CN117512676B - Hierarchical iron doped nickel-carbon structure nanotube and preparation method and application thereof - Google Patents
Hierarchical iron doped nickel-carbon structure nanotube and preparation method and application thereof Download PDFInfo
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- CN117512676B CN117512676B CN202410000524.4A CN202410000524A CN117512676B CN 117512676 B CN117512676 B CN 117512676B CN 202410000524 A CN202410000524 A CN 202410000524A CN 117512676 B CN117512676 B CN 117512676B
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- 239000002071 nanotube Substances 0.000 title claims abstract description 34
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical group [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 83
- 229910052742 iron Inorganic materials 0.000 title claims description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 218
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 105
- 239000006260 foam Substances 0.000 claims abstract description 99
- 239000013099 nickel-based metal-organic framework Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002243 precursor Substances 0.000 claims abstract description 40
- 239000001257 hydrogen Substances 0.000 claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 238000000992 sputter etching Methods 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 238000005406 washing Methods 0.000 claims description 35
- 238000001354 calcination Methods 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 238000011010 flushing procedure Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- VXWSFRMTBJZULV-UHFFFAOYSA-H iron(3+) sulfate hydrate Chemical compound O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VXWSFRMTBJZULV-UHFFFAOYSA-H 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 abstract description 37
- 239000003054 catalyst Substances 0.000 abstract description 16
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 41
- 239000000243 solution Substances 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000012621 metal-organic framework Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- -1 iron ion Chemical class 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000005530 etching Methods 0.000 description 4
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
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- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002110 nanocone Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Organic Chemistry (AREA)
- Nanotechnology (AREA)
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- Physics & Mathematics (AREA)
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Abstract
The invention relates to a hierarchical iron-doped nickel-carbon structure nanotube, a preparation method and application thereof, wherein an in-situ grown iron-doped Ni-MOF@NF precursor is prepared from pretreated foam nickel through ion etching, and the surface of the calcined iron-doped Ni-MOF@NF precursor is converted into an Fe-Ni@C/NF hollow nanotube with excellent difunctional electrolyzed water catalytic capability. The invention synthesizes the Fe-doped Ni-MOF by utilizing the redox micro-reaction of the Fe ions on the surface of the foam nickel under the condition of not introducing exogenous Ni salt. The requirement of synthesizing the Ni-MOF of the nanotube morphology is met by adjusting the concentration of ferric salt. In addition, the doping of Fe is beneficial to improving the local electron distribution of active sites, improves the performance and efficiency of hydrogen and oxygen evolution, and has good performance as a catalyst of electrolyzed water.
Description
Technical Field
The invention relates to the technical field of alkaline electrocatalytic decomposition of water, in particular to a hierarchical iron-doped nickel-carbon structure nanotube and a preparation method and application thereof.
Background
The ever-increasing consumption of fossil fuels and their associated environmental problems, such as air pollution, global warming and sea level rise, have prompted the search and development of safe, clean and renewable energy systems. Hydrogen can be used as a zero-carbon energy carrier, and hydrogen with high energy density is considered as a very promising energy source selection, wherein the electrocatalytic decomposition of water to produce hydrogen is a very potential green approach. The overall water splitting can be divided into two half reactions, including cathodic Hydrogen Evolution (HER) and anodic Oxygen Evolution (OER). Compared with HER, a larger thermodynamic potential is generally required to overcome the slow kinetics of OER caused by the four electron and four proton transfer processes, and the resulting high overpotential inevitably increases the cost, hampers the overall efficiency of the water splitting reaction, and thus inhibits the economic and industrial production of hydrogen by water electrolysis.
Currently, noble metal catalysts such as ruthenium-based and platinum-based have been identified as highly efficient HER/OER catalysts, but their scarcity, high cost and low stability severely limit their wide application. Therefore, the development of noble metal-free materials as alternatives to HER/OER electrocatalysts is of great importance for achieving large-scale commercialization of water electrolysis.
As highly ordered coordination polymers, metal-organic frameworks (MOFs) are self-assemblies of metal ions and organic linkers, which combine the properties of homogeneous and heterogeneous catalysts, and are candidates for HER/OER catalysts due to their high specific surface area, abundant pore structure, diverse composition and well-defined metal centers. In particular, a high specific surface area favors the exposure of more active sites, a porous structure allowing rapid mass transport, a definite metal center being essential for kinetic studies. These properties also impart additional capabilities to the MOF, by pyrolysis under an atmosphere, as ideal templates/precursors for various carbon-related nanocatalysts. MOF-derived hybrid materials tend to inherit the original morphology and develop into porous structures with active sites having a higher exposed area to the electrolyte, while organic ligand-derived nanocarbon matrices can enhance the electronic conductivity of the material.
Chinese patent application discloses a self-supporting Ni-MOF derived Ni for water splitting 3 The preparation method of the C/Ni heterojunction electrocatalyst (application number 202310707523.9) is obtained by hydrothermal synthesis of a precursor and subsequent calcination under nitrogen atmosphere, and more energy is consumed in the synthesis step.
Chinese patent application discloses a preparation method of a nickel-based three-dimensional metal organic framework catalyst and application of the catalyst in electrolytic water oxygen evolution (application number is 201711472653. X), wherein polyaniline is coated on the surface of foamed nickel by a three-electrode system constant potential deposition method, and the nickel-based three-dimensional metal organic framework catalyst is used as a template to undergo multi-step reaction to be derived to form Ni@Co 2 O 3 CN, the preparation steps are more complex.
In addition, in the prior art, other metal salts are utilized to synthesize the metal organic frame to coat the foam nickel in an ectopic manner, so that the combination of the foam nickel and the foam nickel substrate is not tight enough.
Disclosure of Invention
In order to solve the above problems, the present invention aims to provide a graded iron-doped nickel-carbon nanotube, a preparation method and application thereof, wherein the present invention uses nickel foam as a nickel source and a substrate, and a self-derived hollow nanotube array with controllable size is tightly formed through micro-reaction of ion exchange, and simultaneously, part of iron element is doped to improve local electron distribution. The iron doping content and the size of the Ni-MOF hollow nano tube can be simultaneously adjusted by adjusting the concentration of metal ions.
In order to achieve the above purpose, the invention discloses a preparation method of a hierarchical iron doped nickel-carbon structure nanotube, which comprises the following steps:
(1) Pretreatment of foam nickel: immersing foam nickel into an acid solution for ultrasonic washing, and after the ultrasonic treatment is finished, alternately flushing by using deionized water and absolute ethyl alcohol; immersing the foam nickel into an organic solvent for ultrasonic washing, alternately flushing with deionized water and absolute ethyl alcohol after the ultrasonic treatment is finished, and putting the flushed foam nickel into a vacuum oven for drying to obtain pretreated foam nickel;
(2) Ion etching: respectively adding dimethylglyoxime and ferric salt hydrate into absolute ethyl alcohol to prepare a solution A; immersing the pretreated foam nickel obtained in the step (1) into the solution A, standing at room temperature for reaction, taking out the foam nickel after the reaction is finished, and putting the foam nickel into a vacuum oven for drying to obtain a self-derived iron doped Ni-MOF@NF precursor;
(3) Calcining the self-derived iron doped Ni-MOF@NF precursor obtained in the step (2) under a nitrogen-hydrogen mixed atmosphere, naturally cooling to room temperature after calcining, cleaning the cooled substance, and then putting the substance into a vacuum oven for drying to obtain the graded iron doped nickel-carbon structure nanotube, namely the self-derived hollow nanotube array coated foam nickel material, which is marked as Fe-Ni@C/NF.
Further, in the step (1), the foam nickel is immersed in an acid solution for ultrasonic washing to remove impurities and oxides on the surface; immersing foam nickel in an acetone solvent for ultrasonic washing to remove organic impurities on the surface; the times of alternately flushing with deionized water and absolute ethyl alcohol are three times;
further, in the step (1), the thickness of the foam nickel is 1mm, the average pore diameter is 100 mu m, the acid solution is hydrochloric acid solution, and the concentration of the acid solution is 2-6 mol/L; the organic solvent is acetone with the weight percentage of 98 percent; the ultrasonic washing time is 10-30 minutes, the drying temperature of the vacuum oven is 50-80 ℃, and the drying time is 4-12 hours.
Further, the ion etched hydrated ferric salt in the step (2) comprises at least one of ferric nitrate nonahydrate, ferric sulfate hydrate or ferrous sulfate heptahydrate, and the mass concentration of the ferric salt in the solution A is 0.001-0.013 mol/L; the mass concentration of the dimethylglyoxime in the solution A is 0.04-0.2 mol/L; the reaction time of immersing the pretreated foam nickel into the solution A is 6-48 hours; the drying temperature of the vacuum oven is 50-80 ℃ and the drying time is 4-12 hours.
Further, the calcination temperature in the step (3) is 200-500 ℃, the heating rate is 2-10 ℃/min, and the heat preservation time is 1-4 hours.
Further, in the step (3), the volume fraction of hydrogen in the nitrogen-hydrogen mixed atmosphere is 1% -20%, the working pressure of the nitrogen-hydrogen mixed atmosphere is 1% -101 kPa, the drying temperature of the vacuum oven is 40% -80 ℃, and the drying time is 12-24 hours.
The cleaning in the step (3) is to remove the powder impurities which remain uncoated on the surface after calcination, in particular to alternately cleaning with deionized water and absolute ethyl alcohol until the cleaning solution is clear.
The invention also discloses the graded iron-doped nickel-carbon structure nanotube prepared by the method and application of the graded iron-doped nickel-carbon structure nanotube serving as a catalyst in electrolytic water hydrogen evolution reaction and oxygen evolution reaction in alkaline environment.
The technical key points of the preparation method of the graded iron doped nickel-carbon structure nanotube of the invention are as follows:
(1) Controlling a hollow nano-tubular material which is stably self-derived and controllable in size on the foam nickel;
(2) The relationship between the size of the hollow nano tube and the calcination temperature is coordinated so as to maintain the whole tubular structure, and structural change does not occur even after calcination, thereby forming the Fe-Ni@C/NF of the hollow nano tubular structure.
The invention discloses a preparation method of a hierarchical iron-doped nickel-carbon structure nanotube, which comprises the steps of firstly preparing an in-situ grown iron-doped Ni-MOF@NF precursor from pretreated foam nickel through ion etching, then calcining the iron-doped Ni-MOF@NF precursor at a low temperature under a nitrogen-hydrogen mixed atmosphere, naturally cooling to room temperature, cleaning the cooled matter, and drying to obtain a self-derived Fe-Ni@C/NF material with a hollow nano tubular structure. According to the preparation method, the characteristic combination of the dimethylglyoxime ligand is utilized, a self-derived iron ion doped Ni-MOF@NF precursor with a hollow nano tubular structure can be generated through simple ion etching treatment at room temperature, then a stable target product is prepared through one-step calcination treatment, the material can still keep a tubular structure after calcination, the reaction area of the catalyst is increased, and more active sites can be reserved as much as possible. In Fe-Ni@C/NF, the role of the nickel foam is to serve as a substrate for uniform in-situ growth of the material and to form a nickel source for the iron-doped Ni-MOF, as well as to facilitate rapid gas bubble removal. The iron doped active nickel nano particles play a role of synergistic catalysis, act on hydrogen evolution reaction and oxygen evolution reaction of electrolyzed water together, and iron ions serve as important elements of doping and etching steps, so that the doping content and the Ni-MOF morphology can be controlled by adjusting the concentration of the iron ions.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method has the advantages of simple and repeatable steps, cheap and easily-prepared raw materials, harmless products and byproducts, easy recovery and wide application potential.
(2) Compared with the commercial noble metal catalyst commonly used in the electrolyzed water, the raw materials used in the method for preparing Fe-Ni@C/NF disclosed by the invention have relatively large earth abundance, so that the production cost is saved while the relatively good performance is achieved, and the performance similar to that of noble metal is achieved by regulating and controlling the activity and the exposure area of the active site.
(3) The contact area between the commercial block catalyst and the electrolyte is smaller, and the Fe-Ni@C/NF material prepared by the method has a hollow nano tubular structure, and the doping proportion and the Ni-MOF size are controlled by adjusting the concentration of iron ions, so that the full-water-splitting catalyst with the optimal specific surface area and local site activity is optimally synthesized.
(4) Compared with pure foam nickel and iron doped Ni-MOF@NF precursor, fe-Ni@C/NF has better hydrophilicity and lower impedance, so that the precursor has better conductivity, and the hydrogen evolution and oxygen evolution efficiency of electrolytic water in alkaline environment can be correspondingly improved.
(5) Compared with powder materials, the Fe-Ni@C/NF finally obtained by the invention belongs to a self-derived foam nickel support material, and the material not only can promote the surface catalyst to exhaust bubbles, but also can be directly used as a working electrode, so that the operations of material debugging, coating, drying and the like are avoided, the catalyst preparation time is saved, the loss caused by the coating electrode is avoided, and the cost is further reduced.
(6) Compared with a single-metal or pure-phase catalyst material, the addition of Fe in Fe-Ni@C/NF optimizes the local electron distribution of an active site, and the existence of multivalent ions in the catalyst material is beneficial to reducing potential barriers in the process of combining hydrogen and oxygen.
(7) The Fe-Ni@C/NF prepared by the method has relatively excellent hydrogen evolution and oxygen evolution performance of electrocatalytic decomposition water, can keep good stability, has HER performance close to commercial carbon-supported platinum under the same load, and has OER performance close to commercial ruthenium oxide under the same load.
(8) Different from the method for synthesizing the metal organic framework by using other metal salts to ectopic coat the foam nickel, the nano structure formed by the in-situ metal organic framework by using the ion etching method and the derivative coated foam nickel is more uniform, the nano structure is more tightly combined with a foam nickel substrate, the doping amount and the Ni-MOF precursor size are controllable by adjusting the concentration of iron ions, and no additional nickel salt is needed to be added. The preparation method disclosed by the invention has universality and can be used for forming the iron-doped Ni-MOF@NF by using a self-derivatization method with a wide range of transition metal salts.
Drawings
FIG. 1 is an SEM image of a self-derived iron-doped Ni-MOF@NF precursor prepared in example 3 and comparative examples 1 and 2, respectively, wherein upper left corner marks 1 and 2 are prepared in example 3, upper left corner marks 3 and 4 are prepared in comparative example 2, and upper left corner marks 5 and 6 are prepared in comparative example 1;
FIG. 2 is an SEM image of a self-deriving iron-doped Ni-MOF@NF precursor prepared in examples 1-3, marked at the upper left with 0.001M FeSO 4 Corresponds to example 1, upper left corner mark 0.005M FeSO 4 Corresponds to example 2, upper left corner mark 0.01M FeSO 4 Corresponds to example 3;
FIG. 3 is an SEM image of the Fe-Ni@C/NF material prepared in example 3;
FIG. 4 is a Raman spectrum of the Fe-Ni@C/NF material prepared in example 3;
FIG. 5 is an XPS plot of the self-derived iron doped Ni-MOF@NF precursor prepared in example 3, wherein the upper left corner label 1 is a full spectrum, the upper left corner label 2 is a Ni2p orbital XPS fine spectrum, and the upper left corner label 3 is a Fe2p orbital XPS fine spectrum;
FIG. 6 is an XRD pattern of the self-derived iron doped Ni-MOF@NF precursor and Fe-Ni@C/NF material prepared in example 3;
FIG. 7 is a LSV graph showing hydrogen evolution reaction of the Fe-Ni@C/NF material prepared in example 3, fe-Ni@C/NF-S obtained in comparative example 1, and Fe-Ni@C/NF-N, pt/C/NF obtained in comparative example 2 in an alkaline environment;
FIG. 8 is RuO 2 LSV graph of oxygen evolution reaction of/NF and Fe-Ni@C/NF material prepared in example 3 under alkaline environment;
FIG. 9 is a graph showing that the Fe-Ni@C/NF material prepared in example 3 was subjected to oxygen evolution reaction under an alkaline atmosphere at 60 mA cm -2 I-t stability test curve at current density.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the following specific examples and drawings. The following examples are based on the technology of the present invention and give detailed embodiments and operation steps, but the scope of the present invention is not limited to the following examples.
Example 1:
(1) Pretreatment of foam nickel: immersing 10mm multiplied by 1mm foam nickel with the pore diameter of about 100 mu m in 15mL hydrochloric acid solution with the mass concentration of 3mol/L for ultrasonic washing for 20 minutes, and then alternately flushing with deionized water and absolute ethyl alcohol for three times; immersing the foam nickel into 15mL of acetone solvent with the weight fraction of 98%, ultrasonically washing for 20 minutes, and then alternately flushing with deionized water and absolute ethyl alcohol for three times; placing the washed foam nickel into a vacuum oven to be dried for 12 hours at 60 ℃ to obtain pretreated foam nickel;
(2) Ion etching: 0.1742g of dimethylglyoxime and 0.0028g of ferrous sulfate heptahydrate are dissolved in 10mL of absolute ethanol to prepare a solution A; immersing the pretreated foam nickel obtained in the step (1) into a solution A, standing at room temperature for reaction for 6 hours, taking out the foam nickel reacted in the solution A, and putting the foam nickel into a vacuum oven for drying at 60 ℃ for 12 hours to obtain a self-derived iron doped Ni-MOF@NF precursor;
(3) Calcining the self-derived iron doped Ni-MOF@NF precursor obtained in the step (2) under a nitrogen-hydrogen mixed atmosphere with the volume fraction of 2% of hydrogen and at a standard atmospheric pressure, wherein the heating rate is 5 ℃/min, the calcining temperature is 300 ℃, the heat preservation time is 1 hour, naturally cooling to room temperature after calcining, alternately cleaning the cooled substance with deionized water and absolute ethyl alcohol for three times, clarifying the washing liquid, and then placing the washing liquid in a vacuum oven and drying the washing liquid at 60 ℃ for 6 hours to obtain the nano tube with the graded iron doped nickel-carbon structure, namely the self-derived hollow nano tube coated foam nickel material, namely Fe-Ni@C/NF.
Example 2:
(1) Pretreatment of foam nickel: immersing 10mm multiplied by 1mm foam nickel with the pore diameter of about 100 mu m in 15mL hydrochloric acid solution with the mass concentration of 3mol/L for ultrasonic washing for 20 minutes, and then alternately flushing with deionized water and absolute ethyl alcohol for three times; immersing the foam nickel into 15mL of acetone solvent with the weight fraction of 98%, ultrasonically washing for 20 minutes, and then alternately flushing with deionized water and absolute ethyl alcohol for three times; placing the washed foam nickel into a vacuum oven to be dried for 12 hours at 60 ℃ to obtain pretreated foam nickel;
(2) Ion etching: 0.1742g of dimethylglyoxime and 0.0139g of ferrous sulfate heptahydrate are dissolved in 10mL of absolute ethanol to prepare a solution A; immersing the pretreated foam nickel obtained in the step (1) into a solution A, standing at room temperature for reaction for 12 hours, taking out the foam nickel reacted in the solution A, and putting the foam nickel into a vacuum oven for drying at 60 ℃ for 12 hours to obtain a self-derived iron doped Ni-MOF@NF precursor;
(3) Calcining the self-derived iron doped Ni-MOF@NF precursor obtained in the step (2) under a nitrogen-hydrogen mixed atmosphere with the volume fraction of 15% of hydrogen and at a standard atmospheric pressure, wherein the heating rate is 5 ℃/min, the calcining temperature is 250 ℃, the heat preservation time is 1 hour, naturally cooling to room temperature after calcining, alternately cleaning the cooled substance with deionized water and absolute ethyl alcohol for three times, clarifying the washing liquid, and then placing the washing liquid in a vacuum oven and drying the washing liquid at 60 ℃ for 6 hours to obtain the nano tube with the graded iron doped nickel-carbon structure, namely the self-derived hollow nano tube coated foam nickel material, namely Fe-Ni@C/NF.
Example 3:
(1) Pretreatment of foam nickel: immersing 10mm multiplied by 1mm foam nickel with the pore diameter of about 100 mu m in 15mL hydrochloric acid solution with the mass concentration of 3mol/L for ultrasonic washing for 20 minutes, and then alternately flushing with deionized water and absolute ethyl alcohol for three times; immersing the foam nickel into 15mL of acetone solvent with the weight fraction of 98%, ultrasonically washing for 20 minutes, and then alternately flushing with deionized water and absolute ethyl alcohol for three times; placing the washed foam nickel into a vacuum oven to be dried for 12 hours at 60 ℃ to obtain pretreated foam nickel;
(2) Ion etching: 0.1742g of dimethylglyoxime and 0.0278g of ferrous sulfate heptahydrate are dissolved in 10mL of absolute ethanol to prepare a solution A; immersing the pretreated foam nickel obtained in the step (1) into a solution A, standing at room temperature for reaction for 24 hours, taking out the foam nickel reacted in the solution A, and putting the foam nickel into a vacuum oven for drying at 60 ℃ for 12 hours to obtain a self-derived iron doped Ni-MOF@NF precursor;
(3) Calcining the self-derived iron doped Ni-MOF@NF precursor obtained in the step (2) under a nitrogen-hydrogen mixed atmosphere with the volume fraction of 5% of hydrogen and at a standard atmospheric pressure, wherein the heating rate is 5 ℃/min, the calcining temperature is 450 ℃, the heat preservation time is 1 hour, naturally cooling to room temperature after calcining, alternately cleaning the cooled substance with deionized water and absolute ethyl alcohol for three times, clarifying the washing liquid, and then placing the washing liquid in a vacuum oven to dry for 6 hours at the temperature of 60 ℃ to obtain the nano tube with the graded iron doped nickel-carbon structure, namely the self-derived hollow nano tube coated foam nickel material, namely Fe-Ni@C/NF.
Example 4:
(1) Pretreatment of foam nickel: immersing 10mm multiplied by 1mm foam nickel with the pore diameter of about 100 mu m in 15mL hydrochloric acid solution with the mass concentration of 3mol/L for ultrasonic washing for 20 minutes, and then alternately flushing with deionized water and absolute ethyl alcohol for three times; immersing the foam nickel into 15mL of acetone solvent with the weight fraction of 98%, ultrasonically washing for 20 minutes, and then alternately flushing with deionized water and absolute ethyl alcohol for three times; placing the washed foam nickel into a vacuum oven to be dried for 12 hours at 60 ℃ to obtain pretreated foam nickel;
(2) Ion etching: 0.1742g of dimethylglyoxime, 0.0139g of ferrous sulfate heptahydrate and 0.0101g of ferric nitrate nonahydrate are dissolved in 10mL of absolute ethanol to prepare a solution A; immersing the pretreated foam nickel obtained in the step (1) into a solution A, standing at room temperature for reaction for 48 hours, taking out the foam nickel reacted in the solution A, and putting the foam nickel into a vacuum oven for drying at 60 ℃ for 12 hours to obtain a self-derived iron doped Ni-MOF@NF precursor;
(3) Calcining the self-derived iron doped Ni-MOF@NF precursor obtained in the step (2) under a nitrogen-hydrogen mixed atmosphere with the volume fraction of 5% of hydrogen and at a standard atmospheric pressure, wherein the heating rate is 5 ℃/min, the calcining temperature is 450 ℃, the heat preservation time is 1 hour, naturally cooling to room temperature after calcining, alternately cleaning the cooled substance with deionized water and absolute ethyl alcohol for three times, clarifying the washing liquid, and then placing the washing liquid in a vacuum oven to dry for 6 hours at the temperature of 60 ℃ to obtain the nano tube with the graded iron doped nickel-carbon structure, namely the self-derived hollow nano tube coated foam nickel material, namely Fe-Ni@C/NF.
Comparative example 1:
(1) Pretreatment of foam nickel: immersing 10mm multiplied by 1mm foam nickel with the pore diameter of about 100 mu m in 15mL hydrochloric acid solution with the mass concentration of 3mol/L for ultrasonic washing for 20 minutes, and then alternately flushing with deionized water and absolute ethyl alcohol for three times; immersing the foam nickel into 15mL of acetone solvent with the weight fraction of 98%, ultrasonically washing for 20 minutes, and then alternately flushing with deionized water and absolute ethyl alcohol for three times; placing the washed foam nickel into a vacuum oven to be dried for 12 hours at 60 ℃ to obtain pretreated foam nickel;
(2) Ion etching: 0.1742g of dimethylglyoxime and 0.0403g of ferrous sulfate heptahydrate are dissolved in 10mL of absolute ethanol to prepare a solution A; immersing the pretreated foam nickel obtained in the step (1) into a solution A, standing at room temperature for reaction for 12 hours, taking out the foam nickel reacted in the solution A, and putting the foam nickel into a vacuum oven for drying at 60 ℃ for 12 hours to obtain a self-derived iron doped Ni-MOF@NF precursor;
(3) Calcining the self-derived iron doped Ni-MOF@NF precursor obtained in the step (2) under a nitrogen-hydrogen mixed atmosphere with the volume fraction of 5% of hydrogen and at a standard atmospheric pressure, wherein the heating rate is 5 ℃/min, the calcining temperature is 300 ℃, the heat preservation time is 1 hour, naturally cooling to room temperature after calcining, alternately cleaning the cooled substance with deionized water and absolute ethyl alcohol for three times, clarifying the washing liquid, and then drying the substance in a vacuum oven at 60 ℃ for 6 hours, wherein the obtained material is marked as Fe-Ni@C/NF-S.
Comparative example 2:
(1) Pretreatment of foam nickel: immersing 10mm multiplied by 1mm foam nickel with the pore diameter of about 100 mu m in 15mL hydrochloric acid solution with the mass concentration of 3mol/L for ultrasonic washing for 20 minutes, and then alternately flushing with deionized water and absolute ethyl alcohol for three times; immersing the foam nickel into 15mL of acetone solvent with the weight fraction of 98%, ultrasonically washing for 20 minutes, and then alternately flushing with deionized water and absolute ethyl alcohol for three times; placing the washed foam nickel into a vacuum oven to be dried for 12 hours at 60 ℃ to obtain pretreated foam nickel;
(2) Ion etching: 0.1742g of dimethylglyoxime and 0.0404g of ferric nitrate nonahydrate are dissolved in 10mL of absolute ethanol to prepare a solution A; immersing the pretreated foam nickel obtained in the step (1) into a solution A, standing at room temperature for reaction for 12 hours, taking out the foam nickel reacted in the solution A, and putting the foam nickel into a vacuum oven for drying at 60 ℃ for 12 hours to obtain the self-derived iron doped Ni-MOF@NF precursor.
(3) Calcining the self-derived iron doped Ni-MOF@NF precursor obtained in the step (2) under a nitrogen-hydrogen mixed atmosphere with the volume fraction of 5% of hydrogen and at a standard atmospheric pressure, wherein the heating rate is 5 ℃/min, the calcining temperature is 300 ℃, the heat preservation time is 1 hour, naturally cooling to room temperature after calcining, alternately cleaning the cooled substance with deionized water and absolute ethyl alcohol for three times, clarifying the washing liquid, and then drying the washing liquid in a vacuum oven at 60 ℃ for 6 hours, wherein the obtained material is Fe-Ni@C/NF-N.
SEM tests were performed using ZEISS GeminiSEM model 300 scanning electron microscope from ZEISS, germany. And sticking the self-derived iron doped Ni-MOF@NF precursor on a sample stage coated with black conductive adhesive, and then performing metal spraying treatment. SEM testing can analyze the microstructure of the material. Fig. 1 is an SEM image of a self-derived iron-doped Ni-mof@nf precursor prepared in example 3 and comparative examples 1 and 2, respectively, wherein the upper left corner marks 1 and 2 are prepared in example 3, the upper left corner marks 3 and 4 are prepared in comparative example 2, the upper left corner marks 5 and 6 are prepared in comparative example 1, and it can be seen from the figure that the pretreated NF can form MOF structures with different morphologies in situ through different etching conditions, wherein the 0.01M ferrous sulfate etching in example 3 can form a tube structure Ni-mof@nf precursor with controllable size, namely a hollow nanotube array, the Fe-ni@c/NF-N prepared in comparative example 2 is a nano cone array, and the Fe-ni@c/NF-S prepared in comparative example 1 is a nano cluster array.
FIG. 2 is an SEM image of a self-derived iron doped Ni-MOF@NF precursor prepared in examples 1-3, which shows that the integrity of nanotube array formation can be affected by controlling the concentration of ferrous ions.
FIG. 3 is an SEM image of the Fe-Ni@C/NF material prepared in example 3, which shows that the material is still capable of maintaining a tube structure after low-temperature calcination of the self-derived iron-doped Ni-MOF@NF precursor, facilitating exposure of more catalytically active sites and improving catalytic efficiency.
FIG. 4 is a Raman spectrum of the Fe-Ni@C/NF material prepared in example 3, showing that the nanotubes after calcination are composed of a carbon skeleton coated with an active ingredient.
XPS test was performed using a Scientific K-Alpha X-ray photoelectron spectrometer from thermo company, USA, and a self-derived iron doped Ni-MOF@NF precursor was adhered to a sample stage for analysis of the valence state and possible bonding of the surface elements of the material. The full spectrum of the upper left corner mark 1 in fig. 5 shows that the self-derived iron doped Ni-MOF@NF precursor can not only form Ni-MOF through ion etching, but also generate a small amount of iron doping, the Ni2p fine spectrum in the upper left corner mark 2 in fig. 5 corresponds to a Ni-MOF characteristic peak, the appearance of Ni-MOF on the surface of a material is proved, and the Fe2p fine spectrum in the upper left corner mark 3 in fig. 5 corresponds to successful doping of Fe element in the Ni-MOF.
XRD testing was performed using a Rigaku Ultima IV X-ray diffractometer from Japan, and the self-derived material on the nickel foam was scraped off and uniformly filled into a sample stage for analysis of information such as composition of the material and structure or morphology of atoms or molecules within the material. FIG. 6 is an XRD pattern of the self-derived iron-doped Ni-MOF@NF precursor and Fe-Ni@C/NF material prepared in example 1, and a curve corresponding to the self-derived iron-doped Ni-MOF@NF precursor shows that the iron-doped Ni-MOF@NF precursor has typical XRD characteristic peaks of DNi, and shows successful synthesis of the Ni-MOF after etching; fe-Ni@C/NF showed a distinct 44.5 DEG corresponding to the Ni (111) crystal plane, 51.9 DEG corresponding to the (200) crystal plane, and 76.4 DEG corresponding to the (220) crystal plane, and the incorporated Fe was undetected because of the excessively low content.
The pretreated nickel foam is obtained by the method of step (1) in example 3, a certain mass of commercial 5% Pt/C is taken, the mass of the commercial 5% Pt/C is equal to the mass of the surface active component of Fe-ni@c/NF obtained in example 3 (the mass of the surface active component of Fe-ni@c/NF obtained in example 3=the mass of the nickel foam pretreated in step (1)), the commercial 5% Pt/C is added into a mixed solution containing 480 μl of absolute ethanol, 480 μl of deionized water and 40 μl of Nifion to form a suspension, and the suspension is then applied on the surface of the pretreated nickel foam in a drop-coating manner and dried by sun light to obtain 5% Pt/C of the nickel foam load, which is denoted as Pt/C/NF, wherein the commercial 5% Pt/C belongs to the prior art and is not repeated herein.
Electrochemical LSV test was performed on the material using Chenhua CHI760E, and electrocatalytic hydrogen evolution and oxygen evolution capacity analysis was performed using the Fe-Ni@C/NF material prepared in example 3, the Fe-Ni@C/NF-S obtained in comparative example 1, and the Fe-Ni@C/NF-N obtained in comparative example 2, and the Pt/C/NF obtained as described above. The specific implementation method comprises the following steps: testing the material by using a traditional three-electrode system, wherein the working electrode adopts a square electrode plate with the thickness of 10mm or less and is formed by cutting; a carbon rod with the diameter of 6mm is used for the counter electrode; the Hg/HgO electrode was used as the reference electrode. Fig. 7 shows: the nanotube array Fe-Ni@C/NF synthesized in example 3 can be subjected to 80% IR compensation in a 1mol/L KOH solutionCan reach 30.2-mV-10 mA cm -2 Is superior to the Fe-Ni@C/NF-S obtained in comparative example 1 and the Fe-Ni@C/NF-N obtained in comparative example 2, and is also superior to the commercial 5% Pt/C noble metal supported by nickel foam.
The pretreated foam nickel is obtained by the method of the step (1) in the embodiment 3, ruthenium oxide with a certain mass is taken, the ruthenium oxide is equal to the mass of the surface active component of Fe-Ni@C/NF obtained in the embodiment 3 (the mass of the surface active component of Fe-Ni@C/NF obtained in the embodiment 3=the mass of the foam nickel pretreated in the step (1)), the ruthenium oxide is added into a mixed solution containing 480 mu L of absolute ethyl alcohol, 480 mu L of deionized water and 40 mu L of Nifion to form a suspension, and the suspension is coated on the surface of the pretreated foam nickel in a liquid drop manner and is irradiated by a solar lamp to be dry to obtain RuO loaded by the foam nickel 2 Is marked as RuO 2 /NF。
The LSV curve of the oxygen evolution reaction of fig. 8 shows: in a 1mol/L KOH solution, the Fe-Ni@C/NF obtained in example 3, after 80% IR compensation, can reach 392 mV-200 mA cm -2 The Fe-Ni@C/NF has good oxygen evolution reaction kinetics and can be matched with commercial RuO 2 Noble metals are comparable.
The i-t stability test curve in the oxygen evolution reaction of FIG. 9 shows that: at an oxidation current of 60 mA cm -2 The Fe-Ni@C/NF prepared in example 3 was able to stably react for 50 hours or more without performance degradation, and the reaction stability of the material was fully demonstrated.
The foregoing is merely an embodiment of the present invention, and the present invention is not limited in any way, and may have other embodiments according to the above structures and functions, which are not listed. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention without departing from the scope of the technical solution of the present invention will still fall within the scope of the technical solution of the present invention.
Claims (6)
1. A preparation method of a hierarchical iron doped nickel-carbon structure nanotube is characterized by comprising the following steps of: the method specifically comprises the following steps:
(1) Pretreatment of foam nickel: immersing foam nickel into an acid solution for ultrasonic washing, and after the ultrasonic treatment is finished, alternately flushing by using deionized water and absolute ethyl alcohol; immersing the foam nickel into an organic solvent for ultrasonic washing, alternately flushing with deionized water and absolute ethyl alcohol after the ultrasonic treatment is finished, and putting the flushed foam nickel into a vacuum oven for drying to obtain pretreated foam nickel;
(2) Ion etching: respectively adding dimethylglyoxime and ferric salt hydrate into absolute ethyl alcohol to prepare a solution A; immersing the pretreated foam nickel obtained in the step (1) into the solution A, standing at room temperature for reaction, taking out the foam nickel after the reaction is finished, and putting the foam nickel into a vacuum oven for drying to obtain a self-derived iron doped Ni-MOF@NF precursor;
(3) Calcining the self-derived iron doped Ni-MOF@NF precursor in a nitrogen-hydrogen mixed atmosphere, naturally cooling to room temperature after calcining, cleaning the cooled substance, and then putting the substance into a vacuum oven for drying to obtain the graded iron doped nickel-carbon structure nanotube;
the ion etched ferric hydrate salt in the step (2) comprises at least one of ferric nitrate nonahydrate, ferric sulfate hydrate or ferrous sulfate heptahydrate, and the mass concentration of the ferric hydrate salt in the solution A is 0.001-0.013 mol/L; the mass concentration of the dimethylglyoxime in the solution A is 0.04-0.2 mol/L; the reaction time of immersing the pretreated foam nickel into the solution A is 0.1-24 hours; the drying temperature of the vacuum oven is 50-80 ℃ and the drying time is 4-12 hours;
the calcination temperature in the step (3) is 200-500 ℃, the heating rate is 2-10 ℃/min, and the heat preservation time is 1-4 hours.
2. The method for preparing the graded iron-doped nickel-carbon structure nanotube according to claim 1, wherein the method comprises the following steps: the thickness of the foam nickel in the step (1) is 1mm, the average pore diameter is 100 mu m, the acid solution is hydrochloric acid solution, and the concentration of the acid solution is 2-6 mol/L; the organic solvent is acetone with the mass fraction of 98%; the ultrasonic washing time is 10-30 minutes, the drying temperature of the vacuum oven is 50-80 ℃, and the drying time is 4-12 hours.
3. The method for preparing the graded iron-doped nickel-carbon structure nanotube according to claim 1, wherein the method comprises the following steps: in the step (3), the volume fraction of hydrogen in the nitrogen-hydrogen mixed atmosphere is 1% -20%, the working pressure of the nitrogen-hydrogen mixed atmosphere is 1% -101 kPa, the drying temperature of the vacuum oven is 40% -80 ℃, and the drying time is 12-24 hours.
4. The method for preparing the graded iron-doped nickel-carbon structure nanotube according to claim 1, wherein the method comprises the following steps: the washing in the step (3) is specifically carried out by adopting deionized water and absolute ethyl alcohol to alternately wash until the washing liquid is clear.
5. The graded iron-doped nickel-carbon nanotube prepared by the preparation method according to any one of claims 1 to 4.
6. The use of the graded iron-doped nickel-carbon structure nanotube according to claim 5 in an electrolytic water hydrogen evolution reaction and an oxygen evolution reaction in an alkaline environment.
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