CN117352751A - Self-supporting electrode of urea fuel cell and preparation method thereof - Google Patents
Self-supporting electrode of urea fuel cell and preparation method thereof Download PDFInfo
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- CN117352751A CN117352751A CN202311334535.8A CN202311334535A CN117352751A CN 117352751 A CN117352751 A CN 117352751A CN 202311334535 A CN202311334535 A CN 202311334535A CN 117352751 A CN117352751 A CN 117352751A
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 239000004202 carbamide Substances 0.000 title claims abstract description 92
- 239000000446 fuel Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 250
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 122
- 239000006260 foam Substances 0.000 claims abstract description 121
- 239000011259 mixed solution Substances 0.000 claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 claims abstract description 70
- 239000002184 metal Substances 0.000 claims abstract description 70
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000013110 organic ligand Substances 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000002096 quantum dot Substances 0.000 claims description 57
- 239000012621 metal-organic framework Substances 0.000 claims description 42
- 239000003792 electrolyte Substances 0.000 claims description 36
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 22
- 239000002135 nanosheet Substances 0.000 claims description 21
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 18
- 238000000151 deposition Methods 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 18
- 229960002089 ferrous chloride Drugs 0.000 claims description 18
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 17
- 239000010941 cobalt Substances 0.000 claims description 16
- 229910017052 cobalt Inorganic materials 0.000 claims description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 16
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 13
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 238000002484 cyclic voltammetry Methods 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- 238000003760 magnetic stirring Methods 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 238000004070 electrodeposition Methods 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 150000004763 sulfides Chemical class 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical class [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 5
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- WCBFEMZIZMFMPB-UHFFFAOYSA-L dipotassium;naphthalene-1,2-dicarboxylate Chemical compound [K+].[K+].C1=CC=CC2=C(C([O-])=O)C(C(=O)[O-])=CC=C21 WCBFEMZIZMFMPB-UHFFFAOYSA-L 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical class [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 3
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical class [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims description 3
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 3
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical class P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 claims description 3
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical class [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical class [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 3
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 3
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 17
- 239000001301 oxygen Substances 0.000 abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 abstract description 17
- 230000003647 oxidation Effects 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000010718 Oxidation Activity Effects 0.000 abstract description 5
- 239000010405 anode material Substances 0.000 abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 50
- 239000013084 copper-based metal-organic framework Substances 0.000 description 23
- 150000002505 iron Chemical class 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000004502 linear sweep voltammetry Methods 0.000 description 10
- 238000001000 micrograph Methods 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 239000010411 electrocatalyst Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000013384 organic framework Substances 0.000 description 4
- 150000001868 cobalt Chemical class 0.000 description 3
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical class [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
- H01M8/222—Fuel cells in which the fuel is based on compounds containing nitrogen, e.g. hydrazine, ammonia
-
- 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
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides a self-supporting electrode of a urea fuel cell, which structurally comprises foam nickel and a metal-organic frame; the metal-organic frame is loaded on the surface of the foam nickel to form a foam nickel loaded metal-organic frame; the preparation method of the self-supporting electrode of the urea fuel cell comprises the following steps: 1) Dispersing foam nickel, metal salt and organic ligand in absolute ethyl alcohol and deionized water, carrying out ultrasonic treatment and stirring to obtain a uniform mixed solution; 2) Transferring the mixed solution into a hydrothermal reaction kettle, reacting for 12 h-48 hours at a constant temperature of 100-180 ℃, centrifuging, cleaning and drying to obtain a foam nickel-loaded metal-organic frame; the self-supporting electrode of the urea fuel cell prepared by the invention has high-efficiency electrocatalytic oxygen evolution, urea oxidation activity and excellent cycle stability, and can be used as an effective anode material for urea oxidation in the urea fuel cell to realize high-efficiency energy conversion.
Description
Technical Field
The invention relates to a self-supporting electrode of a urea fuel cell and a preparation method thereof, belonging to the field of electrocatalytic materials.
Background
The direct urea fuel cell has wide application prospect in the fields of sustainable energy development and water pollution control; urea oxidation reaction (UOR, CO (NH) 2 ) 2 + 6 OH - → N 2 + 5 H 2 O + CO 2 + 6 e - ) Is a key half-reaction of a direct urea fuel cell; however, UOR in alkaline medium involves complicated hexaelectron transfer steps and adsorption/desorption processes of intermediate products, resulting in problems of slow reaction kinetics, low energy conversion efficiency and the like; the design and construction of the high-efficiency electrocatalyst can promote the UOR reaction (urea oxidation reaction), improve the reaction rate and reduce the reaction energy barrier, thereby realizing the large-scale application of the direct urea fuel cell; currently, noble metal catalysts such as platinum, iridium and ruthenium are commonly used as electrocatalysts, but the large-scale application of direct urea fuel cells is seriously hindered due to the high price and the scarce resources of the noble metal catalysts, so that an efficient and low-cost electrocatalyst is needed to improve the electrocatalytic urea oxidation efficiency and the energy conversion efficiency of the direct urea fuel cells.
The metal-organic framework is a high-order porous crystal material formed by connecting metal ions or clusters and organic ligands through coordination bonds, and has wide application prospects in the fields of energy storage, catalysis, gas adsorption and separation, sensors and the like; the two-dimensional metal-organic framework has the excellent characteristics of larger specific surface area, higher porosity, ultrathin structure, abundant exposed active sites and the like, so that the two-dimensional metal-organic framework becomes a potential UOR electrocatalyst; however, due to the insulation of the organic ligand and the poor conjugation characteristics of the metal-organic ligand, the two-dimensional metal-organic frame still has the problems of poor conductivity, poor stability and the like, which affect the electrocatalytic performance; how to improve the stability and conductivity of metal-organic framework materials is critical to improving the performance of the electrocatalytic UOR.
Disclosure of Invention
The invention provides a self-supporting electrode of a urea fuel cell and a preparation method thereof, and aims to provide an electrode material which can be used for a direct urea fuel cell.
The technical solution of the invention is as follows: a self-supporting electrode of urea fuel cell structurally comprises foam nickel and a metal-organic frame; the metal-organic framework is loaded on the surface of the foam nickel to form the foam nickel-loaded metal-organic framework.
Further, the self-supporting electrode of the urea fuel cell structurally comprises a heterojunction, wherein the heterojunction is deposited on the surface of the metal-organic framework to form a heterojunction deposited foam nickel-loaded metal-organic framework electrode; the heterojunction is a metal quantum dot or a phosphide quantum dot or a sulfide quantum dot.
Further, the metal quantum dots are one or more of iron quantum dots, cobalt quantum dots, nickel quantum dots and copper quantum dots; the phosphide quantum dots are one or more of iron phosphide quantum dots, cobalt phosphide quantum dots, nickel phosphide quantum dots and copper phosphide quantum dots; the sulfide quantum dots are one or more of iron sulfide quantum dots, cobalt sulfide quantum dots, nickel sulfide quantum dots and copper sulfide quantum dots.
Further, the metal in the metal-organic framework comprises one or more of iron, cobalt, nickel and copper; the metal-organic frameworks are in the shape of two-dimensional nano-sheets, and a plurality of two-dimensional nano-sheet metal-organic frameworks are distributed on the surface of the foam nickel to form a densely arranged array structure; the length of the two-dimensional nano sheet metal-organic frame is 300 nm-600 nm, and the thickness of the two-dimensional nano sheet metal-organic frame is 5 nm-10 nm; the particle size of the metal quantum dot, the phosphide quantum dot and the sulfide quantum dot in the heterojunction is 2-10 nm, and the mass ratio of the heterojunction in the heterojunction deposited foam nickel-loaded metal-organic frame electrode is 2 wt% -10 wt%.
A method of making a self-supporting electrode for a urea fuel cell, the method comprising:
1) Dispersing foam nickel, metal salt and organic ligand in absolute ethyl alcohol and deionized water, carrying out ultrasonic treatment and stirring to obtain a uniform mixed solution;
2) Transferring the mixed solution into a hydrothermal reaction kettle, reacting for 12-h-48 h at the constant temperature of 100-180 ℃, centrifuging, cleaning and drying to obtain the foam nickel-loaded metal-organic framework.
Further, dispersing the foam nickel, the metal salt and the organic ligand in absolute ethyl alcohol and deionized water, and carrying out ultrasonic treatment and stirring to obtain a uniform mixed solution, wherein the method specifically comprises the following steps of:
1-1) dispersing metal salt and an organic ligand in a mixed solution of absolute ethyl alcohol and deionized water, and obtaining a uniform solution A through ultrasonic dispersion and magnetic stirring;
1-2) placing the cleaned foam nickel in the solution A, and performing ultrasonic treatment to obtain a uniform mixed solution;
the metal salt comprises one or more of ferrous chloride, cobalt chloride, nickel nitrate, copper acetate and tungsten chloride; the organic ligand comprises one or more of naphthalene dicarboxylic acid dipotassium salt and terephthalic acid; the concentration of metal salt in the mixed solution is 5-15 mmol/L, and the concentration of organic ligand is 5-15 mmol/L; the molar ratio of the metal salt to the organic ligand is (1-3): 1, the volume ratio of the absolute ethyl alcohol to the deionized water is (1-5): 1.
further, a method for preparing a self-supporting electrode of a urea fuel cell, the method further comprising:
3) And obtaining the heterojunction deposited foam nickel-loaded metal-organic frame electrode by electrodeposition on the obtained foam nickel-loaded metal-organic frame.
Further, the method for preparing the heterojunction deposited foam nickel-loaded metal-organic frame electrode by electrodeposition on the prepared foam nickel-loaded metal-organic frame specifically comprises the following steps: electrodepositing an electrolyte onto a nickel foam supported metal-organic frame to form a heterojunction deposited nickel foam supported metal-organic frame electrode; the electrolyte is a metal salt solution or a metal salt-phosphate mixed solution or a metal salt-sulfate mixed solution.
Further, when the electrolyte is a metal salt solution, the foam nickel-loaded metal-organic frame is used as a working electrode, the platinum sheet is used as a counter electrode, the deposition voltage is 2V-10V, and the deposition time is 1 min-10 min; the metal salt solution is a solution formed by one or more of ferrous chloride, cobalt chloride, nickel chloride and copper chloride; the concentration of the metal salt in the metal salt solution is 0.01mol/L to 0.60 mol/L.
Further, when the electrolyte is a metal salt-phosphate mixed solution, the foam nickel-loaded metal-organic frame is used as a working electrode, the platinum sheet is used as a counter electrode, the solvent of the electrolyte is a mixed solvent of water and absolute ethyl alcohol, and a cyclic voltammetry is adopted to perform CV (constant velocity) circulation for a plurality of times within a certain deposition voltage range at a certain voltage change speed, so that the foam nickel-loaded copper-organic frame electrode deposited by the phosphide quantum dots is prepared; the metal salt-phosphate mixed solution is a mixed solution formed by one or more of ferrous chloride, cobalt chloride, nickel chloride and cupric chloride and one or more of potassium hydrogen phosphate, calcium hydrogen phosphate and sodium hypophosphite;
when the electrolyte is a metal salt-sulfate mixed solution, taking a foam nickel-loaded metal-organic frame as a working electrode, taking a platinum sheet as a counter electrode, taking a solvent of the electrolyte as a mixed solvent of water and absolute ethyl alcohol, and performing CV (constant voltage) circulation for a plurality of times within a certain deposition voltage range at a certain voltage change speed by adopting a cyclic voltammetry method to prepare the foam nickel-loaded metal-organic frame electrode deposited by sulfide quantum dots; the metal salt-sulfate mixed solution is a mixed solution formed by one or more of ferrous chloride, cobalt chloride, nickel chloride and copper chloride and one or more of sodium sulfate, sodium sulfide and thiourea.
The invention has the beneficial effects that:
1) According to the invention, through adjusting the microstructure of the organic framework and constructing the heterojunction, different heterojunction structures and multiple synergistic effects of the metal-organic framework are realized, the local electronic structure and the conductivity of the surface of the metal-organic framework electrocatalyst are regulated and controlled, the organic framework-based urea oxidation reaction electrocatalyst material with excellent performance is obtained, and the requirements of a high-efficiency direct urea fuel cell can be met;
2) The preparation method has the advantages of simple and controllable process, mild condition, low cost and the like, and is suitable for industrial production;
3) The self-supporting electrode of the urea fuel cell prepared by the invention has high-efficiency electrocatalytic oxygen evolution, urea oxidation activity and excellent cycle stability, and can be used as an effective anode material for urea oxidation in the urea fuel cell to realize high-efficiency energy conversion.
Drawings
Fig. 1 is a transmission electron microscope image of an iron quantum dot deposited cobalt-iron-organic frame loaded with foam nickel on an iron quantum dot deposited foam nickel loaded cobalt-iron-organic frame electrode prepared in example 1 of the present invention.
FIG. 2 is a LSV plot of the iron-deposited foam nickel-supported cobalt-iron-organic frame electrode Fe@CoFe-MOF/NF in a 1.0mol/L potassium hydroxide solution prepared in example 1 of the present invention.
FIG. 3 is a LSV graph of a foam nickel-loaded cobalt-iron-organic frame electrode Fe@CoFe-MOF/NF in a mixed solution of potassium hydroxide and urea for iron quantum dot deposition prepared in example 1 of the present invention.
FIG. 4 is a scanning electron microscope image of Cu-MOF/NF and FeNi@Cu-MOF/NF prepared in example 2 of the present invention.
FIG. 5 is a transmission electron microscope image of FeNi@Cu-MOF in FeNi@Cu-MOF/NF prepared in example 2 of the present invention.
FIG. 6 is an X-ray diffraction pattern of Cu-MOF/NF and FeNi@Cu-MOF/NF prepared in example 2 of the present invention.
FIG. 7 is a LSV graph of the Cu-MOF/NF and FeNi@Cu-MOF/NF electrodes prepared in example 2 of the present invention in 1.0mol/L potassium hydroxide solution.
FIG. 8 is a graph showing the LSV of the FeNi@Cu-MOF/NF electrode prepared in example 2 of the present invention in a mixed solution of 1.0 mol/L+0.33 mol/L potassium hydroxide/urea.
FIG. 9 is a graph showing i-t of FeNi@Cu-MOF/NF electrodes prepared in example 2 of the present invention in a 1.0 mol/L+0.33 mol/L potassium hydroxide/urea mixed solution.
FIG. 10 is a graph showing the open circuit voltage results of the direct urea fuel cell assembled from the Cu-MOF/NF and FeNi@Cu-MOF/NF electrodes prepared in example 2 of the present invention.
FIG. 11 is a graph of open circuit voltage and maximum power density results for an FeNi@Cu-MOF/NF electrode assembly prepared in example 2 of the present invention into a direct urea fuel cell.
Detailed Description
A self-supporting electrode of urea fuel cell structurally comprises foam nickel and a metal-organic frame; the metal-organic framework is loaded on the surface of the foam nickel to form the foam nickel-loaded metal-organic framework.
The self-supporting electrode of the urea fuel cell also comprises a heterojunction, wherein the heterojunction is deposited on the surface of the metal-organic framework to form a heterojunction deposited foam Nickel (NF) supported metal-organic framework (MOF) electrode.
The foam nickel plays a self-supporting role.
The heterojunction is a metal (M) quantum dot or phosphide (M) x P) Quantum dots or sulfides (M x S) quantum dots, m= Fe, co, ni, cu; the metal quantum dots are one or more of iron (Fe) quantum dots, cobalt (Co) quantum dots, nickel (Ni) quantum dots and copper (Cu) quantum dots; the phosphide quantum dots are one or more of iron phosphide quantum dots, cobalt phosphide quantum dots, nickel phosphide quantum dots and copper phosphide quantum dots; the sulfide quantum dots are one or more of iron sulfide quantum dots, cobalt sulfide quantum dots, nickel sulfide quantum dots and copper sulfide quantum dots.
The metal in the metal-organic framework is one or more of iron (Fe), cobalt (Co), nickel (Ni) and copper (Cu).
The metal-organic frames are in the shape of two-dimensional nano-sheets, and a plurality of two-dimensional nano-sheet metal-organic frames are covered on the surface of the foam nickel to form a densely arranged array structure; the length of the two-dimensional nano sheet metal-organic framework is 300 nm-600 nm, and the thickness of the two-dimensional nano sheet metal-organic framework is 5 nm-10 nm.
The particle size of the metal quantum dot, the phosphide quantum dot and the sulfide quantum dot in the heterojunction is 2-10 nm, and the mass ratio of the heterojunction in the heterojunction deposited foam nickel-loaded metal-organic frame electrode is 2 wt% -10 wt%.
A method of making a self-supporting electrode for a urea fuel cell, the method comprising the steps of:
1) Dispersing foam nickel, metal salt and organic ligand in absolute ethyl alcohol and deionized water, carrying out ultrasonic and magnetic stirring to obtain a uniform mixed solution;
2) Transferring the mixed solution into a hydrothermal reaction kettle, reacting at a constant temperature of 100-180 ℃ for 12 h-48 h, centrifuging, cleaning and drying to obtain a foam nickel-loaded metal-organic frame; the foam nickel-loaded metal-organic frame prepared by the step can be directly used as an electrode, namely the foam nickel-loaded metal-organic frame electrode.
Dispersing foam nickel, metal salt and organic ligand in absolute ethyl alcohol and deionized water, carrying out ultrasonic and magnetic stirring to obtain a uniform mixed solution, wherein the method specifically comprises the following steps of:
1-1) dispersing metal salt and an organic ligand in a mixed solution of absolute ethyl alcohol and deionized water, and obtaining a uniform solution A through ultrasonic dispersion and magnetic stirring;
1-2) placing the cleaned foam nickel in the solution A, and carrying out ultrasonic treatment to obtain a uniform mixed solution.
The metal salt in the step 1) is one or more of ferrous chloride, cobalt chloride, nickel nitrate, copper acetate and tungsten chloride; the organic ligand is one or more of naphthalene dicarboxylic acid dipotassium salt and terephthalic acid.
The concentration of metal salt in the mixed solution obtained in the step 1) is 5-15 mmol/L, and the concentration of organic ligand is 5-15 mmol/L; the molar ratio of the metal salt to the organic ligand is (1-3): 1, the volume ratio of the absolute ethyl alcohol to the deionized water is (1-5): 1.
in the preparation method, the mixed solution is transferred to a hydrothermal reaction kettle in the step 2) to carry out hydrothermal reaction, and the metal-organic framework is gathered on the surface of the foam nickel and is connected with the foam nickel, so that a structure which takes the foam nickel as a substrate and extends outwards from the surface of the foam nickel is formed.
A method of making a self-supporting electrode for a urea fuel cell, the method further comprising the steps of:
3) And 2) obtaining the heterojunction deposited foam nickel-loaded metal-organic frame electrode on the foam nickel-loaded metal-organic frame obtained in the step 2) through electrodeposition.
The foam nickel-loaded metal-organic frame electrode deposited by heterojunction is obtained by electrodeposition on the foam nickel-loaded metal-organic frame obtained in the step 2), and specifically comprises the following steps: electrodepositing an electrolyte onto a nickel foam supported metal-organic frame to form a heterojunction deposited nickel foam supported metal-organic frame electrode; the electrolyte is preferably a metal salt solution or a metal salt-phosphate mixed solution or a metal salt-sulfate mixed solution.
When the electrolyte is a metal salt solution, taking the foam nickel-loaded metal-organic frame as a cathode, taking a platinum sheet as an anode, wherein the deposition voltage is preferably 2-10V, and the deposition time is preferably 1-10 min; the metal salt solution is a solution formed by any one or more of ferrous chloride, cobalt chloride, nickel chloride and copper chloride; the concentration of the metal salt in the metal salt solution is preferably 0.01mol/L to 0.60 mol/L.
When the electrolyte is a metal salt-phosphate mixed solution, taking a foam nickel-loaded metal-organic frame as a working electrode, taking a platinum sheet as a counter electrode, taking a solvent of the electrolyte as a mixed solvent of water and absolute ethyl alcohol, wherein the volume ratio of the water to the ethyl alcohol is preferably 1:1, and carrying out CV (Cyclic Voltammetry) cycles at a deposition voltage range of-1.2V to 0.2V for 5 mV/s by adopting a cyclic voltammetry method to prepare the foam nickel-loaded copper-organic frame electrode deposited by phosphide quantum dots; the metal salt-phosphate mixed solution is a mixed solution formed by any one or a plurality of ferrous chloride, cobalt chloride, nickel chloride and copper chloride and any one or a plurality of potassium hydrogen phosphate, calcium hydrogen phosphate and sodium hypophosphite.
When the electrolyte is a metal salt-sulfate mixed solution, taking the foam nickel-loaded metal-organic frame as a working electrode, taking a platinum sheet as a counter electrode, taking a solvent of the electrolyte as a mixed solvent of water and absolute ethyl alcohol, wherein the volume ratio of the water to the ethyl alcohol is preferably 1:1, and carrying out CV (Cyclic Voltammetry) cycles at a deposition voltage range of-1.2V to 0.2V for 5 mV/s by adopting a cyclic voltammetry method to prepare the foam nickel-loaded metal-organic frame electrode deposited by sulfide quantum dots; the metal salt-sulfate mixed solution is a mixed solution formed by any one or a plurality of ferrous chloride, cobalt chloride, nickel chloride and copper chloride and any one or a plurality of sodium sulfate, sodium sulfide and thiourea.
The heterojunction deposited foam nickel-loaded metal-organic frame electrode obtained in the step 3) is specifically a metal quantum dot deposited foam nickel-loaded metal-organic frame electrode or a phosphide quantum dot deposited foam nickel-loaded metal-organic frame electrode or a sulfide quantum dot deposited foam nickel-loaded metal-organic frame electrode; when the electrolyte is a metal salt solution, the foam nickel-loaded metal-organic frame electrode deposited by the metal quantum dots is obtained; when the electrolyte is a metal salt-phosphate mixed solution, the foam nickel-loaded metal-organic frame electrode deposited by phosphide quantum dots is obtained; the nickel foam loaded metal-organic frame electrode deposited by sulfide quantum dots is obtained when metal salt-sulfate mixed solution is used.
The heterojunction deposited foam nickel in the metal-organic frame electrode has a self-supporting function, the shape of a single metal-organic frame is two-dimensional nano-sheet-shaped, and a plurality of two-dimensional nano-sheet-shaped metal-organic frames are distributed on the surface of the foam nickel to form a densely arranged array structure; the length of the single two-dimensional nano sheet metal-organic frame is 300 nm-600 nm, the thickness of the two-dimensional nano sheet metal-organic frame is 5 nm-10 nm, and the heterojunction is deposited on the surface of the metal-organic frame.
The invention is further illustrated below with reference to examples.
Example 1
A self-supporting electrode for a urea fuel cell, comprising the steps of:
dispersing 0.12 mmol of cobalt chloride and 0.08 mmol of dipotassium naphthalene dicarboxylate in a mixed solution of 10 ml of absolute ethyl alcohol and deionized water, wherein the volume ratio of the absolute ethyl alcohol to the deionized water is 4:1, and performing ultrasonic dispersion and normal-temperature magnetic stirring treatment to obtain a uniform solution A; then placing the cleaned foam nickel in the solution A, and performing ultrasonic treatment for 30 min to obtain a uniformly mixed solution B; then transferring the solution B into a hydrothermal reaction kettle, reacting at a constant temperature of 180 ℃ for 20 h, centrifuging, cleaning and drying to prepare the foamed nickel-supported cobalt-organic frame electrode (Co-MOF/NF).
Placing the obtained foam nickel-loaded cobalt-organic frame (Co-MOF/NF) electrode serving as a cathode, a platinum sheet serving as an anode into an electrolytic cell, wherein electrolyte in the electrolytic cell is ferrous chloride solution, the concentration of ferrous chloride in the electrolyte is 0.01-0.60 mol/L, the deposition voltage is 2V-10V, the deposition time is 1-10 min, and part of Fe and Co in Co-MOF are subjected to displacement reaction during deposition, so that the foam nickel-loaded cobalt-iron-organic frame electrode (Fe@CoFe-MOF/NF) deposited by the iron quantum dots is finally obtained.
The electrocatalytic oxygen evolution and urea oxidation reaction test method is as follows:
using an electrochemical workstation, adopting a three-electrode system, and testing electrocatalytic oxygen evolution and urea oxidation performance of the electrode in an alkaline electrolyte; the test electrolyte used for the electrocatalytic oxygen evolution of the test electrode is a 1.0mol/L potassium hydroxide solution; the test electrolyte used for the urea oxidation reaction of the test electrode is a mixed solution of potassium hydroxide and urea (1. M +0.33M potassium hydroxide/urea mixed solution), wherein the concentration of potassium hydroxide in the mixed solution of potassium hydroxide and urea is 1.0mol/L, and the concentration of urea is 0.33 mol/L; the prepared foam nickel-loaded cobalt-iron-organic frame electrode deposited by the iron quantum dots is used as a working electrode, a platinum sheet is used as a counter electrode, and a mercury oxide electrode is used as a reference electrode; the test conditions are that the linear volt-ampere scanning mode test is carried out at the speed of 5 mV/s; before the electrochemical test, more than 10 CVs were performed (Cyclic Voltammetry,cyclic voltammetry Method of) Or LSV (linear sweep voltammetry ) scan until the curve stabilizes; none of the data from the test was IRCompensation treatment; meanwhile, in the electrochemical test, 10 mA cm was recorded -2 The i-t curve at current density was used to test the urea oxidation stability of the prepared electrode.
The performance of the direct urea fuel cell is tested by adopting constant-current charging and discharging modes under different current densities; the prepared foam nickel-loaded cobalt-iron-organic frame electrode deposited by the iron quantum dots is used as an anode, and a platinum sheet is used as a cathode; the anolyte is a mixed solution of potassium hydroxide and urea, the concentration of the potassium hydroxide in the mixed solution of the potassium hydroxide and the urea is 1.0mol/L, and the concentration of the urea is 0.33 mol/L; the catholyte is a mixed solution of sulfuric acid and hydrogen peroxide, the concentration of sulfuric acid in the mixed solution of sulfuric acid and hydrogen peroxide is 2.0 mol/L, and the concentration of hydrogen peroxide is 2.0 mol/L.
Example 2
Dispersing 0.08 mmol of copper acetate and 0.08 mmol of terephthalic acid in a mixed solution of 10 ml of absolute ethyl alcohol and deionized water, wherein the volume ratio of the absolute ethyl alcohol to the deionized water is 4:1, and performing ultrasonic dispersion and normal-temperature magnetic stirring treatment to obtain a uniform solution A; then placing the cleaned foam nickel in the solution A, and performing ultrasonic treatment for 30 min to obtain a uniformly mixed solution B; then transferring the solution B into a hydrothermal reaction kettle, reacting at a constant temperature of 180 ℃ for 24 h, centrifuging, cleaning and drying to prepare the foam nickel-loaded copper-organic frame electrode (Cu-MOF/NF).
The obtained foam nickel-loaded copper-organic frame (Cu-MOF/NF) electrode is used as a working electrode, a platinum sheet is used as a counter electrode, the working electrode is placed into four electrolytic cells, electrolyte in the four electrolytic cells is respectively ferrous chloride solution, cobalt chloride solution, nickel chloride solution, mixed solution of ferrous chloride and nickel chloride (the concentration of ferrous chloride and nickel chloride in the mixed solution of ferrous chloride and nickel chloride is 0.02 mol/L), the electrolyte concentration in each electrolytic cell is 0.02 mol/L, the deposition voltage is 4V, the deposition time is 5 min, and the foam nickel-loaded copper-organic frame electrode (Fe@Cu-MOF/NF) deposited by iron quantum dots, the foam nickel-loaded copper-organic frame electrode (Co@Cu-MOF/NF) deposited by cobalt quantum dots, the foam nickel-loaded copper-organic frame electrode (Ni@Cu-MOF/NF) deposited by nickel quantum dots and the foam nickel-loaded copper-organic frame electrode (FeNi@Cu-MOF/NF) deposited by iron quantum dots are respectively prepared.
The foam nickel-loaded copper-organic frame electrode (Fe@Cu-MOF/NF) deposited by the iron quantum dots, the foam nickel-loaded copper-organic frame electrode (Co@Cu-MOF/NF) deposited by the cobalt quantum dots, the foam nickel-loaded copper-organic frame electrode (Ni@Cu-MOF/NF) deposited by the nickel quantum dots and the foam nickel-loaded copper-organic frame electrode (FeNi@Cu-MOF/NF) deposited by the iron nickel quantum dots can be used as self-supporting electrodes of urea fuel cells.
The self-supporting electrode of each urea fuel cell prepared in this example was tested for electrocatalytic oxygen evolution and urea oxidation performance, urea oxidation cycling stability, direct urea fuel cell open circuit voltage and maximum power density under alkaline conditions using the electrocatalytic oxygen evolution and urea oxidation experimental test method described in example 1.
Example 3
Dispersing 0.08 mmol of copper nitrate and 0.08 mmol of terephthalic acid in a mixed solution of 10 ml absolute ethyl alcohol and deionized water, wherein the volume ratio of the absolute ethyl alcohol to the deionized water is 4:1, and performing ultrasonic dispersion and normal-temperature magnetic stirring treatment to obtain a uniform solution A; then placing the cleaned foam nickel in the solution A, and performing ultrasonic treatment for 30 min to obtain a uniformly mixed solution B; then transferring the solution B into a hydrothermal reaction kettle, reacting at a constant temperature of 180 ℃ for 24 h, centrifuging, cleaning and drying to prepare the foam nickel-loaded copper-organic frame electrode (Cu-MOF/NF).
Placing the obtained foam nickel-loaded copper-organic frame electrode (Cu-MOF/NF) serving as a working electrode, a platinum sheet serving as a counter electrode into an electrolytic cell, wherein electrolyte in the electrolytic cell is a mixed solution of cobalt chloride and sodium hypophosphite, solvent of the electrolyte is a mixed solvent of water and absolute ethyl alcohol, the volume ratio of water to ethyl alcohol is 1:1, the concentrations of the cobalt chloride and the sodium hypophosphite in the electrolyte are 0.01mol/L, and performing 8 CV cycles at 5 mV/s in a voltage range of-1.2V to 0.2V by adopting a cyclic voltammetry to prepare the foam nickel-loaded copper-organic frame electrode (Co) deposited by cobalt phosphide quantum dots x P@Cu-MOF/NF), the foamed nickel-loaded copper-organic frame electrode deposited by cobalt phosphide quantum dots can be used as a self-supporting electrode of a urea fuel cell.
The electrocatalytic oxygen evolution and urea oxidation performance of the foamed nickel-supported copper-organic frame electrode deposited by the cobalt phosphide quantum dots prepared in the embodiment is tested by adopting the electrocatalytic oxygen evolution and urea oxidation reaction test method in the embodiment 1 under an alkaline condition.
Example 4
Dispersing 0.08 mmol of copper nitrate and 0.08 mmol of terephthalic acid in a mixed solution of 10 ml absolute ethyl alcohol and deionized water, wherein the volume ratio of the absolute ethyl alcohol to the deionized water is 4:1, and performing ultrasonic dispersion and normal-temperature magnetic stirring treatment to obtain a uniform solution A; then placing the cleaned foam nickel in the solution A, and performing ultrasonic treatment for 30 min to obtain a uniformly mixed solution B; then transferring the solution B into a hydrothermal reaction kettle, reacting at a constant temperature of 180 ℃ for 24 h, centrifuging, cleaning and drying to prepare the foam nickel-loaded copper-organic frame electrode (Cu-MOF/NF) electrode.
Placing the obtained foam nickel-loaded copper-organic frame electrode (Cu-MOF/NF) serving as a working electrode, a platinum sheet serving as a counter electrode into an electrolytic cell, wherein electrolyte in the electrolytic cell is a mixed solution of cobalt chloride and sodium sulfide, solvent of the electrolyte is a mixed solvent of water and absolute ethyl alcohol, the volume ratio of water to ethyl alcohol is 1:1, the concentrations of the cobalt chloride and the sodium sulfide in the electrolyte are 0.01mol/L, and performing 8 CV cycles at 5 mV/s in a voltage range of-1.2V to 0.2V by adopting a cyclic voltammetry to prepare the foam nickel-loaded copper-organic frame electrode (Co) deposited by cobalt sulfide quantum dots x s@cu-MOF/NF), the nickel-foam-loaded copper-organic frame electrode deposited by cobalt sulfide quantum dots can be used as a self-supporting electrode for a urea fuel cell.
The electrocatalytic oxygen evolution and urea oxidation experimental test method of the embodiment 1 is adopted to test the electrocatalytic oxygen evolution and urea oxidation performance of the foamed nickel-supported copper-organic frame electrode deposited by the cobalt sulfide quantum dots prepared in the embodiment under alkaline conditions.
FIG. 1 is a transmission electron microscope image of an iron quantum dot deposited cobalt-iron-organic frame carried by foam nickel on an iron quantum dot deposited foam nickel-carried cobalt-iron-organic frame electrode prepared in example 1 of the present invention; as can be seen from a transmission electron microscope image, the cobalt iron-organic frame loaded on the foam nickel presents a two-dimensional nano sheet shape, the diameter of the two-dimensional nano sheet-shaped metal-organic frame is about 300 nm-600 nm, iron quantum dots (part of iron quantum dots are positioned at white circles in the attached drawing 1) with the size of about 5nm are uniformly distributed on the surface of the two-dimensional nano sheet-shaped metal-organic frame, the stripe spacing is 2.02 a, the cobalt iron-organic frame loaded on the foam nickel corresponds to a (110) crystal face of iron, the cobalt iron-organic frame (Fe@CoFe-MOF) deposited by the iron quantum dots can be seen, and the cobalt iron-organic frame deposited by the iron quantum dots and the foam nickel form an iron quantum dot deposited foam nickel loaded cobalt iron-organic frame electrode (Fe@CoFe-MOF/NF).
FIG. 2 is a LSV graph of a foam nickel-loaded cobalt-iron-organic frame electrode Fe@CoFe-MOF/NF deposited with iron quantum dots prepared in example 1 of the present invention in a 1.0mol/L potassium hydroxide solution using the electrocatalytic oxygen evolution test method described in example 1; as seen in FIG. 2, fe@CoFe-MOF/NF has excellent electrocatalytic oxygen evolution activity at a current density of 10 mA cm -2 The overpotential at this time was only 251 mV.
FIG. 3 is a graph of LSV obtained by the method for testing the oxidation reaction of urea described in example 1 in a mixed solution of potassium hydroxide and urea (the concentration of potassium hydroxide in the mixed solution of potassium hydroxide and urea is 1.0mol/L, and the concentration of urea is 0.33 mol/L) for a foamed nickel-loaded cobalt-iron-organic frame electrode Fe@CoFe-MOF/NF deposited with iron quantum dots prepared in example 1 of the present invention; as seen in FIG. 3, fe@CoFe-MOF/NF has excellent electrocatalytic urea oxidation activity at a current density of 10 mA cm -2 The voltage at this time was only 1.36V (vs. RHE).
FIG. 4 is a scanning electron microscope image of Cu-MOF/NF and FeNi@Cu-MOF/NF prepared in example 2 of the present invention; from fig. 4, it is found that the copper-organic frameworks (Cu-MOFs) on the surface of the nickel foam exhibit two-dimensional nano-platelet-shaped copper-organic frameworks (a, b in fig. 4) distributed in an array, each having a diameter of about 300nm to 600 nm; after electrochemical deposition of metal quantum dots, two-dimensional nano-sheet FeNi@Cu-MOF is formed, and the roughness of the nano-sheet surface is increased (c and d in the attached figure 4), which shows that the iron-nickel quantum dots (FeNi) are uniformly covered on the Cu-MOF nano-sheet surface.
FIG. 5 is a transmission electron microscope image of FeNi@Cu-MOF in FeNi@Cu-MOF/NF prepared in example 2 of the invention; as can be seen from the transmission electron microscope, the FeNi@Cu-MOF presents a two-dimensional nano sheet structure, and the surface of a two-dimensional nano sheet metal-organic framework (Cu-MOF) is provided with iron-nickel alloy quantum dots (FeNi) with the size of about 5nm, wherein the white circles in the figure 5 are part of the iron-nickel alloy quantum dots.
FIG. 6 is an X-ray diffraction pattern of Cu-MOF/NF and FeNi@Cu-MOF/NF prepared in example 2 of the present invention, from which it was found that the X-ray diffraction patterns of Cu-MOF/NF and FeNi@Cu-MOF/NF were similar, and both had diffraction peaks of Cu-MOF; a new diffraction peak is observed in the X-ray diffraction spectrum of FeNi@Cu-MOF/NF, and corresponds to a FeNi crystal face, which shows that FeNi nano particles are uniformly deposited on the surface of the Cu-MOF nano sheet by an electrochemical deposition method.
FIG. 7 is a graph of LSV obtained in 1.0mol/L potassium hydroxide solution using the electrocatalytic oxygen evolution test method described in example 1 for Cu-MOF/NF and FeNi@Cu-MOF/NF electrodes prepared in example 2 of the present invention; as seen in FIG. 7, feNi@Cu-MOF/NF had more excellent electrocatalytic oxygen evolution activity than Cu-MOF/NF, at a current density of 10 mA cm -2 The overpotential at this time is only 256 mV.
FIG. 8 is a graph of LSV obtained in a mixed solution of 1. M +0.33M potassium hydroxide/urea in a Cu-MOF/NF and FeNi@Cu-MOF/NF electrode prepared in example 2 of the present invention using the urea oxidation test method described in example 1; as seen in FIG. 8, feNi@Cu-MOF/NF had more excellent electrocatalytic urea oxidation activity than Cu-MOF/NF, at a current density of 10 mA cm -2 The voltage at this time was only 1.39V (vs. RHE).
FIG. 9 is a graph of i-t in a 1. M +0.33M potassium hydroxide/urea mixture for an FeNi@Cu-MOF/NF electrode prepared in example 2 of the present invention; as can be seen from FIG. 9, feNi@Cu-MOF/NF electrodeAt 10 mA cm -2 Under the condition, at least the stable operation 50 and h can be realized.
FIG. 10 is a graph showing the open circuit voltage results of a direct urea fuel cell assembled from Cu-MOF/NF and FeNi@Cu-MOF/NF electrodes prepared in example 2 of the present invention; FIG. 11 is a graph showing the open circuit voltage and maximum power density results for an FeNi@Cu-MOF/NF electrode assembly prepared in example 2 of the present invention into a direct urea fuel cell; as can be seen from fig. 10, the FeNi@Cu-MOF/NF electrode is used as an anode, the platinum sheet is used as a cathode, and a two-electrode constant-current charge-discharge mode is adopted for testing, so that the open-circuit voltage of the direct urea fuel cell is 0.85V; as can be seen from FIG. 11, the FeNi@Cu-MOF/NF electrode was assembled into a direct urea fuel cell with a current density of 40 mA cm -2 The maximum power density is 23.6 mW cm -2 。
Table 1 shows electrocatalytic oxygen evolution and urea oxidation performance data for the self-supporting electrodes of various urea fuel cells prepared in examples 1-2 of the present invention.
Therefore, the self-supporting electrode of the urea fuel cell prepared by the invention shows high-efficiency electrocatalytic oxygen evolution and urea oxidation activity in alkaline environment, and is an effective anode material for urea oxidation in the urea fuel cell.
Claims (10)
1. A self-supporting electrode of urea fuel cell is characterized by comprising foam nickel and a metal-organic frame; the metal-organic framework is loaded on the surface of the foam nickel to form the foam nickel-loaded metal-organic framework.
2. A self-supporting electrode for a urea fuel cell as claimed in claim 1, further comprising a heterojunction deposited on the surface of the metal-organic framework to form a heterojunction deposited foam nickel-loaded metal-organic framework electrode; the heterojunction is a metal quantum dot or a phosphide quantum dot or a sulfide quantum dot.
3. The self-supporting electrode of a urea fuel cell according to claim 2, characterized in that the metal quantum dot is one or more of iron quantum dot, cobalt quantum dot, nickel quantum dot and copper quantum dot; the phosphide quantum dots are one or more of iron phosphide quantum dots, cobalt phosphide quantum dots, nickel phosphide quantum dots and copper phosphide quantum dots; the sulfide quantum dots are one or more of iron sulfide quantum dots, cobalt sulfide quantum dots, nickel sulfide quantum dots and copper sulfide quantum dots.
4. A self-supporting electrode for a urea fuel cell according to claim 2, characterized in that the metal in the metal-organic framework comprises one or several of iron, cobalt, nickel, copper; the metal-organic frameworks are in the shape of two-dimensional nano-sheets, and a plurality of two-dimensional nano-sheet metal-organic frameworks are distributed on the surface of the foam nickel to form a densely arranged array structure; the length of the two-dimensional nano sheet metal-organic frame is 300 nm-600 nm, and the thickness of the two-dimensional nano sheet metal-organic frame is 5 nm-10 nm; the particle size of the metal quantum dot, the phosphide quantum dot and the sulfide quantum dot in the heterojunction is 2-10 nm, and the mass ratio of the heterojunction in the heterojunction deposited foam nickel-loaded metal-organic frame electrode is 2 wt% -10 wt%.
5. A preparation method of a self-supporting electrode of a urea fuel cell is characterized by comprising the following steps:
1) Dispersing foam nickel, metal salt and organic ligand in absolute ethyl alcohol and deionized water, carrying out ultrasonic treatment and stirring to obtain a uniform mixed solution;
2) Transferring the mixed solution into a hydrothermal reaction kettle, reacting for 12-h-48 h at the constant temperature of 100-180 ℃, centrifuging, cleaning and drying to obtain the foam nickel-loaded metal-organic framework.
6. The method for preparing a self-supporting electrode of a urea fuel cell according to claim 5, wherein the method comprises dispersing foam nickel, metal salt and organic ligand in absolute ethanol and deionized water, and performing ultrasonic treatment and stirring to obtain a uniform mixed solution, and specifically comprises the following steps:
1-1) dispersing metal salt and an organic ligand in a mixed solution of absolute ethyl alcohol and deionized water, and obtaining a uniform solution A through ultrasonic dispersion and magnetic stirring;
1-2) placing the cleaned foam nickel in the solution A, and performing ultrasonic treatment to obtain a uniform mixed solution;
the metal salt comprises one or more of ferrous chloride, cobalt chloride, nickel nitrate, copper acetate and tungsten chloride; the organic ligand comprises one or more of naphthalene dicarboxylic acid dipotassium salt and terephthalic acid; the concentration of metal salt in the mixed solution is 5-15 mmol/L, and the concentration of organic ligand is 5-15 mmol/L; the molar ratio of the metal salt to the organic ligand is (1-3): 1, the volume ratio of the absolute ethyl alcohol to the deionized water is (1-5): 1.
7. the method for producing a self-supporting electrode for a urea fuel cell according to claim 5 or 6, characterized by further comprising:
3) And obtaining the heterojunction deposited foam nickel-loaded metal-organic frame electrode by electrodeposition on the obtained foam nickel-loaded metal-organic frame.
8. The method for preparing a self-supporting electrode of a urea fuel cell according to claim 7, characterized in that said method comprises the steps of obtaining a heterojunction deposited foam nickel-supported metal-organic frame electrode by electrodeposition on the obtained foam nickel-supported metal-organic frame, comprising: electrodepositing an electrolyte onto a nickel foam supported metal-organic frame to form a heterojunction deposited nickel foam supported metal-organic frame electrode; the electrolyte is a metal salt solution or a metal salt-phosphate mixed solution or a metal salt-sulfate mixed solution.
9. The method for preparing a self-supporting electrode of a urea fuel cell according to claim 8, wherein when the electrolyte is a metal salt solution, a nickel foam-loaded metal-organic frame is used as a working electrode, a platinum sheet is used as a counter electrode, the deposition voltage is 2V-10V, and the deposition time is 1 min-10 min; the metal salt solution is a solution formed by one or more of ferrous chloride, cobalt chloride, nickel chloride and copper chloride; the concentration of the metal salt in the metal salt solution is 0.01mol/L to 0.60 mol/L.
10. The preparation method of the self-supporting electrode of the urea fuel cell according to claim 9, wherein when the electrolyte is a metal salt-phosphate mixed solution, a foam nickel-loaded metal-organic frame is used as a working electrode, a platinum sheet is used as a counter electrode, a solvent of the electrolyte is a mixed solvent of water and absolute ethyl alcohol, and a cyclic voltammetry is adopted to perform CV (constant velocity) circulation for a plurality of times within a certain deposition voltage range at a certain voltage change speed, so that a foam nickel-loaded copper-organic frame electrode deposited by phosphide quantum dots is prepared; the metal salt-phosphate mixed solution is a mixed solution formed by one or more of ferrous chloride, cobalt chloride, nickel chloride and cupric chloride and one or more of potassium hydrogen phosphate, calcium hydrogen phosphate and sodium hypophosphite;
when the electrolyte is a metal salt-sulfate mixed solution, taking a foam nickel-loaded metal-organic frame as a working electrode, taking a platinum sheet as a counter electrode, taking a solvent of the electrolyte as a mixed solvent of water and absolute ethyl alcohol, and performing CV (constant voltage) circulation for a plurality of times within a certain deposition voltage range at a certain voltage change speed by adopting a cyclic voltammetry method to prepare the foam nickel-loaded metal-organic frame electrode deposited by sulfide quantum dots; the metal salt-sulfate mixed solution is a mixed solution formed by one or more of ferrous chloride, cobalt chloride, nickel chloride and copper chloride and one or more of sodium sulfate, sodium sulfide and thiourea.
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