CN111111678A - Preparation method and application of nickel-iron alloy/iron molybdate hybrid nano material - Google Patents
Preparation method and application of nickel-iron alloy/iron molybdate hybrid nano material Download PDFInfo
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- CN111111678A CN111111678A CN201911219542.7A CN201911219542A CN111111678A CN 111111678 A CN111111678 A CN 111111678A CN 201911219542 A CN201911219542 A CN 201911219542A CN 111111678 A CN111111678 A CN 111111678A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 59
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 48
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000000137 annealing Methods 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 9
- VAWNDNOTGRTLLU-UHFFFAOYSA-N iron molybdenum nickel Chemical compound [Fe].[Ni].[Mo] VAWNDNOTGRTLLU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000009775 high-speed stirring Methods 0.000 claims abstract description 3
- 229910000863 Ferronickel Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 21
- 238000005859 coupling reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000008878 coupling Effects 0.000 abstract description 4
- 238000010168 coupling process Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- -1 molybdenum ions Chemical class 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 2
- 238000001291 vacuum drying Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000000956 alloy Substances 0.000 description 7
- 230000010287 polarization Effects 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 229910021397 glassy carbon Inorganic materials 0.000 description 5
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006181 electrochemical material Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001075 voltammogram 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
The invention belongs to the technical field of preparation of functionalized nano hybrid materials, and relates to a preparation method of a nickel-iron alloy/iron molybdate hybrid nano material, which comprises the following steps: under the condition of high-speed stirring, preparing a soluble divalent nickel source, a trivalent iron source, a hexavalent molybdenum source and deionized water into an aqueous solution, adding an alkali source, and stirring and uniformly mixing; transferring into a high-pressure reaction kettle, carrying out hydrothermal reaction at 100-150 ℃ for 8-15 h, and naturally cooling to room temperature; separating, washing, and vacuum drying at 50-80 ℃ for 6-12 h to obtain a nickel-iron-molybdenum ternary hydroxide precursor; and (3) placing the precursor in a tube furnace, annealing for 0.5-3 h at 300-800 ℃ in reducing gas, and naturally cooling to room temperature to obtain the material. The preparation process is simple and efficient, and the prepared composite material has strong electron coupling interface between two phases, so that molybdenum ions in the iron molybdate can keep the high valence state of active ions in the nickel-iron alloy by utilizing an electron-withdrawing effect, has more active sites, and inherits the good hydrophilicity of the iron molybdate and the excellent conductivity of the nickel-iron alloy.
Description
Technical Field
The invention belongs to the technical field of preparation of functionalized nano hybrid materials, and particularly relates to a preparation method and application of a nickel-iron alloy/iron molybdate hybrid nano material.
Background
The rapid development of energy and environmental problems greatly promotesThe development of clean energy is advanced. Hydrogen energy is a clean, sustainable energy source and is also considered to be a promising alternative to traditional fossil fuels. Electrocatalytic water cracking is considered as an ideal mode for producing hydrogen in a sustainable mode due to the advantages of no carbon emission, low cost and the like in the production process. Because of the anodic reaction of water splitting, the oxygen evolution reaction is a multi-step proton coupling reaction, the reaction kinetics is slow, and a very high overpotential is usually required in the reaction process. Therefore, the search for highly active electrocatalysts is currently the focus of highly efficient water splitting. Some conventional noble metal catalysts, e.g. IrO2And RuO2Their scarce reserves and high prices often limit widespread use. Accordingly, some transition metal catalysts have begun to step into the human eye, and the most representative materials are Fe, Co and Ni based oxides, hydroxyl, phosphate and sulfide. Among them, Layered Double Hydroxides (LDHs) stand out for their excellent properties and excellent stability, but are still limited by factors such as insufficient active sites and poor conductivity properties.
In recent years, bimetallic FeNi3Alloys have been reported to be catalysts with better electron conductivity. In addition, in order to further improve the intrinsic activity of such catalysts, it is feasible to adjust the electronic structure of the catalysts, and the current common method is to dope the catalysts with high-valence metal ions. Wherein Mo is6+、Cr6+And W6+As most reported dopants, their performance can be improved. The main reason for this is that the high valence metal ions can regulate the electron distribution and maintain the high valence state of the active center. Besides introducing high-valence metal ions into the catalyst, the combination of the hybrid which synthesizes a large number of interfaces can also induce strong electronic coupling, thereby obtaining an optimized electronic structure. Through the discussion above, the composite structure can be constructed by hybridization of the nickel-iron alloy and the iron molybdate, the electronic structure of the material is optimized through the interface effect, and meanwhile, the material also inherits the excellent electronic conductivity and hydrophilicity of the two separate phases.
Therefore, the nickel-iron alloy/iron molybdate hybrid nano material with multiple interfaces and strong electron correlation can be applied to various fields such as electrochemical materials, magnetic materials, adsorbing materials and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a nickel-iron alloy/iron molybdate hybrid nano material.
The invention prepares the nickel-iron alloy/iron molybdate hybrid nano material with multiple interfaces and strong electron correlation by using a method of firstly hydrothermal treatment and then calcination.
A preparation method of a nickel-iron alloy/iron molybdate hybrid nano material comprises the following steps:
(1) under the condition of high-speed stirring, preparing a soluble divalent nickel source, a trivalent iron source, a hexavalent molybdenum source and deionized water into a uniform aqueous solution, adding an alkali source, and stirring and mixing uniformly;
(2) transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal reaction at 100-150 ℃ for 8-15 h, preferably hydrothermal reaction at 120 ℃ for 12h, and naturally cooling to room temperature;
(3) separating and washing the obtained product, and drying the product for 6 to 12 hours in vacuum at the temperature of between 50 and 80 ℃ to obtain a nickel-iron-molybdenum ternary hydroxide precursor;
(4) and (2) placing the nickel-iron-molybdenum ternary hydroxide precursor into a tube furnace, annealing at the temperature rising rate of 2-10 ℃/min for 0.5-3 h, preferably annealing at the temperature of 500 ℃ for 1h, in a reducing gas, and naturally cooling to room temperature to obtain the nickel-iron alloy/iron molybdate hybrid nano material.
In a better disclosed example of the invention, the molar weight of the total metal in the step (1) is 4.0-5.0 mmol; the concentration of the divalent nickel source is 2-3 times of the concentrations of the other two metal sources; the volume of the deionized water is 150-200 mL, and the molar weight of the alkali source is 16.7 mmol.
In a preferred embodiment of the invention, the soluble divalent nickel source in the step (1) is one or a mixture of more of nickel chloride, nickel nitrate or hydrates thereof; the ferric iron source is one or a mixture of more of ferric chloride, ferric nitrate or hydrate thereof; the hexavalent molybdenum source is one or a mixture of ammonium molybdate, sodium molybdate or hydrate thereof; the alkali source is urea or ammonia water.
In the better disclosed example of the invention, the separation in the step (3) is centrifugation or suction filtration; the washing is carried out to neutrality by using deionized water and ethanol.
In a preferred embodiment of the present invention, the reducing gas in the step (4) is a hydrogen-argon mixed gas or a hydrogen-nitrogen mixed gas, wherein the content of hydrogen is 5-10%.
The ferronickel/iron molybdate hybrid nano material prepared by the method is nano granular particles with multiple interfaces, and magnified HRTEM images show that the nano particles respectively have obvious lattice stripes of 0.21 nm and 0.47 nm, which respectively correspond to the (111) plane of the ferronickel alloy and the (002) plane of the iron molybdate. In addition, many clearly discernible interfaces were observed in HRTEM images. A strong lattice disorder and lattice distortion structure is found between the edges of the 111 crystal plane of the nickel-iron alloy and the (002) crystal plane of iron molybdate. The formation of these interfaces and lattice distortion illustrate the successful construction of a strongly coupled ferronickel/iron molybdate hybrid, which also provides the requisite environment for strong electron coupling. XPS and Raman characterization prove that strong electronic correlation exists between two-phase substances, and specifically shows that hexavalent molybdenum ions in iron molybdate attract nickel ions in the nickel-iron alloy, high-valence nickel in the process of stabilizing OER is favorably used as an active site, so that the intrinsic characteristics of the material can be changed. In addition, the iron molybdate has excellent hydrophilic performance, the iron-nickel alloy has good conductive performance, and the hybridized ferronickel alloy/iron molybdate material perfectly inherits the characteristics of two-phase substances and can show better hydrophilic and conductive performance.
The other purpose of the invention is to apply the prepared nickel-iron alloy/iron molybdate hybrid nano material to electrochemical oxygen evolution catalysts and other functionalized nano electrode materials.
Specifically, the prepared nickel-iron alloy/iron molybdate hybrid nano material with multiple interfaces and strong electron correlation is uniformly mixed with a mixed solution of isopropanol and water to obtain a dispersed solution, the solution is dropped on a glassy carbon electrode with the diameter of 3mm, and the glassy carbon electrode is dried at 60 ℃ to obtain an electrode loaded with the nickel-iron alloy/iron molybdate hybrid nano material.
In an electrolyte of 1.0M KOH, the prepared electrode loaded with the nickel-iron alloy/iron molybdate hybrid nano material is used as a working electrode, a saturated Ag/AgCl electrode is used as a reference electrode, and a Pt electrode is used as a counter electrode; applying a three-electrode system to an electrochemical oxygen evolution test on an electrochemical workstation, and then performing linear sweep voltammetry at 5mV s-1The scan rate of (a) obtains a polarization curve.
Advantageous effects
The preparation process is simple and efficient, and the strong electron coupling interface between the two phases in the prepared composite material can ensure that the molybdenum ions in the iron molybdate can keep the high valence state of the active ions in the nickel-iron alloy by utilizing the electron-withdrawing effect and have more active sites. In addition, the material inherits the good hydrophilicity of iron molybdate and the excellent conductivity of the nickel-iron alloy. Based on the preparation of the material into an electrocatalytic oxygen generating electrode, the material is found to have good electrocatalytic oxygen generating performance. The nickel-iron alloy/iron molybdate hybrid nano material with multiple interfaces and strong electron correlation prepared by the invention can be applied to various fields such as electrochemical materials, magnetic materials, adsorbing materials and the like. The method disclosed by the invention is simple, feasible and universal, and is expected to realize industrial application.
Drawings
FIG. 1 is an X-ray powder diffraction analysis (XRD) pattern of the nickel-iron alloy/iron molybdate hybrid nanomaterial of example 1 with multiple interfaces and strong electron correlation;
FIG. 2 is a high power projection (HR-TEM) of the Ni-Fe alloy/Mo iron hybrid nanomaterial of example 1 with multiple interfaces and strong electron correlation;
FIG. 3X-ray photoelectron Spectroscopy (XPS) of the nickel-iron alloy/iron molybdate hybrid nanomaterial obtained in example 1 with multiple interfaces and strong electron correlation;
FIG. 4 is an elemental analysis (EDS) chart of the nickel-iron alloy/iron molybdate hybrid nanomaterial obtained in example 1 with multiple interfaces and strong electron correlations;
FIG. 5 is a linear voltammogram (LSV) for water oxidation of the nickel-iron alloy/iron molybdate hybrid nanomaterial obtained in example 1 with multiple interfaces and strong electron correlation and the samples obtained in examples 2-3.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Unless otherwise defined, terms (including technical and scientific terms) used herein should be construed to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art, and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1
A preparation method of a nickel-iron alloy/iron molybdate hybrid nano material comprises the following steps:
0.6844 g of NiCl were added under magnetic stirring2.6H2O, 0.2619 g of FeCl3.6H2O and 0.1703 g of (NH)4）6Mo7O24.4H2Dissolving O in 160 mL of deionized water to form a green acidic solution; then under the condition of continuous stirring, 1.0 g of urea is added into the solution and is uniformly stirred for 10 min; the obtained homogeneous solution was transferred on average to 4 50 mL stainless steel autoclaves and reacted in an electronic oven for 12h with the reaction temperature maintained at 120 ℃; after the reaction is finished and the reaction product is naturally cooled to room temperature, collecting the obtained yellow product, respectively washing the yellow product with deionized water and ethanol for 3 times, and then drying the product in a vacuum oven at 60 ℃ for 12 hours; finally, the precursor is put into a tube furnace and Ar/H is used2(19: 1) mixing atmosphere at 5 ℃ for min-1The heating rate is increased to 500 ℃ for annealing treatment, and the annealing treatment is kept for 1h at 500 ℃ to obtain the nickel-iron alloy/iron molybdate hybrid nano material with multiple interfaces and strong electron correlation.
The XRD pattern is shown in figure 1, and the XRD curve conforms to XRD standard cards (JCPDSNO. 88-17153, JCPDS number 85-2287) of the ferronickel alloy and the iron molybdate, which indicates that the two-phase material of the ferronickel alloy and the iron molybdate is successfully prepared. As shown in fig. 2, which is an enlarged HRTEM image, these nanoparticles have significant lattice striations of nickel-iron alloy and iron molybdate. In addition, many well-defined interfaces, lattice disordered and lattice distorted structures, successful construction of surface ferronickel/iron molybdate hybrid materials, were also observed in HRTEM images. XPS survey (FIG. 3) and EDS elemental analysis (FIG. 4) show that the catalyst material contains the characteristic elements of Ni, Fe, Mo and O, and the hybridization ratio of the nickel-iron alloy and iron molybdate is 1: 1.
Uniformly mixing 4mg of the obtained nickel-iron alloy/iron molybdate hybrid nano material with multiple interfaces and strong electron correlation with 1mL of mixed solution of isopropanol and water (the volume ratio is 3: 1), adding 10 mu L of Nafion binder to obtain dispersed solution, dripping 5 mu L of the solution on a glassy carbon electrode with the diameter of 3mm, and finally naturally drying in a 60 ℃ oven to obtain the nickel-iron alloy/iron molybdate hybrid nano material electrode.
Taking a nickel-iron alloy/iron molybdate hybrid nano material electrode as a working electrode, and carrying out a polarization curve test of oxygen evolution reaction in a 1.0M KOH solution by adopting a three-electrode system, wherein the polarization curve test is carried out at 10mA cm-2The overpotential of (a) is only 248 mV.
Example 2
A preparation method of a nickel-iron alloy/iron molybdate hybrid nano material comprises the following steps:
0.6844 g of NiCl were added under magnetic stirring2.6H2O, 0.2619 g of FeCl3.6H2O and 0.1703 g of (NH)4）6Mo7O24.4H2Dissolving O in 160 mL of deionized water to form a green acidic solution; then under the condition of continuous stirring, 1.0 g of urea is added into the solution and is uniformly stirred for 10 min; the obtained homogeneous solution was transferred on average to 4 stainless steel autoclaves of 50 mL, and the reaction temperature was maintained at 120 ℃ in an electronic oven for 12 h; after the reaction is finished and the reaction solution is naturally cooled to room temperature, collecting the obtained yellow product, and thenWashing with deionized water and ethanol for 3 times, respectively, and drying the product in a vacuum oven at 60 deg.C for 12 h; finally, the precursor is put into a tube furnace and Ar/H is used2(19: 1) mixing atmosphere at 5 ℃ for min-1The heating rate is increased to 300 ℃ for annealing treatment, and the annealing treatment is kept for 1h at 300 ℃ to obtain the hybridized nano material which does not have multiple interfaces and strong electron correlation, and the phase of the material is the nano material taking the nickel-iron-molybdenum ternary hydroxide as the main body.
Uniformly mixing 4mg of the obtained nano-sheet nickel-iron-molybdenum ternary hydroxide material with 1mL of mixed solution of isopropanol and water (the volume ratio is 3: 1), adding 10 mu L of Nafion binder to obtain dispersed solution, dripping 5 mu L of the solution on a glassy carbon electrode with the diameter of 3mm, and finally naturally drying in a 60 ℃ oven to obtain the nickel-iron-molybdenum ternary hydroxide nano-material electrode.
Taking a nickel-iron-molybdenum ternary hydroxide nano material electrode as a working electrode, and performing a polarization curve test of oxygen evolution reaction in a 1.0M KOH solution by adopting a three-electrode system, wherein the polarization curve test is performed at 10mA cm-2The overpotential of (3) is 463 mV.
Example 3
A preparation method of a nickel-iron alloy/iron molybdate hybrid nano material comprises the following steps:
0.6844 g of NiCl were added under magnetic stirring2.6H2O, 0.2619 g of FeCl3.6H2O and 0.1703 g of (NH)4）6Mo7O24.4H2Dissolving O in 160 mL of deionized water to form a green acidic solution; then under the condition of continuous stirring, 1.0 g of urea is added into the solution and is uniformly stirred for 10 min; the obtained homogeneous solution was transferred on average to 4 stainless steel autoclaves of 50 mL, and the reaction temperature was maintained at 120 ℃ in an electronic oven for 12 h; after the reaction is finished and the reaction product is naturally cooled to room temperature, collecting the obtained yellow product, respectively washing the yellow product with deionized water and ethanol for 3 times, and then drying the product in a vacuum oven at 60 ℃ for 12 hours; finally, the precursor is put into a tube furnace and Ar/H is used2(19: 1) mixing atmosphere at 5 ℃ for min-1The heating rate is increased to 700 ℃ for annealing treatment, and the annealing treatment is kept for 1h at 700 ℃ to obtain the hybridized nano material which does not have multiple interfaces and strong electron correlation, and the phase of the material is the nano material taking the nickel-iron alloy as the main body.
Uniformly mixing 4mg of the obtained nano-bulk nickel-iron alloy material with 1mL of mixed solution of isopropanol and water (the volume ratio is 3: 1), adding 10 mu L of Nafion binder to obtain dispersed solution, dripping 5 mu L of the solution on a glassy carbon electrode with the diameter of 3mm, and finally naturally drying in a 60 ℃ oven to obtain the nickel-iron alloy nano-material electrode.
Taking a nickel-iron alloy nano material electrode as a working electrode, and carrying out a polarization curve test of oxygen evolution reaction in a 1.0M KOH solution by adopting a three-electrode system, wherein the polarization curve test is carried out at 10mA cm-2The overpotential of (2) is 278 mV.
In combination with the catalyst material prepared under the conditions of the above example (fig. 5), the ni-fe alloy/mo hybrid nanomaterial with multiple interfaces and strong electron correlation exhibited the most excellent electrochemical oxygen evolution performance, and under the same comparison conditions, it not only had a smaller overpotential, but also had the largest current density. Due to special structural characteristics, the material can meet the future energy preparation requirement and is expected to play a great role.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (10)
1. A preparation method of a nickel-iron alloy/iron molybdate hybrid nano material is characterized by comprising the following steps:
(1) under the condition of high-speed stirring, preparing a soluble divalent nickel source, a trivalent iron source, a hexavalent molybdenum source and deionized water into a uniform aqueous solution, adding an alkali source, and stirring and mixing uniformly;
(2) transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal reaction for 8-15 h at the temperature of 100-150 ℃, and naturally cooling to room temperature;
(3) separating and washing the obtained product, and drying the product for 6 to 12 hours in vacuum at the temperature of between 50 and 80 ℃ to obtain a nickel-iron-molybdenum ternary hydroxide precursor;
(4) and (2) placing the nickel-iron-molybdenum ternary hydroxide precursor into a tube furnace, heating at the rate of 2-10 ℃/min, annealing in reducing gas at the temperature of 300-800 ℃ for 0.5-3 h, and naturally cooling to room temperature to obtain the nickel-iron alloy/iron molybdate hybrid nano material.
2. The method for preparing ferronickel/iron molybdate hybrid nano-materials according to claim 1, which is characterized in that: the molar weight of the total metal in the step (1) is 4.0-5.0 mmol; the concentration of the divalent nickel source is 2-3 times of the concentrations of the other two metal sources; the volume of the deionized water is 150-200 mL, and the molar weight of the alkali source is 16.7 mmol.
3. The method for preparing ferronickel/iron molybdate hybrid nano-materials according to claim 1, which is characterized in that: in the step (1), the soluble divalent nickel source is one or a mixture of nickel chloride, nickel nitrate or hydrates thereof; the ferric iron source is one or a mixture of more of ferric chloride, ferric nitrate or hydrate thereof; the hexavalent molybdenum source is one or a mixture of ammonium molybdate, sodium molybdate or hydrate thereof; the alkali source is urea or ammonia water.
4. The method for preparing ferronickel/iron molybdate hybrid nano-materials according to claim 1, which is characterized in that: and (2) moving the mixed solution obtained in the step (1) into a high-pressure reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 12 hours, and naturally cooling to room temperature.
5. The method for preparing ferronickel/iron molybdate hybrid nano-materials according to claim 1, which is characterized in that: the separation in the step (3) is centrifugation or suction filtration; the washing is carried out to neutrality by using deionized water and ethanol.
6. The method for preparing ferronickel/iron molybdate hybrid nano-materials according to claim 1, which is characterized in that: and (4) the reducing gas in the step (4) is hydrogen-argon mixed gas or hydrogen-nitrogen mixed gas, wherein the content of hydrogen is 5-10%.
7. The method for preparing ferronickel/iron molybdate hybrid nano-materials according to claim 1, which is characterized in that: and (4) annealing for 1h at 500 ℃ in a reducing gas.
8. Ferronickel/iron molybdate hybrid nanomaterial prepared by the method according to any one of claims 1 to 7.
9. The ferronickel/iron molybdate hybrid nanomaterial of claim 8, wherein: the nanomaterial is nanoparticulate particles having multiple interfaces.
10. Use of the ferronickel/iron molybdate hybrid nanomaterial as defined in claim 8 or 9, wherein: it is applied to an electrochemical oxygen evolution catalyst.
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