CN111450889B - Ni (nickel) 2 Fe-ICP nano-sheet and preparation method for room temperature growth thereof - Google Patents
Ni (nickel) 2 Fe-ICP nano-sheet and preparation method for room temperature growth thereof Download PDFInfo
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- CN111450889B CN111450889B CN202010260739.1A CN202010260739A CN111450889B CN 111450889 B CN111450889 B CN 111450889B CN 202010260739 A CN202010260739 A CN 202010260739A CN 111450889 B CN111450889 B CN 111450889B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 195
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 64
- 239000002135 nanosheet Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000006260 foam Substances 0.000 claims abstract description 57
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 45
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000002791 soaking Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229920001940 conductive polymer Polymers 0.000 description 58
- 238000009616 inductively coupled plasma Methods 0.000 description 58
- 239000010411 electrocatalyst Substances 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 4
- 239000002064 nanoplatelet Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 229920001795 coordination polymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 101100317222 Borrelia hermsii vsp3 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B01J35/33—
-
- B01J35/40—
-
- B01J35/61—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- 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
- C25B11/095—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 at least one of the compounds being organic
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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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
Abstract
The invention relates to the technical field of electrocatalytic oxygen evolution, in particular to Ni 2 Fe-ICP nano-sheet and preparation method for room temperature growth of Fe-ICP nano-sheet, wherein Ni is the same as Ni 2 The Fe-ICP nano-sheet is prepared according to the following method: after the surface of the foam nickel is subjected to the pretreatment of oxide removal, the treated foam nickel is immersed into a ferric salt solution for soaking, a terephthalic acid solution is continuously added, a mixed solution of triethylamine and ethanol is added after the uniform mixing, the foam nickel is grown by a room temperature growth method, and Ni growing on the foam nickel is prepared 2 Fe-ICP nano-sheet. The invention adopts a normal temperature standing method to prepare Ni 2 The Fe-ICP nano-sheet is simple to operate and easy to realize, and the Ni prepared by the method 2 The Fe-ICP nano-sheet has low oxygen evolution overpotential and high stability.
Description
Technical Field
The invention relates to the technical field of electrocatalytic oxygen evolution, in particular to Ni 2 Fe-ICP nanometer sheet and its room temperature growth preparation method.
Background
Electrochemical water splitting is an effective method for producing the cleanest hydrogen, however, the oxygen evolution reaction (oxygen evolution reaction, OER) at the anode is a kinetically slow step-by-step limiting the development of hydrogen production by water splitting, and thus the research and development of non-noble metal oxygen evolution electrocatalysts is of great significance. The metal-organic framework (MOF) can become an excellent electrocatalytic oxygen evolution catalyst due to the high specific surface area and the adjustable pore structure, and although the research of directly using the MOF as an OER electrocatalyst has been greatly progressed, most MOF electrocatalysts reported at present are synthesized by a hydrothermal method, and meanwhile, the overpotential and the stability of the MOF electrocatalyst are tested under the condition of low current density, which is far lower than the practical application requirement.
Compared to MOF, amorphous infinite coordination polymers (infinite coordination polymers, ICPs) are oxygen evolution electrocatalysts with great potential due to their rich active metal sites, particularly their simple synthetic methods and rich active metal sites. However, few reports have been made on ICPs as electrocatalysts, and ICPs of NiFe have not been reported so far.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a Ni 2 The invention relates to a Fe-ICP nano-sheet and a preparation method for the room temperature growth thereof, which adopts a normal temperature standing method to prepare Ni 2 The Fe-ICP nano-sheet has simple experimental operation and easy realization, and the Ni prepared by the method 2 The Fe-ICP nano-sheet has low oxygen evolution overpotential and high stability.
In order to solve the technical problems, the invention adopts the following technical scheme:
ni (nickel) 2 Fe-ICP nanosheets, the Ni 2 The Fe-ICP nano-sheet is prepared according to the following method: after the surface of the foam nickel is subjected to the pretreatment of oxide removal, the treated foam nickel is immersed into a ferric salt solution for soaking, a terephthalic acid solution is continuously added, a mixed solution of triethylamine and ethanol is added after the uniform mixing, the foam nickel is grown by a room temperature growth method, and Ni growing on the foam nickel is prepared 2 Fe-ICP nano-sheet.
The invention also protects a Ni 2 The preparation method for the room temperature growth of the Fe-ICP nanosheets comprises the following steps:
(1) Performing surface oxide removal pretreatment on the foam nickel to obtain treated foam nickel;
(2) Growth of Ni on foam Nickel 2 Preparation of Fe-ICP nanosheets: immersing the treated foam nickel prepared in the step (1) into an iron salt solution with the mass concentration of 0.035-0.04mol/L, and immersing to obtain a material A;
terephthalic acid is dissolved in a solvent to obtain a material B, wherein the ratio of the amount of terephthalic acid substance to the volume of the solvent is 1mmol:20-30mL;
the material B is added into the material A,mixing at room temperature, adding the mixed solution of triethylamine and ethanol into the solution, mixing uniformly, and standing for 9-10h; taking out the foam nickel, drying, washing and re-drying to obtain Ni 2 Fe-ICP nanosheets;
wherein the ratio of the volume of triethylamine to the amount of terephthalic acid material is 60-120 μl:1mmol; the mass ratio of terephthalic acid to iron salt was 2:3.
Preferably, the drying, washing and re-drying method in the step (2) is as follows: drying at 45-50deg.C for 20min, soaking in deionized water for 30min, and drying at 40-50deg.C for 10-12 hr.
Preferably, in the step (2), the volume ratio of the triethylamine to the ethanol is 1:2-4.
Preferably, the ferric salt solution in the step (2) is FeCl 3 ·6H 2 Aqueous solutions of O or Fe (NO 3 ) 3 Is a solution of (a) and (b).
Preferably, the solvent in the step (2) is N, N '-dimethylformamide or N, N' -dimethylacetamide.
Preferably, the uniformly mixing mode in the step (2) is stirring for 20-25min.
The invention also protects Ni 2 The Fe-ICP nano-sheet is used as an anode material in water electrolysis.
Preferably, the Ni 2 The Fe-ICP nano-sheet is used for a self-supporting electrode for electrocatalytic oxygen evolution reaction.
Compared with the prior art, the invention has the following beneficial effects:
1. ni prepared by the invention 2 Fe-ICP nanosheets are amorphous Ni 2 Fe and terephthalic acid complex, the preparation method of the complex is simple, and the complex is prepared under normal temperature condition, and the obtained Ni 2 The Fe-ICP nano-sheet shows low oxygen evolution overpotential and high stability, and can be directly used as a self-supporting electrode for electrocatalytic oxygen evolution reaction.
2. The invention provides a method for growing Ni on foam nickel under room temperature condition 2 Method of Fe-ICP nanoplatelet arrays providing large electrochemically active surface area and electronic andconvenient transfer paths of electrolyte ions, thus Ni 2 Fe-ICP shows excellent electrocatalytic oxygen evolution performance at high current density; in addition, ruO with excellent OER performance compared with the prior art 2 In comparison, ni prepared by the invention 2 The Fe-ICP nanosheets have lower overpotential and lower Taphenanthrer slope, indicating bimetallic Ni 2 The Fe-ICP nano-sheet array has faster oxygen evolution reaction kinetics, and the invention also carries out the research of timing current, and the result shows that the Ni prepared by the invention 2 Fe-ICP nano-sheet at 150 mA.cm -2 The electrocatalytic oxygen evolution activity can be maintained for at least 30 hours at high current densities, confirming long-term stability.
3. The preparation method of the invention selects the conditions to achieve Ni 2 The present invention studied and analyzed the preparation conditions of the array structure of Fe-ICP nanoplatelets, and in the conditions of dissolving 1mmol of terephthalic acid in N, N ' -dimethylformamide, if the amount of N, N ' -dimethylformamide is less than 20mL, the terephthalic acid cannot be completely dissolved, and if the amount of N, N ' -dimethylformamide is more than 30mL, ni is caused 2 The amount of terephthalic acid in the Fe-ICP nanosheets is reduced; when triethylamine was added to 1mmol of terephthalic acid, ni could not be obtained under the condition that the amount of triethylamine was less than 60. Mu.L 2 In the array structure of the Fe-ICP nanosheets, under the condition that the amount of triethylamine is higher than 120 mu L, the phenomenon of powder coagulation easily occurs in the solution, so that the powder cannot grow on the foam nickel; and only in terephthalic acid and FeCl 3 ·6H 2 The Ni with the array structure can be prepared under the condition that the mass ratio of O is 2:3 2 Fe-ICP nano-sheet.
Drawings
FIG. 1 shows Ni obtained in example 1 of the present invention 2 SEM image of Fe-ICP nanoplatelets; wherein a graph a is a low-power scanning electron microscope, and b graph b is a high-power scanning electron microscope;
FIG. 2 shows Ni obtained in example 1 of the present invention 2 Fe-ICP and commercialized RuO 2 Linear Sweep Voltammetric (LSV) curve comparison plot;
FIG. 3 is a drawing of Ni obtained in example 1 of the present invention 2 Fe-ICP and commercialized RuO 2 Is a taffy slope comparison graph;
FIG. 4 shows Ni obtained in example 1 of the present invention 2 Timing current plot of Fe-ICP.
Detailed Description
The following description is of the preferred embodiments and accompanying figures 1-4, taken in conjunction with the embodiments of the present invention. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Example 1
Ni (nickel) 2 The preparation method for the Fe-ICP nanosheets growing at room temperature comprises the following steps:
(1) Performing surface oxide removal pretreatment on the foam nickel to obtain treated foam nickel:
cutting foam nickel into 1cm multiplied by 12cm, putting the foam nickel into dilute hydrochloric acid with the volume fraction of 25% for ultrasonic treatment for 20min, removing oxides on the surface of the foam nickel, then carrying out ultrasonic treatment with deionized water for 40min, finally repeatedly cleaning with deionized water and ethanol, putting the cleaned foam nickel into a vacuum drying oven, and drying at 60 ℃ for 30min to obtain treated foam nickel;
(2) Growth of Ni on foam Nickel 2 Preparation of Fe-ICP nanosheets:
immersing the treated Nickel Foam (NF) prepared in the step (1) into 15ml deionized water and 1.688mmol FeCl 3 ·6H 2 O, soaking for 20min to obtain a material A;
1.125mmol of terephthalic acid was dissolved in 30mL of N, N-dimethylformamide to give material B;
pouring the solution B into the solution A under magnetic stirring, maintaining at room temperature for 20min, adding 135 μl of mixed solution of triethylamine and 540 μl of ethanol into the solution, stirring for 20min, standing for 10h, taking out the nickel foam, drying at 45deg.C for 20min, and adding into deionized waterSoaking for 30min, and drying at 45deg.C for 10 hr to obtain Ni 2 Fe-ICP nano-sheet.
Example 2
Ni (nickel) 2 The preparation method for the Fe-ICP nanosheets growing at room temperature comprises the following steps:
(1) Performing surface oxide removal pretreatment on the foam nickel to obtain treated foam nickel:
cutting foam nickel into 1.2cm multiplied by 12.5cm, putting the foam nickel into dilute hydrochloric acid with the volume fraction of 25% for ultrasonic treatment for 18min, removing oxides on the surface of the foam nickel, then carrying out ultrasonic treatment with deionized water for 42min, finally repeatedly cleaning with deionized water and ethanol, putting the cleaned foam nickel into a vacuum drying oven, and drying at 55 ℃ for 35min to obtain treated foam nickel;
(2) Growth of Ni on foam Nickel 2 Preparation of Fe-ICP nanosheets:
immersing the treated foam Nickel (NF) prepared in the step (1) into FeCl with the mass concentration of 0.038mol/L and the mass of 1.688mmol 3 ·6H 2 Soaking in the O solution for 25min to obtain a material A;
1.125mmol of terephthalic acid was dissolved in 25mL of N, N' -dimethylformamide to give material B;
adding the material B into the material A, stirring at room temperature for 22min, adding 90 mu L of a mixed solution of triethylamine and 270 mu L of ethanol into the solution, continuously stirring for 23min, and standing for 9.5h; taking out the foam nickel, drying at 42 ℃ for 20min, soaking in deionized water for 30min, and drying at 42 ℃ for 11h to obtain Ni 2 Fe-ICP nano-sheet.
Example 3
Ni (nickel) 2 The preparation method for the Fe-ICP nanosheets growing at room temperature comprises the following steps:
(1) Performing surface oxide removal pretreatment on the foam nickel to obtain treated foam nickel;
cutting foam nickel into 1.5cm multiplied by 13cm, putting the foam nickel into dilute hydrochloric acid with the volume fraction of 25% for ultrasonic treatment for 15min, removing oxides on the surface of the foam nickel, then carrying out ultrasonic treatment with deionized water for 45min, finally repeatedly cleaning with deionized water and ethanol, putting the cleaned foam nickel into a vacuum drying oven, and drying at 50 ℃ for 40min to obtain treated foam nickel;
(2) Growth of Ni on foam Nickel 2 Preparation of Fe-ICP nanosheets:
immersing the treated foam Nickel (NF) prepared in the step (1) into FeCl with the mass concentration of 0.04mol/L and the mass of 1.688mmol 3 ·6H 2 Soaking in the O solution for 30min to obtain a material A;
1.125mmol of terephthalic acid was dissolved in 36mL of N, N' -dimethylformamide to give material B;
adding the material B into the material A, stirring for 25min at room temperature, adding 75 mu L of a mixed solution of triethylamine and 150 mu L of ethanol into the solution, continuously stirring for 25min, and standing for 10h; taking out the foam nickel, drying at 50deg.C for 20min, soaking in deionized water for 30min, and drying at 50deg.C for 10 hr to obtain Ni 2 Fe-ICP nano-sheet.
Comparative example 1
RuO (Ruo) device 2 The preparation method for the growth of the nano-sheet at room temperature comprises the following steps:
30mg RuO 2 The powder was dispersed in a solution containing PVDF (polyvinylidene fluoride) as a binder, 50. Mu.l of NMP (N-methylpyrrolidone) was added thereto, and then coated on nickel foam, thereby obtaining RuO 2 Working electrode, ruO 2 The loading was 4.5mg cm -2 。
Ni prepared in examples 1 to 3 of the present invention 2 The Fe-ICP nanosheets have the advantages of large electrochemical active surface area, convenient electron and ion transmission paths, easy removal of separated oxygen and the like, and similar performances, so the Ni prepared by the method of the invention in the embodiment 1 2 The Fe-ICP nanosheets are detected and researched, and the specific method is as follows:
electrocatalytic performance of samples was tested using a three electrode system of VMP3 electrochemical workstation (biologicc, france), graphite rod and Ag/AgCl were used as counter and reference electrodes, respectively, directly using Ni grown on nickel foam 2 Fe-ICP was used as working electrode. The electrolyte was a 1mol/L KOH solution and was prepared at 50 mV.s by Cyclic Voltammetry (CV) prior to OER measurement -1 Activating the working electrode at a scan rate of (1) and a polarization curve (LSV) by compensating for iR at 5 mV.s -1 Obtained at a scan rate of 150mA cm -2 Is tested by means of a chronoamperometric curve at high current densities.
FIG. 1 shows Ni obtained in example 1 of the present invention 2 SEM image of Fe-ICP nano-sheet, a graph a in FIG. 1 is a low-power scanning electron microscope, b in FIG. 1 is a high-power scanning electron microscope, and as can be seen from graphs a and b, ni is obtained by the preparation method 2 Fe-ICP nano-sheet array and Ni with nano structure 2 The Fe-ICP has high specific surface area, increases the contact area with electrolyte, and improves the electrocatalytic oxygen evolution performance.
FIG. 2 shows Ni obtained in example 1 of the present invention 2 Fe-ICP and commercialized RuO 2 As can be seen from FIG. 2, ni is a comparison of Linear Sweep Voltammetry (LSV) curves 2 Fe-ICP has excellent OER performance, ni 2 The overpotential of Fe-ICP was 50 mA.cm -2 256mV at a current density of 100 mA.cm -2 275mV at a current density of (c); ruO with excellent OER performance compared with the prior art 2 In comparison, although Ni 2 Fe-ICP shows a slightly higher overpotential at low current density but a significantly lower overpotential at high current density, which is very important for practical applications.
FIG. 3 is a drawing of Ni obtained in example 1 of the present invention 2 Fe-ICP and commercialized RuO 2 As can be seen from FIG. 3, ni 2 The Taffner slope of Fe-ICP was 59.6 mV.dec -1 Ratio RuO 2 (86.3mV·dec -1 ) Low, indicating bimetallic Ni 2 The Fe-ICP nano-sheet array has faster oxygen evolution reaction kinetics.
FIG. 4 shows Ni obtained in example 1 of the present invention 2 As can be seen from FIG. 4, the timing current curve of Fe-ICP is Ni 2 Fe-ICP at 150 mA.cm -2 The electrocatalytic oxygen evolution activity can be maintained for at least 30h at high current densities confirming long-term stability.
In summary, the invention provides a method for growing Ni on foam nickel at room temperature 2 Method of Fe-ICP nanoplatelet arrays providing large electrochemically active surface area and convenient transfer of electrons and electrolyte ions, thus Ni 2 Fe-ICP shows excellent electrocatalytic oxygen evolution performance at high current density and is superior to commercial RuO with excellent OER performance 2 Meanwhile, the invention shows ultra-high electrochemical stability, and provides a new opportunity for designing and utilizing ICP as an efficient and low-cost electrochemical oxygen evolution reaction catalyst.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (8)
1. Ni (nickel) 2 The Fe-ICP nanosheets are characterized in that the Ni 2 The Fe-ICP nano-sheet is prepared according to the following method: after the surface of the foam nickel is subjected to the pretreatment of oxide removal, the treated foam nickel is immersed into a ferric salt solution for soaking, a terephthalic acid solution is continuously added, a mixed solution of triethylamine and ethanol is added after the uniform mixing, the foam nickel is grown by a room temperature growth method, and Ni growing on the foam nickel is prepared 2 Fe-ICP nanosheets;
Ni 2 the Fe-ICP nano-sheet is prepared according to the following steps:
(1) Performing surface oxide removal pretreatment on the foam nickel to obtain treated foam nickel;
(2) Growth of Ni on foam Nickel 2 Preparation of Fe-ICP nanosheets: immersing the treated foam nickel prepared in the step (1) into an iron salt solution with the mass concentration of 0.035-0.04mol/L, and immersing to obtain a material A;
terephthalic acid is dissolved in a solvent to obtain a material B, wherein the ratio of the amount of terephthalic acid substance to the volume of the solvent is 1mmol:20-30mL;
adding the material B into the material A, uniformly mixing at room temperature, adding a mixed solution of triethylamine and ethanol into the solution, uniformly mixing, and standing for 9-10h; taking out the foam nickel, drying, washing and re-drying to obtain Ni 2 Fe-ICP nanosheets;
wherein the ratio of the volume of triethylamine to the amount of terephthalic acid material is 60-120 μl:1mmol; the mass ratio of terephthalic acid to iron salt was 2:3.
2. The Ni of claim 1 2 The Fe-ICP nano sheet is characterized in that the drying, washing and re-drying method in the step (2) is as follows: drying at 45-50deg.C for 20min, soaking in deionized water for 30min, and drying at 40-50deg.C for 10-12 hr.
3. The Ni of claim 1 2 The Fe-ICP nano sheet is characterized in that the volume ratio of triethylamine to ethanol in the step (2) is 1:2-4.
4. The Ni of claim 1 2 The Fe-ICP nano-sheet is characterized in that the ferric salt solution in the step (2) is FeCl 3 ·6H 2 Aqueous solutions of O or Fe (NO 3 ) 3 Is a solution of (a) and (b).
5. The Ni of claim 1 2 The Fe-ICP nano-sheet is characterized in that the solvent in the step (2) is N, N '-dimethylformamide or N, N' -dimethylacetamide.
6. The Ni of claim 1 2 The Fe-ICP nano sheet is characterized in that the uniformly mixing mode in the step (2) is stirring for 20-25min.
7. A Ni according to claim 1 2 The Fe-ICP nano-sheet is used as an anode material in water electrolysis.
8. According to claim7 of a Ni 2 The application of Fe-ICP nano-sheets as anode materials in electrolysis of water is characterized in that the Ni 2 The Fe-ICP nano-sheet is used for a self-supporting electrode for electrocatalytic oxygen evolution reaction.
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