CN113285081A - FeCo-PPc catalyst and preparation method and application thereof - Google Patents
FeCo-PPc catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical class NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 6
- 239000004202 carbamide Chemical class 0.000 claims abstract description 6
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical class C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical class [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 5
- 239000011609 ammonium molybdate Chemical class 0.000 claims abstract description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 235000013877 carbamide Nutrition 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000009776 industrial production Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 5
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 5
- 230000010287 polarization Effects 0.000 description 4
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004769 chrono-potentiometry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920003240 metallophthalocyanine polymer Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 phthalocyanine macrocycles Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- 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
-
- 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
- H01M4/9008—Organic or organo-metallic compounds
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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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
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- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention relates to a FeCo-PPc catalyst and a preparation method and application thereof. In one embodiment of the present invention, a method for preparing a FeCo-PPc catalyst comprises the steps of: mixing PMDA, urea, ammonium chloride, ammonium molybdate, Fe salt and Co salt according to a preset proportion, grinding, heating the obtained mixture at 220 ℃ for 3 hours, cooling to room temperature, washing with water and an organic solvent in sequence, and finally drying to obtain the catalyst. The FeCo-PPc catalyst has excellent catalytic activity and stability when being applied to OER reaction, and has the advantages of simple preparation method and easy realization of large-scale industrial production.
Description
Technical Field
The present invention relates to the field of OER catalysts; more particularly, it relates to a FeCo-PPc catalyst applied to OER reaction and its preparation method.
Background
With the rapid increase of energy demand, the increasingly serious energy crisis and environmental problems have become important factors restricting the development of energy industry, and therefore, there is a need to establish a clean energy system capable of sustainable development. Among them, electrochemical-related energy conversion and storage devices are receiving increasing attention, and the two most representative research directions are metal-air batteries and electrolytic water.
The OER reaction (oxygen evolution reaction) is one of the important reactions in many energy storage processes, such as metal-air batteries and electrolytic water, while the four electron transfer OER reaction process (4 OH)-→2H2O+4e-+O2In alkaline medium) is a key factor limiting the efficiency of water electrolysis. Such as RuO2And IrO2The noble metal oxides of (a) are currently the most effective OER catalysts, but the problems of high cost, limited resources and poor stability greatly limit their large-scale commercial use. Therefore, designing a low-cost, high-performance non-noble metal-based OER catalyst to promote reaction kinetics is a key step to accelerate the industrialization of electrolyzed water.
Among non-noble metal-based OER catalysts, MOFs (metal organic framework) materials have received a great deal of attention due to their tunable structure, large specific surface area and controllable electrical properties. The MOFs materials can be used as precursors for the preparation of various OER catalysts, or can be used directly as OER catalysts. Currently, effective strategies for developing MOFs material OER catalysts are mainly focused on increasing their intrinsic activity and exposing a large number of active sites.
M-PPc (metallophthalocyanine) is a conjugated aromatic structure consisting of a transition metal center with adjustable oxidation state and a macrocyclic ligand backbone. M-PPc is different from M-Pc (metal phthalocyanine) in that it is not a polymer of M-Pc; that is, the monomer unit of the polyphthalocyanine is not a phthalocyanine, nor does the catalytic characteristics of the polyphthalocyanine correspond to a phthalocyanine. In the prior art, M-PPc is generally used as a template or precursor for preparing an electrocatalyst, and is not directly used for electrocatalysis of an OER reaction.
Disclosure of Invention
The invention mainly aims to provide a FeCo-PPc catalyst, a preparation method and an application thereof, wherein the FeCo-PPc catalyst is easy to prepare and realize large-scale industrial production, and has excellent catalytic activity and stability for OER reaction in an industrial operation environment.
One aspect of the present invention relates to a FeCo-PPc catalyst for OER reaction having a structural formula as shown below:
wherein the molar ratio of Fe to Co is 1: 1.
Another aspect of the invention relates to the use of the FeCo-PPc catalyst described above in OER reactions.
Yet another aspect of the present invention relates to a method for preparing a FeCo-PPc catalyst for OER reaction, comprising the steps of:
s1, mixing and grinding PMDA (pyromellitic dianhydride), urea, ammonium chloride, ammonium molybdate, Fe salt and Co salt according to a preset proportion; wherein the molar ratio of the Fe salt to the Co salt is 1: 1;
s2, heating the mixture obtained in the step S1 at 200-320 ℃ for 2-5 hours;
and S3, cooling the product obtained in the step S2, washing the product with water and an organic solvent in sequence, and drying the product to obtain the FeCo-PPc catalyst.
Specifically, in step S1, 1.7 parts by mole of PMDA, 10 parts by mole of urea, 3 parts by mole of ammonium chloride, 0.35 parts by mole of ammonium molybdate, 0.37 parts by mole of iron salt, and 0.37 parts by mole of cobalt salt are mixed and ground.
Specifically, the Fe salt is ferric chloride.
Specifically, the Co salt is cobalt chloride.
Specifically, in step S2, the mixture was heated at 220 ℃ for 3 hours.
Specifically, the organic solvent includes acetone and/or ethanol.
Still another aspect of the present invention relates to the use of the FeCo-PPc catalyst prepared by the above preparation method in OER reaction.
As described in detail later, the FeCo-PPc catalyst of the present invention has excellent catalytic activity and stability when applied to OER reaction even under industrial operation environment; the FeCo-PPc catalyst can be prepared by a one-step solid-phase synthesis method, and has the advantages of simple preparation method and easy realization of large-scale industrial production.
To more clearly illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described in detail with reference to the accompanying drawings and detailed description.
Drawings
FIG. 1a shows FeCo-PPc, Fe2XRD diffraction patterns of Co-PPc, Fe-PPc, Co-PPc and PPc samples;
FIG. 1b is an FT-IR spectrum of FeCo-PPc, Fe-PPc, Co-PPc and PPc samples;
FIGS. 1c, d and e are FESEM, TEM and HRTEM images, respectively, of FeCo-PPc samples;
FIG. 2a is a Fe 2p high resolution XPS spectrum of FeCo-PPc and Fe-PPc;
FIG. 2b is a Co 2p high resolution XPS spectrum of FeCo-PPc and Co-PPc;
FIG. 2c is a N1s high resolution XPS map of FeCo-PPc;
FIG. 2d is a C1s high resolution XPS spectrum of FeCo-PPc, Fe-PPc and Fe-PPc;
FIG. 3a is an IR-corrected polarization curve for FeCo-PPc, Fe-PPc and PPc at 1.0M KOH at room temperature;
FIG. 3b is a stability test curve of FeCo-PPc under 1M KOH, room temperature conditions;
FIG. 3c is a stability test curve of FeCo-PPc in 6M KOH, 85 ℃ industrial operating environment;
FIG. 3d is a polarization curve (not IR corrected) of FeCo-PPc before and after stability testing in 6M KOH at 85 ℃ industrial service environment;
FIG. 4 is Fe3Co-PPc、Fe2Co-PPc、FeCo-PPc、FeCo2PPc and FeCo3-IR-corrected polarization curve of PPc at 1.0M KOH at room temperature.
Detailed Description
Examples
The FeCo-PPc catalyst disclosed by the embodiment of the invention has the following structural formula:
wherein the molar ratio of Fe to Co is 1: 1.
The FeCo-PPc catalyst disclosed by the embodiment of the invention can be prepared by adopting a one-step solid-phase synthesis method. Specifically, the embodiment of the preparation method of the FeCo-PPc catalyst comprises the following steps:
first, 1.7mol of PMDA, 10mol of urea and 3mol of NH were mixed4Cl (ammonium chloride), 0.35mmol H24Mo7N6O24·4H2O (ammonium molybdate tetrahydrate), 0.37mol FeCl3·6H2O (ferric trichloride hexahydrate) and 0.37mol of CoCl2·6H2O (cobalt chloride hexahydrate) was mixed and milled.
The milled mixture was then transferred to a crucible and heated in a muffle furnace at 220 ℃ for 3 hours in an atmosphere of air. And after cooling to room temperature, washing the obtained product with water, acetone and ethanol in sequence, and drying at 60 ℃ for 12 hours to obtain the FeCo-PPc catalyst.
Comparative example
By adjusting the amounts of ferric chloride and cobalt chloride with reference to the preparation methods of the foregoing examples, the following comparative M-PPc catalysts were prepared: fe2Co-PPc (comparative example 1), FeCo2PPc (comparative example 2), Fe3Co-PPc (comparative example 3), FeCo3-PPc (comparative example 4), Fe-PPc (comparative example 5), Co-PPc (comparative example 6).
Structural and topographical characterization
FIG. 1a shows FeCo-PPc, Fe2XRD patterns of Co-PPc, Fe-PPc, Co-PPc and PPc samples. In FeCo-PPc, Fe2In the XRD patterns of the Co-PPc, Fe-PPc and Co-PPc samples, main diffraction peaks at 2 theta angles of 17.3 degrees, 18.4 degrees, 18.9 degrees, 25.7 degrees, 29.5 degrees and 30.4 degrees correspond to (200), (001), (101), (310), (001) and (101) crystal planes of the respective samples, respectively.
Infrared Spectroscopy (FT-IR) by Fourier transform) At 400-4000cm–1The functional groups and the molecular structures of the M-PPc samples are analyzed in the wavelength range of (A), and the results show that all the samples show infrared characteristic peaks of phthalocyanine macrocycles. In particular, FIG. 1b shows FT-IR spectra of FeCo-PPc, Fe-PPc, Co-PPc and PPc samples, 1699cm–1The absorption peak at (a) can be attributed to C ═ C aromatic extension; FT-IR spectra of all samples were 1699cm–1、1465cm–1And 1371cm–1All have the same phthalocyanine skeleton signal at 1308cm–1And 1150cm–1Has C-N telescopic vibration absorption peak at 945cm–1Has a vibration absorption peak of metal-ligand bond (M-N) at 638-–1Has a swing and torsion vibration absorption peak of a C-H group at 1063-1465cm–1Has an isoindole ring stretching vibration absorption peak, and the stretching vibration absorption peaks of C-O and C ═ O are respectively 1063cm–1And 1769cm–1And (c) occurs. These results confirm that the catalyst samples have the characteristic vibration of metal-N coordination and phthalocyanine macrocycle skeleton.
Further, the bulk morphology of FeCo-PPc, Fe-PPc and Co-PPc was confirmed using Field Emission Scanning Electron Microscopy (FESEM), and FeCo-PPc has a rougher surface than Fe-PPc and Co-PPc, which facilitates exposure of more active sites. FIG. 1c is a FESEM image of FeCo-PPc, from which it can be seen that FeCo-PPc has a layered stack structure. In addition, it can be further confirmed from the TEM image of FIG. 1d that FeCo-PPc has a bulk stacked structure.
FIG. 1e is a High Resolution TEM (HRTEM) image of FeCo-PPc, which clearly shows highly ordered crystal planes, indicating that FeCo-PPc has good crystallinity. FeCo-PPc disclosed by the invention can be deconvoluted into two pi-pi stacked crystal forms of alpha and beta, and lattice stripes with the spacing of 0.304nm and 0.265nm in FIG. 1e respectively correspond to the (001) crystal face of the alpha-FeCo-PPc and the (002) crystal face of the beta-FeCo-PPc.
XPS analysis
The chemical composition and state of FeCo-PPc, Fe-PPc and Co-PPc samples were further analyzed by X-ray photoelectron spectroscopy (XPS). Wherein, the XPS analysis of the FeCo-PPc sample shows that the FeCo-PPc sample has the following element compositions and atomic percentages: c (68.2 at%), O (16.4 at%), N (12.8 at%), Fe (1.3 at%), Co (1.3 at%).
As shown in FIG. 2a, Fe 2p high resolution XPS spectra of FeCo-PPc showed Fe 2p at 711.71eV and 725.12eV respectively3/2And Fe 2p1/2Two main peaks, of which the doublets correspond to Fe respectively2+(710.90eV, 725.10eV) and Fe3+(713.26eV, 727.59 eV). It can be seen that Fe 2P in FeCo-PPc is comparable to Fe-PPc3/2The electron binding energy of (a) is shifted to higher energy (Δ E ═ 0.65eV), indicating that the chemical environment changes with increasing Co central electron density, which is favorable for improvement of OER catalytic activity.
As shown in FIG. 2b, Co 2p high resolution XPS spectra of FeCo-PPc showed Co 2p at 781.17 and 796.54eV, respectively3/2And Co 2p1/2Two major peaks, two of the major peaks of FeCo-PPc have higher binding energy than Co-PPc. A shift in the XPS peak is observed in FeCo-PPc compared to Fe-PPc and Co-PPc, indicating that some of the charge is transferred from Co to Fe centers, resulting in Fe centers with greater electron density.
Fig. 2c is a N1s high resolution XPS spectrum of FeCo-PPc, in which peaks 400.8eV, 399.4eV and 398.7eV may be attributed to the M-N bond (M ═ Co, Fe), the nitrogen atom (N β) connecting the isoindole ring and the nitrogen atom (N α) adjacent to the central metal atom, respectively.
Application as OER reaction catalyst
Samples were tested for electrocatalytic performance for OER reactions by Linear Sweep Voltammetry (LSV) and Cyclic Voltammetry (CV), under the following test conditions: three electrode cell system, 1.0M KOH solution saturated with oxygen, room temperature.
From the LSV curve of FIG. 3a, FeCo-PPc at 20mA cm-2Shows a minimum overpotential of 237mV, which is much lower than Fe-PPc (330.3mV), Co-PPc (390.6mV), and PPc (393.6mV), indicating that FeCo-PPc has better catalytic activity.
It is particularly pointed out that the OER catalytic activity of FeCo-PPc prepared by the invention in alkaline medium is obviously superior to that of the known electric catalyst based on phthalocyanine or MOFs. The excellent OER activity of FeCo-PPc can be attributed to the strong electronegativity of the N atom, which regulates the electron cloud density of neighboring atoms and forms active sites to promote the adsorption of reactants.
Further, the stability of the FeCo-PPc catalyst was tested by Chronopotentiometry (CP). The chronopotentiometric curve shown in FIG. 3b indicates that FeCo-PPc has very strong stability at 100mA cm-2Can maintain the OER activity for at least 24 hours under the constant current density.
In particular, it can be seen from fig. 3c-d that the FeCo-PPc catalyst shows excellent activity and stability even in 6M KOH solution, 85 ℃ industrial application environment: keeping at 100 and 500mA cm-2While the high current density of (c) exceeds 21 hours, only potentials below about 0.64V (vs. hg/HgO) increase.
The inventors have found that the molar ratio of Fe and Co in M (M ═ Fe, Co) -PPC has a significant effect on its OER activity. FIG. 4 is Fe3Co-PPc、Fe2Co-PPc、FeCo-PPc、FeCo2PPc and FeCo3Comparison of IR-corrected polarization curves of-PPc at 1.0M KOH at room temperature, it can be seen from FIG. 4 that FeCo-PPc has significantly better OER catalytic activity.
In addition, the test calculation shows that the Tafel slope of FeCo-PPc is 41.57mV dec–1This ratio is Fe2Co-PPc(43.28mV·dec–1)、FeCo2-PPc(55.98mV·dec–1)、Fe3Co-PPc(61.91mV·dec–1)、FeCo3-PPc(64.81mV·dec–1)、Fe-PPc(55.7mV·dec–1) And Co-PPc (83.26mV dec)–1) Is much lower. It can be seen that the FeCo-PPc catalyst can accelerate the OER kinetic reaction more rapidly and has better catalytic activity for the OER reaction than the catalysts of comparative examples 1-6.
In conclusion, the FeCo-PPc catalyst of the present invention has excellent catalytic activity and stability for OER reaction even under industrial application environment. In addition, the FeCo-PPc catalyst can be prepared by a one-step solid-phase synthesis method, and has the advantages of simple preparation method and easy realization of large-scale industrial production.
Although the invention has been described with reference to specific embodiments, it will be appreciated by those skilled in the art that equivalent modifications made in accordance with the present invention are intended to be included within the scope of the present invention without departing from the scope thereof.
Claims (9)
1. A FeCo-PPc catalyst for OER reaction having the structural formula shown below:
wherein the molar ratio of Fe to Co is 1: 1.
2. Use of the FeCo-PPc catalyst of claim 1 in OER reactions.
3. A preparation method of FeCo-PPc catalyst for OER reaction comprises the following steps:
s1, mixing and grinding PMDA, urea, ammonium chloride, ammonium molybdate, Fe salt and Co salt according to a preset proportion; wherein the molar ratio of the Fe salt to the Co salt is 1: 1;
s2, heating the mixture obtained in the step S1 at 200-320 ℃ for 2-5 hours;
and S3, cooling the product obtained in the step S2, washing the product with water and an organic solvent in sequence, and drying the product to obtain the FeCo-PPc catalyst.
4. The method according to claim 3, wherein 1.7 parts by mole of PMDA, 10 parts by mole of urea, 3 parts by mole of ammonium chloride, 0.35 parts by mole of ammonium molybdate, 0.37 parts by mole of iron salt and 0.37 parts by mole of cobalt salt are mixed and ground in step S1.
5. The production method according to claim 3, wherein the Fe salt is ferric chloride.
6. The production method according to claim 3, wherein the Co salt is cobalt chloride.
7. The method of claim 3, wherein the mixture is heated at 220 ℃ for 3 hours in step S2.
8. The production method according to claim 3, wherein the organic solvent comprises ethanol and/or acetone.
9. Use of a FeCo-PPc catalyst prepared by the preparation method of any of claims 3 to 8 in OER reactions.
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