CN114433156A - Fe/Fe with 3D structure3C @ FeNC difunctional oxygen electrocatalyst and preparation method and application thereof - Google Patents
Fe/Fe with 3D structure3C @ FeNC difunctional oxygen electrocatalyst and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000001301 oxygen Substances 0.000 title claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 20
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 17
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 229910001567 cementite Inorganic materials 0.000 claims abstract description 19
- 239000004005 microsphere Substances 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 229960003638 dopamine Drugs 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 92
- 238000010438 heat treatment Methods 0.000 claims description 40
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920001690 polydopamine Polymers 0.000 abstract description 34
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000002073 nanorod Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000012643 polycondensation polymerization Methods 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 42
- 239000003792 electrolyte Substances 0.000 description 16
- 229920006395 saturated elastomer Polymers 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Images
Classifications
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- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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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
- H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses Fe/Fe with a 3D structure3A C @ FeNC difunctional oxygen electrocatalyst and a preparation method and application thereof belong to the technical field of energy materials and electrocatalysis. First, Fe assembled from nanorods having a 3D structure was prepared2O3Microspheres, wherein the 3D Fe is coated with polydopamine formed by condensation polymerization of dopamine under the alkaline condition at room temperature2O3Fe of the surface2O3@ PDA, then, Fe of 3D structure2O3@ PDA and a certain mass ratio g-C3N4Grinding uniformly, and finally, pyrolyzing at 600-700 ℃ to obtain Fe/Fe3C @ FeNC bifunctional oxygen electrocatalyst. The inventionThe prepared catalyst can improve the nitrogen content and ensure the stability of a 3D structure, is favorable for improving the ORR/OER catalytic performance of the material, and has simple process and universal usability.
Description
Technical Field
The invention belongs to the technical field of energy materials and electrocatalysis, and particularly relates to Fe/Fe with a 3D structure constructed by a dopamine protection strategy3C @ FeNC difunctional oxygen electrocatalyst and a preparation method and application thereof.
Background
Oxygen Reduction Reactions (ORR) have found widespread use in both fuel cells and metal air cells. The fuel cell, the metal air cell and other energy devices have the advantages of high energy conversion efficiency, environmental friendliness and the like, and have important significance for solving the increasingly severe problems of energy shortage and environmental pollution. However, the oxygen reduction reaction and oxygen evolution reaction process are complex, and electrochemistry involving a series of slow-kinetic multi-step electron transfer is a main problem limiting the performance of related energy devices. In order to solve the outstanding problem, a high-performance bifunctional oxygen electrocatalyst is designed, the catalytic activity of the catalyst in ORR/OER is improved, the energy conversion efficiency can be greatly improved, and the method is very important for developing energy devices.
Currently, platinum (Pt) -based materials are widely considered to be the best performing ORR catalysts, and the only commercially available ORR catalyst, IrO2Is the best OER catalyst. However, the large-scale application of the noble metal such as Pt and Ir is severely limited due to the shortage of noble metal resources and high cost. Therefore, the preparation of Pt and Ir which have high activity and low price to replace catalysts is the key for realizing the large-scale commercialization of fuel cells and metal-air cells.
In recent years, non-noble metal catalysts with high electrocatalytic activity have attracted wide attention, especially iron-nitrogen co-doped carbon nanomaterials, which provide sufficient active sites for oxygen (O) due to the Fe-N-C structure2) Thereby having excellent ORR catalytic activity. Many carbon nanocomposites with Fe-N-C structure have ORR performance settings comparable to commercial Pt-based catalysts. However, containing Fe-NXThe carbon material with a 3D structure of the ligand has excellent ORR catalytic activity as an electrocatalyst, but the OER activity is not outstanding, which seriously limits the application of the material in rechargeable zinc-air batteries.
Disclosure of Invention
In view of the problems, the invention provides a preparation method for constructing a bifunctional oxygen electrocatalyst with a stable 3D structure and high nitrogen content by utilizing a dopamine protection strategy. Using Fe2O3As template and iron source, dopamine and g-C3N4Simultaneously used as a carbon source and a nitrogen source, firstly prepared into Fe-glycerol microspheres assembled by nano-sheets through hydrothermal reaction, and calcined in the air to prepare Fe assembled by nano-rods2O3Microspheres, then dopamine polymerization in Fe at room temperature2O3Form Fe on the surface2O3@PDA，g-C3N4As nitrogen-rich precursor, by milling with Fe2O3@ PDA is evenly mixed, and in-situ carbonization of PDA is coated on Fe in the pyrolysis process2O3Surface of (g-C)3N4Decomposing into CN gas, forming Fe-N by nitrogen atom and ironXA ligand. In addition, carbon as a reducing agent is Fe2O3Reducing the iron into simple substance iron, and reacting part of the simple substance iron with carbon to generate Fe3C. Wherein, the 3D hollow structure plays a great promoting role in enhancing the catalyst, and Fe-NXThe ligand is the main active center of ORR, and the presence of the iron-based nanoparticles greatly enhances the OER activity of the catalyst. Fe/Fe synthesized by the method3C @ FeNC catalyst, in 1M KOH solution, having an OER performance of 10mA cm-2The corresponding voltage is 1.45V, which is better than IrO2(1.51V)60 mV; the half-wave potential of ORR is 0.83V, which is superior to the catalytic activity of commercial 20% Pt/C. Simultaneously, Fe/Fe produced3C @ FeNC has better ORR and OER stability. The preparation process has universality.
The technical scheme adopted by the invention is as follows:
Fe/Fe with 3D structure3The preparation method of the C @ FeNC dual-functional oxygen electrocatalyst mainly comprises the following steps:
(1) preparation of Fe2O3Microsphere preparation: dispersing ferric salt into a solvent, transferring the mixed solution into a reaction container, reacting for 6-24 h at 160-220 ℃, washing, drying, heating to 350-450 ℃ in an air atmosphere, and preserving heat for 2-5h to obtain Fe with a 3D structure2O3Microspheres;
(2) preparation of Fe2O3@ PDA: fe prepared in the step (1)2O3Dispersing the microspheres in deionized water, and magnetizingStirring for 0.5-5 h, adding trihydroxymethyl aminomethane and dopamine, stirring and reacting for 2-10h at room temperature in air to obtain Fe2O3@ PDA material;
(3) preparation of g-C3N4: heating melamine or urea to 500-600 ℃ in air atmosphere, and preserving heat for 2-6 hours to obtain g-C3N4；
(4) Preparation of Fe/Fe3C @ FeNC microspherical catalyst: fe obtained in the step (2)2O3@ PDA and g-C3N4Grinding, mixing, placing in a reaction furnace, heating to 600-700 ℃ under inert atmosphere, calcining for 0.5-3 h to obtain Fe/Fe3C @ FeNC bifunctional oxygen electrocatalyst.
Further, the iron salt in the step (1) comprises ferric nitrate, ferric sulfate and ferric chloride; the concentration of the ferric salt is 0.01-1 mM, and the solvent is a mixed solution of glycerol, isopropanol and deionized water.
Further, the volume ratio of glycerol, isopropanol and deionized water in the solvent is (5-10): (60-80): 1.
further, the reaction vessel in the step (1) is a high-pressure reaction kettle; washing is carried out for 2-5 times by sequentially using alcohol and deionized water, and the heating rate is 1-3 ℃ for min-1。
Further, Fe in step (2)2O3The mass ratio of the microspheres to the deionized water is (0.5-2): 1, Fe2O3The mass ratio of the microspheres to the trihydroxymethyl aminomethane to the dopamine is (2-6): 1: (2-4).
Further, the specific step of the step (3) is to add melamine or urea into a quartz boat, place the quartz boat in a tube furnace, and heat the quartz boat to 500-600 ℃ in the air atmosphere at a heating rate of 3-6 ℃ for min-1And keeping the temperature for 2-6 h.
Further, said Fe in step (4)2O3@ PDA and g-C3N4The mass ratio of (1: 2) to (50: 1).
Further, the reaction furnace in the step (4) is a tube furnace, and the inert gas comprises argonGas, helium, nitrogen; the temperature rise rate is 1-3 ℃ min-1。
The invention also provides Fe/Fe with a 3D structure prepared by the preparation method3C @ FeNC bifunctional oxygen electrocatalyst.
The invention also provides the 3D structure Fe/Fe3The C @ FeNC bifunctional oxygen electrocatalyst is applied to fuel cells and metal air cells.
Compared with the prior art, the invention has the following beneficial effects:
(1) using Fe assembled from nanorods2O3The hollow microspheres are used as templates and are subjected to dopamine in-situ polymerization to obtain Fe2O3The @ PDA can reproduce the microscopic morphology of the template to form a hollow porous open skeleton, the large pore channel and the high specific surface area of the skeleton can expose more active sites, and the mass transfer of reactants, intermediates and products can be promoted, thereby being beneficial to improving the ORR/OER catalytic activity of the material.
(2) After the iron-based nanoparticles are coated by nitrogen-doped carbon, the oxidation agglomeration of the iron-based nanoparticles and the dissolution in a strong alkali environment are avoided, so that the catalyst has good stability. Meanwhile, the iron agent nano particles enrich the electron density on the carbon surface, promote the surface reaction and further improve the electrocatalytic activity of the material.
(3) In the form of Fe2O3And nitrogen-rich precursor g-C3N4The middle part is introduced with a polydopamine layer to slow down g-C3N4With Fe2O3The shape of the template is protected, namely the structure of the template is protected, the content of nitrogen is increased, and in addition, in the high-temperature pyrolysis process, nitrogen atoms and Fe atoms form Fe-NXThe ligand, the active site of the ORR reaction.
(4) The presence of iron-based nanoparticles promotes Fe/Fe3OER performance of C @ FeNC.
(5) Fe/Fe according to the invention3The ORR and OER activity/stability and methanol resistance of the C @ FeNC catalyst under alkaline conditions are superior to those of commercial noble metal catalysts.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings to which the embodiments relate will be briefly described below.
FIG. 1 is an XRD pattern of samples prepared in example 2, example 11 and example 12.
FIG. 2 is SEM images of samples obtained in example 2, example 11 and example 12; wherein a is Fe in example 22O3SEM pictures of @ PDA, b, c and d are SEM pictures of calcined samples of example 2, example 11 and example 12, respectively.
FIG. 3 is an XPS chart of samples prepared in example 2, example 11 and example 12.
FIG. 4 is a graph of the results of samples obtained in examples 2, 11, 12 and 1 in O2ORR performance LSV curve in saturated 0.1M KOH electrolyte.
FIG. 5 shows the results of samples obtained in examples 2, 11, 12 and 2 in O2OER performance LSV curve in saturated 1m koh electrolyte.
FIG. 6 is a graph of the results of samples prepared in examples 1, 2, 3, 4 and 5 at O2ORR performance LSV curve in saturated 0.1M KOH electrolyte.
FIG. 7 is a graph of the results of samples prepared in examples 1, 2, 3, 4 and 5 at O2OER performance LSV curve in saturated 1M KOH electrolyte.
FIG. 8 is a plot of the samples prepared in examples 2, 6, 7, 8, 9 and 10 at O2ORR performance LSV curve in saturated 0.1M KOH electrolyte.
FIG. 9 shows the results of samples prepared in examples 2, 7, 8, 9 and 10 at O2OER performance LSV curve in saturated 1M KOH electrolyte.
FIG. 10 shows the results of the samples of example 2 and comparative example 1 at O2Chronoamperometric profile in saturated 0.1M KOH electrolyte.
Fig. 11 is a graph showing the results of testing the metal-air battery in example 13 of the sample of example 2.
Detailed Description
The present invention is described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto, and it is obvious that the examples in the following description are only some examples of the present invention, and it is obvious for those skilled in the art to obtain other similar examples without inventive labor and falling into the scope of the present invention.
Example 1:
Fe/Fe with 3D structure3The preparation method of the C @ FeNC dual-function oxygen electrocatalyst comprises the following steps:
(1) 0.4mmol of Fe (NO)3)3·9H2Dissolving O in a mixed solution of 60ml of glycerol and 420ml of isopropanol until Fe (NO) is obtained3)3·9H2And after the O is completely dissolved, adding 6ml of deionized water, stirring for 15min, pouring into a high-temperature reaction kettle, and reacting for 12h at 190 ℃. Washing with alcohol and deionized water for several times, drying at 60 deg.C, transferring into a tubular furnace, heating to 400 deg.C in air atmosphere, maintaining for 3 hr at a heating rate of 1 deg.C for min-1To obtain 3D Fe2O3Microspheres;
(2) mixing 100mg of Fe2O3Dispersing microspheres in 75ml of water, magnetically stirring for 1h to form uniform suspension, adding 25mg of tris (hydroxymethyl) aminomethane and 75mg of dopamine into the suspension, magnetically stirring for 6h, centrifugally washing for several times, and drying at 60 ℃ to obtain Fe2O3@PDA；
(3) Adding melamine or urea into quartz boat, placing in tube furnace, heating to 550 deg.C in air, and heating at 6 deg.C for min-1Keeping the temperature for 4 hours to prepare g-C3N4；
(4) Mixing Fe2O3@ PDA and g-C3N4According to the mass ratio of 1: 1 grinding uniformly, transferring into a tube furnace, N2Heating to 650 deg.C under atmosphere, maintaining for 0.5h at a heating rate of 2 deg.C for min-1To obtain Fe/Fe3C@FeNC。
Example 2:
this example and implementationThe experimental procedure of example 1 is the same, differing only in that: fe2O3@ PDA and g-C3N4According to the mass ratio of 1: 1 grinding uniformly, transferring into a tube furnace, N2Heating to 650 ℃ under the atmosphere, keeping the temperature for 0.75h, wherein the heating rate is 2 ℃ for min-1To obtain Fe/Fe3C@FeNC。
Example 3:
this example is identical to the experimental procedure of example 1, except that: fe2O3@ PDA and g-C3N4According to the mass ratio of 1: 1 grinding uniformly, transferring into a tube furnace, N2Heating to 650 deg.C under atmosphere, maintaining for 1h at a heating rate of 2 deg.C for min-1To obtain Fe/Fe3C@FeNC-1。
Example 4:
this example is identical to the experimental procedure of example 1, except that: fe2O3@ PDA and g-C3N4According to the mass ratio of 1: 1 grinding uniformly, transferring into a tube furnace, N2Heating to 650 ℃ under the atmosphere, keeping the temperature for 2h, wherein the heating rate is 2 ℃ for min-1To obtain Fe/Fe3C@FeNC-2。
Example 5:
this example is identical to the experimental procedure of example 1, except that: fe2O3@ PDA and g-C3N4According to the mass ratio of 1: 1 grinding uniformly, transferring into a tube furnace, N2Heating to 650 ℃ under the atmosphere, and keeping the temperature for 3h, wherein the heating rate is 2 ℃ for min-1To obtain Fe/Fe3C@FeNC-3。
Example 6:
this example is identical to the experimental procedure of example 1, except that: fe2O3@ PDA and g-C3N4According to the mass ratio of 50: 1 grinding uniformly, transferring into a tube furnace, N2Heating to 650 ℃ under the atmosphere, keeping the temperature for 0.75h, wherein the heating rate is 2 ℃ for min-1To obtain Fe/Fe3C@FeNC-50/1。
Example 7:
this example is the same as the experimental procedure of example 1,the only difference is that: fe2O3@ PDA and g-C3N4According to the mass ratio of 20: 1 grinding uniformly, transferring into a tube furnace, N2Heating to 650 ℃ under the atmosphere, keeping the temperature for 0.75h, wherein the heating rate is 2 ℃ for min-1To obtain Fe/Fe3C@FeNC-20/1。
Example 8:
this example is identical to the experimental procedure of example 1, except that: fe2O3@ PDA and g-C3N4According to the mass ratio of 10: 1 grinding uniformly, transferring into a tube furnace, N2Heating to 650 ℃ under the atmosphere, keeping the temperature for 0.75h, wherein the heating rate is 2 ℃ for min-1To obtain Fe/Fe3C @ FeNC-10/1.
Example 9:
this example is identical to the experimental procedure of example 1, except that: fe2O3@ PDA and g-C3N4According to the mass ratio of 1: 1.5 grinding uniformly, transferring into a tube furnace, and N2Heating to 650 ℃ under the atmosphere, keeping the temperature for 0.75h, wherein the heating rate is 2 ℃ for min-1To obtain Fe/Fe3C@FeNC-1/1.5。
Example 10:
this example is identical to the experimental procedure of example 1, except that: fe2O3@ PDA and g-C3N4According to the mass ratio of 1: 2 grinding uniformly, transferring into a tube furnace, N2Heating to 650 deg.C under atmosphere, maintaining for 0.75h at a heating rate of 2 deg.C for min-1To obtain Fe/Fe3C@FeNC-1/2。
Example 11:
this example is identical to the experimental procedure of example 1, except that: mixing Fe2O3Directly with g-C3N4According to the mass ratio of 1: 1 grinding uniformly, transferring into a tube furnace, N2Heating to 650 ℃ under the atmosphere, keeping the temperature for 0.75h, wherein the heating rate is 2 ℃ for min-1To obtain Fe/Fe3C@FeNC-nP-1/1。
Example 12:
25mg of tris-hydroxymethyl aminomethane, 75mg of dopamine are addedMagnetically stirring 75ml water for 6 hr, centrifuging for several times, drying at 60 deg.C to obtain PDA, and mixing PDA with g-C3N4According to the mass ratio of 1: 1 grinding uniformly, transferring into a tube furnace, N2Heating to 650 deg.C under atmosphere, maintaining for 0.5h at a heating rate of 2 deg.C for min-1And obtaining NC.
Example 13:
the metal-air battery of this example is a zinc-air battery comprising an air diffusion electrode/electrolyte and a metal electrode; the air diffusion electrode is 3D hollow Fe/Fe to be prepared3C @ FeNC material is dispersed in isopropanol to prepare dispersion liquid, and then the dispersion liquid is coated on carbon cloth and naturally dried to obtain the carbon cloth; 3D hollow Fe/Fe3The loading capacity of the C @ FeNC material on the carbon cloth is 1.0mg cm-2(ii) a The electrolyte is 0.2M zinc acetate and 6M potassium hydroxide aqueous solution; the metal electrode is a polished zinc plate.
Comparative example 1:
this example is the same experiment as example 13 except that a commercial 20% Pt/C catalyst was used.
Comparative example 2:
this example is the same as the experiment of example 13, except that commercial IrO was used2A catalyst.
FIG. 1 is an XRD pattern of samples prepared in example 2, example 11 and example 12; as can be seen from the figure, diffraction peaks of the iron simple substance and the iron carbide appear in both example 2 and example 11.
FIG. 2 is an SEM image of samples prepared in example 2, example 11 and example 12; wherein a is Fe in example 22O3SEM pictures of @ PDA, b, c and d are SEM pictures of example 2, example 11 and example 12 after calcination, respectively; as can be seen from the figure, Fe2O3@ PDA is hollow microspheres assembled from nanorods; as is clear from the SEM images of fig. 2b and c, when dopamine is not added, the microsphere structure of the template is destroyed after pyrolysis to form individual nanorods, and after coating with dopamine, the 3D structure of the template is retained; from fig. d it can be seen that PDA and g-C3N4By high temperature heatingThe structure of the PDA nanospheres remained after the solution.
FIG. 3 is an XPS chart of samples prepared in example 2, example 11 and example 12. FIG. 3a is the XPS medium spectrum of example 2, example 11 and example 12, and FIG. 3b is the Fe 2p high resolution spectrum of example 2 and example 11, wherein 706.1, 720.1eV is Fe0709.3, 723.2eV is Fe2+A peak of (a); FIG. 3c is a high resolution spectrum of N1s of example 2, example 11 and example 12, wherein example 2 and example 11 can deconvolute well the four peaks at 397.8, 398.8, 399.9 and 4002eV, respectively, which are attributed to pyridine N, Fe-NXPyrrole N and graphite N; and example 12 is Fe-N freeX(ii) a FIG. 3d is the relative N content of examples 2, 11, and 12.
FIG. 4 shows the results of samples obtained in examples 2, 11, 12 and 1 in O2ORR performance LSV curve in saturated 0.1M KOH electrolyte. As can be seen from the graph, example 2 has the best ORR performance, with a half-wave potential of 0.83V and a current density of 7.7mA cm-2。
FIG. 5 shows the results of samples obtained in examples 2, 11, 12 and 2 in O2OER performance LSV curve in saturated 1m koh electrolyte. It can be seen from FIG. 5 that example 2 has the optimum OER performance of 10mA cm-2The corresponding voltage is minimum (1.45V).
FIG. 6 is a graph of the results of samples prepared in examples 1, 2, 3, 4 and 5 at O2ORR Performance LSV Curve in saturated 0.1M KOH electrolyte, sweep Rate of 10mV s-1And the rotating speed: 1600rpm, room temperature; as can be seen from FIG. 6, the best ORR performance was obtained at a calcination time of 0.75h, a half-wave potential of 0.83V and a current density of 7.7mA cm-2。
FIG. 7 is a graph of the results of samples prepared in examples 1, 2, 3, 4 and 5 at O2OER Performance LSV Curve in saturated 1M KOH electrolyte, sweep Rate of 10mV s-1And the rotating speed: 1600rpm, room temperature; it can be seen from FIG. 7 that the best OER performance is obtained at a calcination time of 0.75h, which is 10mA cm-2Corresponding voltage is maximumSmall (1.45V).
FIG. 8 is a plot of the samples prepared in examples 2, 6, 7, 8, 9 and 10 at O2ORR Performance LSV Curve in saturated 0.1M KOH electrolyte, sweep Rate of 10mV s-1And the rotating speed: 1600rpm, room temperature. It can be seen from FIG. 8 that the following Fe2O3@ PDA and g-C3N4The half-wave potential is increased first and then decreased. In Fe2O3@ PDA and g-C3N4The mass ratio of (1): 1, the best ORR performance is achieved, the half-wave potential is 0.83V, and the current density is 7.7mA cm-2。
FIG. 9 is a graph of the results of samples prepared in examples 2, 7, 8, 9 and 10 at O2OER Performance LSV Curve in saturated 1M KOH electrolyte, sweep Rate of 10mV s-1And the rotating speed: 1600rpm, room temperature. It can be seen from FIG. 8 that the following Fe2O3@ PDA and g-C3N4At 10mA cm-2The corresponding voltage is increased after being decreased; in Fe2O3@ PDA and g-C3N4The mass ratio of (1): 1 hour, has the best OER performance, which is 10mA cm-2The corresponding voltage is minimum (1.45V).
FIG. 10 shows the results of the samples of example 2 and comparative example 1 at O2Chronoamperometric curve in saturated 0.1M KOH electrolyte, potential 0.60V (vs RHE), room temperature. As can be seen from FIG. 10, the Pt/C catalyst decays to 64% after 18000s cycles, while the Fe/Fe catalyst decays to3The decrease of C @ FeNC is only 6%, which indicates that Fe/Fe3The stability of C @ FeNC is obviously superior to that of Pt/C catalyst, which shows that the nitrogen-doped carbon-coated 3D Fe/Fe3The C @ FeNC catalyst has excellent catalytic stability.
FIG. 11 is a graph showing the results of testing the sample of example 2 in the metal-air battery of example 13, wherein a is a schematic diagram of a rechargeable zinc-air battery, b is an open circuit potential of the zinc-air battery, c is a charge-discharge polarization curve and a corresponding power density, and d is a value obtained by using Fe/Fe3C @ FeNC as the specific capacity and energy density of the battery, and (e) Fe/Fe3Rechargeable zinc-air battery assembled by C @ FeNCThe current density of the gas battery is 5mA cm-2Discharge-charge cycle curve of time.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. Fe/Fe with 3D structure3The preparation method of the C @ FeNC dual-functional oxygen electrocatalyst is characterized by mainly comprising the following steps of:
(1) preparation of Fe2O3Microsphere preparation: dispersing ferric salt into a solvent, transferring the mixed solution into a reaction container, reacting for 6-24 h at 160-220 ℃, washing, drying, heating to 350-450 ℃ in an air atmosphere, and preserving heat for 2-5h to obtain Fe with a 3D structure2O3Microspheres;
(2) preparation of Fe2O3@ PDA: fe prepared in the step (1)2O3Dispersing the microspheres in deionized water, adding trihydroxymethyl aminomethane and dopamine, stirring and reacting for 2-10h to obtain Fe2O3@ PDA material;
(3) preparation of g-C3N4: heating melamine or urea to 500-600 ℃ in air atmosphere, and preserving heat for 2-6 hours to obtain g-C3N4；
(4) Preparation of Fe/Fe3C @ FeNC microsphere catalyst: fe obtained in the step (2)2O3@ PDA with g-C prepared in step (3)3N4Grinding, mixing, placing in a reaction furnace, heating to 600-700 ℃ under inert atmosphere, calcining for 0.5-3 h to obtain Fe/Fe3C @ FeNC bifunctional oxygen electrocatalyst.
2. The method according to claim 1, wherein the iron salt in step (1) comprises ferric nitrate, ferric sulfate, ferric chloride; the concentration of the ferric salt is 0.01-1 mM, and the solvent is a mixed solution of glycerol, isopropanol and deionized water.
3. The preparation method according to claim 2, wherein the volume ratio of glycerol, isopropanol and deionized water in the solvent is (5-10): (60-80): 1.
4. the production method according to claim 1, wherein the reaction vessel in the step (1) is an autoclave; washing is carried out for 2-5 times by sequentially using alcohol and deionized water; the heating rate is 1-3 ℃ min-1。
5. The method according to claim 1, wherein Fe is used in the step (2)2O3The mass ratio of the microspheres to the deionized water is (0.5-2): 1, Fe2O3The mass ratio of the microspheres to the trihydroxymethyl aminomethane to the dopamine is (2-6): 1: (2-4).
6. The preparation method according to claim 1, wherein the step (3) comprises adding melamine or urea into a quartz boat, placing in a tube furnace, and heating to 500-600 deg.C in air atmosphere at a heating rate of 3-6 deg.C for min-1And keeping the temperature for 2-6 h.
7. The method according to claim 1, wherein the Fe in the step (4)2O3@ PDA and g-C3N4The mass ratio of (1: 2) to (50: 1).
8. The method according to claim 1, wherein the reaction furnace in the step (4) is a tube furnace, and the inert gas includes argon, helium, nitrogen; the heating rate is 1-3 ℃ min-1。
9. 3D structure Fe/Fe prepared by the preparation method of any one of claims 1 to 83C @ FeNC bifunctional oxygen electrocatalyst.
10. The 3D structure of claim 9 Fe/Fe3The C @ FeNC bifunctional oxygen electrocatalyst is applied to a fuel cell or/and a metal air cell.
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