CN117089874A - Preparation method and application of self-supporting electrode with nano-super structure - Google Patents
Preparation method and application of self-supporting electrode with nano-super structure Download PDFInfo
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- CN117089874A CN117089874A CN202210521054.7A CN202210521054A CN117089874A CN 117089874 A CN117089874 A CN 117089874A CN 202210521054 A CN202210521054 A CN 202210521054A CN 117089874 A CN117089874 A CN 117089874A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004202 carbamide Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000006260 foam Substances 0.000 claims description 15
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 150000001868 cobalt Chemical class 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000004729 solvothermal method Methods 0.000 claims description 8
- 239000013110 organic ligand Substances 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- -1 organic acid salt Chemical class 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 3
- 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 2
- ZEVWQFWTGHFIDH-UHFFFAOYSA-N 1h-imidazole-4,5-dicarboxylic acid Chemical compound OC(=O)C=1N=CNC=1C(O)=O ZEVWQFWTGHFIDH-UHFFFAOYSA-N 0.000 claims description 2
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 claims description 2
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 2
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 2
- WJJMNDUMQPNECX-UHFFFAOYSA-N Dipicolinic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- MUYSADWCWFFZKR-UHFFFAOYSA-N cinchomeronic acid Chemical compound OC(=O)C1=CC=NC=C1C(O)=O MUYSADWCWFFZKR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 claims description 2
- 239000006262 metallic foam Substances 0.000 claims description 2
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 description 6
- 150000004692 metal hydroxides Chemical class 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002064 nanoplatelet Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 238000002493 microarray Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001075 voltammogram 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Metallurgy (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a preparation method and application of a self-supporting electrode with a nano-super structure, wherein in the preparation process of the electrode, a conductive substrate is introduced, and a MOF precursor self-template effect is utilized to regulate and control a material structure so that more active sites can be exposed, thereby improving the mass transfer and charge transfer capacity, and finally remarkably enhancing the electrochemical performance of the electrode in a novel electrolytic water hydrogen production system of organic micromolecule oxidation reaction and coupling thereof. The preparation process is simple, the cost is low, and the super-structure material has excellent catalytic performance on the OER substitution reaction and the OER substitution reaction coupled full-solution system, and has industrial application prospect.
Description
Technical Field
The invention belongs to the field of electrochemistry, and relates to a preparation method and application of a self-supporting electrode with a nano-super structure.
Background
Development and utilization of clean energy to reduce artificial carbon emissions is an urgent task. The hydrogen energy is used as clean energy with the advantages of high energy density, zero carbon emission and the like, so that the hydrogen energy is an ideal choice for replacing the traditional fossil energy. But how to produce hydrogen in a large scale in an efficient and economical manner still presents a significant challenge. In a plurality of hydrogen production systems, the electrolytic water system can prepare hydrogen at normal temperature and normal pressure, and the required electric energy can be provided by clean energy (such as solar energy, wind energy and the like) for power generation, so that the hydrogen production cost can be obviously reduced, and the large-scale preparation of hydrogen is realized.
Conventional electrolytic water systems include cathodic Hydrogen Evolution (HER) and anodic Oxygen Evolution (OER). Because the thermodynamic potential of the anode OER is large (1.23V), and the kinetics of the four-electron reaction process are slow, high overpotential is generally required, which leads to the requirement of high electrolysis voltage for the whole electrolysis system, thus being unfavorable for large-scale application. Oxidation reactions of small organic molecules generally require lower oxidation potentials than OER and may also produce oxidation products of high added value. If organic micromolecule oxidation reaction is used for replacing OER, a novel electrolytic water system is constructed, and the energy required by the hydrogen production by the electrolytic water is expected to be reduced, and meanwhile, an anodic oxidation product with high added value is obtained, so that the hydrogen production efficiency by the electrolytic water can be further improved, and the method has important potential application value. In order to achieve the above objective, it is important to develop an efficient, stable electrocatalyst. With conventional noble metal-based electrocatalysts (e.g. Pt, ruO 2 Etc.), the design and development of a novel non-noble metal catalyst with comparable and even better performance has greater practical and economic significance. Layered metal hydroxides (LDHs) have been reported to receive a great deal of attention in the application of small organic molecule oxidation reaction coupled electrolyzed water systems due to their unique microscopic morphology and electronic structure. However, in the examples reported so far, most layered metal hydroxide (LDHs) catalysts are in powder form, so that the stability of the finally prepared electrode is poor. Meanwhile, the layered metal hydroxides (LDHs) reported so far are rarely availableThe microcosmic morphology and the electronic structure of the catalyst can be accurately regulated and controlled on the molecular scale, so that the catalytic performance of the corresponding layered metal hydroxides (LDHs) is insufficient. Therefore, how to accurately regulate the microscopic morphology and electronic structure of layered metal hydroxide (LDHs) catalysts on a molecular scale so as to obtain layered metal hydroxides (LDHs) with excellent stability and catalytic performance is a technical problem to be solved in the art.
Disclosure of Invention
In order to improve the above technical problems, the present invention provides a method for preparing an electrode, including: cobalt salt and an organic ligand are dissolved in a solvent, a Co-MOFs precursor grows in situ on a substrate through liquid phase reaction, then the Co-MOFs precursor is immersed in a solution containing transition metal ions, and an electrode carrying LDHs material is prepared through self-sacrifice template solvothermal reaction.
According to the invention, the molar ratio of cobalt salt to organic ligand is 1 (0.01-20), such as 1:0.01, 1:0.1, 1:0.5, 1:1, 1:2, 1:4, 1:8, 1:10, 1:20.
According to the invention, the cobalt salt is at least one of nitrate, halide, sulfate, organic acid salt or organic salt of cobalt and hydrate thereof, such as at least one of cobalt nitrate hexahydrate, cobalt chloride hexahydrate, cobalt sulfate heptahydrate, cobalt acetate, cobalt acetylacetonate and the like.
According to the present invention, the organic ligand is at least one of 2-methylimidazole, 1, 4-naphthalene dicarboxylic acid, 1, 4-terephthalic acid, 2-amino terephthalic acid, 2, 5-dihydroxyterephthalic acid, 1,3, 5-trimesic acid, 2, 6-pyridine dicarboxylic acid, imidazole-4, 5-dicarboxylic acid, 3, 4-pyridine dicarboxylic acid, and the like.
According to the present invention, the solvent is at least one of water, methanol, ethanol, ethylene glycol, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMA), and the like.
According to the present invention, the solution containing a transition metal ion is a nitrate, a halide salt, a sulfate, an organic acid salt or an organic salt containing at least one transition metal ion of V, cr, mn, fe, co, ni, cu, zn, nb, mo, W or the like, or a hydrate solution thereof. An exemplary is a nickel nitrate hexahydrate solution.
According to the invention, the molar ratio of cobalt salt to the salt of transition metal ion in the solution containing transition metal ion is 1: (0.01-10), such as 1:0.01, 1:0.1, 1:0.5, 1:1, 1:2, 1:5, 1:8, 1:10.
According to the invention, the solution containing transition metal ions also contains urea. Preferably, the molar ratio of the salt of the transition metal ion to urea is 1: (5-100), such as 1:5, 1:10, 1:20, 1:50, 1:80, 1:100.
According to the invention, the substrate is a conductive substrate. Preferably, the substrate includes, but is not limited to, at least one of metal foam, metal mesh, and conductive carbon substrate, such as nickel-iron foam, nickel foam, copper foam, iron foam, cobalt foam, nickel mesh, copper mesh, titanium mesh, stainless steel mesh, carbon cloth, carbon paper, and the like.
According to the invention, the preparation method further comprises pretreatment of the substrate. For example, the substrate is sonicated in an acid solution, then washed, and dried.
According to the present invention, the reaction temperature of the liquid phase reaction is-10 to 100 ℃, such as-10 ℃, 0 ℃,4 ℃, 10 ℃, 20 ℃, 50 ℃, 80 ℃, 100 ℃; the reaction time of the liquid phase reaction is 1 to 150 hours, such as 1 hour, 12 hours, 24 hours, 48 hours, 100 hours and 150 hours.
According to the invention, the solvothermal reaction temperature is 80-200 ℃, such as 80 ℃, 100 ℃, 120 ℃, 150 ℃, 200 ℃; the solvothermal reaction time is 1-120 h, such as 1h, 12h, 24h, 48h, 100h and 120h.
According to the invention, the electrode is a self-supporting electrode with a nano-superstructure.
The invention also provides an electrode prepared by the preparation method.
According to the invention, the substrate has the definition and the selection as described above.
According to the invention, the electrode comprises a substrate and an LDHs material supported on the substrate. Preferably, the load of the LDHs material on the electrode is 0.5-40 mg cm –2 。
The invention also provides application of the electrode in an electrolytic water hydrogen production system, an oxidation reaction (such as UOR) of environmental sewage treatment, an organic micromolecule upgrading reaction and the like. Preferably, the electrode is applied to an electrolytic water hydrogen production system coupled with an organic small molecule oxidation reaction.
According to the invention, the dimensions of the electrode are (0.5 cm x 0.5 cm) to (10 cm x 10 cm).
According to the invention, the organic small molecule oxidation reaction is at least one of Urea Oxidation Reaction (UOR), hydrazine hydrate oxidation reaction (HzOR), methanol Oxidation Reaction (MOR), ethanol Oxidation Reaction (EOR), ethylene glycol oxidation reaction, glycerol Oxidation Reaction (GOR), glucose oxidation reaction, 5-hydroxymethylfurfural oxidation reaction and the like.
The invention has the beneficial effects that:
the invention uses Co-based MOFs as a precursor, and obtains the self-supporting LDHs-based electrode material with a nano-super structure by a self-sacrifice template solvothermal method. The method comprises the following steps: primary structure-LDH structural unit; secondary structure-ultrathin LDH nanoneedles; three-stage structure-hollow slab array composed of LDH nanoneedles; four-level structure-three-dimensional conductive base frame modified by hollow slab array. The nano super structure obviously increases the number of active sites and the intrinsic activity, thereby improving the mass transfer and charge transfer capacity, and finally obviously enhancing the electrochemical performance of the nano super structure in the organic micromolecule oxidation reaction and the novel water electrolysis hydrogen production system coupled with the organic micromolecule oxidation reaction. Taking UOR as an example, the self-supporting electrode of the invention can obtain 100mA cm only by 1.368V -2 And has excellent stability. Furthermore, in the UOR-coupled electrolyzed water system, 100mA cm was obtained as compared with the conventional electrolyzed water system -2 The input voltage required for the current density of (c) may be reduced by 213mV.
According to the invention, parameters such as components, size, thickness and the like of the prepared LDH can be controlled by changing the types and the proportion of cobalt salt, organic ligand and reaction solvent in precursor synthesis and/or changing the types and the concentration of transition metal ions added in solvothermal reaction, so that the quantity of catalytic activity points and intrinsic activity are changed. At the same time, the electrode material is rich in raw materialsThe synthesis method is simple and has excellent catalytic effect, so that the electrode material is more suitable for industrial application. In addition, the self-supporting electrode prepared by the invention can be used for oxidation reaction (such as UOR) of environmental sewage treatment, organic micromolecular upgrading reaction and the like. Furthermore, the electrode materials prepared according to the present invention can also be used to design new electrolysis systems that use a novel anodic reaction coupled with cathodic reduction reactions, including but not limited to HER, CO 2 Reduction reaction (CO) 2 RR)、 N 2 Reduction Reaction (NRR), oxygen Reduction Reaction (ORR), and the like.
Drawings
FIG. 1 is the powder XRD patterns of the Co-MOF experimentally measured in examples 1 and 2.
FIG. 2 is a Scanning Electron Microscope (SEM) image of Co-MOF in examples 1 and 2.
FIG. 3 is a scanning electron microscope image of the NiCo-ZLDH/NF (1.0) electrode prepared in example 1.
FIG. 4 is an Atomic Force Microscope (AFM) image of a NiCo-ZLDH/NF (1.0) electrode prepared in example 1, scale 100nm.
FIG. 5 is a scanning electron microscope image of a NiCo-ZLDH/NF (0.2) electrode prepared in example 2.
FIG. 6 is a scanning electron microscope image of a NiCo-ZLDH/NF (2.0) electrode prepared in example 3.
FIG. 7 is a graph of the electrochemical performance of UOR in example 4.
Fig. 8 is a HER test chart in example 4.
Fig. 9 is a constant voltage stability test chart in example 4.
Fig. 10 is a full solution system performance test chart of example 5.
Detailed Description
The invention is further described below in connection with specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on this disclosure are intended to be within the scope of the present invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
(1) Pretreatment of a Nickel Foam (NF) substrate: taking NF with the diameter of 20 mm and the diameter of 30mm, carrying out ultrasonic treatment on the NF for 10 minutes by using 1mol/L hydrochloric acid solution, washing the NF with deionized water and absolute ethyl alcohol for a plurality of times to remove surface oxide layers and organic matters, and then drying the NF in an oven at the temperature of 60 ℃ for standby.
(2) Synthesis of Co-MOF (ZIF-67/NF) arrays: ZIF-67/NF was prepared by a one-step simple low temperature synthetic strategy. 2mmol of cobalt nitrate hexahydrate and 8mmol of 2-methylimidazole were each dissolved in 20mL of deionized water. The two solutions were then mixed rapidly and a piece of nickel foam (2 x 3 cm) pretreated in step (1) was added. Then sealed with a sealing film and placed in a refrigerator at 4 ℃ for reaction for 18 hours. And after the reaction is finished, the ZIF-67 coated nickel foam can be obtained, and after the nickel foam is taken out, deionized water and absolute ethyl alcohol are used for washing for a plurality of times, and then the obtained Co-MOF (ZIF-67/NF) array precursor is dried in a baking oven at 60 ℃ for standby.
And (3) analyzing the structural composition and morphology of the Co-MOF (ZIF-67/NF) array precursor sample prepared in the step (2). FIG. 1 is an XRD spectrum of ZIF-67/NF showing the results: the invention successfully prepares the sample Co-MOF (ZIF-67/NF) array precursor. The SEM image of fig. 2 can be seen: the MOF array was grown uniformly on the nickel foam substrate.
(3) Synthesizing a nano super-structure integrated electrode: the preparation of the self-supporting NiCo-ZLDH/NF electrode adopts an etching half-sacrificial template process. First, 10mmol of urea and 1.0mmol of NiCl are added 2 ·6H 2 O was dissolved in a mixed solution of 5.0mL deionized water (DI) and 10mL n, n-dimethylformamide (volume ratio DI: dmf=1:2). The solution was then transferred to a teflon autoclave liner and immersed in a piece of ZIF-67/NF (2 x 3 cm) synthesized in step (2) and hydrothermally reacted in an oven at 120 ℃ for 24h. After naturally cooling to room temperature, the sample was taken out, rinsed with deionized water and absolute ethanol, and then dried overnight at 60 ℃ to prepare a self-supporting NiCo-ZLDH/NF (1.0) electrode.
FIGS. 3 and 4 are SEM and AFM images of self-supporting NiCo-ZLDH/NF (1.0) electrode samples prepared in this example, as can be seen from the figures: the super-structured electrode consists of nanoplatelets of about 7.0nm.
Example 2
(1) Pretreatment of the foam nickel substrate was the same as in step (1) of example 1.
(2) Co-MOF microarray synthesis was the same as in step (2) of example 1.
(3) Preparation of a nano-superstructural integrated electrode: the preparation of the self-supporting NiCo-ZLDH/NF electrode uses an etching semi-sacrificial template method. First, 10mmol of urea and 0.2mmol of NiCl are added 2 ·6H 2 O was dissolved in a mixed solution of 5.0mL deionized water and 10mL N, N-dimethylformamide. The solution was then transferred to a teflon autoclave liner and immersed in a piece of ZIF-67/NF (2 x 3 cm) synthesized in step (2) and hydrothermally reacted in an oven at 120 ℃ for 24h. After naturally cooling to room temperature, the sample was taken out, rinsed with deionized water and absolute ethanol, and then dried overnight at 60 ℃ to prepare a self-supporting NiCo-ZLDH/NF (0.2) electrode.
SEM of the self-supporting NiCo-ZLDH/NF (0.2) electrode sample prepared in this example is shown in FIG. 5. From the figure it can be seen that the surface-densely distributed nanoplatelets have a thickness of about 5-10nm.
Example 3
The only difference from example 1 is that: in step (3) 2.0mmol of NiCl was used 2 ·6H 2 O, thereby preparing the self-supporting NiCo-ZLDH/NF (2.0) electrode.
FIG. 6 is a scanning electron microscope image of the NiCo-ZLDH/NF (2.0) electrode prepared in example 3, and the densely distributed nanoplatelets, which are about 7.0nm thick, can be seen from the SEM image shown in FIG. 6.
Example 4
Electrochemical performance test with nano-superstructural integrated electrode (NiCo-ZLDH/NF).
Electrochemical performance characterization of the nanostructure integrated electrode: electrochemical performance of Urea Oxidation (UOR) using a reference electrode (Ag/AgCl), working electrode (electrodes prepared in example 1, example 2 and example 3, 1.0 x 1.0cm 2 ) And an auxiliary electrode (platinum mesh). The electrolyte used was 1.0M KOH or 1.0M KOH and 0.5M Urea (Urea). Measured byThe potential is converted to a potential value relative to the Reversible Hydrogen Electrode (RHE): e (E) RHE ＝E Ag/AgCl +0.197+0.059ph. Both the Linear Sweep Voltammogram (LSV) and the Cyclic Voltammogram (CV) were measured at 5mV s –1 Is recorded at the sweep rate of (2). Unless specifically stated, electrochemical data is IR compensated. Electrochemical Impedance Spectroscopy (EIS) test at an alternating current amplitude of 5mV of 0.05 to 10 5 In the frequency range of Hz.
FIG. 7 is a graph of UOR performance of electrode NiCo-ZLDH/NF using different nickel content synthesis catalysts (electrolyte using 1.0M KOH and 0.5M Urea). As can be seen from the graph, the current density was 200mA cm -2 When the potential of NiCo-ZLDH/NF (1.0) is 1.36V, the catalyst has the optimal catalytic effect on UOR.
Fig. 8 is a graph of HER performance of electrode NiCo-ZLDH/NF (1.0) in 1.0M KOH, 1.0M koh+0.5M urea electrolyte, respectively, from which it can be seen that urea addition has no significant effect on the hydrogen evolution process.
Fig. 9 shows UOR and HER constant voltage stability tests of the self-supporting electrode (NiCo-ZLDH/NF) prepared in example 1, and the test results show that the prepared multi-stage integrated electrode has good structural stability.
Example 5
And (3) performing performance test on the self-supporting electrode (NiCo-ZLDH/NF) urea oxidation reaction coupling hydrogen evolution full solution tank with the nano super structure.
The full-cell electrochemical performance testing process of the nano super-structure self-supporting electrode comprises the following steps: UOR// HER and OER// HER were tested using a two electrode system (both electrodes were self-supporting electrodes (NiCo-ZLDH/NF) prepared in example 1) with a working electrode area of 1.0cm 2 The electrolytes were 1.0M KOH (UOR// HER), 1.0M KOH plus 0.5M urea (OER// HER), respectively.
Figure 10 is a graph showing the results of the full solution performance test of UOR// HER and OER// HER in a single cell in example 5, and it is evident that the activity of the UOR// HER system is higher than that of the OER// HER system.
The embodiments of the present invention have been described above by way of example. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method of making an electrode comprising: cobalt salt and an organic ligand are dissolved in a solvent, a Co-MOF precursor is synthesized on a conductive substrate through liquid phase reaction, then the Co-MOF precursor is immersed in a solution containing transition metal ions, and an electrode carrying LDHs material is prepared through self-sacrifice template solvothermal reaction.
2. The process according to claim 1, wherein the molar ratio of cobalt salt to organic ligand is 1 (0.01-20).
Preferably, the cobalt salt is at least one of a nitrate, a halide, a sulfate, an organic acid salt, or an organic salt of cobalt and a hydrate thereof.
Preferably, the organic ligand is at least one of 2-methylimidazole, 1, 4-naphthalene dicarboxylic acid, 1, 4-terephthalic acid, 2-amino terephthalic acid, 2, 5-dihydroxyterephthalic acid, 1,3, 5-trimellitic acid, 2, 6-pyridine dicarboxylic acid, imidazole-4, 5-dicarboxylic acid, 3, 4-pyridine dicarboxylic acid, and the like.
3. The method according to claim 1 or 2, wherein the solvent is at least one of water, methanol, ethanol, ethylene glycol, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMA), and the like.
Preferably, the solution containing the transition metal ions is nitrate, halide salt, sulfate, organic acid salt or organic salt containing at least one transition metal ion of V, cr, mn, fe, co, ni, cu, zn, nb, mo, W and the like, or a hydrate solution thereof.
Preferably, the molar ratio of cobalt salt to the salt of transition metal ion in the solution containing transition metal ion is 1: (0.01-20).
Preferably, the solution containing transition metal ions further contains urea.
Preferably, the molar ratio of the salt of the transition metal ion to urea is 1: (5-100).
4. A method of preparation as claimed in any one of claims 1 to 3 wherein the substrate is a conductive substrate. Preferably, the substrate includes, but is not limited to, metal foam, metal mesh, and conductive carbon substrates.
Preferably, the substrate is at least one of nickel foam, copper foam, iron foam, cobalt foam, nickel mesh, copper mesh, titanium mesh, stainless steel mesh, carbon cloth, carbon paper, and the like.
5. The method of any one of claims 1-4, wherein the reaction temperature of the liquid phase reaction at the time of synthesis of the MOF precursor is-10 to 100 ℃; the reaction time of the liquid phase reaction is 1-150 h.
Preferably, the temperature of the solvothermal reaction is 80-200 ℃; the solvothermal reaction time is 1-120 h.
6. An electrode prepared by the method of any one of claims 1 to 5.
7. The electrode of claim 6, wherein the electrode comprises a substrate and an LDHs material supported on the substrate.
Preferably, the load of the LDHs material on the electrode is 0.5-40 mg cm –2 。
8. The electrode prepared by the preparation method of any one of claims 1 to 5, and/or the application of the electrode in an electrolytic water hydrogen production system, an oxidation reaction (such as UOR) of environmental sewage treatment, an organic small molecule upgrading reaction and the like.
9. The use of claim 8, wherein the electrode is used in a small organic molecule oxidation reaction coupled electrolyzed water hydrogen production system.
10. The use according to claim 9, wherein the electrodes have dimensions of (0.5 cm x 0.5 cm) to (10 cm x 10 cm).
Preferably, the organic small molecule oxidation reaction is at least one of Urea Oxidation Reaction (UOR), hydrazine hydrate oxidation reaction (HzOR), methanol Oxidation Reaction (MOR), ethanol Oxidation Reaction (EOR), ethylene glycol oxidation reaction, glycerol Oxidation Reaction (GOR), glucose oxidation reaction, 5-hydroxymethylfurfural oxidation reaction, and the like.
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