molybdenum disulfide hollow nanoparticles prepared in example 1;
FIG. 10 is a 24h constant voltage test at-0.156V (vs. Ag/AgCl electrode) of nickel cobalt-molybdenum disulfide hollow nanoparticles prepared in example 1;
fig. 11 is a photograph of polarization curves of the nickel cobalt-molybdenum disulfide hollow nanoparticles prepared in example 1 and examples 2-5.
Fig. 12 is a transmission electron microscope picture of the nickel cobalt-molybdenum disulfide hollow nanomaterial obtained in example 2;
fig. 13 is a transmission electron microscope picture of the nickel cobalt-molybdenum disulfide hollow nanomaterial obtained in example 3;
fig. 14 is a transmission electron microscope picture of the nickel cobalt-molybdenum disulfide hollow nanomaterial obtained in example 4;
FIG. 15 is a TEM image of the Ni-Co-Mo disulfide hollow nanomaterial obtained in example 5;
fig. 16 is a process flow diagram of the nickel cobalt-molybdenum disulfide hollow nanomaterial prepared in example 1.
Detailed Description
The method for preparing the nickel cobalt-molybdenum disulfide hollow nanocomposite material according to the present invention is described in detail below with reference to specific examples and drawings. The raw materials and reagents in the examples are all commercially available products.
The main experimental reagents and instruments used in the examples are listed below:
cobalt nitrate hexahydrate (Co (NO)3)2·2H2O), 2-methylimidazole (C)4H6N2) Methanol, sodium molybdate dihydrate (Na)2MoO4.2H2O), thioacetamide (CH)3CSNH2) Absolute ethanol, Nafion (5 wt%), 20% Pt/C, magnetic stirrer (Color liquid [ white ]]) A bench top high speed centrifuge (TG16-WS), an analytical electronic balance (BS210S), an electrothermal blowing dry box (DHG-9015A), an ultrasonic cleaner (KQ2200B type), an X-ray diffractometer (X' Pert PRO MPD), a transmission electron microscope (JEM-2100(UHR), an electrochemical workstation (CHI 660E).
The electrochemical experiments in the examples were carried out as follows:
a working electrode preparation step: 5mg of the powdery catalyst sample was dispersed in 15. mu.L of a mixed solution of 5 wt% Nafion and 500. mu.L of absolute ethanol, sonicated for 30min to form a uniform solution, and then 100. mu.L of the mixed solution was extracted and dropped on a pretreated carbon paper (area of 1 cm)2The loading concentration is 1mg cm-2) As the working electrode.
The polarization curve (LSV) and cyclic voltammetry Curve (CV) were tested in a 1M KOH solution using a CHI660E electrochemical workstation, using Ag/AgCl (in 3M KCl) as a reference electrode and a carbon rod electrode as a counter electrode, and the electrolyte was deoxygenated by introducing nitrogen gas in advance for 30min before each experiment, with the sweep rate set at 5 mV. s-1And a stable polarization curve was obtained after 20 scans.
In an alternating current impedance (EIS) test, the open circuit potential parameter was set to-0.18V (vs. Ag/AgCl electrode) and the frequency was set from 100000Hz to 0.1 Hz.
And (3) obtaining a tafel curve by the overpotential (eta) to log (j), and then calculating the tafel slope to evaluate the dynamic performance of the electro-catalytic hydrogen production of the catalyst.
Wherein all potential values in the experiment are corrected by a standard hydrogen electrode, and the electrode potential calibration equation is an equation:
ERHE＝EAg/AgCl+0.059pH+E0 Ag/AgCl(E0 Ag/AgCl＝0.209V)。
example 1 preparation of a Nickel cobalt-molybdenum disulfide hollow nanocomposite
1.455g (5mmol) of cobalt nitrate hexahydrate and 3.28g (40mmol) of 2-methylimidazole are weighed into beakers containing 100mL of methanol, respectively, and the cobalt nitrate hexahydrate solution is poured into the 2-methylimidazole solution by a magnetic stirring method. After stirring for 10min, standing at room temperature for 24h to obtain a purple product, and centrifugally drying to obtain a ZIF-67 precursor (about 0.37 g).
Dispersing 0.04g of ZIF-67 into 25mL of ethanol, performing ultrasonic dispersion to form a uniform solution, adding 0.08g (0.275mmol) of nickel nitrate hexahydrate, stirring for 45min at room temperature, centrifuging the obtained dark purple precipitate (nickel cobalt-hydroxide), then re-dispersing the precipitate in 10mL of ethanol, adding 300mg (1.24mmol) of sodium molybdate dihydrate (the molar ratio of a molybdenum source to a cobalt source is 2.2: 1) and 372mg (4.96mmol) of thioacetamide into the solution, heating the solution at 200 ℃ for 12h, naturally cooling the solution to room temperature, and performing centrifugal drying to obtain a nickel cobalt-molybdenum disulfide hollow nano composite material product.
Test example 1 electrochemical Hydrogen production Performance test
Linear sweep voltammetry was performed by dispersing 5mg of a powdered catalyst sample in 15. mu.L of a mixed solution of 5 wt% Nafion and 500. mu.L of absolute ethanol, sonicating for 30min to form a uniform solution, and then drawing 100. mu.L of the mixed solution and dropping it on pretreated carbon paper (area of 1 cm)2The loading concentration is 1mg cm-2) As the working electrode.
The polarization curve (LSV) and cyclic voltammetry Curve (CV) were tested in a 1.0M KOH solution using a CHI660E electrochemical workstation, using Ag/AgCl (in 3M KCl) as a reference electrode and a graphite electrode as a counter electrode, and the electrolyte was deoxygenated by introducing nitrogen gas for 30min before each experiment, with a sweep rate set at 5 mV. s-1And a stable polarization curve was obtained after 20 scans. The polarization curve (LSV) of the nickel cobalt-molybdenum disulfide hollow nanocomposite material of example 1 is shown in FIG. 6, the cyclic voltammetry curve pictures at different sweep rates are shown in FIG. 7, the sweep rate is 5-40mV/s, and it can be seen from FIG. 6 that the hydrogen evolution performance of the nickel cobalt-molybdenum disulfide hollow nanocomposite material is better than that of pure phase molybdenum disulfide and two molybdenum disulfide groupsAnd (3) nano materials.
The nickel cobalt-molybdenum disulfide hollow nanocomposite of example 1 was subjected to 24h constant voltage testing under-0.156V (vs Ag/AgCl electrode) conditions as shown in figure 10. Fig. 10 shows that the nickel cobalt-molybdenum disulfide hollow nanocomposite has good stability in the hydrogen evolution reaction.
Alternating current impedance (EIS) testing, open circuit potential parameters were set to-0.18V (versus Ag/AgCl electrodes) and frequencies were set from 100000Hz to 0.1 Hz. Fig. 8 is a graph showing the ac impedance of the nickel cobalt-molybdenum disulfide hollow nanocomposite material of example 1, and it can be seen from fig. 8 that the nickel cobalt-molybdenum disulfide hollow nanocomposite material has a smaller electron transfer resistance.
And (3) obtaining a tafel curve by the overpotential (eta) to log (j), and then calculating the tafel slope to evaluate the dynamic performance of the electro-catalytic hydrogen production of the catalyst. From FIG. 9, it can be seen that the Ni-Co-Mo sulfide hollow nanocomposite material has a smaller Tafel slope of 87.6mV Dec-1。
Test example 2, characterization test
A transmission electron microscope photograph of the ZIF-67 precursor prepared according to the method of example 1 is shown in FIG. 1, and it can be seen from FIG. 1 that the ZIF-67 precursor is a rhombohedral.
Fig. 2 shows a transmission electron microscope photograph of the nickel cobalt metal hydroxide prepared according to the method of example 1, wherein the nickel cobalt metal hydroxide prepared according to fig. 2 has a hollow cubic structure and a lamellar structure around the hollow cubic structure.
The transmission electron microscope picture of the nickel cobalt-molybdenum disulfide hollow nanomaterial prepared in example 1 is shown in fig. 3, and the high-resolution transmission electron microscope picture is shown in fig. 4. As can be seen from FIG. 3, the prepared hollow nano nickel cobalt-molybdenum disulfide material has a hollow structure, and the particle size of the product is about 370 nm; as can be seen from FIG. 4, the interlayer spacing of the (002) crystal plane of the synthesized nickel-cobalt-molybdenum disulfide hollow nano material is 0.62nm, and the nickel-cobalt-molybdenum disulfide hollow nano material can be judged to be molybdenum disulfide and is consistent with the XRD result.
The X-ray diffraction pattern of the nickel cobalt-molybdenum disulfide hollow nanomaterial prepared according to the method of example 1 is shown in fig. 5, and molybdenum disulfide in 2H phase is obtained from fig. 5.
Example 2 preparation of Nickel cobalt-molybdenum disulfide hollow nanocomposite
Preparation of ZIF-67 precursor was as described in example 1. The difference is that:
taking 0.04g of ZIF-67 purple powder, dispersing into 25mL of ethanol by ultrasonic dispersion to form a uniform solution, adding 0.08g (0.275mmol) of nickel nitrate hexahydrate, stirring for 45min at room temperature, centrifuging the obtained purple precipitate, re-dispersing in 10mL of ethanol, adding 37.5mg (0.155mmol) of sodium molybdate dihydrate (the molar ratio of a molybdenum source to a cobalt source is 0.287: 1) and 46.5mg (0.62mmol) of thioacetamide into the solution, heating for 12h at 200 ℃, naturally cooling to room temperature, and centrifugally drying to obtain a nickel cobalt-molybdenum disulfide hollow nano material product, wherein a transmission electron microscope picture of the product is shown in figure 12, and the particle size of the product is about 220 nm. The polarization curve (LSV) of the resulting nickel cobalt-molybdenum disulfide hollow nanocomposite is shown in fig. 11.
Example 3 preparation of Nickel cobalt-molybdenum disulfide hollow nanocomposite
Preparation of ZIF-67 precursor was as described in example 1. The difference is that:
taking 0.04g of ZIF-67 purple powder, dispersing into 25mL of ethanol by ultrasonic dispersion to form a uniform solution, adding 0.08g (0.275mmol) of nickel nitrate hexahydrate, stirring for 45min at room temperature, centrifuging the obtained purple precipitate, re-dispersing in 10mL of ethanol, adding 75mg (0.31mmol) of sodium molybdate dihydrate (the molar ratio of a molybdenum source to a cobalt source is 0.57: 1) and 78mg (1.04mmol) of thioacetamide into the solution, heating for 12h at 200 ℃, naturally cooling to room temperature, and centrifuging and drying to obtain a nickel cobalt-molybdenum disulfide hollow nano material product, wherein a transmission electron microscope picture of the product is shown in figure 13, and the particle size of the product is about 270 nm. The polarization curve (LSV) of the resulting nickel cobalt-molybdenum disulfide hollow nanocomposite is shown in fig. 11.
Example 4 preparation of Nickel cobalt-molybdenum disulfide hollow nanocomposite
1.6g (5.5mmol) of cobalt nitrate hexahydrate and 4.1g (50mmol) of 2-methylimidazole are weighed into beakers respectively containing 100mL of methanol, and the cobalt nitrate hexahydrate solution is poured into the 2-methylimidazole solution by a magnetic stirring method. After stirring for 10min, the mixture was allowed to stand at room temperature for 24h to obtain a purple product, which was then centrifuged and dried to obtain ZIF-67(0.407 g).
Dispersing 0.04g of ZIF-67 purple powder into 25mL of ethanol for ultrasonic dispersion to form a uniform solution, adding 0.08g (0.275mmol) of nickel nitrate hexahydrate, stirring for 45min at room temperature, centrifuging the obtained purple precipitate, re-dispersing the purple precipitate into 10mL of ethanol, adding 150mg (0.62mmol) of sodium molybdate dihydrate (the molar ratio of a molybdenum source to a cobalt source is 1.15: 1) and 186mg (2.48mmol) of thioacetamide into the solution, heating for 12h at 200 ℃, naturally cooling to room temperature, and performing centrifugal drying to obtain a nickel cobalt-molybdenum disulfide hollow nano material product, wherein a transmission electron microscope picture of the product is shown in figure 14, and the particle size of the product is about 340 nm. The polarization curve (LSV) of the resulting nickel cobalt-molybdenum disulfide hollow nanocomposite is shown in fig. 11.
Example 5 preparation of Nickel cobalt-molybdenum disulfide hollow nanocomposite
Preparation of ZIF-67 precursor was as described in example 1. The difference is that:
0.04g of ZIF-67 purple powder is dispersed into 25mL of ethanol for ultrasonic dispersion to form a uniform solution, 0.04g (0.1375mmol) of nickel nitrate hexahydrate is added, the mixture is stirred for 45min at room temperature, the obtained purple precipitate is re-dispersed into 10mL of ethanol after being centrifuged, 450mg (1.86mmol) of sodium molybdate dihydrate ((the molar ratio of a molybdenum source to a cobalt source is 3.44: 1)) and 628mg (8.37mmol) of thioacetamide are added into the solution, the solution is heated for 12h at 200 ℃, after being naturally cooled to room temperature, the product is centrifugally dried to obtain a nickel cobalt-molybdenum disulfide hollow nano material product, and the transmission electron microscope picture of the product is shown in figure 15, and the particle size of the product is about 270 nm. The polarization curve (LSV) of the resulting nickel cobalt-molybdenum disulfide hollow nanocomposite is shown in fig. 11.
To evaluate the hydrogen evolution performance of the nickel cobalt-molybdenum disulfide hollow nanocomposites of the present invention, comparison was made with the products of comparative examples 1-3 below.
Comparative example 1 preparation of molybdenum disulfide-based Material (Ni-MoS)2)
0.08g of nickel nitrate hexahydrate is dispersed into 10mL of ethanol and ultrasonically dispersed to form a uniform solution,adding 300mg (1.24mmol) of sodium molybdate dihydrate and 312mg (4.16mmol) of thioacetamide into the solution, heating at 200 ℃ for 12h, naturally cooling to room temperature, and centrifugally drying to obtain Ni-MoS2And (5) producing the product.
Comparative example 2 preparation of molybdenum disulfide-based Material (Co-MoS)2)
Dispersing 0.04g ZIF-67 purple powder into 10mL ethanol, performing ultrasonic dispersion to form a uniform solution, adding 300mg (1.24mmol) of sodium molybdate dihydrate and 312mg (4.16mmol) of thioacetamide into the solution, heating at 200 ℃ for 12h, naturally cooling to room temperature, and performing centrifugal drying to obtain Co-MoS2And (5) producing the product.
Comparative example 3 preparation of molybdenum disulfide Material
300mg (1.24mmol) of sodium molybdate dihydrate and 312mg (4.16mmol) of thioacetamide are dispersed in 10mL of ethanol solvent, heated for 12h at 200 ℃, naturally cooled to room temperature, and centrifugally dried to obtain the product, namely the molybdenum disulfide.
The polarization curves (LSV) of the nickel cobalt-molybdenum disulfide hollow nanoparticles prepared in example 1 and the samples in comparative examples 1-3 are shown in FIG. 6, the cyclic voltammetry curve graph at different sweep rates is shown in FIG. 7, the sweep rate is 5-40mV/s, and it can be seen from FIG. 6 that the hydrogen evolution performance of the nickel cobalt-molybdenum disulfide hollow nanocomposite is better than that of pure phase molybdenum disulfide (comparative example 3) and two molybdenum disulfide based nanomaterials (comparative examples 1-2).
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. A nickel cobalt-molybdenum disulfide hollow nano composite material is provided, the shape of which is polyhedral nano particles, the particle diameter of which is 250-500 nm; the nickel cobalt-molybdenum disulfide hollow nano composite material is prepared by taking an organic metal framework precursor formed by a cobalt source and an organic ligand as a self-sacrifice template, firstly reacting with a nickel source in a solvent, and then adding a sulfur source and a molybdenum source to carry out hydrothermal reaction.
2. The nickel cobalt-molybdenum disulfide hollow nanocomposite material as claimed in claim 1, wherein the nickel cobalt-molybdenum disulfide hollow nanocomposite material has a dodecahedral hollow structure, and the particle size is 300-400 nm; preferably, the thickness of the molybdenum disulfide at the edge is 60-65 nm.
3. The method of synthesizing the nickel cobalt-molybdenum disulfide hollow nanocomposite of claim 1, comprising:
dissolving a cobalt source and an organic ligand in a solvent, and reacting at room temperature to form an organic metal framework precursor (ZIF-67 precursor);
dispersing the obtained precursor into a solvent, adding a nickel source, and stirring at room temperature;
and then adding a sulfur source and a molybdenum source to perform a hydrothermal reaction step.
4. The method of synthesizing the nickel cobalt-molybdenum disulfide hollow nanocomposite as claimed in claim 3 wherein the reaction includes one or more of the following conditions:
a. the cobalt source is cobalt nitrate hexahydrate, and the organic ligand is 2-methylimidazole;
b. the molar ratio of cobalt source to organic ligand is 1:6-9, preferably 1: 7-8;
c. the nickel source is nickel nitrate hexahydrate;
d. the molar ratio of the cobalt source to the nickel source is 1-5:1, preferably 3.5-4: 1;
e. the molar ratio of the molybdenum source to the sulfur source is 1: 3-5, preferably the molar ratio of the molybdenum source to the sulfur source is 1: 4;
f. the sulfur source is thioacetamide, and the molybdenum source is sodium molybdate dihydrate;
g. the molar ratio of the molybdenum source to the cobalt source is 0.1-5: 1, preferably 1-3: 1; the optimal molybdenum-cobalt molar ratio is 2.0-2.5: 1;
h. the reaction time of the cobalt source and the organic ligand at room temperature is 20-28h, and preferably the reaction time is 24 h;
i. dispersing the precursor into a solvent, and stirring the precursor and a nickel source at room temperature for reaction for 30-60 min; preferably, the reaction time is 45 min;
j. the hydrothermal reaction temperature is 180-210 ℃, and the preferred hydrothermal reaction temperature is 200 ℃;
k. the hydrothermal reaction time is 6-18h, and the preferred hydrothermal reaction time is 12 h.
5. The method for synthesizing the nickel cobalt-molybdenum disulfide hollow nanocomposite material as claimed in claim 3 or 4, comprising the steps of:
(1) respectively dissolving cobalt nitrate hexahydrate serving as a cobalt source and 2-methylimidazole serving as an organic ligand in methanol, mixing, standing at room temperature for reacting for 20-28 hours, and centrifuging and drying after the reaction is finished to obtain a ZIF-67 precursor;
(2) dissolving the ZIF-67 precursor obtained in the step (1) in an ethanol solvent, adding nickel nitrate hexahydrate serving as a nickel source, stirring and reacting at room temperature for 30-60min to obtain a product, and centrifuging and washing;
(3) re-dispersing the product obtained in the step (2) into an ethanol solvent, and adding molybdenum source sodium molybdate dihydrate and sulfur source thioacetamide;
(4) pouring the mixed solution obtained in the step (3) into a hydrothermal kettle, and reacting for 6-18h at the temperature of 180-;
(5) after the reaction is finished, cooling to room temperature, and centrifugally washing and drying the product to obtain the nickel-cobalt-molybdenum disulfide hollow nano composite material.
6. The method for synthesizing the nickel cobalt-molybdenum disulfide hollow nanocomposite material as claimed in claim 5, wherein in the step (1), the concentration of the methanol solution of cobalt nitrate hexahydrate is 0.04-0.055mol L-1。
7. The method for synthesizing nickel cobalt-molybdenum disulfide hollow nanocomposite material as claimed in claim 5, wherein in the step (1), the concentration of the 2-methylimidazole methanol solution is 0.3-0.5mol L-1。
8. The method for synthesizing nickel cobalt-molybdenum disulfide hollow nanocomposite as claimed in claim 5, wherein in the step (3), the concentration of sodium molybdate dihydrate in ethanol solvent is controlled to be 0.01-0.19mol L-1(ii) a Preferably 0.12 to 0.13mol L-1。
9. The method for synthesizing nickel cobalt-molybdenum disulfide hollow nanocomposite as claimed in claim 5, wherein in the step (3), the concentration of thioacetamide in ethanol solvent is controlled to be 0.06-0.7mol L-1Preferably 0.4 to 0.5mol L-1。
10. Use of the nickel cobalt-molybdenum disulfide hollow nanocomposite material of claim 1 or 2 in the evolution of hydrogen by an electrocatalyst.
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| CN112958124A (en) * | 2021-02-07 | 2021-06-15 | 同济大学 | Indium-doped molybdenum carbide nanoflower core-shell structure photocatalyst and preparation and application thereof |
| CN112958124B (en) * | 2021-02-07 | 2021-12-31 | 同济大学 | Indium-doped molybdenum carbide nanoflower core-shell structure photocatalyst and preparation and application thereof |
| CN113193198A (en) * | 2021-04-30 | 2021-07-30 | 陕西科技大学 | Cobalt-doped vanadium disulfide micron sheet and preparation method thereof |
| WO2023174768A1 (en) | 2022-03-18 | 2023-09-21 | IFP Energies Nouvelles | Catalytic material based on a group vib element and a group ivb element for the production of hydrogen by electrolysis of water |
| FR3133544A1 (en) | 2022-03-18 | 2023-09-22 | IFP Energies Nouvelles | Catalytic material based on a group VIB element and a group IVB element for the production of hydrogen by water electrolysis |
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