CN116445972A - Cerium dioxide-transition metal phosphide composite self-supporting electrode material and preparation method and application thereof - Google Patents
Cerium dioxide-transition metal phosphide composite self-supporting electrode material and preparation method and application thereof Download PDFInfo
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- CN116445972A CN116445972A CN202310525155.6A CN202310525155A CN116445972A CN 116445972 A CN116445972 A CN 116445972A CN 202310525155 A CN202310525155 A CN 202310525155A CN 116445972 A CN116445972 A CN 116445972A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 70
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 112
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 56
- 239000006260 foam Substances 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 11
- 150000000703 Cerium Chemical class 0.000 claims abstract description 8
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
- 150000002815 nickel Chemical class 0.000 claims abstract description 8
- 239000013110 organic ligand Substances 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 25
- 239000012498 ultrapure water Substances 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- 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
- GPPINYIMHYYTNR-UHFFFAOYSA-N OC1=C(C(=O)O)C=CC(C1)(C(=O)O)O Chemical compound OC1=C(C(=O)O)C=CC(C1)(C(=O)O)O GPPINYIMHYYTNR-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000001257 hydrogen Substances 0.000 description 23
- 229910052739 hydrogen Inorganic materials 0.000 description 23
- 239000000463 material Substances 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 230000007935 neutral effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 238000004506 ultrasonic cleaning Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000011010 flushing procedure Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000013112 stability test Methods 0.000 description 5
- 238000001075 voltammogram Methods 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical class [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000007704 transition Effects 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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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)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to the technical field of electrolyzed water catalysts, in particular to a ceria-transition metal phosphide composite self-supporting electrode material, a preparation method and application thereof. The preparation method comprises (1) taking foam nickel as a substrate, dispersing nickel salt, cobalt salt, cerium salt and organic ligand in a solvent for hydrothermal reaction to obtain foam nickel with ternary metal organic framework compound precursor growing on the surface; (2) And (3) placing sodium hypophosphite at an upper air port of the tubular furnace, placing the foam nickel sample obtained in the step (1) at a lower air port of the tubular furnace, sealing the tubular furnace, enabling the tubular furnace to be anaerobic, introducing inert gas, heating, preserving heat and cooling to obtain the nickel foam. The invention prepares the cerium oxide-transition metal phosphide composite material with unique morphology structure by taking the ternary metal organic framework compound growing in situ on the foam nickel as a precursor, further optimizes the overall catalytic activity of the catalyst, has good commercial application prospect, and is suitable for popularization and commercial production.
Description
Technical Field
The invention relates to the technical field of electrolyzed water catalysts, in particular to a ceria-transition metal phosphide composite self-supporting electrode material, a preparation method and application thereof.
Background
For a long time, problems such as greenhouse effect, environmental pollution, and energy shortage due to the rapid consumption of fossil fuel have prompted human beings to reduce the use of non-renewable resources and to actively develop efficient, renewable clean energy. The hydrogen energy is a promising energy source due to the characteristics of wide source, high combustion energy density, high energy conversion efficiency, cleanness, reproducibility and the like. The water electrolysis hydrogen production is outstanding in various hydrogen production technologies, and the water electrolysis process generally comprises two half reactions, namely a Hydrogen Evolution Reaction (HER) and an Oxygen Evolution Reaction (OER), because the water electrolysis hydrogen production has the characteristics of higher energy conversion efficiency, zero carbon emission, simple process flow and the like, and is an ideal way for converting the current renewable energy sources into the hydrogen energy. Oxygen generated by the oxygen evolution reaction is also an important reaction gas, and slow oxygen evolution reaction kinetics are also one of factors affecting hydrogen evolution performance.
At present, the best-performing electrolytic water catalysts are electrocatalysts made of noble metals, such as platinum, ruthenium and iridium, but the metals have the problems of high cost, lack of earth reserves and poor stability. Transition metal phosphides are often considered ideal alternatives to noble metal catalysts due to their suitable electronic configuration, metal properties and cost effectiveness. In particular, transition bimetallic phosphides exhibit better full water splitting activity due to interatomic synergism, however their poor conductivity and catalytic activity have hindered further development and application. Combining with another oxide to form a composite is one of the strategies that are effective in improving the conductivity and activity of the material. In addition, the material is synthesized in situ on the self-supporting body, so that the use of an organic adhesive can be avoided, the charge transmission between a catalyst and an electrode is improved, the catalytic activity and stability of the material are improved, and the method has profound significance for popularization of clean energy industrialization.
Disclosure of Invention
Aiming at the technical problems of poor conductivity and catalytic activity of transition metal phosphide, the invention provides a ceria-transition metal phosphide composite self-supporting electrode material, a preparation method and application thereof, and a ceria-transition metal phosphide composite material with a unique morphology structure is prepared by taking a ternary metal organic framework compound grown in situ on foam nickel as a precursor, so that the overall catalytic activity of the catalyst is further optimized, the catalyst is used as a bifunctional catalyst for full water decomposition application, the full water decomposition performance of the catalyst is superior to that of a commercial catalyst, the clean energy is prepared by using low-energy-consumption electrolyzed water, and the catalyst has good commercial application prospect and is suitable for popularization and commercial production.
In a first aspect, the present invention provides a method for preparing a ceria-transition metal phosphide composite self-supporting electrode material, comprising the steps of:
(1) Preparation of metal organic framework compound precursors
Dispersing cerium salt, nickel salt, cobalt salt and an organic ligand in a solvent to perform hydrothermal reaction by taking foamed nickel as a substrate to obtain foamed nickel with ternary metal organic framework compound precursors growing on the surface;
(2) Preparation of cerium dioxide-transition metal phosphide composite self-supporting electrode material
And (3) placing sodium hypophosphite at an upper air port of the tubular furnace, placing foam nickel with ternary metal organic framework compound precursors growing on the surface at a lower air port of the tubular furnace, sealing the tubular furnace, enabling the interior of the tubular furnace to be anaerobic, introducing inert gas, then heating, preserving heat and cooling to obtain the cerium oxide-transition metal phosphide composite self-supporting electrode material growing on the foam nickel in situ.
Further, the step (1) specifically comprises: by adopting a hydrothermal growth method, a certain amount of nickel salt, cobalt salt, cerium salt and organic ligand are weighed and dispersed in a certain volume of solvent, stirred and dissolved uniformly, transferred into a high-pressure reaction kettle containing pretreated foam nickel, packaged into a shell, transferred into a constant-temperature oven, kept for a certain period of time and cooled naturally. And after the reaction is finished, taking out the product from the reaction kettle, repeatedly flushing the product with ultrapure water and absolute ethyl alcohol, and drying the product in a vacuum oven for a certain time to obtain the foam nickel with the ternary metal organic framework compound precursor growing on the surface.
Further, in the step (1), the cerium salt is one or more of cerium chloride, cerium nitrate and ammonium cerium nitrate, the nickel salt is one or more of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate, and the cobalt salt is one or more of cobalt nitrate, cobalt acetate and cobalt chloride; the organic ligand is one or more of trimesic acid, terephthalic acid, 2-amino terephthalic acid and 2, 4-dihydroxyterephthalic acid.
Further, in the step (1), the addition amount of cerium salt is 0.01-1mmol, the addition amount of nickel salt is 0.05-0.3mmol, the addition amount of cobalt salt is 0.05-0.7mmol, the addition amount of organic ligand is 0.1-1mmol, and the volume of solvent is 25-50mL.
Further, in the step (1), the solvent is one or more of N, N-dimethylformamide, ultrapure water, absolute ethyl alcohol and ethylene glycol.
Further, in the step (1), the temperature of the hydrothermal reaction is 100-140 ℃, and the time of the hydrothermal reaction is 6-24 hours.
Further, the step (1) further comprises pretreatment of the foam nickel, firstly ultrasonic cleaning for 20-30min by using hydrochloric acid solution, then ultrasonic cleaning for 5-10min by using ultrapure water, and finally treatment for 5-10min by using absolute ethanol solution so as to remove grease and an oxide layer on the surface of the foam nickel.
Further, the step (2) specifically comprises: and (3) placing a certain amount of sodium hypophosphite at an upper tuyere of a tubular furnace by adopting an in-situ low-temperature phosphating method, placing the foam nickel sample obtained in the step (1) at a lower tuyere of the tubular furnace, sealing the tubular furnace and enabling the tubular furnace to be anaerobic, then introducing inert gas, heating to a certain temperature according to a certain heating rate, maintaining for a certain period of time, and then cooling to room temperature according to a certain cooling rate to obtain the ceria-transition metal phosphide composite self-supporting electrode material growing on the foam nickel in situ.
Further, in the step (2), the inert gas is argon or nitrogen.
Further, in the step (2), sodium hypophosphite is added in an amount of 0.5-1.5g/11.25cm 3 The amount of sodium hypophosphite per piece of foamed nickel substrate is 0.5-1.5g for foamed nickel substrate with the specification of 3cm long by 2.5cm wide by 1.5mm thick.
Further, in the step (2), the temperature is raised to 300-400 ℃ at a heating rate of 1-5 ℃/min, then maintained for 0.5-3h, and then cooled to room temperature at a cooling rate of 1-5 ℃/min.
In a second aspect, the invention provides a ceria-transition metal phosphide composite self-supporting electrode material prepared by the preparation method.
In a third aspect, the invention provides an application of the ceria-transition metal phosphide composite self-supporting electrode material as an electrolyzed water catalyst.
The invention has the beneficial effects that:
1. the ceria-transition metal phosphide composite self-supporting electrode material prepared by the invention has the advantages of low cost of raw materials, few preparation steps, simple operation, low-cost and easily available equipment, high repeatability and easy mass production.
2. The ceria-transition metal phosphide composite self-supporting electrode material prepared by the invention has good electrolytic water hydrogen-separating performance in alkaline, neutral and acid electrolyte, can stably run for 100 hours in alkaline, neutral and acid electrolyte, and has good stability. In particular to the oxygen evolution performance of electrolytic water under alkaline condition and the full water decomposition catalytic performance, which are superior to commercial catalysts.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
Fig. 1 is a scanning electron microscope image of the self-supporting electrode material prepared in example 1.
Fig. 2 is a scanning electron microscope image of the self-supporting electrode material prepared in example 2.
Fig. 3 is a scanning electron microscope image of the self-supporting electrode material prepared in example 3.
Fig. 4 is a linear sweep voltammogram of the hydrogen evolution performance of the self-supporting electrode materials prepared in examples 1 to 3 and comparative example 1 in alkaline electrolyte.
Fig. 5 is a linear sweep voltammogram of the hydrogen evolution performance of the self-supporting electrode materials prepared in examples 1-3 and comparative example 1 in neutral electrolytes for electrolyzed water.
Fig. 6 is a linear sweep voltammogram of the hydrogen evolution performance of the self-supporting electrode materials prepared in examples 1-3 and comparative example 1 in acidic electrolytes for electrolyzed water.
Fig. 7 is a graph of current density versus time stability test for hydrogen evolution of electrolyzed water in alkaline electrolyte for the self-supporting electrode material prepared in example 1.
Fig. 8 is a graph of current density versus time stability test for hydrogen evolution of electrolyzed water in a neutral electrolyte for the self-supporting electrode material prepared in example 1.
Fig. 9 is a graph of current density versus time stability test for hydrogen evolution of electrolyzed water in an acidic electrolyte for the self-supporting electrode material prepared in example 1.
FIG. 10 is a linear sweep voltammogram of the oxygen evolution performance of the self-supporting electrode materials prepared in examples 1-3 and comparative example 1 in alkaline electrolytes.
FIG. 11 is a graph showing the current density versus time stability test of the self-supporting electrode material prepared in example 1 for electrolysis of water in alkaline electrolyte for oxygen evolution.
Fig. 12 is a linear sweep voltammogram of the full water splitting performance of the self-supporting electrode materials prepared in examples 1-3 and comparative example 1, as well as the purchased commercial electrode materials in alkaline electrolyte.
Fig. 13 is a graph of current density versus time stability test for the fully hydrolyzed water of the self-supporting electrode material prepared in example 1 in an alkaline electrolyte.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Example 1
A ceria-transition metal phosphide composite self-supporting electrode material is prepared by the following preparation method:
(1) Foam nickel (length 3 cm. Times.width 2.5 cm. Times.thickness 1.5 mm) was put into a hydrochloric acid solution composed of 5mL of concentrated hydrochloric acid and 55mL of ultrapure water, and after ultrasonic cleaning for 20 minutes, rinsed to neutrality with ultrapure water. And sequentially placing the foam nickel into ultrapure water and absolute ethyl alcohol, and respectively carrying out ultrasonic treatment for 5min to obtain the pretreated foam nickel.
Weighing 0.25mmol of cerium nitrate, 0.11mmol of nickel chloride, 0.34mmol of cobalt nitrate and 0.45mmol of terephthalic acid, dispersing in a solvent containing 36mL of N, N-dimethylformamide, 3.6mL of ultrapure water and 3.6mL of absolute ethyl alcohol, uniformly stirring for dissolving, transferring to a high-pressure reaction kettle containing pretreated foam nickel, packaging a shell, transferring to a constant-temperature oven at 120 ℃, keeping for 12 hours, and naturally cooling. And after the reaction is finished, taking out the product from the reaction kettle, repeatedly flushing the product with ultrapure water and absolute ethyl alcohol, and drying the product in a vacuum oven at 60 ℃ for 12 hours to obtain the foam nickel with the ternary metal organic framework compound precursor growing on the surface.
(2) Placing 1g of sodium hypophosphite at an upper tuyere of a tube furnace, placing the foam nickel sample obtained in the step (1) at a lower tuyere of the tube furnace, sealing the tube furnace and enabling the tube furnace to be anaerobic, then introducing nitrogen, raising the temperature to 350 ℃ at a heating rate of 3 ℃/min, maintaining for 2h, and then lowering the temperature to room temperature at a cooling rate of 3 ℃/min to obtain the ceria-transition metal phosphide composite self-supporting electrode material (hereinafter referred to as self-supporting electrode material) growing on the foam nickel in situ, wherein the self-supporting electrode material grows uniformly and has a unique morphology structure as shown in figure 1.
Example 2
A ceria-transition metal phosphide composite self-supporting electrode material is prepared by the following preparation method:
(1) Foam nickel (length 3 cm. Times.width 2.5 cm. Times.thickness 1.5 mm) was put into a hydrochloric acid solution composed of 5mL of concentrated hydrochloric acid and 55mL of ultrapure water, and after ultrasonic cleaning for 20 minutes, rinsed to neutrality with ultrapure water. And sequentially placing the foam nickel into ultrapure water and absolute ethyl alcohol, and respectively carrying out ultrasonic treatment for 5min to obtain the pretreated foam nickel.
Weighing 0.1mmol of cerium nitrate, 0.11mmol of nickel chloride, 0.34mmol of cobalt nitrate and 0.45mmol of terephthalic acid, dispersing in a solvent containing 36mL of N, N-dimethylformamide, 3.6mL of ultrapure water and 3.6mL of absolute ethyl alcohol, uniformly stirring for dissolving, transferring to a high-pressure reaction kettle containing pretreated foam nickel, packaging a shell, transferring to a constant-temperature oven at 120 ℃, keeping for 12 hours, and naturally cooling. And after the reaction is finished, taking out the product from the reaction kettle, repeatedly flushing the product with ultrapure water and absolute ethyl alcohol, and drying the product in a vacuum oven at 60 ℃ for 12 hours to obtain the foam nickel with the binary metal organic framework compound precursor growing on the surface.
(2) And (3) placing 1g of sodium hypophosphite at an upper tuyere of a tube furnace, placing the foam nickel sample obtained in the step (1) at a lower tuyere of the tube furnace, sealing the tube furnace and enabling the tube furnace to be anaerobic, then introducing nitrogen, heating to 350 ℃ at a heating rate of 3 ℃/min, maintaining for 2h, and then cooling to room temperature at a cooling rate of 3 ℃/min to obtain the transition metal phosphide composite self-supporting electrode material growing on the foam nickel in situ.
Example 3
A ceria-transition metal phosphide composite self-supporting electrode material is prepared by the following preparation method:
(1) Foam nickel (length 3 cm. Times.width 2.5 cm. Times.thickness 1.5 mm) was put into a hydrochloric acid solution composed of 5mL of concentrated hydrochloric acid and 55mL of ultrapure water, and after ultrasonic cleaning for 20 minutes, rinsed to neutrality with ultrapure water. And sequentially placing the foam nickel into ultrapure water and absolute ethyl alcohol, and respectively carrying out ultrasonic treatment for 5min to obtain the pretreated foam nickel.
Weighing 0.4mmol of cerium nitrate, 0.11mmol of nickel chloride, 0.34mmol of cobalt nitrate and 0.45mmol of terephthalic acid, dispersing in a solvent containing 36mL of N, N-dimethylformamide, 3.6mL of ultrapure water and 3.6mL of absolute ethyl alcohol, uniformly stirring for dissolving, transferring to a high-pressure reaction kettle containing pretreated foam nickel, packaging a shell, transferring to a constant-temperature oven at 120 ℃, keeping for 12 hours, and naturally cooling. And after the reaction is finished, taking out the product from the reaction kettle, repeatedly flushing the product with ultrapure water and absolute ethyl alcohol, and drying the product in a vacuum oven at 60 ℃ for 12 hours to obtain the foam nickel with the binary metal organic framework compound precursor growing on the surface.
(2) And (3) placing 1g of sodium hypophosphite at an upper tuyere of a tube furnace, placing the foam nickel sample obtained in the step (1) at a lower tuyere of the tube furnace, sealing the tube furnace and enabling the tube furnace to be anaerobic, then introducing nitrogen, raising the temperature to 350 ℃ at a heating rate of 3 ℃/min, maintaining for 2 hours, and then cooling to room temperature at a cooling rate of 3 ℃/min to obtain the transition metal phosphide composite self-supporting electrode material (hereinafter referred to as the self-supporting electrode material) growing on the foam nickel in situ.
Comparative example 1
A self-supporting transition metal phosphide composite electrolytic water electrode catalyst material is prepared by the following preparation method:
(1) The nickel foam is put into a hydrochloric acid solution composed of 5mL of concentrated hydrochloric acid and 55mL of ultrapure water, and after ultrasonic cleaning for 20min, the nickel foam is rinsed to be neutral by the ultrapure water. And sequentially placing the foam nickel into ultrapure water and absolute ethyl alcohol, and respectively carrying out ultrasonic treatment for 5min to obtain the pretreated foam nickel.
Weighing 0.11mmol of nickel chloride, 0.34mmol of cobalt nitrate and 0.45mmol of terephthalic acid, dispersing in a solvent containing 36mL of N, N-dimethylformamide, 3.6mL of ultrapure water and 3.6mL of absolute ethyl alcohol, uniformly stirring for dissolving, transferring to a high-pressure reaction kettle containing pretreated foam nickel, packaging a shell, transferring to a constant-temperature oven at 120 ℃, keeping for 12 hours, and naturally cooling. And after the reaction is finished, taking out the product from the reaction kettle, repeatedly flushing the product with ultrapure water and absolute ethyl alcohol, and drying the product in a vacuum oven at 60 ℃ for 12 hours to obtain the foam nickel with the binary metal organic framework compound precursor growing on the surface.
(2) And (3) placing 1g of sodium hypophosphite at an upper tuyere of a tube furnace, placing the foam nickel sample obtained in the step (1) at a lower tuyere of the tube furnace, sealing the tube furnace and enabling the tube furnace to be anaerobic, then introducing nitrogen, raising the temperature to 350 ℃ at a heating rate of 3 ℃/min, maintaining for 2 hours, and then cooling to room temperature at a cooling rate of 3 ℃/min to obtain the transition metal phosphide composite self-supporting electrode material (hereinafter referred to as the self-supporting electrode material) growing on the foam nickel in situ.
Example 4
The self-supporting electrode materials prepared in examples 1 to 3 and comparative example 1 were used as working electrodes, respectively, saturated silver chloride electrodes were used as reference electrodes, graphite rod electrodes were used as counter electrodes, and alkaline solution (potassium hydroxide solution with a concentration of 1.0 mol/L), neutral solution (phosphate buffer salt solution with a concentration of 1.0 mol/L) and acidic solution (sulfuric acid solution with a concentration of 0.5 mol/L) were used as electrolyte, respectively, and an electrolytic cell was assembled to analyze the hydrogen evolution performance of the self-supporting electrode materials from electrolytic water.
As shown in fig. 4, compared with examples 2 and 3 and comparative example 1, the self-supporting electrode material prepared in example 1 requires smaller voltage at the same current density, which indicates that the self-supporting electrode material prepared in example 1 has more excellent hydrogen evolution performance of electrolyzed water in alkaline electrolyte, and further proves that the introduction of oxide can obviously improve the hydrogen evolution performance of electrolyzed water in alkaline electrolyte.
As shown in fig. 5, compared with examples 2 and 3 and comparative example 1, the self-supporting electrode material prepared in example 1 requires smaller voltage at the same current density, which indicates that the self-supporting electrode material prepared in example 1 has more excellent hydrogen evolution performance of electrolyzed water in neutral electrolyte, and further proves that the introduction of oxide can obviously improve the hydrogen evolution performance of electrolyzed water in neutral electrolyte.
As shown in fig. 6, compared with examples 2 and 3, the self-supporting electrode material prepared in example 1 requires smaller voltage at the same current density, which indicates that the self-supporting electrode material prepared in example 1 has more excellent electrolytic water hydrogen evolution performance in the acidic electrolyte, and further proves that the introduction of oxide can obviously improve the electrolytic water hydrogen evolution performance of the material in the acidic electrolyte.
The self-supporting electrode material prepared in the embodiment 1 has good electrolytic water hydrogen-separating performance in alkaline, neutral and acid electrolyte, which is shown by combining fig. 4, 5 and 6, and the self-supporting electrode material is a good electrolytic water hydrogen-separating catalyst material, has a wider action range and has good application prospect.
As can be seen by combining fig. 7, fig. 8 and fig. 9, the self-supporting electrode material prepared in example 1 can keep a certain current density in alkaline, neutral and acidic electrolytes for stable operation for 100 hours, which shows that the material has good electrolytic water hydrogen evolution stability and corrosion resistance in alkaline, neutral and acidic electrolytes.
Example 5
The self-supporting electrode materials prepared in examples 1 to 3 and comparative example 1 were used as working electrodes, saturated silver chloride electrodes were used as reference electrodes, graphite rod electrodes were used as counter electrodes, alkaline solution (potassium hydroxide solution with concentration of 1.0 mol/L) was used as electrolyte, and an electrolytic cell was assembled to analyze the oxygen evolution performance of the self-supporting electrode materials by electrolysis water.
As shown in fig. 10, compared with examples 2 and 3 and comparative example 1, the self-supporting electrode material prepared in example 1 requires smaller voltage at the same current density, which indicates that the self-supporting electrode material prepared in example 1 has more excellent electrolytic water oxygen evolution performance in alkaline electrolyte, and further proves that the introduction of oxide can significantly improve the electrolytic water oxygen evolution performance of the material in alkaline electrolyte.
As shown in FIG. 11, the self-supporting electrode material prepared in example 1 can keep a certain current density in alkaline electrolyte to stably run for 100 hours, which shows that the material has good electrolytic water oxygen evolution stability and corrosion resistance in alkaline electrolyte. As can be seen in connection with fig. 10, the self-supporting electrode material prepared in example 1 is a good electrolytic water oxygen evolution catalyst material.
Example 6
Since the self-supporting electrode material prepared in example 1 exhibited good hydrogen and oxygen evolution properties of electrolyzed water, which indicated that the material was a bifunctional catalyst having the potential to drive the full water evolution reaction to occur, the self-supporting electrode material prepared in example 1 was assembled as a cathode and an anode to an electrolytic cell, the full water evolution properties of the electrode material was tested using a two-electrode system, the electrolyte was an alkaline solution (potassium hydroxide solution having a concentration of 1.0 mol/L), and the self-supporting electrode material prepared in comparative example 1 and the commercially available catalyst material (commercially available hydrogen evolution catalyst was platinum carbon catalyst (20 wt%) commercially available from Shanghelsen electric company; commercially available oxygen evolution catalyst was iridium oxide (99.9%) commercially available from sigma aldrich (Shanghai)) were used as a control.
As shown in fig. 12, as the applied voltage increases, the current density of the electrolytic cell composed of example 1 also increases, indicating that the self-supporting electrode material prepared in example 1 is indeed a catalyst material having full water-splitting performance. Compared with examples 2 and 3 and comparative example 1, the self-supporting electrode material prepared in example 1 requires smaller voltage at the same current density, which indicates that the self-supporting electrode material prepared in example 1 has more excellent full water-splitting performance in alkaline electrolyte, and further proves that the introduction of oxide can obviously improve the full water-splitting performance of the material in alkaline electrolyte. The lower voltage required for the self-supporting electrode material prepared in example 1 compared to the commercial catalyst material purchased at the same current density indicates that the self-supporting electrode material prepared in example 1 is a good full water splitting catalyst material and the full water splitting performance exceeds that of the commercial catalyst.
As shown in fig. 13, the self-supporting electrode material prepared in example 1 can keep a certain current density in alkaline electrolyte to stably run for 100 hours, which indicates that the material has good full water dissolution stability and corrosion resistance in alkaline electrolyte. With reference to fig. 12, it is further demonstrated that the self-supporting electrode material prepared in example 1 is an electrolyzed water catalyst with good catalytic performance and stability and great commercial application value.
Although the present invention has been described in detail by way of preferred embodiments with reference to the accompanying drawings, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims.
Claims (10)
1. The preparation method of the ceria-transition metal phosphide composite self-supporting electrode material is characterized by comprising the following steps of:
(1) Dispersing cerium salt, nickel salt, cobalt salt and an organic ligand in a solvent to perform hydrothermal reaction by taking foamed nickel as a substrate to obtain foamed nickel with ternary metal organic framework compound precursors growing on the surface;
(2) And (3) placing sodium hypophosphite at an upper air port of the tubular furnace, placing foam nickel with ternary metal organic framework compound precursors growing on the surface at a lower air port of the tubular furnace, sealing the tubular furnace, enabling the interior of the tubular furnace to be anaerobic, introducing inert gas, then heating, preserving heat and cooling to obtain the cerium oxide-transition metal phosphide composite self-supporting electrode material growing on the foam nickel in situ.
2. The method according to claim 1, wherein in the step (1), the cerium salt is one or more of cerium chloride, cerium nitrate and ammonium cerium nitrate, the nickel salt is one or more of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate, and the cobalt salt is one or more of cobalt nitrate, cobalt acetate and cobalt chloride; the organic ligand is one or more of trimesic acid, terephthalic acid, 2-amino terephthalic acid and 2, 4-dihydroxyterephthalic acid.
3. The process according to claim 1, wherein in the step (1), cerium salt is added in an amount of 0.01 to 1mmol, nickel salt is added in an amount of 0.05 to 0.3mmol, cobalt salt is added in an amount of 0.05 to 0.7mmol, organic ligand is added in an amount of 0.1 to 1mmol, and the volume of the solvent is 25 to 50mL.
4. The method according to claim 1, wherein in the step (1), the solvent is one or more of N, N-dimethylformamide, ultrapure water, absolute ethanol, and ethylene glycol.
5. The process according to claim 1, wherein in step (1), the hydrothermal reaction is carried out at a temperature of 100 to 140℃for a period of 6 to 24 hours.
6. The method of claim 1, wherein step (1) further comprises pretreating the nickel foam, ultrasonically cleaning the nickel foam with a hydrochloric acid solution for 20-30min, ultrasonically cleaning the nickel foam with ultrapure water for 5-10min, and finally treating the nickel foam with an absolute ethanol solution for 5-10min.
7. The process according to claim 1, wherein in the step (2), sodium hypophosphite is added in an amount of 0.5 to 1.5g/11.25cm 3 A foamed nickel substrate.
8. The preparation method according to claim 1, wherein in the step (2), the temperature is raised to 300-400 ℃ at a temperature-raising rate of 1-5 ℃/min, then maintained for 0.5-3 hours, and then cooled to room temperature at a temperature-lowering rate of 1-5 ℃/min.
9. A ceria-transition metal phosphide composite self-supporting electrode material produced by the production process according to any one of claims 1 to 8.
10. Use of the ceria-transition metal phosphide composite self-supporting electrode material as defined in claim 9 as an electrolytic water catalyst.
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