CN110947387B - Preparation method and application of nickel-iron double metal hydroxide nano film material - Google Patents
Preparation method and application of nickel-iron double metal hydroxide nano film material Download PDFInfo
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- CN110947387B CN110947387B CN201911168663.3A CN201911168663A CN110947387B CN 110947387 B CN110947387 B CN 110947387B CN 201911168663 A CN201911168663 A CN 201911168663A CN 110947387 B CN110947387 B CN 110947387B
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- 239000002120 nanofilm Substances 0.000 title claims abstract description 154
- 239000000463 material Substances 0.000 title claims abstract description 136
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims description 32
- 150000004692 metal hydroxides Chemical class 0.000 title claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 116
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229960003351 prussian blue Drugs 0.000 claims abstract description 94
- 239000013225 prussian blue Substances 0.000 claims abstract description 94
- 238000000034 method Methods 0.000 claims abstract description 50
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 239000003792 electrolyte Substances 0.000 claims abstract description 32
- 229910000863 Ferronickel Inorganic materials 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 238000004070 electrodeposition Methods 0.000 claims abstract description 22
- 238000005530 etching Methods 0.000 claims abstract description 12
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 238000000151 deposition Methods 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 18
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- 229920006395 saturated elastomer Polymers 0.000 claims description 14
- 238000002484 cyclic voltammetry Methods 0.000 claims description 12
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 12
- -1 potassium ferricyanide Chemical compound 0.000 claims description 10
- 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 9
- 239000001103 potassium chloride Substances 0.000 claims description 9
- 235000011164 potassium chloride Nutrition 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 abstract description 4
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910003271 Ni-Fe Inorganic materials 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- JLFVIEQMRKMAIT-UHFFFAOYSA-N ac1l9mnz Chemical compound O.O.O JLFVIEQMRKMAIT-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 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
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- DMTIXTXDJGWVCO-UHFFFAOYSA-N iron(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Fe++].[Ni++] DMTIXTXDJGWVCO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/33—
-
- B01J35/59—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method and application of a ferronickel double-metal hydroxide nano-film material, which are characterized in that carbon paper is used as a substrate, a two-step electrodeposition and one-step etching method is selected to prepare the ferronickel double-metal hydroxide electrocatalyst, a Prussian blue nano-film material loaded on the carbon paper is obtained by the first-step electrodeposition method, a nickel hydroxide/Prussian blue nano-film material loaded on the carbon paper is obtained by the second-step electrodeposition method, and finally the nickel hydroxide/Prussian blue nano-film material is put into a strong alkaline solution to be etched to obtain the ferronickel double-metal hydroxide nano-film material loaded on the carbon paper. The method is simple and easy to implement, safe to operate, green and pollution-free. Secondly, the material is an amorphous nano film material which is rich in oxygen vacancy and has a plurality of holes, has ultralow overpotential and Tafel slope, and shows excellent oxygen evolution catalytic activity; and when the electrolysis is carried out in the alkaline electrolyte, the potential of the electrolyte is almost kept unchanged, and the excellent electrolytic stability is shown.
Description
Technical Field
The invention belongs to the field of hydrogen production and oxygen evolution by electrochemically decomposing water with a non-noble metal catalyst, and particularly relates to a preparation method and application of a nickel-iron double-metal hydroxide nano-film material.
Background
With the increasing consumption of non-renewable energy and the increasing severity of environmental pollution problems, there is a pressing need to replace fossil fuels, such as wind energy and solar energy, with renewable clean energy. This can be achieved by the vigorous development of efficient and inexpensive energy conversion and storage technologies, such as renewable fuel cells, metal-air cells, hydrogen production from water splitting plants, and the like. The perfect clean energy utilization closed loop utilizes hydrogen as an energy substrate, performs hydrogen production by electrolyzing water by electric energy generated by renewable clean energy, and generates electric energy by hydrogen used by a fuel cell, wherein no pollutant is generated. However, the key one in this loop, the epoxide evolution reaction (OER), is a thermodynamically upslope reaction involving a complex four proton coupled electron transfer process, and the slow kinetic process presents a significant challenge to the large-scale use of these renewable energy devices. Therefore, it is important to develop an efficient and durable OER catalyst to lower the reaction barrier and improve the conversion efficiency. Currently, noble metals (iridium, ruthenium) and oxides thereof are widely considered as benchmark catalysts for OER, but their commercial development is severely hampered by the rare reserves, high price and poor stability.
Considerable effort has been devoted to finding highly efficient, inexpensive non-noble transition metal catalysts to date. Of these, nickel iron oxide/hydroxide is considered a catalyst material with faster OER kinetics. At present, rational design strategies for such catalysts mainly include three aspects: (1) optimizing the intrinsic activity of the catalyst. Through the introduction of different types of defects and disordered/deformed nano structures, the electronic neutrality of the original crystal framework is destroyed and unsaturated atom active sites are generated, so that the surface adsorption energy is adjusted. (2) The multi-stage or porous nanostructured catalysts can expose more active sites and accelerate charge transfer, which can reduce the charge transfer resistance compared to reducing the nanoparticle size. (3) In order to enhance the conductivity and stability of the compound, in-situ growth, in-situ electrodeposition and other methods are generally adopted, so that the catalyst can be prevented from falling off in the oxygen evolution catalysis process.
Recently, prussian blue and the like as perovskite type materials have shown wide prospects in the aspects of energy conversion and storage due to the fact that the composition and the appearance of prussian blue are controllable and environment-friendly. A great deal of research work proves the superiority of the Prussian blue analogue as a precursor for preparing the OER catalyst. However, the currently reported prussian blue analogue-derived catalyst is mainly in a powder state, and few reports on the application of a nano-film structure thereof to the preparation of a high-efficiency OER catalyst greatly limit the application in electrocatalytic oxygen evolution. In this regard, some researchers have used an ion exchange method to grow prussian blue film on the surface of conductive carbon paper as a precursor of the OER catalyst. These works show that continuous prussian blue nano-films as precursors of OER catalysts have a great improvement in both catalytic activity and stability. The method has the advantages of convenient and fast electro-deposition, energy conservation and environmental protection, is suitable for the surface deposition of the conductive substrate, is basically not limited by the type and the shape of the conductive substrate, is consistent with the requirement of the electro-catalyst on the conductivity of the electrode, and greatly expands the application range. However, the electrodeposition technology has attracted little attention as a rapid preparation method of a continuous prussian blue film.
Disclosure of Invention
The invention provides a preparation method and application of a nickel-iron bimetal hydroxide nano film material in order to solve the preparation problem of a high-performance nickel-iron bimetal hydroxide oxygen evolution catalyst.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a ferronickel double-metal hydroxide nano-film material specifically comprises the following steps:
s1: taking the treated carbon paper as a substrate, immersing the carbon paper into an electrolyte A consisting of ferric nitrate, potassium ferricyanide and potassium chloride, and obtaining a Prussian blue nano film material deposited on the surface of the carbon paper by adopting an electrodeposition method, namely the Prussian blue nano film substrate loaded on the carbon paper;
s2: immersing the carbon paper Prussian blue nano-film substrate obtained in the step S1 in an electrolyte B of nickel nitrate, depositing nickel ions in the electrolyte B on the surface of the Prussian blue nano-film material in a nickel hydroxide nano-film form by adopting an electrodeposition method, and cleaning and drying the nickel hydroxide/Prussian blue nano-film material by using deionized water to obtain a nickel hydroxide/Prussian blue nano-film material loaded on the carbon paper;
s3: and (3) putting the nickel hydroxide/Prussian blue nano-film material obtained in the step (S2) into a strong alkali solution for etching, washing and drying to obtain the electrocatalyst of the nickel-iron double-metal hydroxide nano-film material loaded on the carbon paper, wherein the electrocatalyst is an amorphous nano-film material which is rich in oxygen vacancies and has a porous structure.
Further, the carbon paper is sequentially placed in hydrochloric acid, acetone and ethanol with the concentration of 0.1-6 mol/L for ultrasonic cleaning for 5-15 minutes for treatment, and then is cleaned by deionized water and dried to obtain the treated carbon paper.
Further, the molar concentration of ferric nitrate in the electrolyte A is 0.1-10 mmol/L, the molar concentration of potassium ferricyanide is 0.1-10 mmol/L, and the molar concentration of potassium chloride is 0.01-3 mol/L.
Furthermore, the molar concentration of the nickel nitrate in the electrolyte B is 0.1-50 mmol/L.
Further, the three-electrode system adopted in the S1 electrodeposition process comprises a working electrode of carbon paper, a counter electrode of a platinum sheet and a reference electrode of saturated Ag/AgCl.
Further, the three-electrode system adopted in the S2 electrodeposition process comprises a working electrode of carbon paper loaded with Prussian blue nano-film, a counter electrode of a platinum sheet and a reference electrode of saturated Ag/AgCl.
Further, the S1 electrodeposition method is a cyclic voltammetry method, the potential range of an Ag/AgCl reference electrode is-0.2-1.2V, the scanning rate is 1-100 mV/S, and at least 1 electrodeposition cycle is carried out.
Furthermore, the S2 electrodeposition method is a potentiostatic method, the potential range of the reference electrode is-1.5 to-0.5V by using Ag/AgCl, and the deposition time is 60 to 36000S.
Further, the strong base solution in the S3 is a KOH solution, and the etching time of the nickel hydroxide/Prussian blue nano-film material is not less than 5 min.
The invention also aims to provide the application of the ferronickel double-metal hydroxide nano-film material as an electrocatalyst.
Compared with the prior art, the invention has the following beneficial effects:
(1) the ferronickel double-metal hydroxide nano-film material loaded on the carbon paper obtained by the method is an amorphous nano-film material rich in oxygen vacancies and having a porous structure, shows excellent oxygen precipitation activity in alkaline electrolyte, has ultralow overpotential and Tafel slope, and has excellent long-time electrolytic stability and high application value.
(2) The nickel-iron double-metal hydroxide nano-film material obtained by the method has higher specific surface area and good conductivity, the Prussian blue nano-film material directly grows on the surface of the carbon paper in situ by an electrodeposition method, and the nickel hydroxide/Prussian blue nano-film material directly grows on the surface of the Prussian blue nano-film material in situ by the electrodeposition method, so that the obtained nickel-iron double-metal hydroxide nano-film material is not easy to fall off from the carbon paper substrate. Meanwhile, the ferronickel double-metal hydroxide nano-film material has excellent catalytic activity and long-term oxygen precipitation stability. In addition, the amorphous crystalline state and the porous structure of the ferronickel double-metal hydroxide nano-film material can bring more oxygen vacancies and defects, thereby providing more catalytic active sites and enhancing the intrinsic catalytic performance of the material.
(3) The invention adopts cheap, nontoxic and environment-friendly raw materials, thereby not only saving the cost, but also protecting the environment. In addition, the preparation process is simple, complex and expensive equipment is not needed, the large-area ferronickel bimetallic hydroxide nano-film material can be prepared, the batch production is easy, and the method has the prospect of industrial production.
(4) According to the invention, the carbon paper is subjected to ultrasonic treatment by hydrochloric acid, acetone and ethanol, so that on one hand, impurities on the surface of the carbon paper are removed, on the other hand, the carbon paper subjected to hydrochloric acid treatment has better hydrophilicity, the nucleation of prussian blue on the surface of the carbon paper is more uniform, the prussian blue nano-film material is stably loaded on the carbon paper, and the prussian blue nano-film material is prevented from falling off from the carbon paper.
Drawings
FIG. 1 is a schematic diagram of the preparation process of the ferronickel bimetal hydroxide nano-film material of the invention.
FIG. 2 shows a Ni-Fe double metal hydroxide nano-film material (NiFe (OH)x/CP), Carbon Paper (CP), Prussian blue nano-film material (PB/CP), nickel hydroxide nano-material (Ni (OH) loaded on carbon paperx/CP), nickel hydroxide/Prussian blue nano-film material (Ni (OH)x/PB/CP).
Fig. 3a and 3b in fig. 3 are SEM characterization diagrams of prussian blue nano-film material, fig. 3c is an SEM characterization diagram of nickel hydroxide/prussian blue nano-film material, fig. 3d is an SEM characterization diagram of nickel-iron double hydroxide nano-film material, fig. 3e is a TEM characterization diagram of a focused ion beam slice of the nickel-iron double hydroxide nano-film material, and fig. 3f is an HRTEM characterization diagram of a nickel-iron double hydroxide nano-film material slice.
Fig. 4 is an XPS spectrum of a nickel-iron double metal hydroxide nano-film material.
FIG. 5 shows a Ni-Fe double metal hydroxide nano-film material (NiFe (OH)x/CP), carbon paper material (CP), Prussian blue nano-film material (PB/CP), nickel hydroxide nano-particles (Ni (OH) loaded on carbon paperx/CP), nickel hydroxide/Prussian blue nano-film material (Ni (OH)x/PB/CP) is used.
FIG. 6 shows a Ni-Fe double metal hydroxide nano-film material (NiFe (OH)x/CP), carbon paper material (CP), Prussian blue nano film material (PB/CP), nickel hydroxide nano particle (Ni (OH) loaded on carbon paperx/CP), nickel hydroxide/Prussian blue nano film material(Ni(OH)xPB/CP) polarization curve (a) and corresponding Tafel curve (b) of electrochemical oxygen evolution in alkaline electrolyte environment (1mol/L KOH).
FIG. 7 shows the Ni-Fe bimetallic hydroxide nano-film material in the alkaline electrolyte environment (1mol/L KOH) when the current is 20mA/cm2The overpotential is plotted against time.
Detailed Description
The invention provides a preparation method and application of a nickel-iron double-metal hydroxide nano-film material, which are used for overcoming the technical defects in the prior art.
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of the present invention.
Wherein, the raw materials used in the embodiment of the invention are all commercially available.
Example 1
The method comprises the following steps: treatment of carbon paper substrates
And sequentially placing the carbon paper with the size of 0.5 multiplied by 1cm into 1mol/L hydrochloric acid solution, acetone and ethanol for ultrasonic cleaning for 10min, cleaning the carbon paper subjected to ultrasonic cleaning with deionized water, and drying to obtain the usable carbon paper substrate.
Step two: preparation of carbon paper supported Prussian blue nano film substrate
The Prussian blue nano film material is prepared by adopting a cyclic voltammetry method, the carbon paper substrate obtained in the step one is immersed into an electrolyte A, the molar concentration of ferric nitrate in the electrolyte A is 0.5mmol/L, the molar concentration of potassium ferricyanide is 0.5mmol/L, and the molar concentration of potassium chloride is 0.1mol/L, then a three-electrode system consisting of a working electrode of carbon paper (0.5 multiplied by 0.5cm), a counter electrode of a platinum sheet and a reference electrode of saturated Ag/AgCl is adopted for carrying out cyclic voltammetry, Ag/AgCl is taken as the reference electrode, the potential range is-0.2 to 1.2V, 5mV/s scanning rate is carried out for 5 cycles, and then the Prussian blue nano film material loaded on the carbon paper is obtained by washing with deionized water and drying, namely the Prussian blue nano film substrate loaded on the carbon paper.
Step three: preparation of nickel hydroxide/Prussian blue nano-film material
And (2) preparing the nickel hydroxide/Prussian blue nano film material by adopting a constant potential deposition method, immersing the carbon paper loaded Prussian blue nano film substrate obtained in the step two into an electrolyte B with the molar concentration of nickel nitrate of 1.2mmol/L, then performing constant potential deposition by adopting a three-electrode system consisting of a working electrode of the carbon paper loaded with the Prussian blue nano film, a counter electrode of a platinum sheet and a reference electrode of saturated Ag/AgCl, depositing for 1200s under the condition that the potential is-1V by taking Ag/AgCl as the reference electrode, washing by adopting deionized water, and naturally drying to obtain the nickel hydroxide/Prussian blue nano film material loaded on the carbon paper.
Step four: preparation of nickel-iron double metal hydroxide nano film material
And (3) placing the nickel hydroxide/Prussian blue nano-film material loaded on the carbon paper obtained in the step three in 1mol/L potassium hydroxide (KOH) for etching for 5min, then washing with deionized water and naturally drying to obtain the nickel-iron double-metal hydroxide nano-film material loaded on the carbon paper.
Example 2
The method comprises the following steps: treatment of carbon paper substrates
And sequentially placing the carbon paper with the size of 0.5 multiplied by 1cm into 0.1mol/L hydrochloric acid solution, acetone and ethanol for ultrasonic cleaning for 5min, cleaning the carbon paper subjected to ultrasonic cleaning with deionized water, and drying to obtain the usable carbon paper substrate.
Step two: preparation of carbon paper supported Prussian blue nano film substrate
The Prussian blue nano film material is prepared by adopting a cyclic voltammetry method, the carbon paper substrate obtained in the step one is immersed into an electrolyte A, the molar concentration of ferric nitrate in the electrolyte A is 0.1mmol/L, the molar concentration of potassium ferricyanide is 0.1mmol/L, and the molar concentration of potassium chloride is 0.01mol/L, then a three-electrode system consisting of a working electrode of carbon paper (0.5 multiplied by 0.5cm), a counter electrode of a platinum sheet and a reference electrode of saturated Ag/AgCl is adopted for carrying out cyclic voltammetry, Ag/AgCl is taken as the reference electrode, the potential range is-0.2 to 1.2V, the scanning rate of 1mV/s is carried out for 1 cycle, and then the Prussian blue nano film material loaded on the carbon paper is obtained by washing with deionized water and drying, namely the Prussian blue nano film substrate loaded on the carbon paper.
Step three: preparation of nickel hydroxide/Prussian blue nano-film material
And (2) preparing the nickel hydroxide/Prussian blue nano film material by adopting a constant potential deposition method, immersing the carbon paper loaded Prussian blue nano film substrate obtained in the step two into an electrolyte B with the molar concentration of nickel nitrate of 0.1mmol/L, then performing constant potential deposition by adopting a three-electrode system consisting of a working electrode of the carbon paper loaded with the Prussian blue nano film, a counter electrode of a platinum sheet and a reference electrode of saturated Ag/AgCl, depositing for 60s under the condition that the potential is-1.5V by taking Ag/AgCl as the reference electrode, washing by adopting deionized water, and naturally drying to obtain the nickel hydroxide/Prussian blue nano film material loaded on the carbon paper.
Step four: preparation of nickel-iron double metal hydroxide nano film material
And (4) placing the nickel hydroxide/Prussian blue nano film material loaded on the carbon paper obtained in the third step into 1mol/L potassium hydroxide (KOH) for etching for 2min, then washing with deionized water, and naturally drying to obtain the nickel-iron double-metal hydroxide nano film material loaded on the carbon paper.
Example 3
The method comprises the following steps: treatment of carbon paper substrates
And sequentially placing the carbon paper with the size of 0.5 multiplied by 1cm into 6mol/L hydrochloric acid solution, acetone and ethanol for ultrasonic cleaning for 15min, cleaning the carbon paper subjected to ultrasonic cleaning with deionized water, and drying to obtain the usable carbon paper substrate.
Step two: preparation of carbon paper supported Prussian blue nano film substrate
The Prussian blue nano film material is prepared by adopting a cyclic voltammetry method, the carbon paper substrate obtained in the step one is immersed into an electrolyte A, the molar concentration of ferric nitrate in the electrolyte A is 10mmol/L, the molar concentration of potassium ferricyanide is 10mmol/L, and the molar concentration of potassium chloride is 3mol/L, then a three-electrode system consisting of a working electrode of carbon paper (0.5 multiplied by 0.5cm), a counter electrode of a platinum sheet and a reference electrode of saturated Ag/AgCl is adopted for carrying out cyclic voltammetry, Ag/AgCl is taken as the reference electrode, the potential range is-0.2V to 1.2V, the scanning rate of 100mV/s is carried out for 20 cycles, and then the Prussian blue nano film material loaded on the carbon paper, namely the carbon paper Prussian blue nano film substrate is obtained by washing with deionized water and drying.
Step three: preparation of nickel hydroxide/Prussian blue nano-film material
And (2) preparing the nickel hydroxide/Prussian blue nano film material by adopting a constant potential deposition method, immersing the carbon paper loaded Prussian blue nano film substrate obtained in the step two into an electrolyte B with the molar concentration of nickel nitrate of 50mmol/L, then performing constant potential deposition by adopting a three-electrode system consisting of a working electrode of the carbon paper loaded with the Prussian blue nano film, a counter electrode of a platinum sheet and a reference electrode of saturated Ag/AgCl, depositing 36000s by taking Ag/AgCl as the reference electrode under the condition that the potential is-0.5V, washing by adopting deionized water, and naturally drying to obtain the nickel hydroxide/Prussian blue nano film material loaded on the carbon paper.
Step four: preparation of nickel-iron double metal hydroxide nano film material
And (3) placing the nickel hydroxide/Prussian blue nano-film material loaded on the carbon paper obtained in the step three in 1mol/L potassium hydroxide (KOH) for etching for 20min, then washing with deionized water and naturally drying to obtain the nickel-iron double-metal hydroxide nano-film material loaded on the carbon paper.
Example 4
The method comprises the following steps: treatment of carbon paper substrates
And sequentially placing the carbon paper with the size of 0.5 multiplied by 1cm into 2mol/L hydrochloric acid solution, acetone and ethanol for ultrasonic cleaning for 10min, cleaning the carbon paper subjected to ultrasonic cleaning with deionized water, and drying to obtain the usable carbon paper substrate.
Step two: preparation of carbon paper supported Prussian blue nano film substrate
The Prussian blue nano film material is prepared by adopting a cyclic voltammetry method, the carbon paper substrate obtained in the step one is immersed in an electrolyte A, the molar concentration of ferric nitrate in the electrolyte A is 1.5mmol/L, the molar concentration of potassium ferricyanide is 1.5mmol/L, and the molar concentration of potassium chloride is 0.3mol/L, then a three-electrode system consisting of a working electrode of carbon paper (0.5 multiplied by 0.5cm), a counter electrode of a platinum sheet and a reference electrode of saturated Ag/AgCl is adopted for carrying out cyclic voltammetry, Ag/AgCl is taken as the reference electrode, the potential range is-0.2 to 1.2V, the scanning rate of 15mV/s is carried out for 8 cycles, and then the Prussian blue nano film material loaded on the carbon paper, namely the Prussian blue nano film substrate loaded on the carbon paper, is obtained by washing with deionized water and drying.
Step three: preparation of nickel hydroxide/Prussian blue nano-film material
And (2) preparing the nickel hydroxide/Prussian blue nano film material by adopting a constant potential deposition method, immersing the Prussian blue nano film substrate loaded on the carbon paper obtained in the step two into an electrolyte B with the molar concentration of nickel nitrate of 3.6mmol/L, then performing constant potential deposition by adopting a three-electrode system consisting of a working electrode of the Prussian blue nano film loaded carbon paper, a counter electrode of a platinum sheet and a reference electrode of saturated Ag/AgCl, depositing 3800s at the potential of-0.75V by taking Ag/AgCl as the reference electrode, washing by adopting deionized water and naturally drying to obtain the nickel hydroxide/Prussian blue nano film material loaded on the carbon paper.
Step four: preparation of nickel-iron double metal hydroxide nano film material
And (4) placing the nickel hydroxide/Prussian blue nano film material loaded on the carbon paper obtained in the third step into 1mol/L potassium hydroxide (KOH) for etching for 8min, then washing with deionized water, and naturally drying to obtain the nickel-iron double-metal hydroxide nano film material loaded on the carbon paper.
Example 5
The method comprises the following steps: treatment of carbon paper substrates
And sequentially placing the carbon paper with the size of 0.5 multiplied by 1cm into 3mol/L hydrochloric acid solution, acetone and ethanol for ultrasonic cleaning for 10min, cleaning the carbon paper subjected to ultrasonic cleaning with deionized water, and drying to obtain the usable carbon paper substrate.
Step two: preparation of carbon paper supported Prussian blue nano film substrate
The Prussian blue nano-film material is prepared by adopting a cyclic voltammetry method, a carbon paper substrate obtained in the step one is immersed into an electrolyte A, the molar concentration of ferric nitrate in the electrolyte A is 5mmol/L, the molar concentration of potassium ferricyanide is 5mmol/L, and the molar concentration of potassium chloride is 1.5mol/L, then a three-electrode system consisting of a working electrode of carbon paper (0.5 multiplied by 0.5cm), a counter electrode of a platinum sheet and a reference electrode of saturated Ag/AgCl is adopted to carry out cyclic voltammetry, Ag/AgCl is taken as the reference electrode, the potential range is-0.2 to 1.2V, 10 cycles are carried out at the scanning rate of 50mV/s, and then the Prussian blue nano-film material loaded on the carbon paper, namely the Prussian blue nano-film substrate loaded on the carbon paper, is obtained by washing with deionized water and drying.
Step three: preparation of nickel hydroxide/Prussian blue nano-film material
And (2) preparing the nickel hydroxide/Prussian blue nano film material by adopting a constant potential deposition method, immersing the carbon paper loaded Prussian blue nano film substrate obtained in the step two into an electrolyte B with the molar concentration of nickel nitrate of 25mmol/L, then performing constant potential deposition by adopting a three-electrode system consisting of a working electrode of the carbon paper loaded with the Prussian blue nano film, a counter electrode of a platinum sheet and a reference electrode of saturated Ag/AgCl, depositing 18000s under the condition that the potential is-1V by taking Ag/AgCl as the reference electrode, washing by adopting deionized water, and naturally drying to obtain the nickel hydroxide/Prussian blue nano film material loaded on the carbon paper.
Step four: preparation of nickel-iron double metal hydroxide nano film material
And (3) placing the nickel hydroxide/Prussian blue nano-film material loaded on the carbon paper obtained in the step three in 1mol/L potassium hydroxide (KOH) for etching for 10min, then washing with deionized water and naturally drying to obtain the nickel-iron double-metal hydroxide nano-film material loaded on the carbon paper.
According to the Raman spectrum shown in FIG. 2, the cyanide in the Prussian blue nano-film material can be known in the etching processIs replaced by hydroxyl in KOH to obtain the ferronickel double-metal hydroxide nano-film material. According to SEM pictures in figures 3a and 3b, the Prussian blue nano-film material is uniformly and continuously deposited on the surface of the carbon paper, and shows a regular cubic nanocrystalline structure. According to the comparison between fig. 3a and fig. 3c, it is found that the nickel hydroxide/prussian blue nano-film material is formed by uniformly covering a layer of nickel hydroxide nano-film on the surface of the prussian blue nano-film material. According to the comparison between fig. 3d and fig. 3c, many obvious holes appear on the surface of the etched ferronickel double-metal hydroxide nanometer thin film material. The film thickness of the NiFe bimetal hydroxide nano film material is about 100-200 nm according to FIG. 3e, and the NiFe bimetal hydroxide nano film material is amorphous according to FIG. 3 f. According to the XPS spectrum in figure 4, the nickel, iron and oxygen elements are contained in the ferronickel double-metal hydroxide nanometer thin film material, and the peak of O1s in XPS is composed of a crystal lattice oxygen peak and a vacancy oxygen peak, which indicates that oxygen vacancies exist in the ferronickel double-metal hydroxide nanometer thin film material. According to the mechanism that the adsorption energy of the reaction intermediate can be reduced by the oxygen vacancy, so that the reaction energy barrier is reduced, the electron paramagnetic resonance wave spectrum of fig. 5 further proves that the ferronickel bimetal hydroxide nano-film material has a large number of oxygen vacancies. The nickel-iron double-metal hydroxide nano-film material with a large number of oxygen vacancies is used for the electrochemical oxygen evolution performance test, and an electrocatalytic oxygen evolution polarization curve and a Tafel slope curve of the nickel-iron double-metal hydroxide nano-film material in a 1M KOH aqueous solution are seen from FIG. 6, and the overpotential of the nickel-iron double-metal hydroxide nano-film material is only 261mV (j is 10 mA/cm)2)、303mV(j＝100mA/cm2) The Tafel slope is only 33.8mV/dec, and the oxygen evolution performance is high. The nickel-iron double metal hydroxide nano film material is in alkaline electrolyte of 1mol/L KOH and the current is 20mA/cm2The nickel-iron double-metal hydroxide nano-film material is electrolyzed for 50 hours, and the overpotential of the nickel-iron double-metal hydroxide nano-film material is almost kept unchanged in the electrolysis process according to the graph shown in fig. 7, which shows that the nickel-iron double-metal hydroxide nano-film material has excellent long-time electrolysis stability and great practicability.
The invention takes the carbon paper as a substrate and adopts two simple stepsElectrodeposition and one-step etching process to obtain the nanometer ferronickel double metal hydroxide film material loaded on the carbon paper, and the material is an amorphous nanometer film material rich in oxygen vacancy and having a porous structure. The method is a universal method, is not limited by conductive carbon paper, is simple and easy to operate, is safe to operate, and is green and pollution-free. Secondly, the potential of the material is only 261mV (j is 10 mA/cm)2)、303mV(j＝100mA/cm2) The Tafel slope is only 33.8mV/dec, and excellent oxygen evolution catalytic activity is shown; when electrolysis is performed in an alkaline electrolyte, the potential thereof is almost maintained and excellent electrolytic stability is exhibited.
Claims (10)
1. A preparation method of a ferronickel double metal hydroxide nano film material is characterized by comprising the following steps:
s1: immersing the carbon paper into an electrolyte A consisting of ferric nitrate, potassium ferricyanide and potassium chloride by taking the treated carbon paper as a substrate, and obtaining a Prussian blue nano-film material deposited on the surface of the carbon paper by adopting an electrodeposition method, namely the carbon paper-loaded Prussian blue nano-film substrate;
s2: immersing the carbon paper Prussian blue nano-film substrate obtained in the step S1 in an electrolyte B of nickel nitrate, depositing nickel ions in the electrolyte B on the surface of the Prussian blue nano-film material in a nickel hydroxide nano-film form by adopting an electrodeposition method, and cleaning and drying the nickel hydroxide/Prussian blue nano-film material by using deionized water to obtain a nickel hydroxide/Prussian blue nano-film material loaded on the carbon paper;
s3: and (3) putting the nickel hydroxide/Prussian blue nano-film material obtained in the step (S2) into a strong alkali solution for etching, washing and drying to obtain the electrocatalyst of the nickel-iron double-metal hydroxide nano-film material loaded on the carbon paper, wherein the electrocatalyst is an amorphous nano-film material which is rich in oxygen vacancies and has a porous structure.
2. The preparation method of the ferronickel bimetal hydroxide nano-film material according to claim 1, wherein the carbon paper is sequentially placed in hydrochloric acid with a concentration of 0.1-6 mol/L, acetone and ethanol for ultrasonic cleaning for 5-15 minutes for treatment, and then is cleaned with deionized water and dried to obtain the treated carbon paper.
3. The method for preparing the ferronickel double metal hydroxide nano-film material according to claim 1, wherein the molar concentration of ferric nitrate in the electrolyte A is 0.1-10 mmol/L, the molar concentration of potassium ferricyanide is 0.1-10 mmol/L, and the molar concentration of potassium chloride is 0.01-3 mol/L.
4. The preparation method of the ferronickel double metal hydroxide nano-film material according to claim 3, wherein the molar concentration of nickel nitrate in the electrolyte B is 0.1-50 mmol/L.
5. The method for preparing the ferronickel double metal hydroxide nano-film material according to claim 4, wherein a three-electrode system adopted in the S1 electrodeposition process comprises a working electrode of carbon paper, a counter electrode of a platinum sheet and a reference electrode of saturated Ag/AgCl.
6. The method for preparing the ferronickel double metal hydroxide nano-film material according to claim 5, wherein a three-electrode system adopted in the S2 electrodeposition process comprises a working electrode of carbon paper loaded with Prussian blue nano-film, a counter electrode of platinum sheet and a reference electrode of saturated Ag/AgCl.
7. The method for preparing the ferronickel double metal hydroxide nano-film material according to claim 6, wherein the electrodeposition method S1 is cyclic voltammetry, the potential range of Ag/AgCl as a reference electrode is-0.2-1.2V, the scanning rate is 1-100 mV/S, and at least 1 electrodeposition cycle is carried out.
8. The method for preparing the ferronickel bimetal hydroxide nano-film material according to claim 7, wherein the S2 electrodeposition method is a potentiostatic method, the potential range of Ag/AgCl as a reference electrode is-1.5 to-0.5V, and the deposition time is 60 to 36000S.
9. The method for preparing the ferronickel double metal hydroxide nano-film material according to any one of claims 1 to 8, wherein the strong alkali solution in S3 is a KOH solution, and the etching time of the nickel hydroxide/Prussian blue nano-film material is not less than 5 min.
10. Use of a nickel iron double hydroxide nano-film material prepared according to the preparation method of claim 9 as an electrocatalyst.
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