CN109317205B - Nickel-iron-based metal organic framework material rich in cyano-vacancy, preparation method and application thereof - Google Patents
Nickel-iron-based metal organic framework material rich in cyano-vacancy, preparation method and application thereof Download PDFInfo
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- 239000013082 iron-based metal-organic framework Substances 0.000 title claims abstract description 90
- 239000000463 material Substances 0.000 title claims abstract description 87
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910005809 NiMoO4 Inorganic materials 0.000 claims abstract description 29
- 239000002073 nanorod Substances 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 26
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 239000000276 potassium ferrocyanide Substances 0.000 claims abstract description 10
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 potassium ferricyanide Chemical compound 0.000 claims abstract description 7
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000264 sodium ferrocyanide Substances 0.000 claims abstract description 7
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims abstract description 7
- DCXPBOFGQPCWJY-UHFFFAOYSA-N trisodium;iron(3+);hexacyanide Chemical compound [Na+].[Na+].[Na+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCXPBOFGQPCWJY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 13
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 9
- PANJMBIFGCKWBY-UHFFFAOYSA-N iron tricyanide Chemical compound N#C[Fe](C#N)C#N PANJMBIFGCKWBY-UHFFFAOYSA-N 0.000 claims description 9
- 150000002815 nickel Chemical class 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910003271 Ni-Fe Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 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 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 14
- 239000001301 oxygen Substances 0.000 abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000010953 base metal Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000007661 iron cyano complex Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910020435 K2MoO4 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002825 nitriles Chemical group 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- 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
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- 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
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- 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
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Abstract
The invention provides a compound of formula (I)) The nickel-iron-based metal organic framework material rich in cyano-vacancy is shown; the application also provides a preparation method of the nickel-iron-based metal organic framework material rich in cyano-vacancy, which comprises the following steps: A) mixing NiMoO4Mixing the nanorod precursor with a cyanide complex solution of iron, and reacting to obtain the nickel-iron-based metal organic framework material, wherein the cyanide complex solution of iron is a potassium ferricyanide solution, a sodium ferricyanide solution, a potassium ferrocyanide solution or a sodium ferrocyanide solution; B) and (3) carrying out plasma bombardment on the nickel-iron-based metal organic framework material to obtain the nickel-iron-based metal organic framework material rich in cyano vacancy as shown in the formula (I). In the invention, the nickel-iron-based metal organic framework material rich in cyano-vacancy has excellent catalytic electrochemical oxygen generation performance.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a nickel-iron-based metal organic framework material rich in cyano-vacancy, and a preparation method and application thereof.
Background
Hydrogen is considered as a clean energy source having high energy density and no environmental pollution, and is expected to replace the current fossil energy. Therefore, how to synthesize hydrogen fuel cheaply and on a large scale becomes a research hotspot at present. The hydrogen production by water electrolysis is an environment-friendly hydrogen production method, and the main process comprises an oxygen evolution reaction at an anode and a hydrogen evolution reaction at a cathode. The reduction of the electrolytic potential energy of the electrolytic reaction can reduce the corresponding hydrogen production cost. The oxygen precipitation reaction of the anode is a four-electron transfer process, the consumed voltage is high, the dynamic process is very slow, and the generation of the full reaction of water electrolysis for hydrogen production is restricted. At present, noble metal catalysts such as ruthenium-based and iridium-based catalysts have good electrocatalytic oxygen production performance, but the high cost limits the large-scale application of the noble metal catalysts. Therefore, the development of non-noble metal electrocatalyst materials with high efficiency and low price becomes a current research hotspot and difficulty.
The metal organic framework material is an organic-inorganic hybrid material with intramolecular pores formed by the interaction of metal ions or clusters and organic ligands through coordination bonds, and various metal organic framework materials with specific functions and properties can be synthesized by regulating the types of the metal ions and the ligands. Recently, researchers find that the metal organic framework material can effectively catalyze the electrolysis of water to produce hydrogen and oxygen, and has a good electrochemical application prospect. However, the catalytic activity of metal organic framework materials is still difficult to match with the best noble metal catalysts. Researchers have attempted to compound them with other materials to further improve their catalytic activity. However, the operation process of the strategy is complex, the structural components are more than one, and the actual large-scale preparation and research of the catalytic active site are not facilitated. How to further optimize the structural characteristics of the material is the key to realize the improvement of the catalytic performance.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a nickel-iron-based metal organic framework material rich in cyano-vacancy, and the nickel-iron-based metal organic framework material rich in cyano-vacancy has high electrocatalytic activity.
In view of the above, the present application provides a nickel-iron-based metal-organic framework material rich in cyano-vacancy as shown in formula (I),
M2NiFe(CN)6-x(Ⅰ)；
wherein M is K or Na;
x is 0 to 0.5 and is not equal to 0.
Preferably, the specific surface area of the nickel-iron-based metal organic framework material rich in cyano-vacancy is 60-70 m2/g。
The application also provides a preparation method of the nickel-iron-based metal organic framework material rich in cyano-vacancy, which comprises the following steps:
A) mixing NiMoO4Mixing the nanorod precursor with a cyanide complex solution of iron, and reacting to obtain the nickel-iron-based metal organic framework material, wherein the cyanide complex solution of iron is a potassium ferricyanide solution, a sodium ferricyanide solution, a potassium ferrocyanide solution or a sodium ferrocyanide solution;
B) carrying out plasma bombardment on the nickel-iron-based metal organic framework material to obtain the nickel-iron-based metal organic framework material rich in cyano-vacancy as shown in the formula (I),
M2NiFe(CN)6-x(Ⅰ)；
wherein M is K or Na;
x is 0 to 0.5 and is not equal to 0.
Preferably, the NiMoO4The preparation method of the nanorod precursor comprises the following steps:
mixing molybdate, nickel salt and water to obtain a mixed solution;
carrying out hydrothermal reaction on the mixed solution to obtain NiMoO4And (4) a nanorod precursor.
Preferably, the nickel salt is selected from one or more of nickel nitrate, nickel chloride and nickel acetate, and the molybdate is selected from sodium molybdate or potassium molybdate; the temperature of the hydrothermal reaction is 120-180 ℃, and the time is 2-8 h.
Preferably, the NiMoO4The ratio of the nanorod precursor, the iron cyanide complex in the iron cyanide complex solution and the water in the iron cyanide complex solution is (10-60 mg): (30 mg-180 mg): (10 mL-50 mL).
Preferably, in the step of obtaining the nickel-iron-based metal organic framework material, the reaction temperature is 10-50 ℃ and the reaction time is 1-6 h.
Preferably, the power of the plasma bombardment is 40W-200W, the pressure is 0.2-40 Pa, and the protective atmosphere is one or two of nitrogen and argon; the temperature of the plasma bombardment is 20-60 ℃, and the time is 1-6 h.
The application also provides the application of the nickel-iron-based metal organic framework material rich in the cyano-vacancy or the nickel-iron-based metal organic framework material rich in the cyano-vacancy, prepared by the preparation method, as a catalyst in electrochemical catalytic oxidation reaction.
The application provides a nickel-iron-based metal organic framework material rich in cyano-vacancy, unstable cyano-groups in the nickel-iron-based metal organic framework material are partially deleted to form the cyano-vacancy, so that Fe and Ni are unsaturated in coordination, the coordination number is reduced, and the unsaturated sites of Fe and Ni are used as catalytic active sites for electrocatalytic oxygen generation and react with an intermediate product in the oxygen generation process, so that the electrocatalytic activity is improved.
Drawings
FIG. 1 is a NiMoO prepared according to example 1 of the present invention4Transmission electron microscope photo of the nano rod;
FIG. 2 is a TEM image of a Ni-Fe-based metal organic framework without cyano vacancies prepared in example 1 of the present invention;
FIG. 3 is a TEM image of a Ni-Fe-based metal organic framework rich in cyano-vacancy prepared in example 1 of the present invention;
FIG. 4 shows NiMoO prepared according to example 1 of the present invention4XRD patterns of nanorods, nickel-iron-based metal-organic frameworks without and rich in cyano-vacancies;
FIG. 5 is a TEM image of a Ni-Fe-based metal organic framework rich in cyano-vacancy prepared in example 2 of the present invention;
FIG. 6 is a TEM image of a Ni-Fe-based metal organic framework rich in cyano-vacancy prepared in example 3 of the present invention;
FIG. 7 is a TEM image of a Ni-Fe-based metal organic framework rich in cyano-vacancy prepared in example 4 of the present invention;
FIG. 8 is a graph of cyano vacancy concentration versus a nickel-iron-based metal-organic framework rich in cyano vacancies prepared in examples 1-4 of the present invention;
FIG. 9 is a polarization curve of the electrocatalytic oxygen evolution reaction of nickel-iron-based metal organic frameworks rich in cyano-vacancies prepared in examples 1-4 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Aiming at the current application requirements, the application provides a nickel-iron-based metal organic framework material rich in cyano-vacancy, and the material has a higher active site in the field of electrochemical oxygen generation as a catalyst, namely has excellent catalytic electrochemical oxygen generation performance. Specifically, the nickel-iron-based metal organic framework material rich in cyano-vacancy is shown as a formula (I):
M2NiFe(CN)6-x(Ⅰ)；
wherein M is K or Na;
x is 0 to 0.5 and is not equal to 0.
Nickel-iron-based metal organic frame rich in cyano-vacancies provided hereinThe specific surface area of the frame material is 60-70 m2(ii) in terms of/g. The specific surface area of the nickel-iron-based metal organic framework material has a high numerical value, so that the nickel-iron-based metal organic framework material can be ensured to be fully contacted with electrolyte in a catalytic process as a catalyst, and catalytic active sites can be better utilized. The molar concentration of the cyano-vacancy in the nickel-iron-based metal organic framework material rich in the cyano-vacancy is 0-8% and is not equal to 0%.
The application also provides a preparation method of the nickel-iron-based metal organic framework material rich in cyano-vacancy, which comprises the following steps:
A) mixing NiMoO4Mixing the nanorod precursor with a cyanide complex solution of iron, and reacting to obtain the nickel-iron-based metal organic framework material, wherein the cyanide complex solution of iron is a potassium ferricyanide solution, a sodium ferricyanide solution, a potassium ferrocyanide solution or a sodium ferrocyanide solution;
B) carrying out plasma bombardment on the nickel-iron-based metal organic framework material to obtain the nickel-iron-based metal organic framework material rich in cyano-vacancy as shown in the formula (I),
M2NiFe(CN)6-x(Ⅰ)；
wherein M is K or Na;
x is 0 to 0.5 and is not equal to 0.
In the process of preparing the nickel-iron-based metal organic framework material rich in cyano-vacancy, NiMoO is firstly added into the preparation method4Mixing the nanorod precursor with a cyanide complex solution of iron, and reacting to obtain the nickel-iron-based metal organic framework material, wherein the cyanide complex solution of iron is a potassium ferricyanide solution, a sodium ferricyanide solution, a potassium ferrocyanide solution or a sodium ferrocyanide solution; in this process, the NiMoO4Nanorod precursors can be prepared according to methods well known to those skilled in the art, as exemplified by the NiMoO4The preparation method of the nanorod precursor comprises the following steps:
mixing molybdate, nickel salt and water to obtain a mixed solution;
carrying out hydrothermal reaction on the mixed solution to obtain NiMoO4And (4) a nanorod precursor.
In the above-mentioned NiMoO4In the preparation process of the nanorod precursor, the nickel salt is well known to those skilled in the art, and is exemplified by one or more of nickel nitrate, nickel chloride and nickel acetate; the molybdate is well known to those skilled in the art and is exemplified by sodium molybdate or potassium molybdate. Wherein the molar ratio of the molybdate to the nickel salt is 1: 1; in the embodiment of the invention, the ratio of the molybdate to the nickel salt to the water is preferably (1-3) mmol: (1-3) mmol: 35 mL. The present invention preferably stirs the resulting mixture, such as on a magnetic stirrer, to achieve uniform mixing and to obtain a clear mixed solution.
According to the invention, the obtained mixed solution is transferred to a 45mL reaction kettle and put into an oven for hydrothermal reaction to obtain a reaction mixture. Wherein the temperature of the hydrothermal reaction is 120-180 ℃, and in a specific embodiment, the temperature of the hydrothermal reaction is 140-160 ℃; the time of the hydrothermal reaction is 2-8 h, and in a specific embodiment, the time of the hydrothermal reaction is 4-6 h.
The invention finally centrifugalizes and washes the obtained reaction mixture, and dries the reaction mixture in a vacuum drying oven to obtain NiMoO4And (4) nanorods. Wherein the centrifugation is a separation means commonly used in the art; the washing is a technical means well known to those skilled in the art, and the present invention is not particularly limited. In the invention, the drying temperature is 40-80 ℃, in a specific embodiment, the drying temperature is 60 ℃; the drying time is 4-18 h, and in a specific embodiment, the drying time is 8-12 h.
To obtain NiMoO4Mixing the nanorods with a cyanide complex solution of iron, and reacting to obtain the nickel-iron-based metal organic framework material, wherein the cyanide complex solution of iron is a potassium ferricyanide solution, a sodium ferricyanide solution, a potassium ferrocyanide solution or a sodium ferrocyanide solution; the cyanogen complex of iron takes potassium ferrocyanide as an example, and the following reaction specifically occurs in the step: NiMoO4+K4Fe(CN)6→K2NiFe(CN)6+K2MoO4The reaction isExchange reaction, NiMoO4Nanorod as template, K4Fe(CN)6Is a reaction solution; as the reaction proceeds, NiMoO4MoO of a template4 2-Ions will diffuse into the solution, NiMoO4Ni of template2+Will be in contact with K4Fe(CN)6Combine to obtain K2NiFe(CN)6Nickel-iron-based metal organic framework materials. The nickel-iron-based metal organic framework material without cyano-vacancy is obtained in the step, and the specific surface area of the nickel-iron-based metal organic framework material is 50-60 m2The specific surface area (10 m) of the nickel-iron-based metal organic framework material prepared by the method in the prior art is far larger than that of the nickel-iron-based metal organic framework material prepared by the method in the prior art2/g)。
In the above reaction, the NiMoO4The ratio of the nanorod precursor, the iron cyanide complex in the iron cyanide complex solution and the water in the iron cyanide complex solution is (10-60 mg): (30 mg-180 mg): (10 mL-50 mL), preferably (20 mg-40 mg): (60 mg-140 mg): (20 mL-40 mL); in this ratio, the iron cyanocomplex is in excess to ensure NiMoO4The template is completely converted into the nickel-iron-based metal organic framework material, and if the template is not completely converted, the nickel-iron-based metal organic framework material contains NiMoO4If the template remains, the phase will have mixed phase; the amount of water is such as to ensure the concentration of the iron cyanocomplex, too high a concentration will react too quickly and too low a concentration will react too slowly, both of which will affect the final morphology.
Stirring the mixed solution, and reacting to obtain a nickel-iron-based metal organic framework material; the reaction temperature is 10-50 ℃, and preferably 20-40 ℃; the reaction time is 1-6 h, preferably 2-4 h.
The invention preferably centrifugalizes and washes the product after the reaction, and dries the product in a vacuum drying oven to obtain the nickel-iron-based metal organic framework material. Wherein the centrifugation is a separation means commonly used in the art; the washing is a technical means well known to those skilled in the art, and the present invention is not particularly limited. In the present invention, the drying temperature is 40 to 80 ℃, preferably 60 ℃. The drying time is 4-18 h, preferably 8-12 h.
The invention finally makes the obtained nickel-iron base metal haveAnd carrying out plasma bombardment treatment on the frame material to obtain the nickel-iron-based metal organic frame material rich in cyano-vacancy. In the process, after the nickel-iron-based metal organic framework material is bombarded by plasma, Cyanide (CN) groups in the nickel-iron-based metal organic framework material are unstable, so that the cyanide can be taken away by the plasma bombardment to form cyano-vacancy, and M is obtained2NiFe(CN)6-xThis molecular nickel-iron-based metal-organic framework material rich in cyano-vacancies; the longer the bombardment time, the more cyano vacancies will be generated. In the present example, the plasma bombardment technique is performed by a plasma apparatus commonly used in the art. The power of the plasma bombardment is preferably 40-200W, and more preferably 80-150W; the pressure of the plasma bombardment is preferably 0.2Pa to 40Pa, and more preferably 0.4Pa to 10 Pa; the protective atmosphere for the plasma bombardment is preferably nitrogen or argon, more preferably nitrogen; the temperature of the plasma bombardment is preferably 20-60 ℃, and more preferably 30-40 ℃; the time of the plasma bombardment is preferably 0min to 120min, more preferably 30min to 120min, and most preferably 60 min.
After the nickel-iron-based metal organic framework rich in cyano-vacancy is obtained, the nickel-iron-based metal organic framework is subjected to tests such as electron microscope analysis and the like. The analysis result of one embodiment of the invention shows that the nickel-iron-based metal organic framework rich in the cyano-vacancy has a porous rod-like structure and uniform size, and the molar fraction of the cyano-vacancy in the nickel-iron-based metal organic framework is 0-8% and is not equal to 0%.
The invention also provides application of the nickel-iron-based metal organic framework material rich in cyano vacancy as a catalyst in electrochemical catalytic oxidation reaction.
The electrochemical test of the nickel-iron-based metal organic framework material rich in the cyano-vacancy is determined under the common three-electrode condition, the electrolyte of the electrochemical reaction is a KOH solution with the concentration of 1mol/L, and the scanning rate of a polarization curve is 5 mV/s; wherein the rotating disk electrode is loaded with a catalyst as a working electrode, and the loading amount of the catalyst is 0.25mg/cm2The platinum sheet is used as a counter electrode, and the Ag/AgCl electrode is used as a reference electrode. The experiment shows that the content of the catalyst is 6.3 mol percentSeveral cyano-vacancy nickel-iron-base metal organic frame materials are used as catalysts in oxygen production reaction, and the current density can reach 115mA/cm when the over potential is 0.35V2Is more than 60 times of that of the nickel-iron-based metal organic framework material without cyano vacancy. The material has excellent performance and good application prospect in the fields of electrocatalysis oxygen generation and total water decomposition.
For further understanding of the present invention, the following examples are provided to illustrate the preparation method and application of the Ni-Fe-based metal-organic framework material rich in cyano vacancy, and the scope of the present invention is not limited by the following examples.
Example 1
(1)NiMoO4Preparing a nanorod precursor: weighing 2mmol of nickel nitrate and 2mmol of sodium molybdate, and respectively dissolving in 17.5ml of deionized water; adding the nickel nitrate solution into a sodium molybdate solution, and stirring for 10 minutes to form a uniformly mixed solution; transferring the mixed solution into a 45ml reaction kettle, and putting the reaction kettle into a 150 ℃ oven for reaction for 6 hours; taking out the reaction kettle, finding a large amount of precipitates, centrifuging, washing with deionized water and ethanol, and drying in a vacuum drying oven at 60 ℃ for 12h to obtain NiMoO4A nanorod precursor;
(2) preparing a nickel-iron-based metal organic framework material: dissolving 120mg of potassium ferrocyanide in 30mL of deionized water, and stirring to fully dissolve; 40mg of the above NiMoO was added4Adding the nanorod precursor into a potassium ferrocyanide solution, stirring at room temperature for 3h, centrifuging, washing with deionized water and ethanol, and drying in a vacuum drying oven at 60 ℃ for 12h to obtain a nickel-iron-based metal organic framework material;
(3) preparation of nickel-iron metal organic framework catalyst rich in cyano vacancy: placing the 40mg of the nickel-iron-based metal organic framework material in a tube furnace of a plasma bombardment instrument; the bombardment power of the plasma is 100W, the pressure is 0.4Pa, the protective atmosphere is nitrogen, the bombardment temperature is 30 ℃, and the bombardment time is 60 min; after the plasma bombardment is finished, obtaining the nickel-iron-based metal organic framework catalyst rich in cyano-vacancy;
analyzing the product by electron microscopy, wherein the results are shown in figures 1-3NiMoO4A transmission electron microscope photo of the precursor, the nickel-iron-based metal organic framework and the nickel-iron-based metal organic framework rich in cyano vacancy; as can be seen, NiMoO4The precursor is of a solid nanorod structure, and the diameter of the precursor is 60-120 nm; the nickel-iron-based metal organic framework material (figure 2) is a porous rod-shaped structure, and the diameter of the porous rod-shaped structure is 80-140 nm; compared with the sample shown in FIG. 2, the nickel-iron-based metal organic framework material (FIG. 3) which is further subjected to plasma bombardment and is rich in cyano-vacancy has no obvious difference, and the morphology of the material can be better maintained. The XRD spectrum of FIG. 4 shows that NiMoO4The precursor is completely converted into the nickel-iron-based metal organic framework material, has completely different XRD spectrums, does not contain and is rich in cyano-vacancy, has similar XRD spectrums, and shows that the plasma bombardment does not change the phase of the material.
Example 2
The same preparation method as in example 1 is adopted, except that: and (4) changing the plasma bombardment time in the step (3) to 10 min.
And (3) analyzing the obtained sample by a transmission electron microscope, and obtaining a result shown in figure 5, wherein the product has a porous rod-like structure and the diameter of the product is 80-140 nm, so that the condition that the bombardment time of the plasma is shortened and the appearance of the product is not influenced can be known.
Example 3
The same preparation method as in example 1 is adopted, except that: and (4) changing the plasma bombardment time in the step (3) to 30 min.
And (3) analyzing the obtained sample by a transmission electron microscope, and referring to a result in FIG. 6, wherein the product has a porous rod-like structure and the diameter of the product is 80-140 nm, so that the condition that the bombardment time of the plasma is shortened and the appearance of the product is not influenced can be known.
Example 4
The same preparation method as in example 1 is adopted, except that: and (4) changing the plasma bombardment time in the step (3) to 120 min.
The transmission electron microscope analysis of the obtained sample is carried out, and the result is shown in fig. 7, wherein a part of the product has a rod-like structure, and a part of the product has a nano-particle structure, so that the appearance of the product can be influenced by prolonging the bombardment time of the plasma.
Example 5
The content analysis of the cyano-vacancy is performed on the nickel-iron-based metal organic framework obtained in the above examples 1 to 4 at different plasma bombardment times, and the results are shown in fig. 8, wherein the molar content of the cyano-vacancy is 0%, 1.8%, 4.3%, 6.3% and 7.7% in sequence for the material with the plasma bombardment time of 0min, 10min, 30min, 60min and 120min, and thus it can be seen that the longer the plasma bombardment time is, the higher the content of the cyano-vacancy is.
Example 6
The nickel-iron-based metal organic framework obtained in the above examples 1-4 at different plasma bombardment times is subjected to electrocatalytic oxygen evolution performance test, and the result is shown in fig. 9, which shows that the electrocatalytic activity of the nickel-iron-based metal organic framework is gradually improved as the cyano-vacancy concentration is increased from 0% to 6.3%, and the electrocatalytic activity of the nickel-iron-based metal organic framework is deteriorated when the vacancy concentration is continuously increased to 7.7%; the bombardment time of the plasma is 60min, the obtained nickel-iron-based metal organic framework catalyst with 6.3 percent of cyano-vacancy has the best electrocatalytic oxygen evolution activity, and the current density can reach 115mA/cm when the overpotential is 0.35V2More than 60 times of the nickel-iron-based metal organic framework material with 0% cyano vacancy.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A nickel-iron-based metal organic framework material rich in cyano-vacancy as shown in formula (I),
M2NiFe(CN)6-x(Ⅰ)；
wherein M is K or Na;
x is 0-0.5 and is not equal to 0;
the preparation method of the nickel-iron-based metal organic framework material rich in cyano-vacancy comprises the following steps:
A) mixing NiMoO4Mixing the nanorod precursor with a cyanide complex solution of iron, and reacting to obtain the nickel-iron-based metal organic framework material, wherein the cyanide complex solution of iron is a potassium ferricyanide solution, a sodium ferricyanide solution, a potassium ferrocyanide solution or a sodium ferrocyanide solution;
B) carrying out plasma bombardment on the nickel-iron-based metal organic framework material to obtain a nickel-iron-based metal organic framework material rich in cyano-vacancy as shown in a formula (I);
the NiMoO4The preparation method of the nanorod precursor comprises the following steps:
mixing molybdate, nickel salt and water to obtain a mixed solution;
carrying out hydrothermal reaction on the mixed solution to obtain NiMoO4And (4) a nanorod precursor.
2. The Ni-Fe-based metal-organic framework material of claim 1, wherein the specific surface area of the Ni-Fe-based metal-organic framework material rich in cyano-vacancy is 60-70 m2/g。
3. The method of making a cyano-vacancy rich nickel-iron-based metal-organic framework material of claim 1, comprising the steps of:
A) mixing NiMoO4Mixing the nanorod precursor with a solution of a cyanogen complex of iron, wherein the solution of the cyanogen complex of iron is a potassium ferricyanide solution, a sodium ferricyanide solution, a potassium ferrocyanide solution orA sodium ferrocyanide solution;
B) carrying out plasma bombardment on the nickel-iron-based metal organic framework material to obtain the nickel-iron-based metal organic framework material rich in cyano-vacancy as shown in the formula (I),
M2NiFe(CN)6-x(Ⅰ)；
wherein M is K or Na;
x is 0-0.5 and is not equal to 0;
the NiMoO4The preparation method of the nanorod precursor comprises the following steps:
mixing molybdate, nickel salt and water to obtain a mixed solution;
carrying out hydrothermal reaction on the mixed solution to obtain NiMoO4And (4) a nanorod precursor.
4. The method according to claim 3, wherein the nickel salt is selected from one or more of nickel nitrate, nickel chloride and nickel acetate, and the molybdate is selected from sodium molybdate or potassium molybdate; the temperature of the hydrothermal reaction is 120-180 ℃, and the time is 2-8 h.
5. The method according to claim 3, wherein the NiMoO is used as a catalyst4The ratio of the nanorod precursor, the iron cyanide complex in the iron cyanide complex solution and the water in the iron cyanide complex solution is (10-60 mg): (30 mg-180 mg): (10 mL-50 mL).
6. The preparation method according to claim 3, wherein the reaction temperature in the step of obtaining the nickel-iron-based metal organic framework material is 10-50 ℃ and the reaction time is 1-6 h.
7. The preparation method according to claim 3, wherein the power of the plasma bombardment is 40W-200W, the pressure is 0.2-40 Pa, and the protective atmosphere is one or two of nitrogen and argon; the temperature of the plasma bombardment is 20-60 ℃, and the time is 1-6 h.
8. Use of the cyano-vacancy-rich nickel-iron-based metal organic framework material as defined in any one of claims 1 to 2 or the cyano-vacancy-rich nickel-iron-based metal organic framework material prepared by the preparation method as defined in any one of claims 3 to 7 as a catalyst in electrochemical catalytic oxidation reactions.
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