CN114709436A - Has Fe2Preparation and application of oxygen evolution/hydrogen evolution/oxygen reduction electrocatalyst with P/Co nano-particle synergistic effect - Google Patents
Has Fe2Preparation and application of oxygen evolution/hydrogen evolution/oxygen reduction electrocatalyst with P/Co nano-particle synergistic effect Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000001301 oxygen Substances 0.000 title claims abstract description 25
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000001257 hydrogen Substances 0.000 title claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 14
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 14
- 230000009467 reduction Effects 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 239000000446 fuel Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 84
- 239000000243 solution Substances 0.000 claims description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 239000012528 membrane Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 13
- 238000011068 loading method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 238000000197 pyrolysis Methods 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910002849 PtRu Inorganic materials 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 238000009792 diffusion process Methods 0.000 claims description 3
- 238000003487 electrochemical reaction Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000002441 reversible effect Effects 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 claims description 2
- 229930024421 Adenine Natural products 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229960000643 adenine Drugs 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 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
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229920000554 ionomer Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 10
- 238000006722 reduction reaction Methods 0.000 abstract description 8
- 238000001354 calcination Methods 0.000 abstract description 3
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
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- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 7
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- 229910052742 iron Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 4
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- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- -1 oxides Chemical class 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 description 1
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 1
- 229910017677 NH4H2 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000034964 establishment of cell polarity Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- JLHMVTORNNQCRM-UHFFFAOYSA-N ethylphosphine Chemical compound CCP JLHMVTORNNQCRM-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 210000002216 heart Anatomy 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
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- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000011574 phosphorus Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- 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
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—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
- C25B11/065—Carbon
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/08—Fuel cells with aqueous electrolytes
- H01M8/083—Alkaline fuel cells
Abstract
Has Fe2Preparation and application of an oxygen evolution/hydrogen evolution/oxygen reduction electrocatalyst with P/Co nano-particle synergistic effect, belonging to the technical field of electrocatalysis. Mixing zinc salt, cobalt salt and 1, 1' -bis (diphenylphosphino) ferrocene with a nitrogen-containing substance for reaction to obtain a precursor, and then carrying out high-temperature reaction in an inert gasAnd (4) calcining. Obtained Fe2P and Co nanoparticles in Fe2The synergistic effect of the P/Co @ NC catalyst enables the catalyst to have higher catalytic activity on Oxygen Reduction Reaction (ORR), Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER). Notably, Fe is used2The P/Co @ NC catalyst assembled zinc-air cell showed 219.66mW cm‑2The peak power density of the constructed alkaline fuel cell is 1.25W cm‑2。
Description
Technical Field
The invention relates to a catalyst containing Fe2Oxygen-evolving/harvesting based on P/Co nanoparticlesPreparation and application of three-functional electro-catalyst for hydrogen evolution/oxygen reduction reaction, belonging to the technical field of electro-catalysis.
Background
With the rapid development of industry and agriculture, the energy consumption is increased rapidly, and the development of renewable energy technologies such as fuel cells, water electrolysis hydrogen production and metal-air batteries has very important significance. The core of these energy technologies requires catalysts for electrochemical processes such as Oxygen Evolution Reaction (OER), Hydrogen Evolution Reaction (HER) and Oxygen Reduction Reaction (ORR). The most commonly used ORR and HER catalysts are Pt/C and the OER catalyst is IrO2And RuO2Their use is greatly limited due to the scarcity and high cost of precious metal materials. In addition, the anode and cathode reactions usually need to support different types of catalysts, which have different potential windows, different pH values and different electrolytes, and the problems inevitably complicate the system construction and increase the cost. Therefore, the development of a low-cost, high-efficiency non-noble metal three-functional electrocatalyst capable of simultaneously catalyzing ORR, OER and HER is urgently needed.
In recent years, much effort has been devoted to the development of non-noble metal electrocatalysts, including transition metal nanoparticles and their phosphides, sulfides, oxides, nitrides, and the like. Among them, the transition metal phosphide has an obvious metalloid property, multiple electron orbitals and favorable electron arrangement, and thus not only can exhibit a higher catalytic activity, but also can improve the corrosion resistance and stability of the pure transition metal. However, the preparation of phosphides typically involves a lengthy multi-step process involving the preparation of a precursor and subsequent phosphating. Usually NaH is used2PO2Or NH4H2PO2As a phosphorus source, the tail gas PH is generated in the process3。PH3Is a highly toxic gas and can cause damage to the nervous system, heart and respiratory system of a human body. In addition, the pH if encountered with other minor amounts of phosphine, such as ethyl phosphine3Spontaneous combustion can occur. 1, 1' -bis (diphenylphosphino) ferrocene (DPPF) is a common organic reaction catalyst and is low in price. The invention firstly uses the Fe and P sources simultaneously, thereby simplifying the synthesis method and avoiding the generation of Fe and P sourcesThe generation of toxic gas in the process of phosphorization.
The invention adopts a simple one-pot method to prepare Fe2P/Co @ NC, which comprises the steps of preparing a precursor through a solvothermal reaction and carrying out a subsequent high-temperature pyrolysis process. This one-pot strategy facilitates the growth of a rationally designed electrocatalyst made of Fe2P nano particles and highly dispersed Co nano particles are wrapped with a layer of graphite carbon film, and the Fe2The P nano particles and the Co nano particles are loaded on the outer layer of the nitrogen-phosphorus Co-doped carbon nano cage. Synthetic Fe2P/Co @ NC has excellent conductivity, high specific surface area and a rich layered porous structure. Fe2P, Co synergistic effect of nano particle and nitrogen-phosphorus doped carbon matrix to make Fe2P/Co @ NC has excellent ORR, OER and HER three-functional electrocatalytic activity. Fe2The P/Co @ NC composite nano material is applied to fuel cells, zinc-air cells and full-hydrolysis electrocatalysts, and has good electrochemical activity.
Disclosure of Invention
The invention aims to design a three-function electrocatalyst based on the synergistic effect of iron phosphide and cobalt nanoparticles, and solve the problems in the background art. The non-noble metal composite material designed by the invention has lower cost and higher activity, and can be popularized and applied in the technical fields of fuel cells, zinc-air cells, electrolytic water and the like.
The technical scheme of the invention is as follows:
has Fe2The preparation method of the three-functional electrocatalyst with the P/Co nano-particle synergistic effect for oxygen evolution/hydrogen evolution/oxygen reduction is characterized by comprising the following steps:
step (1), adopting a zeolite imidazole framework as a carbon substrate, dissolving a certain amount of zinc salt, cobalt salt and 1, 1' -bis (diphenylphosphino) ferrocene in a methanol solution, and stirring to obtain a uniform solution A; dissolving a certain amount of nitrogen-containing substances in a methanol solution, performing ultrasonic treatment to obtain a uniform solution B, quickly pouring the solution A into the solution B, stirring, transferring into a reaction kettle, heating, centrifuging, washing, and drying to obtain a precursor with a dodecahedron structure;
and (2) putting the precursor obtained in the step (1) into a tube furnace, and performing high-temperature pyrolysis in an inert gas atmosphere such as argon.
The cobalt salt in the step (1) is selected from one or more of cobalt nitrate, cobalt acetate and the like; the zinc salt is selected from one or more of zinc nitrate, zinc acetate and the like. The nitrogen-containing substance is selected from one or more of 2-methylimidazole, adenine, dicyandiamide, urea and the like;
in the step (1), fixing cobalt salt: the molar ratio of the ferric salt is 3: 1; the molar ratio of the zinc salt to the sum of the cobalt salt and the iron salt is 1-12: 1, and the preferable ratio is 1: 1.
The mass of the nitrogen-containing substance is 1-5 times of that of the iron salt.
In the step (1), the reaction temperature is 100-150 ℃, and the reaction time is 3-5 h. The preferred conditions are 120 ℃ and 4h of reaction.
In the step (2), the high-temperature pyrolysis condition is that inert gas is introduced for 1.0-5.0 h, then the temperature is raised to 850-. The preferable conditions are that the air is firstly ventilated for 1.0h at room temperature, then the temperature is raised to 950 ℃ at the temperature raising rate of 5 ℃/min, and the temperature is kept for 3.0 h.
The electrocatalyst prepared by the invention is made of Fe2P nano particles and highly dispersed Co nano particles are wrapped with a layer of graphite carbon film, and the Fe2The P nano particles and the Co nano particles are loaded on the outer layer of the nitrogen-phosphorus Co-doped carbon nano cage.
The Fe-containing alloy prepared by the invention2The application of the three-functional electro-catalyst of oxygen evolution/hydrogen evolution/oxygen reduction with P/Co nano-particle synergistic effect, namely the application in alkaline membrane fuel cells, zinc-air cells and electrolytic water.
The alkaline membrane fuel cell is used as follows: commercial 60% PtRu/C is selected as an anode catalyst, the catalyst prepared by the method is used as a cathode catalyst, and the loading capacity of the catalyst is more than or equal to 0.5mg cm-2Less than or equal to 2.5mg cm-2. PAP-TP-85 is used as a hydroxide exchange membrane, PAP-TP-85 solution is used as an ionomer, a membrane electrode is prepared by a CCM (catalyst coated membrane) method or a GDL (gas diffusion electrode) method, and then the membrane electrode is used for assembling a battery and testing an alkaline membrane fuel cell.
Zinc-air electricityThe pool application is as follows: the catalyst prepared by the invention is loaded on carbon paper to be used as an air anode, and the loading capacity of the catalyst is more than or equal to 0.1mg cm-21.5 mg/cm or less-2Polished Zn plate as negative electrode, 6mol L-1KOH and 0.2mol L of-1The zinc oxide mixed solution is used as electrolyte to ensure the smooth proceeding of the Zn reversible electrochemical reaction.
The electrolytic water is applied as follows: the three-function catalyst is loaded on a carbon paper substrate to be used as a catalytic electrode, and the loading amount of the catalyst is more than or equal to 0.1mg cm-2Less than or equal to 3.5mg cm-2Two identical electrodes were used as positive and negative electrodes simultaneously, at 1mol L-1The KOH solution of (2) is an electrolyte.
The invention has the advantages that:
1. the invention uses 1, 1' -bis (diphenylphosphino) ferrocene with low price as Fe and P sources for the first time, thereby simplifying the synthesis method and avoiding the generation of toxic gas in the phosphorization process. In the high-temperature carbonization process, ZnCo-ZIF is converted into a porous carbon nanocage, cobalt nitrate is reduced to form Co nano particles fixed on a carbon matrix, and a part of P element in DPPF is coordinated with Fe to form Fe2P, and the other part is fixed on a carbon substrate.
From the SEM of a in FIG. 1, it can be seen that the precursor, DPPF @ ZnCo-ZIF, has a uniform dodecahedral morphology with a particle size of about 200 nm. And calcining the obtained Fe in SEM picture of b in attached figure 12The shape of P/Co @ NC is approximately the same as that of the precursor, and the size is about 180 nm. Fe after pyrolysis, compared to a smooth surface of DPPF @ ZnCo-ZIF2The surface of the P/Co @ NC became rough. Indicating that the structure of the precursor is not damaged during the calcination process. FIG. 1d, e shows Fe2The lattice spacing of the P nanoparticles is about 0.22nm, corresponding to Fe2The (111) plane of P. The lattice spacing of 0.20nm and 0.35nm respectively corresponds to the (111) crystal face of Co and the (002) crystal face of graphite carbon, and meanwhile, a graphene layer with the thickness of about 3.5nm is wrapped on the outer layer of Co particles. And the EDS-mapping of FIGS. 1f-j demonstrates C, N, P, Fe and the uniform distribution of Co elements. As can be seen from FIG. 2, Fe2XRD of P/Co @ NC mainly corresponds to Fe2P and Co nanoparticles, consistent with TEM results.
2. The catalyst prepared by the invention has excellent ORR, OER and HER performances. FIG. 3 illustrates that Fe2P/Co@NC(E1/20.876V) shows the ratio Pt/C (E)1/20.854V) higher half-wave potential, proving Fe2P/Co @ NC has higher ORR activity. FIG. 4 shows that Fe2P/Co @ NC at 10mA cm-2Shows a significantly higher OER activity at a current density of 331mV compared to other samples with a lower value of Co @ NC (420mV), Fe2P @ NC (639mV) and IrO2(384 mV). FIG. 5 illustrates that Fe2P/Co @ NC has the highest HER catalytic activity at 10mAcm-2The overpotential at this time was 235mV, close to commercial Pt/C. Fe2P, Co synergistic effect of nano particle and nitrogen-phosphorus doped carbon matrix to make Fe2The P/Co @ NC has excellent ORR, OER and HER three-function electrocatalytic activity.
3. The catalyst prepared by the invention has wide application and can be applied to fuel cells, zinc-air cells and full-hydrolysis water. At H2-O2Under the system, when the loading of the cathode in the MEA is 1mg cm-2At a backpressure of 2.5bar, Fe2The P/Co @ NC catalyst has excellent performance in an alkaline membrane fuel cell, and the maximum power density reaches 1.25W cm-2. When applied to zinc-air batteries, based on Fe2The maximum power density of the P/Co @ NC battery reaches 219.66mW cm-2Based on Pt/C-IrO2Battery (141.5mW cm)-2) More than 1.5 times of the total amount of the active ingredients. When applied to full water splitting, Fe2P/Co @ NC can reach 10mA cm only by 1.73V-2The current density of (1).
Drawings
FIG. 1 a) scanning electron microscope images of DPPF @ ZnCo-ZIF; b) fe2A scanning electron microscope image of P/Co @ NC; c-e) Fe2Transmission electron microscope images of P/Co @ NC under different magnification; f-j) Fe2Element map of P/Co @ NC.
FIG. 2 is Fe2P/Co @ NC, Co @ NC and Fe2XRD spectrum of P @ NC catalyst.
FIG. 3 shows Fe2P/Co@NC,Co@NC,Fe2ORR polarization plots for P @ NC and Pt/C.
FIG. 4 is Fe2P/Co@NC,Co@NC,Fe2P @ NC and IrO2OER polarization graph of (a).
FIG. 5 is Fe2P/Co@NC,Co@NC,Fe2HER polarization plots for P @ NC and Pt/C.
FIG. 6 is a graph of the fuel cell performance in alkaline membrane fuel cell tests at H2-O2Cathode catalyst Fe under the backpressure condition of 2.5bar of the system2P/Co @ NC is 1mg cm-2I-V curve and I-P curve at loading are compared.
FIG. 7 is Fe2P/Co @ NC and Pt/C/IrO2Zinc air cell polarization curve and power density curve of the catalyst.
FIG. 8 is a graph of polarization of fully hydrolyzed water in a two-electrode system.
Detailed Description
The technical solutions of the present invention will be described in further detail with reference to the following embodiments and the accompanying drawings, but the present invention is not limited to the following embodiments.
Example 1:
step (1) preparation of DPPF @ ZnCo-ZIF precursor
207.84mg of 1, 1' -bis (diphenylphosphino) ferrocene and 446.88mg of Zn (NO) were weighed out3)2·6H2O，327.91mg Co(NO3)2·6H2O is mixed in a certain molar ratio (Zn (NO)3)2·6H2O and Co (NO)3)2·6H2Dissolving O, 1, 1' -bis (diphenylphosphino) ferrocene with a molar ratio of 4:3:1) in 30mL of anhydrous methanol solution, and stirring at room temperature for 1h to obtain a uniform solution A; weighing 615.80mg (7.5mmol) of 2-methylimidazole, dissolving in 15mL of anhydrous methanol solution, and performing ultrasonic treatment for 10min to obtain solution B; quickly pouring the solution A into the solution B, stirring at room temperature for 1.5h, transferring into a reaction kettle, reacting at 120 ℃ for 4h, centrifuging (9500r/min), washing with an anhydrous methanol solution for more than 3 times, putting into a blast drying oven, and vacuum-drying at 70 ℃ for 12h to obtain a DPPF @ ZnCo-ZIF precursor;
step (2) Fe2P/CPreparation of o @ NC
Fully grinding the DPPF @ ZnCo-ZIF precursor obtained in the step (1), placing the ground DPPF @ ZnCo-ZIF precursor into a porcelain boat, placing the porcelain boat into a tube furnace for high-temperature carbonization treatment, introducing air into the porcelain boat for 1.0h at the room temperature in the Ar atmosphere, heating the porcelain boat to 950 ℃ at the speed of 5 ℃/min, keeping the temperature for 3.0h, and naturally cooling the porcelain boat to the room temperature to obtain Fe2P/Co @ NC catalyst.
Example 2 (comparative):
step (1) preparation of DPPF @ Zn-ZIF precursor
207.84mg of 1, 1' -bis (diphenylphosphino) ferrocene and 446.88mg of Zn (NO) were weighed out3)2·6H2O, mixed in a certain molar ratio (Zn (NO)3)2·6H2Dissolving O and 1, 1' -bis (diphenylphosphino) ferrocene in a molar ratio of 4:1) in 30mL of anhydrous methanol solution, and stirring at room temperature for 1h to obtain a uniform solution A; weighing 615.80mg (7.5mmol) of 2-methylimidazole, dissolving in 15mL of anhydrous methanol solution, and performing ultrasonic treatment for 10min to obtain solution B; quickly pouring the solution A into the solution B, stirring at room temperature for 1.5h, transferring into a reaction kettle, reacting at 120 ℃ for 4h, centrifuging (9500r/min), washing with an anhydrous methanol solution for more than 3 times, putting into a blast drying oven, and vacuum-drying at 70 ℃ for 12h to obtain a DPPF @ Zn-ZIF precursor;
step (2) Fe2Preparation of P/@ NC
Fully grinding the DPPF @ Zn-ZIF precursor obtained in the step (1), placing the ground DPPF @ Zn-ZIF precursor into a porcelain boat, placing the porcelain boat into a tube furnace for high-temperature carbonization, introducing air into the Ar atmosphere at room temperature for 1.0h, heating to 950 ℃ at the speed of 5 ℃/min, keeping the temperature for 3.0h, and naturally cooling to room temperature to obtain Fe2P/@ NC catalyst.
Example 3 (comparative):
step (1) preparation of ZnCo-ZIF precursor
Weighing 446.88mg Zn (NO)3)2·6H2O，327.91mg Co(NO3)2·6H2O, mixed in a certain molar ratio (Zn (NO)3)2·6H2O and Co (NO)3)2·6H2O molar ratio of 4:3) and dissolved in 30mL of anhydrous methanol solution at room temperatureStirring for 1h to obtain a uniform solution A; weighing 615.80mg (7.5mmol) of 2-methylimidazole, dissolving in 15mL of anhydrous methanol solution, and performing ultrasonic treatment for 10min to obtain solution B; quickly pouring the solution A into the solution B, stirring at room temperature for 1.5h, transferring into a reaction kettle, reacting at 120 ℃ for 4h, centrifuging (9500r/min), washing with an anhydrous methanol solution for more than 3 times, and vacuum-drying in a forced air drying oven at 70 ℃ for 12h to obtain a ZnCo-ZIF precursor;
step (2) preparation of Co/@ NC
And (2) fully grinding the ZnCo-ZIF precursor obtained in the step (1), placing the ZnCo-ZIF precursor into a porcelain boat, placing the porcelain boat into a tubular furnace for high-temperature carbonization treatment, introducing air for 1.0h under the Ar atmosphere at room temperature, heating to 950 ℃ at the speed of 5 ℃/min, keeping the temperature for 3.0h, and naturally cooling to room temperature to obtain the Co/@ NC catalyst.
Example 4: with Fe2Application of oxygen evolution/hydrogen evolution/oxygen reduction electrocatalyst with P/Co nanoparticle synergistic effect according to the following steps
Step (1) alkaline Membrane Fuel cell
Catalyst ink (Fe) preparation2P/Co @ NC was 10mg, isopropyl alcohol (IPA) was 1000 mL: deionized water 40 μ L), polyarylpiperidine (poly (aryl piperidine)), PAP) -terphenyl (terphenyl, TP) -85(85 is N-methyl-4-piperidone/terphenyl monomer molar ratio) (PAP-TP-85): preparing a membrane electrode by a CCM method, wherein the mass ratio of C in the catalyst is 0.45: 1; the anode is commercial 60% PtRu/C, and the cathode is corresponding Fe2P/Co @ NC with cathode loading of 1mg cm-2. Soaking the prepared Membrane Electrode (MEA) in 3M KOH solution for 2.0h (replacing solution every 1.0 h), thoroughly washing residual KOH on the membrane surface by the soaked MEA with deionized water, and mixing the washed MEA with fluorinated ethylene propylene gasket and gas diffusion layer with 5cm2The graphite bipolar plates and metal collector plates of the flow field assemble the entire alkaline fuel cell unit cell (fig. 8). A fuel cell test system (Scribner 850e) equipped with a back pressure module was used for the fuel cell test. All gases were 100% humidified, cell test temperature was 80 ℃, back pressure 2.5bar, H2And O2Respectively at a flow rate of 1.0L min-1And 1.5L min-1. Wherein Fe2The power density of the P/Co @ NC catalyst reaches 1.25W cm-2。
Step (2) Zinc-air Battery
Fe prepared by the invention2The P/Co @ NC catalyst is used as an air anode, and the loading capacity of the catalyst is 1mg cm-2Polished Zn plate as negative electrode, 6mol L-1KOH and 0.2mol L of-1The ZnO mixed solution is used as electrolyte to ensure the smooth proceeding of the Zn reversible electrochemical reaction.
Step (3) full hydrolysis
Mixing Fe2The P/Co @ NC load is used as a catalytic electrode on a carbon paper substrate, and the load of the catalyst is 2mg cm-2With two identical Fe2The P/Co @ NC electrode is used as a positive electrode and a negative electrode at the same time, and 1mol L of the P/Co @ NC electrode is used-1The KOH solution of (2) is an electrolyte.
FIG. 1a illustrates that the synthesized DPPF @ ZnCo-ZIF precursor has a uniform dodecahedral morphology with a particle size of about 200 nm.
FIG. 1b, c shows that Fe2After high-temperature calcination, the P/Co @ NC keeps the appearance of a precursor and has the size of about 180 nm. Fe after pyrolysis, compared to a smooth surface of DPPF @ ZnCo-ZIF2The surface of the P/Co @ NC became rough.
FIG. 1d, e shows, Fe2The lattice spacing of the P nanoparticles is about 0.22nm, corresponding to Fe2The (111) plane of P. The lattice spacing of 0.20nm and 0.35nm respectively corresponds to the (111) crystal face of Co and the (002) crystal face of graphite carbon, and meanwhile, a graphene layer with the thickness of about 3.5nm is wrapped on the outer layer of Co particles.
FIG. 1f-j illustrates that Fe2The spectrum of the P/Co @ NC shows C, N, P, Fe and a uniform distribution of Co elements.
FIG. 2 illustrates, Fe2P/Co @ NC, Co @ NC and Fe2XRD pattern of P @ NC. Wherein, the wider diffraction peak near 26 degrees corresponds to the (002) plane of the graphite carbon, which indicates that a graphite carbon structure is formed in the high-temperature treatment process, and the electrical conductivity and the electrocatalytic performance of the material are improved. The peaks at the 40.27 DEG, 44.20 DEG, 47.28 DEG, 52.91 DEG and 54.61 DEG correspond to Fe respectively2P/Co @ NC and Fe2Fe in P @ NC material2The (111), (201), (210), (002), (211) crystal planes of P. While the peaks at 44.22 °, 51.52 °, 75.85 ° correspond to Fe2P/Co @ NC and Fe2The Co (111), (200), (220) planes of P @ NC.
FIG. 3 illustrates that Fe2P/Co@NC(E1/20.876V) shows the ratio Pt/C (E)1/20.854V) higher half-wave potential, proving Fe2P/Co @ NC has higher ORR activity.
FIG. 4 shows that Fe2P/Co @ NC at 10mA cm-2Shows a significantly higher OER activity at a current density of 331mV compared to other samples with a lower value of Co @ NC (420mV), Fe2P @ NC (639mV) and IrO2(384mV)。
FIG. 5 illustrates that Fe2P/Co @ NC has the highest HER catalytic activity at 10mA cm-2The overpotential at this time was 235mV, close to commercial Pt/C. However, the Co-undoped catalyst Fe2P @ NC, the activity is greatly reduced, which means that the introduction of Co nanoparticles into porous carbon is of great significance for improving HER activity thereof.
FIG. 6 illustrates that in H2-O2Under the system, when the loading of the cathode in the MEA is 1mg cm-2At a backpressure of 2.5bar, Fe2The P/Co @ NC catalyst has excellent performance in an alkaline membrane fuel cell, and the maximum power density reaches 1.25W cm-2。
FIG. 7 illustrates, Fe2The open circuit potential of P/Co @ NC is 1.444V. Based on Fe2Battery 335mA cm of P/Co @ NC-2The maximum power density reaches 219.66mW cm-2Based on Pt/C-IrO2Battery (141.5mW cm)-2) More than 1.5 times of the total amount of the active ingredients.
FIG. 8 illustrates that Fe2P/Co @ NC can reach 10mA cm only by 1.73V-2The current density of (1).
It should be noted that the above-mentioned embodiments are only used for helping to understand the core idea of the present invention, the application of the present invention is not limited to the above examples, and the simplification, change, modification and the like for the above description are all within the protection scope of the present invention for those skilled in the art.
Claims (8)
1. Has Fe2The preparation method of the P/Co nanoparticle synergistic effect oxygen evolution/hydrogen evolution/oxygen reduction electrocatalyst is characterized by comprising the following steps of:
step (1), adopting a zeolite imidazole framework as a carbon substrate, dissolving a certain amount of zinc salt, cobalt salt and 1, 1' -bis (diphenylphosphino) ferrocene in a methanol solution, and stirring to obtain a uniform solution A; dissolving a certain amount of nitrogen-containing substances in a methanol solution, performing ultrasonic treatment to obtain a uniform solution B, quickly pouring the solution A into the solution B, stirring, transferring into a reaction kettle, heating, centrifuging, washing, and drying to obtain a precursor with a dodecahedron structure;
and (2) putting the precursor obtained in the step (1) into a tube furnace, and performing high-temperature pyrolysis in an inert gas atmosphere such as argon.
2. A catalyst containing Fe according to claim 12The preparation method of the oxygen evolution/hydrogen evolution/oxygen reduction electrocatalyst with P/Co nano-particle synergistic effect is characterized in that the cobalt salt in the step (1) is selected from one or more of cobalt nitrate, cobalt acetate and the like; the zinc salt is selected from one or more of zinc nitrate, zinc acetate and the like; the nitrogen-containing substance is selected from one or more of 2-methylimidazole, adenine, dicyandiamide, urea and the like;
in the step (1), fixing cobalt salt: the molar ratio of the ferric salt is 3: 1; the molar ratio of the zinc salt to the sum of the cobalt salt and the iron salt is 1-12: 1, and the preferred ratio is 1: 1.
The mass of the nitrogen-containing substance is 1-5 times of that of the iron salt.
3. A catalyst containing Fe according to claim 12The preparation method of the P/Co nanoparticle synergistic effect oxygen evolution/hydrogen evolution/oxygen reduction electrocatalyst is characterized in that in the step (1), the reaction temperature is 100-. The preferred conditions are 120 ℃ and 4h of reaction.
4. According to claim 1Said one containing Fe2The preparation method of the P/Co nanoparticle synergistic effect oxygen evolution/hydrogen evolution/oxygen reduction electrocatalyst is characterized in that in the step (2), inert gas is introduced for 1.0-5.0 h under the high-temperature pyrolysis condition, then the temperature is raised to 850-. The preferable conditions are that air is firstly ventilated for 1.0h at room temperature, then the temperature is increased to 950 ℃ at the heating rate of 5 ℃/min, and the temperature is kept for 3.0 h.
5. An electrocatalyst prepared according to the process of any one of claims 1 to 4.
6. Use of the electrocatalyst prepared according to any one of claims 1 to 4 as a tri-functional electrocatalyst for ORR, OER or HER.
7. Use according to claim 6 as an ORR, OER, HER three-function electrocatalyst for alkaline membrane fuel cells, zinc-air cells and for the electrolysis of water.
8. Use according to claim 7, as follows:
the alkaline membrane fuel cell is used as follows: commercial 60% PtRu/C is selected as an anode catalyst, the catalyst prepared by the method is used as a cathode catalyst, and the loading capacity of the catalyst is more than or equal to 0.5mg cm-2Less than or equal to 2.5mg cm-2. PAP-TP-85 is used as a hydroxide exchange membrane, PAP-TP-85 solution is used as an ionomer, a membrane electrode is prepared by a CCM (catalyst coated membrane) method or a GDL (gas diffusion electrode) method, and then the membrane electrode is used for assembling a battery and is used for an alkaline membrane fuel cell;
the zinc-air cell was used as follows: the catalyst prepared by the invention is loaded on carbon paper to be used as an air anode, and the loading capacity of the catalyst is more than or equal to 0.1mg cm-21.5 mg/cm or less-2Polished Zn plate as negative electrode, 6mol L-1KOH and 0.2mol L of-1The zinc oxide mixed solution is used as electrolyte to ensure the smooth proceeding of the Zn reversible electrochemical reaction;
the electrolytic water is applied as follows: the three-function catalyst is loaded on a carbon paper substrate to be used as a catalytic electrode, and the loading amount of the catalyst is more than or equal to 0.1mg cm-2Less than or equal to 3.5mg cm-2Two identical electrodes were used as positive and negative electrodes simultaneously, at 1mol L-1The KOH solution of (2) is an electrolyte.
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