CN117004983A - Cobalt-iron bimetal organic hybridization electrode material and preparation and application thereof - Google Patents
Cobalt-iron bimetal organic hybridization electrode material and preparation and application thereof Download PDFInfo
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- CN117004983A CN117004983A CN202310855735.1A CN202310855735A CN117004983A CN 117004983 A CN117004983 A CN 117004983A CN 202310855735 A CN202310855735 A CN 202310855735A CN 117004983 A CN117004983 A CN 117004983A
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- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000007772 electrode material Substances 0.000 title claims abstract description 69
- 238000009396 hybridization Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 107
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 54
- 229910052759 nickel Inorganic materials 0.000 claims description 54
- 239000006260 foam Substances 0.000 claims description 51
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 27
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 26
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 18
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 18
- 239000001509 sodium citrate Substances 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 16
- 239000004202 carbamide Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- -1 amine compound Chemical class 0.000 claims description 15
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 15
- 229920001690 polydopamine Polymers 0.000 claims description 13
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 12
- 150000001868 cobalt Chemical class 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004201 L-cysteine Substances 0.000 claims description 3
- 235000013878 L-cysteine Nutrition 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 18
- 239000001257 hydrogen Substances 0.000 abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 18
- 238000005868 electrolysis reaction Methods 0.000 abstract description 4
- 239000011800 void material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000001075 voltammogram Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010351 charge transfer process Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 208000010110 spontaneous platelet aggregation Diseases 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The application relates to a cobalt-iron bimetal organic hybridization electrode material and preparation and application thereof. The cobalt-iron bimetal organic hybridization electrode material has a large void structure, a high specific surface area, excellent conductivity and stability, and high catalytic activity for producing hydrogen by water electrolysis.
Description
Technical Field
The application relates to the field of catalytic electrode materials, in particular to a cobalt-iron bimetal organic hybrid electrode material, and preparation and application thereof.
Background
With the over development of fossil fuels, global energy scarcity crisis is faced, and therefore, the focus of attention is on finding pollution-free renewable energy sources. Hydrogen is considered to replace one of the most promising new energy sources for fossil fuels. However, the too high electro-catalytic hydrogen evolution overpotential in the process of producing hydrogen by electrolyzing water severely reduces the utilization rate of electric energy and limits the development of the industry of producing hydrogen by electrolyzing water. Therefore, the research and development of the stable and efficient electrocatalytic hydrogen evolution electrode material is of particular importance to the improvement of the electric energy utilization rate of the electrolytic water industry.
At present, the most effective electrocatalytic material for hydrogen evolution reaction is mainly platinum-based material, however, the noble metal material has the defects of high cost, low reserves and the like, and the wide application of the noble metal material is limited. In order to reduce the cost of electrocatalytic materials, the development of non-noble metal electrocatalytic materials has become a research hotspot. The non-noble metal hydrogen evolution catalytic material mainly comprises phosphide, sulfide and alloys thereof based on transition metals such as Mo, W, fe, co, ni. Since the content of Mo and W in the crust (about 0.00011%) is far lower than the content of Fe (6.8%), co (0.003%) and Ni (0.0089%), the development of electrocatalytic hydrogen evolution catalytic materials based on Fe, co and Ni is more beneficial to the large-scale industrialization of electrocatalytic hydrogen evolution technology. In recent years, electrocatalytic hydrogen evolution catalytic materials based on Fe, co and Ni are greatly developed, and catalytic materials with excellent performances are prepared, so that the method plays a good role in promoting industrialization of electrocatalytic hydrogen evolution technology. These catalytic materials mainly include alloys of Fe, co, ni, phosphides, sulfides, etc. In addition, compared with single metal oxide, the conductivity of the core-shell structure or the two hybridized catalytic materials is improved by 1-2 orders of magnitude, the number of metal active sites of the materials is obviously improved, the activity of the water cracking catalytic materials is greatly improved, and the catalytic cost is reduced.
As a novel two-dimensional material, carbides, nitrides and carbonitrides (MXenes) not only have good mechanical properties and large specific surface areas, but also have conductivity and abundant active sites on the basal plane, which play an important role in promoting sustainable energy development. MXnes and composites thereof with multiple elements for electrocatalytic reactions were predicted and synthesized since MXnes was first used for Hydrogen Evolution Reactions (HERs). The diversity of atomic species and arrangements determines that the synthetic MXenes can be designed at the atomic level. The introduction of heteroatoms into the MXenes can result in a single-atom catalyst with excellent electrocatalytic properties. The coupling between the active phase (with its own active site) and the highly conductive mxnes reduces the surface work function, improves the stability of mxnes, avoids platelet aggregation, improves the active site utilization, and thus improves the electrocatalytic activity. The MXene-based hybrids can incorporate both catalytically active sites from the active phase and retain the high conductivity of MXene. In addition, the active phase is loaded on the surface of the MXene, so that the oxidation of the metal layer is slowed down, meanwhile, the negative charge on the surface of the MXene is neutralized, and the aggregation of the sheets is avoided. Metal nanoparticles, oxides, hydroxides, halides, phosphides, carbon materials, etc. can form different types of heterojunctions with MXene, exhibiting good electrocatalytic activity.
The metal organic framework is an important carbon material precursor, and the carbon material generated by the organic matters in the framework at high temperature provides a large number of space sites for in-situ doped metal and plays an important role in uniformly distributing metal particles in the carbon material. Meanwhile, the metal-organic framework derived metal-doped carbon material has a larger specific surface area and excellent catalytic activity. However, the metal organic frame is easy to collapse in the high-temperature (600-800 ℃) preparation process to cause the agglomeration of the generated nano oxide, the product preparation efficiency is low, the conductivity of the metal organic frame is not strong, the metal organic frame cannot be directly used as a catalytic material for water electrolysis, the active center of the metal organic frame is easy to lose efficacy in the catalytic process, and the material stability is poor.
Therefore, if the organic hybridization electrode material containing cobalt and iron bimetallic elements and the preparation method thereof can be provided, the preparation efficiency of the product can be improved, and the electrode material has better conductivity, stability and catalytic activity, thereby being more beneficial to the development of the water electrolysis hydrogen production technology.
Disclosure of Invention
The application aims to provide a cobalt-iron bimetal organic hybridization electrode material, which solves the problems of poor conductivity, easy failure of an active center, poor stability and the like of a metal-organic frame material in the prior art; the second aim is to provide a preparation method of the cobalt-iron bimetal organic hybridization electrode material, which solves the problems of high temperature, high reaction energy consumption, easy collapse of a metal organic frame and the like in the preparation process in the prior art; a third object is to provide an electrochemical device; the fourth object is to provide an electronic device.
In order to achieve the above and related objects, the present application adopts the following technical solutions:
the first aspect of the application provides a cobalt-iron bimetallic organic hybrid electrode material, which comprises a foam nickel substrate, a cobalt-iron bimetallic organic frame growing on the foam nickel substrate and a porous nitrogen-carbon layer coated on the surface of the cobalt-iron bimetallic organic frame, wherein the cobalt-iron bimetallic organic frame comprises a plurality of cobalt-iron bimetallic sulfide nano particles.
The second aspect of the application provides a preparation method of a cobalt-iron bimetallic organic hybrid electrode material, which comprises the following steps:
(1) Dissolving cobalt salt and ferric salt in a solution containing urea and a reducing agent, and stirring to prepare a solution A;
(2) Immersing the pretreated foam nickel in the solution A in the step (1), stirring, adding an amine compound, heating, stirring, washing and drying to obtain a cobalt-iron bimetallic organic precursor;
(3) And (3) placing the cobalt-iron bimetal organic precursor in the step (2) in a tube furnace, adding a sulfur source, calcining and preserving heat in an inert gas atmosphere, and cooling to obtain the cobalt-iron bimetal organic hybridization electrode material.
In some embodiments, the cobalt salt in step (1) comprises at least one of cobalt nitrate, cobalt nitrate hexahydrate, cobalt sulfate, cobalt acetate; the ferric salt comprises at least one of ferric nitrate, ferrous sulfate heptahydrate and ferric nitrate nonahydrate; the reducing agent comprises at least one of sodium borohydride, trisodium citrate, sodium citrate, hydrazine hydrate and ascorbic acid.
In some embodiments, the molar ratio of cobalt salt to iron salt in step (1) is (1-4): (1-3), the mol ratio of the reducing agent to the ferric salt is (1-10): (1-2).
In some embodiments, the amine compound in step (2) comprises at least one of polydopamine, dicyandiamide, polyethylenimine, polyacrylamide.
In some embodiments, the molar mass ratio of amine compound in step (2) to iron salt in step (1) is (1-4): (1-10); and (2) adding amine compounds, and stirring for 1-10 h at 60-120 ℃.
In some embodiments, the sulfur source in step (3) comprises at least one of sodium sulfide, thiourea, sodium persulfate, sodium thiosulfate, thioacetamide, L-cysteine.
In some embodiments, the calcination temperature in step (3) is 300 to 450 ℃ and the calcination time is 1 to 6 hours.
The third aspect of the application provides an electrochemical device comprising a cobalt-iron bimetal organic hybrid electrode material as described above or comprising a cobalt-iron bimetal organic hybrid electrode material prepared by the preparation method of a cobalt-iron bimetal organic hybrid electrode material as described above.
A fourth aspect of the application provides an electronic device comprising an electrochemical apparatus as described above.
The beneficial technical effects of the application are as follows:
(1) The cobalt-iron bimetal organic framework (cobalt-iron bimetal precursor) directly grows on the foam nickel substrate, so that the cost of a synthesis technology can be reduced, the electron transmission between the foam nickel and an active site is promoted, and the catalytic activity and stability of an electrode material are improved. In addition, the amine compound and the cobalt-iron bimetallic ion coordinate, so that the cobalt-iron bimetallic ion is synchronously introduced to the surface of the foam nickel when the amine compound is attached to the foam nickel. In addition, the porous nitrogen-carbon layer is directly carbonized into nitrogen-doped carbon in one step by utilizing amine compounds, and the porous nitrogen-carbon layer is used for coating non-noble metal cobalt-iron bimetallic sulfide nano particles, so that the porous nitrogen-carbon layer has high conductivity and excellent catalytic stability, and simultaneously, the porous nitrogen-carbon layer is favorable for accelerating a liquid phase mass transfer process and a charge transfer process of an electrocatalytic reaction, so that the porous nitrogen-carbon layer has excellent catalytic activity and stability. The porous nitrogen-carbon layer is used for wrapping cobalt-iron bimetallic sulfide nano ions, so that agglomeration of metal nano particles can be effectively prevented, and stability of electrode materials is improved.
(2) In the calcining process, the application carries out sulfuration treatment to lead the cobalt-iron bimetallic ions to be sulfurated to form cobalt-iron bimetallic sulfide nano ions, more oxidation reduction/conversion reactions can occur, and the synergistic effect between the cobalt-iron bimetallic ions is beneficial to the promotion of catalytic performance and cycle stability. In the application, iron, cobalt and nickel are used as transition metals, the electrochemical activity can be improved by adjusting the electronic structure, and the carbonized electrode material is fluffy and porous by utilizing the framework of foam nickel, so that the proton adsorption capacity of the electrode material is improved, and the hydrogen evolution capacity of electrolytic water is further improved. The application also improves the catalysis efficiency of the metal center by introducing non-metal elements such as nitrogen, carbon and sulfur, thereby improving the stability of the electrode material.
(3) The cobalt-iron bimetal organic hybridization electrode material has a large void structure, a high specific surface area and good conductivity, nitrogen atoms are doped in situ to enable the cobalt-iron bimetal sulfide nano particles to generate more catalytic active sites, the effective surface area of the electrode material can be increased, the effective surface area of the porous nitrogen-carbon layer can be increased, electrolyte transfer on the surface of the electrode material is improved, a large number of N-C and M-N-C active centers are formed with carbon and metal nano particles, and the catalytic performance of the electrode material is improved.
(4) The preparation method provided by the application is simple, high in efficiency, low in reaction energy consumption, suitable for large-scale industrial production, and capable of reducing economic cost.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the application as claimed.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application. It is evident that the drawings in the following description are only some embodiments of the present application and that other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art. In the drawings:
FIG. 1 is a graph showing the linear sweep voltammogram of electrode materials of example 1 and comparative examples 1-2 of the present application;
FIG. 2 is a graph showing the stability test results of example 1 of the present application.
Detailed Description
Further advantages and effects of the present application will become readily apparent to those skilled in the art from the disclosure herein, by referring to the accompanying drawings and the preferred embodiments. The application may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present application. It should be understood that the preferred embodiments are presented by way of illustration only and not by way of limitation.
It should be noted that the illustrations provided in the following embodiments merely illustrate the basic concept of the present application by way of illustration, and only the components related to the present application are shown in the drawings and are not drawn according to the number, shape and size of the components in actual implementation, and the form, number and proportion of the components in actual implementation may be arbitrarily changed, and the layout of the components may be more complicated.
The application provides a preparation method of a cobalt-iron bimetal organic hybridization electrode material, which comprises the following steps:
(1) Dissolving cobalt salt and ferric salt in a solution containing urea and a reducing agent, and stirring to prepare a solution A;
(2) Immersing the pretreated foam nickel in the solution A in the step (1), stirring, adding an amine compound, heating, stirring, washing and drying to obtain a cobalt-iron bimetallic organic precursor;
(3) And (3) placing the cobalt-iron bimetal organic precursor in the step (2) in a tube furnace, adding a sulfur source, calcining and preserving heat in an inert gas atmosphere, and cooling to obtain the cobalt-iron bimetal organic hybridization electrode material.
In a specific embodiment, the cobalt salt in step (1) comprises at least one of cobalt nitrate, cobalt nitrate hexahydrate, cobalt sulfate, cobalt acetate; the ferric salt comprises at least one of ferric nitrate, ferrous sulfate heptahydrate and ferric nitrate nonahydrate; the reducing agent comprises at least one of sodium borohydride, trisodium citrate, sodium citrate, hydrazine hydrate and ascorbic acid.
In a specific embodiment, the molar ratio of cobalt salt to iron salt in step (1) is (1-4): (1-3), the mol ratio of the reducing agent to the ferric salt is (1-10): (1-2).
In one embodiment, the mass ratio of cobalt salt to urea in step (1) is 1: (0.5-10)
In a specific embodiment, the amine compound in the step (2) includes at least one of polydopamine, dicyandiamide, polyethylenimine and polyacrylamide.
In one embodiment, the molar mass ratio of the amine compound in step (2) to the iron salt in step (1) is (1-4): (1-10); and (2) adding amine compounds, and stirring for 1-10 h at 60-120 ℃.
In a specific embodiment, the sulfur source in step (3) comprises at least one of sodium sulfide, thiourea, sodium persulfate, sodium thiosulfate, thioacetamide, and L-cysteine.
In a specific embodiment, the calcination temperature in the step (3) is 300-450 ℃ and the calcination time is 1-6 h.
In one embodiment, in the step (3), the mass ratio of the cobalt-iron bimetallic organic precursor to the sulfur source is 1: (5-20).
In one embodiment, the method for pretreating the foam nickel comprises the following steps:
cutting foam nickel into foam nickel sheets with the size of 2cm multiplied by 2cm, placing the foam nickel sheets into a beaker containing 50ml of acetone, sealing the beaker, placing the beaker into an ultrasonic cleaner for ultrasonic treatment, wherein the power of the ultrasonic cleaner is 90W, the ultrasonic treatment time is 30min, and degreasing the foam nickel sheets at the room temperature of 25 ℃. And cleaning the deoiled foam nickel sheet with deionized water for 5 times, then placing the foam nickel sheet which is treated with acetone and washed clean into a beaker containing 50ml of hydrochloric acid with the concentration of 2mol for acidizing treatment, sealing the mouth of the container, and then placing the beaker into an ultrasonic cleaner for ultrasonic treatment, wherein the power of the ultrasonic cleaner is 90W, and the ultrasonic treatment time is 30min. And then taking out the foam nickel sheet after the acidification treatment, washing the foam nickel sheet with deionized water for 5 times, and finally placing the foam nickel sheet after the acidification treatment and washed cleanly into a beaker containing 50ml of absolute ethyl alcohol to remove other impurities. And (3) sealing the beaker, placing the beaker in an ultrasonic cleaner for ultrasonic treatment, wherein the power of the ultrasonic cleaner is 90W, the ultrasonic treatment time is 30min, taking out the foam nickel sheet, cleaning the foam nickel sheet with deionized water for 5 times, placing the foam nickel sheet in a vacuum drying oven, and drying the foam nickel sheet at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying oven is-0.1 MPa, thus obtaining the foam nickel substrate.
Example 1
(1) Dissolving cobalt nitrate and ferric nitrate in a solution containing urea and sodium citrate, and uniformly stirring to prepare a solution A, wherein the molar ratio of the cobalt nitrate to the ferric nitrate is 1:1, the molar ratio of sodium citrate to ferric nitrate is 8:1, the mass ratio of the cobalt nitrate to the urea is 1:0.5;
(2) Immersing the pretreated foam nickel in the solution A, stirring, adding polydopamine, and stirring for 8 hours at 60 ℃, wherein the molar mass ratio of polydopamine to ferric nitrate is 1:2, ultrasonically washing foam nickel by deionized water, and drying the washed foam nickel in a baking oven at 60 ℃ for 8 hours to obtain a cobalt-iron bimetallic organic precursor;
(3) Placing the cobalt-iron bimetallic precursor into a tube furnace, adding thiourea, calcining for 1h at 300 ℃ in a nitrogen gas atmosphere, and preserving heat for 0.5h, wherein the mass ratio of the cobalt-iron bimetallic precursor to the thiourea is 1: and 5, naturally cooling to room temperature to obtain the cobalt-iron bimetal organic hybridization electrode material.
Example 2
(1) Dissolving cobalt nitrate and ferric nitrate in a solution containing urea and sodium citrate, and uniformly stirring to prepare a solution A, wherein the molar ratio of the cobalt nitrate to the ferric nitrate is 1:1.5, the molar ratio of sodium citrate to ferric nitrate is 8:1, the mass ratio of the cobalt nitrate to the urea is 1:1, a step of;
(2) Immersing the pretreated foam nickel in the solution A, stirring, adding polydopamine, and stirring for 7 hours at 70 ℃, wherein the molar mass ratio of polydopamine to ferric nitrate is 1:2.5, ultrasonic washing foam nickel by deionized water, and drying the washed foam nickel in a baking oven at 60 ℃ for 8 hours to obtain a cobalt-iron bimetallic organic precursor;
(3) Placing the cobalt-iron bimetallic precursor into a tube furnace, adding thiourea, calcining for 1h at 350 ℃ in a nitrogen gas atmosphere, and preserving heat for 0.5h, wherein the mass ratio of the cobalt-iron bimetallic precursor to the thiourea is 1: and 6, naturally cooling to room temperature to obtain the cobalt-iron bimetal organic hybridization electrode material.
Example 3
(1) Dissolving cobalt nitrate and ferric nitrate into a solution containing urea and sodium citrate, and uniformly stirring to prepare a solution A, wherein the molar ratio of the cobalt nitrate to the ferric nitrate is 3:2, the molar ratio of sodium citrate to ferric nitrate is 8:1, the mass ratio of the cobalt nitrate to the urea is 1:5, a step of;
(2) Immersing the pretreated foam nickel in the solution A, stirring, adding polydopamine, and stirring for 6 hours at 80 ℃, wherein the molar mass ratio of polydopamine to ferric nitrate is 2:5, ultrasonically washing foam nickel by deionized water, and drying the washed foam nickel in a baking oven at 60 ℃ for 8 hours to obtain a cobalt-iron bimetallic organic precursor;
(3) Placing the cobalt-iron bimetallic precursor into a tube furnace, adding thiourea, calcining for 2 hours at 400 ℃ in a nitrogen gas atmosphere, and preserving heat for 0.5 hour, wherein the mass ratio of the cobalt-iron bimetallic precursor to the thiourea is 1: and 8, naturally cooling to room temperature to obtain the cobalt-iron bimetal organic hybridization electrode material.
Example 4
(1) Dissolving cobalt nitrate and ferric nitrate in a solution containing urea and sodium citrate, and uniformly stirring to prepare a solution A, wherein the molar ratio of the cobalt nitrate to the ferric nitrate is 1:1, the molar ratio of sodium citrate to ferric nitrate is 8:1, the mass ratio of the cobalt nitrate to the urea is 1:0.5;
(2) Immersing the pretreated foam nickel in the solution A, stirring, adding dicyandiamide, and stirring for 6 hours at 60 ℃, wherein the molar mass ratio of the dicyandiamide to the ferric nitrate is 1:2, ultrasonically washing foam nickel by deionized water, and drying the washed foam nickel in a baking oven at 60 ℃ for 8 hours to obtain a cobalt-iron bimetallic organic precursor;
(3) Placing the cobalt-iron bimetallic precursor into a tube furnace, adding thiourea, calcining for 1h at 400 ℃ in a nitrogen gas atmosphere, and preserving heat for 0.5h, wherein the mass ratio of the cobalt-iron bimetallic precursor to the thiourea is 1: and 5, naturally cooling to room temperature to obtain the cobalt-iron bimetal organic hybridization electrode material.
Comparative example 1
(1) Dissolving ferric nitrate in a solution containing urea and sodium citrate, and uniformly stirring to prepare a solution A, wherein the molar ratio of the sodium citrate to the ferric nitrate is 8:1, the mass ratio of ferric nitrate to urea is 1:0.5;
(2) Immersing the pretreated foam nickel in the solution A, stirring, adding polydopamine, and stirring for 8 hours at 60 ℃, wherein the molar mass ratio of polydopamine to ferric nitrate is 1:2, ultrasonically washing foam nickel by deionized water, and drying the washed foam nickel in a baking oven at 60 ℃ for 8 hours to obtain a metal organic precursor;
(3) Placing a metal precursor into a tube furnace, adding thiourea, calcining for 1h at 300 ℃ in a nitrogen gas atmosphere, and preserving heat for 0.5h, wherein the mass ratio of the metal precursor to the thiourea is 1: and 3, naturally cooling to room temperature to obtain the monometal organic hybridization electrode material.
Comparative example 2
(1) Dissolving cobalt nitrate and ferric nitrate in a solution containing urea and sodium citrate, and uniformly stirring to prepare a solution A, wherein the molar ratio of the cobalt nitrate to the ferric nitrate is 1:1, the molar ratio of sodium citrate to ferric nitrate is 8:1, the mass ratio of the cobalt nitrate to the urea is 1:0.5;
(2) Immersing the pretreated foam nickel in the solution A, stirring, adding polyethylene glycol, and stirring for 8 hours at 60 ℃, wherein the molar mass ratio of the polyethylene glycol to the ferric nitrate is 1:2, ultrasonically washing foam nickel by deionized water, and drying the washed foam nickel in a baking oven at 60 ℃ for 8 hours to obtain a cobalt-iron bimetallic organic precursor;
(3) And (3) placing the cobalt-iron bimetallic precursor in a tube furnace, calcining for 1h at 300 ℃ in an argon gas atmosphere, preserving heat for 0.5h, and naturally cooling to room temperature to obtain the cobalt-iron bimetallic organic electrode material.
Performance testing
Activity test: the electrode materials of example 1 and comparative examples 1-2 were respectively subjected to linear sweep voltammograms at a sweep rate of 5mV/s to characterize the hydrogen production activity of the electrode materials by electrolysis of water, and the test results are shown in FIG. 1.
Stability test: the electrode materials of the example 1 and the comparative examples 1-2 are respectively cut into samples to be tested of 1cm multiplied by 2cm to be used as working electrodes by taking a saturated calomel electrode as a reference electrode and a graphite electrode as a counter electrode, each electrode is connected with an electrochemical workstation and stretches into sulfuric acid solution (electrolyte solution) of 0.5mol/L, the working electrode stretches into the liquid level to a depth of 0.5cm, a constant voltage method is used for testing, the testing voltage is-0.3V, the testing time is 12h, and the testing result is shown in figure 2.
Tafel curve: the results of the test of fig. 1 were subjected to tafel curve fitting, and the slope of tafel curves of example 1 and comparative examples 1 to 2 were calculated, respectively, and the calculation results are shown in table 1.
FIG. 1 is a graph showing the linear sweep voltammogram of the electrode materials of example 1 and comparative examples 1-2 of the present application. As can be seen from FIG. 1, when the current density is-50 mA/cm 2 When the overpotential of the cobalt-iron bimetallic organic hybridization electrode material prepared in the example 1 is 190mV, which is far lower than the 315mV overpotential of the single-metal organic hybridization electrode material prepared in the comparative example 1 and the 350mV overpotential of the cobalt-iron bimetallic organic electrode material prepared in the comparative example 2. In addition, the current density of the cobalt-iron bimetallic organic hybrid electrode material in the embodiment 1 of the application is-10 mA/cm 2 The overpotential was only 96mV. This shows that the cobalt-iron bimetallic organic hybrid electrode material prepared by the preparation method has excellent electrocatalytic hydrogen evolution activity, because the cobalt-iron bimetallic precursor is directly grown on the foam nickel substrate, the electron transmission between the foam nickel and the active site is promoted, and the catalytic activity of the electrode material is improved, and the polydopamine is coordinated with cobalt-iron bimetallic ions, so that polydopamine is attachedWhen the cobalt-iron bimetallic ions are adhered to the surface of the foam nickel, the cobalt-iron bimetallic ions are synchronously introduced to the surface of the foam nickel. In addition, the porous nitrogen-carbon layer is favorable for accelerating the liquid phase mass transfer process and the charge transfer process of the electrocatalytic reaction, so that 5 shows excellent catalytic activity.
TABLE 1 Tafil slope tables for electrode materials of example 1 and comparative examples 1-2
| Tafil slope (mV/dec) | |
| Example 1 | 55 |
| Comparative example 1 | 83 |
| Comparative example 2 | 96 |
As can be seen from Table 1, the gradient of the Tafil curve of the cobalt-iron bimetal organic hybridization electrode material in the embodiment 1 of the application is lower than that of the single-metal organic hybridization electrode material in the comparative example 1 and that of the organic electrode material in the comparative example 2, and the comparison of the overpotential and the Tafil curve shows that the hydrogen production kinetic efficiency of the electrolytic water of the cobalt-iron bimetal organic hybridization electrode material prepared by the preparation method of the application is far higher than that of the electrode materials in the comparative example 1 and the comparative example 2.
FIG. 2 is a graph showing the stability test results of example 1 of the present application, and it can be seen from FIG. 2 that the cobalt-iron bimetal organic hybridization electrode material prepared in example 1 of the present application is stable at a current of 4.2mA/cm in a 12-hour test 2 The current density does not change obviously, which indicates that the cobalt-iron bimetal organic hybridization electrode material has excellent cycling stability.
The application also provides a cobalt-iron bimetal organic hybrid electrode material, which comprises a foam nickel substrate, a cobalt-iron bimetal organic frame growing on the foam nickel substrate and a porous nitrogen-carbon layer coated on the surface of the cobalt-iron bimetal organic frame, wherein the cobalt-iron bimetal organic frame comprises a plurality of cobalt-iron bimetal sulfide nano particles.
The application also provides an electrochemical device, which comprises the cobalt-iron bimetal organic hybridization electrode material or the cobalt-iron bimetal organic hybridization electrode material prepared by the preparation method of the cobalt-iron bimetal organic hybridization electrode material.
The application also provides an electronic device comprising an electrochemical apparatus as described above.
The above embodiments are merely illustrative of the principles of the present application and its effectiveness, and are not intended to limit the application. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the application. Accordingly, it is intended that all equivalent modifications and variations of the application be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. The cobalt-iron bimetal organic hybridization electrode material is characterized by comprising a foam nickel substrate, a cobalt-iron bimetal organic frame and a porous nitrogen-carbon layer, wherein the cobalt-iron bimetal organic frame grows on the foam nickel substrate, the porous nitrogen-carbon layer is coated on the surface of the cobalt-iron bimetal organic frame, and the cobalt-iron bimetal organic frame comprises a plurality of cobalt-iron bimetal sulfide nano particles.
2. A method for preparing a cobalt-iron bimetallic organic hybrid electrode material, which is characterized by comprising the following steps:
(1) Dissolving cobalt salt and ferric salt in a solution containing urea and a reducing agent, and stirring to prepare a solution A;
(2) Immersing the pretreated foam nickel in the solution A in the step (1), stirring, adding an amine compound, heating, stirring, washing and drying to obtain a cobalt-iron bimetallic organic precursor;
(3) And (3) placing the cobalt-iron bimetal organic precursor in the step (2) in a tube furnace, adding a sulfur source, calcining and preserving heat in an inert gas atmosphere, and cooling to obtain the cobalt-iron bimetal organic hybridization electrode material.
3. The method for preparing a cobalt-iron bimetallic organic hybrid electrode material according to claim 2, wherein the cobalt salt in the step (1) comprises at least one of cobalt nitrate, cobalt nitrate hexahydrate, cobalt sulfate and cobalt acetate; the ferric salt comprises at least one of ferric nitrate, ferrous sulfate heptahydrate and ferric nitrate nonahydrate; the reducing agent comprises at least one of sodium borohydride, trisodium citrate, sodium citrate, hydrazine hydrate and ascorbic acid.
4. The method for preparing the cobalt-iron bimetallic organic hybrid electrode material according to claim 2, wherein the molar ratio of cobalt salt to iron salt in the step (1) is (1-4): (1-3), the mol ratio of the reducing agent to the ferric salt is (1-10): (1-2).
5. The method for preparing a cobalt-iron bimetallic organic hybrid electrode material according to claim 2, wherein the amine compound in the step (2) comprises at least one of polydopamine, dicyandiamide, polyethyleneimine and polyacrylamide.
6. The method for preparing a cobalt-iron bimetallic organic hybrid electrode material according to claim 2, wherein the molar mass ratio of the amine compound in the step (2) to the iron salt in the step (1) is (1-4): (1-10); and (2) adding amine compounds, and stirring for 1-10 h at 60-120 ℃.
7. The method for preparing a cobalt-iron bimetal organic hybridization electrode material according to claim 2, wherein the sulfur source in the step (3) comprises at least one of sodium sulfide, thiourea, sodium persulfate, sodium thiosulfate, thioacetamide and L-cysteine.
8. The method for preparing a cobalt-iron bimetallic organic hybrid electrode material according to claim 2, wherein the calcining temperature in the step (3) is 300-450 ℃ and the calcining time is 1-6 h.
9. An electrochemical device comprising a cobalt-iron bimetal organic hybrid electrode material according to claim 1 or a cobalt-iron bimetal organic hybrid electrode material prepared by the method for preparing a cobalt-iron bimetal organic hybrid electrode material according to any one of claims 2 to 8.
10. An electronic device comprising the electrochemical device according to claim 9.
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| CN117463342B (en) * | 2023-12-27 | 2024-04-05 | 山东海化集团有限公司 | Preparation method of porous hollow tubular heterojunction catalyst for electrolyzing seawater and oxygen evolution application of porous hollow tubular heterojunction catalyst |
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